JP2010118434A - Curable composition for optical nano-imprint, and cured material and manufacturing method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for optical nano-imprint that has a low viscosity, excellent pattern-accuracy, excellent heat-resistance, and excellent mechanical-strength. <P>SOLUTION: The curable composition for optical nano-imprint includes (A) a (meth) acrylate compound expressed by general formula (1), (B) a photopolymerization initiator, and (D) a mold release agent. Here, in general formula (1), R<SP>1</SP>and R<SP>4</SP>respectively represent a hydrogen atom or a methyl group, each X represents a divalent organic group, R<SP>2</SP>and R<SP>3</SP>respectively represent a hydrogen atom, a methyl group, or a halogen atom, R<SP>2</SP>and R<SP>3</SP>may be bonded to each other so as to form a ring, and n is an integer of 1-3. When n is ≥2, each of R<SP>2</SP>and R<SP>3</SP>respectively may be the same or different. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable composition for optical nanoimprint, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device using the cured product. More specifically, a curable composition for optical nanoimprint suitable for the production of so-called permanent films, such as thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers, and other microfabrication applications for liquid crystal display device members. The present invention also relates to a cured product using the same, a method for producing the same, and a member for a liquid crystal display device using the cured product.

  The optical nanoimprint method includes a thermal nanoimprint method using a thermoplastic resin as a material to be processed (for example, see Non-Patent Document 1) and an optical nanoimprint method using a photocurable composition (for example, Non-Patent Document 2). Two techniques have been proposed. In the case of the thermal nanoimprint method, the mold is pressed onto a polymer resin heated to a temperature higher than the glass transition temperature, and after cooling, the mold is released to transfer the microstructure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, it is expected to be applied to various fields. For example, Patent Document 1 and Patent Document 2 below disclose a thermal nanoimprint method for forming a nanopattern at low cost using a thermoplastic resin.

  On the other hand, in the optical nanoimprint method that irradiates light through a transparent mold or a transparent substrate and photocures the photocurable composition, it is not necessary to heat the material for transferring the pattern when the mold is pressed, and imprinting at room temperature is possible. It becomes possible. Moreover, the photocurable resin applied to the optical nanoimprint is roughly classified into a radical polymerization type and an ion polymerization type from the difference in reaction mechanism, and these hybrid types are further added. Any type of curable composition can be used for nanoimprint applications, but since a wide range of materials can be selected, generally a radical polymerization type photocurable composition is often used (for example, non-patented). Reference 3).

  As the radical polymerization type curable composition, a composition containing a monomer (monomer) or oligomer having a vinyl group or (meth) acryl group capable of radical polymerization and a photopolymerization initiator is generally used. It is done. When the radically polymerizable curable composition is irradiated with light, the radical generated by the photopolymerization initiator attacks the vinyl group and chain polymerization proceeds to form a polymer. Moreover, when a bifunctional or higher polyfunctional group monomer or oligomer is used, a crosslinked structure can be obtained.

The performance required for the curable composition for optical nanoimprinting can be roughly classified into two types. The first is performance required for pattern formation by the nanoimprint method, and the second is required performance from the use of the formed structure.
The performance required for pattern formation by the optical nanoimprint method includes 1) low viscosity, 2) curability, 3) mold releasability and substrate adhesion. 1) Low viscosity is calculated | required in order to make the uneven | corrugated | grooved part of a mold fill a curable composition appropriately. 3) Mold releasability and substrate adhesion are required for the mold and the pattern to be appropriately peeled when the mold is released, and for the pattern not being peeled from the substrate.
In addition, as the required performance from the use of the formed structure, for the production of so-called permanent films, such as thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers, and other fine processing applications for liquid crystal display device members, etc. When used, 1) mechanical properties as a permanent film, 2) transparency in the visible range, 3) light resistance, and heat resistance can be mentioned.
Here, it is difficult to achieve both imprint pattern formation (pattern accuracy) and required performance as a permanent film at a high level.

Here, a curable composition comprising a styrene / methyl methacrylate copolymer, dipentaerythritol pentaacrylate, and a photopolymerization initiator as a curable composition for a nanoimprint for a permanent film application of a liquid crystal display is reported. (Patent Document 3).
However, the viscosity of the composition is 1000 mPa · s or more, and a pattern cannot be formed unless a quartz mold is used and the mold is pressed under high pressure. In order to form a pattern with a low-pressure (several atmospheres or less) mold pressing pressure using an inexpensive resin mold, the composition viscosity needs to be 100 mPa · s or less, but there is no description about this. Moreover, there is no description regarding light resistance, and no improvement policy is described.

On the other hand, when the composition (patent documents 3 and 4) reported as a curable composition for optical nanoimprint is used, the mechanical strength of a cured film required as a permanent film cannot be satisfied. However, these patents do not describe mechanical strength improvement.
Moreover, there is no description regarding the heat resistance of the cured film.

  Furthermore, although patent document 5 describes acrylic acid ester, there is neither description nor suggestion about using it for the curable composition for optical nanoimprint in this literature.

US Pat. No. 5,772,905 (US Pat. No. 5,956,216) JP 2007-186570 A JP 2006-310565 A JP-A-1-283255 S.Chou et al.:Appl.Phys.Lett.Vol.67,3114 (1995) M.Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999) (F.Xu et al .: SPIE Microlithography Conference, 5374,232 (2004))

  An object of the present invention is to provide a curable composition for optical nanoimprint that has a low viscosity, excellent pattern accuracy, and excellent heat resistance and mechanical strength. And

  As a result of intensive studies by the inventors of the present invention under the above problems, it has been found that the above problems can be solved by using the (meth) acrylate compound represented by the general formula (1). Specifically, the object of the present invention has been achieved by the following means.

（一般式（１）中、Ｒ¹およびＲ⁴は、それぞれ、水素原子またはメチル基を表し、Ｘは、それぞれ、２価の有機基を表し、Ｒ²およびＲ³は、それぞれ、水素原子、メチル基、または、ハロゲン原子を表し、Ｒ²およびＲ³は互いに結合して環を形成しても良く、ｎは１〜３の整数である。ｎが２以上のとき、それぞれの、Ｒ²およびＲ³は、それぞれ、同一であっても異なっていても良い。）
（２）一般式（１）のＲ¹〜Ｒ⁴の少なくとも１つが水素原子である（１）に記載の光ナノインプリント用硬化性組成物。
（３）一般式（１）のＲ¹〜Ｒ⁴の全部が水素原子である（１）に記載の光ナノインプリント用硬化性組成物。
（４）一般式（１）のＸが炭化水素基である、（１）〜（３）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（５）一般式（１）のＸがアルキレン基である、（１）〜（３）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（６）一般式（１）のＸが炭素数１の有機基である、（１）〜（５）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（７）一般式（１）のＸが置換または無置換のメチレン基である、（１）〜（６）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（８）一般式（１）のｎが１である（１）〜（７）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（９）さらに、（Ｃ）重合性単量体（上記（Ａ）一般式（１）で表される（メタ）アクリレート化合物を除く）を含む、（１）〜（８）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（１０）（Ａ）一般式（１）で表される（メタ）アクリレート化合物と（Ｃ）重合性単量体の合計含有量が７０質量％以上である、（１）〜（９）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（１１）さらに、（Ｅ）界面活性剤を含む、（１）〜（１０）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（１２）さらに、（Ｆ）酸化防止剤を含む、（１）〜（１１）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（１３）（Ｆ）酸化防止剤として、ヒンダードフェノール系酸化防止剤およびヒンダードアミン系酸化防止剤から選ばれる少なくとも１種を含む、（１２）に記載の光ナノインプリント用硬化性組成物。
（１４）分子量が２０００を超える化合物の含量が２質量％以下である、（１）〜（１３）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（１５）光ナノインプリント用硬化性組成物の粘度が３０ｍＰａ・ｓ以下である（１）〜（１４）のいずれか１項に記載の光ナノインプリント用硬化性組成物。
（１６）（１）〜（１５）のいずれか１項に記載の光ナノインプリント用硬化性組成物を硬化させた硬化物。
（１７）（１）〜（１５）のいずれか１項に記載の光ナノインプリント用硬化性組成物を用いることを特徴とする、硬化物の製造方法。
（１８）（１）〜（１５）のいずれか１項に記載の光ナノ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。
（１９）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（１８）に記載の硬化物の製造方法。
（２０）（１６）に記載の硬化物を含む液晶表示装置用部材。 (1) A curable composition for optical nanoimprints comprising (A) a (meth) acrylate compound represented by the following general formula (1), (B) a photopolymerization initiator, and (D) a release agent.

(In General Formula (1), R ¹ and R ⁴ each represent a hydrogen atom or a methyl group, X represents a divalent organic group, R ² and R ³ represent a hydrogen atom, methyl group, or a halogen atom, R ² and R ³ may be bonded to each other to form a ring, when n is an integer of 1 to 3 .n is 2 or more, respectively, R ² And R ³ may be the same or different.
(2) The curable composition for optical nanoimprints according to (1), wherein at least one of R ^{1 to} R ^{4 in} the general formula (1) is a hydrogen atom.
(3) The curable composition for optical nanoimprints according to (1), wherein all of R ^{1 to} R ^{4 in} the general formula (1) are hydrogen atoms.
(4) The curable composition for optical nanoimprints according to any one of (1) to (3), wherein X in the general formula (1) is a hydrocarbon group.
(5) The curable composition for optical nanoimprints according to any one of (1) to (3), wherein X in the general formula (1) is an alkylene group.
(6) The curable composition for optical nanoimprints according to any one of (1) to (5), wherein X in the general formula (1) is an organic group having 1 carbon atom.
(7) The curable composition for optical nanoimprints according to any one of (1) to (6), wherein X in the general formula (1) is a substituted or unsubstituted methylene group.
(8) The curable composition for optical nanoimprints according to any one of (1) to (7), wherein n in the general formula (1) is 1.
(9) Any one of (1) to (8), further including (C) a polymerizable monomer (excluding the (meth) acrylate compound represented by the above (A) general formula (1)). The curable composition for optical nanoimprints described in 1.
(10) Any of (1) to (9), wherein the total content of the (meth) acrylate compound represented by (A) the general formula (1) and the (C) polymerizable monomer is 70% by mass or more. The curable composition for optical nanoimprints of Claim 1.
(11) The curable composition for optical nanoimprints according to any one of (1) to (10), further comprising (E) a surfactant.
(12) The curable composition for optical nanoimprints according to any one of (1) to (11), further comprising (F) an antioxidant.
(13) The curable composition for optical nanoimprints according to (12), comprising (F) at least one selected from a hindered phenol-based antioxidant and a hindered amine-based antioxidant as an antioxidant.
(14) The curable composition for optical nanoimprints according to any one of (1) to (13), wherein the content of the compound having a molecular weight exceeding 2000 is 2% by mass or less.
(15) The curable composition for optical nanoimprints according to any one of (1) to (14), wherein the viscosity of the curable composition for optical nanoimprints is 30 mPa · s or less.
(16) A cured product obtained by curing the curable composition for optical nanoimprints according to any one of (1) to (15).
(17) A method for producing a cured product, wherein the curable composition for optical nanoimprints according to any one of (1) to (15) is used.
(18) A step of applying the curable composition for optical nanoimprint according to any one of (1) to (15) 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.
(19) The method for producing a cured product according to (18), further comprising a step of heating the pattern forming layer irradiated with light.
(20) A liquid crystal display member comprising the cured product according to (16).

 According to the present invention, it is possible to provide a curable composition for optical nanoimprint that has low viscosity, excellent pattern accuracy, and excellent heat resistance and mechanical strength.

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” means “acrylate” and “methacrylate”. The polymerizable 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 addition, the nanoimprint referred to in the present invention refers to pattern transfer having a size of about several tens of nanometers to several tens of micrometers, and is not limited to nano-order ones.

[Curable composition for optical nanoimprint]
The curable composition for optical nanoimprint of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is (A) a (meth) acrylate compound represented by the general formula (1), and (B) light. A polymerization initiator and (D) a mold release agent are included, and (A) a polymerizable monomer other than the (meth) acrylate compound represented by the general formula (1) is also included.
By adopting such a configuration, the composition of the present invention can be used, for example, for semiconductor integrated circuits and liquid crystal display devices that have been difficult to develop (particularly, thin film transistors for liquid crystal displays, protective films for liquid crystal color filters, spacers). And other applications, such as partition materials for plasma display panels, flat screens, micro electromechanical systems (MEMS), sensor elements, optical discs, and the like. Magnetic recording media such as density 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, rib materials for liquid crystal alignment, Microlens array, immunoassay chip, DNA separation chip, Lee black reactor, nanobio devices, optical waveguides, can also be widely applied to manufacturing, such as an optical filter, photonic crystal.
Hereinafter, these will be described in detail.

（一般式（１）中、Ｒ¹およびＲ⁴は、それぞれ、水素原子またはメチル基を表し、Ｘは、それぞれ、２価の有機基を表し、Ｒ²およびＲ³は、それぞれ、水素原子、メチル基、または、ハロゲン原子を表し、Ｒ²およびＲ³は互いに結合して環を形成しても良く、ｎは１〜３の整数である。ｎが２以上のとき、それぞれの、Ｒ²およびＲ³は、それぞれ、同一であっても異なっていても良い。） (A) (Meth) acrylate compound represented by general formula (1)

(In General Formula (1), R ¹ and R ⁴ each represent a hydrogen atom or a methyl group, X represents a divalent organic group, R ² and R ³ represent a hydrogen atom, methyl group, or a halogen atom, R ² and R ³ may be bonded to each other to form a ring, when n is an integer of 1 to 3 .n is 2 or more, respectively, R ² And R ³ may be the same or different.

In the general formula (1), R ¹ and R ⁴ are each preferably a hydrogen atom.
X is preferably a hydrocarbon group, and more preferably an alkylene group. These groups may have a substituent without departing from the gist of the present invention. The substituent is preferably an alkyl group. The number of carbon atoms in X is not particularly defined, but is preferably 1.
R ² and R ³ each represent a hydrogen atom, a methyl group, or a halogen atom, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
In the general formula (1) is preferably at least one of hydrogen atoms of R ¹ to R ^4, and more preferably all of R ¹ to R ⁴ is a hydrogen atom.
n is preferably 1 or 2, and more preferably 1.

Although the (meth) acrylate compound represented with General formula (1) below is illustrated below, it cannot be overemphasized that this invention is not limited to these.

(B) Photopolymerization initiator The curable composition for nanoimprints of the present invention contains a photopolymerization initiator (usually a photoradical polymerization initiator). The composition of this invention can make the pattern precision after light irradiation favorable by including the photoinitiator which starts radical polymerization reaction by light irradiation. As content of the photoinitiator used for this invention, 0.1-15 mass% is preferable in all the compositions, for example, More preferably, it is 0.2-12 mass%, Most preferably, it is 0. 3 to 10% by mass. When using 2 or more types of photoinitiators, the total amount becomes the said range.
When the ratio 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 ratio of the photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable.

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

  As a photoinitiator used by this invention, the initiator marketed can be used, for example. Examples of these include Irgacure® 2959 available from Ciba: (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure (Registered trademark) 184: (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 50: (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651: (2,2-dimethoxy-1,2 -Diphenylethane-1-one), Irgacure® 369: (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907: (2- Methyl-1 [4-methylthiophenyl] -2-mol Forinopropan-1-one, Irgacure® 819: (Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800: (Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure (R) 1800: (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl) -Pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure (R) OXE01: (1,2-octanedione, 1- [4- (phenylthio)) Phenyl] -2- (O-benzoyloxime), D rocur® 1173: (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI242: (ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO available from BASF: (2,4,6-trimethylbenzoyldiphenyl) Phosphine oxide), Lucirin TPO-L: (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE 1001M available from Nippon Siebel Hegner, Inc .: (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl -2- (4- (Tilphenylsulfonyl) propan-1-one, N-1414 Adekatopomer (registered trademark) N-1414 available from Asahi Denka Co., Ltd. (carbazole phenone series), Adekaoptomer (registered trademark) N-1717: ( Acridine), Adekaoptomer (registered trademark) N-1606: (triazine), TFE-triazine manufactured by Sanwa Chemical: (2- [2- (furan-2-yl) vinyl] -4,6-bis (Trichloromethyl) -1,3,5-triazine), TME-triazine manufactured by Sanwa Chemical: (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) ) -1,3,5-triazine), MP-triazine manufactured by Sanwa Chemical: (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3 -Triazine), Midori Chemical TAZ-113: (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), Midori Chemical TAZ-108 (2- (3,4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4′-bisdiethylaminobenzophenone, methyl-2-benzophenone 4-benzoyl-4′-methyldiphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1 -Chloro-4-propoxythioxanthone, 2- Methyl thioxanthone, thioxanthone ammonium salt, benzoin, 4,4′-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and Dibenzosuberone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methyl Phenylthio) phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4) 5-trimethoxyphenyl) 1,2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethyl) Aminophenyl) methane, ethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

  Furthermore, in addition to the photopolymerization initiator, a photosensitizer may be added to the curable composition for nanoimprinting of the present invention to adjust the wavelength in the UV region. Typical sensitizers that can be used in the present invention include those disclosed in Krivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically, pyrene. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

(C) Polymerizable monomer It is preferable that the composition of this invention contains polymerizable monomers other than (A) (meth) acrylate compound represented by General formula (1). The kind of the polymerizable monomer is not particularly defined, but preferably a (meth) acrylic acid ester monomer is used. The composition of this invention can obtain a more favorable pattern precision after light irradiation by containing a (meth) acrylic acid ester monomer. In the present invention, the term “(meth) acrylic acid ester monomer” means a monomer having at least one (meth) acryloyl group and capable of causing a polymerization reaction by light irradiation to form a high molecular weight product. To do.

  The polymerizable monomer used in the present invention is appropriately selected in consideration of viscosity adjustment of the composition and mechanical properties of the cured film. From the viewpoint of adjusting the viscosity of the composition, it is preferable to use a (meth) acrylic acid ester monomer having a low viscosity. In order to improve the pattern accuracy of the cured product, the viscosity of the composition is usually preferably 18 mPa · s or less, and for that purpose, a polymerizable monomer having a viscosity as low as possible is used. preferable. Since the viscosity of (meth) acrylate monomer is related to molecular weight, intermolecular interaction, etc., low viscosity of (meth) acrylic acid ester monomer should consider low molecular weight and low molecular interaction. Can be achieved.

The (meth) acrylic acid ester monomer used in the present invention is preferably a compound having a viscosity of 100 mPa · s or less, more preferably 50 mPa · s or less, particularly preferably 10 mPa · s or less, from the viewpoint of adjusting the viscosity of the composition. preferable.
The weight average molecular weight of the (meth) acrylic acid ester monomer in the present invention is preferably 500 or less, more preferably 100 to 400, and particularly preferably 100 to 300, from the viewpoint of adjusting the viscosity of the composition.

  Moreover, 1 type may be sufficient as the (meth) acrylic acid ester monomer contained in the composition of this invention, and 2 or more types may be sufficient as it.

  From the viewpoint of imparting mechanical properties to the cured film, it is also preferred to use a bifunctional or higher polyfunctional monomer. Such a polyfunctional monomer inevitably has a high molecular weight and thus has a high viscosity, and the pattern accuracy may be lowered by increasing the viscosity of the composition. Therefore, the polymerizable monomer used in the present invention is comprehensively selected in consideration of a combination of a low viscosity monomer for adjusting the viscosity and a polyfunctional monomer for imparting mechanical properties of the cured film.

  In the curable composition for nanoimprints of the present invention, the content of the polymerizable monomer in the whole composition is (A) the total amount with the (meth) acrylate compound represented by the general formula (1), 70 It is at least mass%. The content is preferably 70 to 99% by mass, and more preferably 80 to 99% by mass.

Examples of the (meth) acrylic acid ester monomer in the present invention include a monofunctional (meth) acrylic acid ester monomer having one acryloyl group. 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, butanediol mono (meth) acrylate Rate, 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, dicyclohentanyl (meth) acrylate, dicyclo Pentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate Methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Nonylphenoxy polypropylene 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, phenoxytetraethyl Lenglycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl ( Examples include meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, acrylonitrile, ethyl oxetanylmethyl acrylate.
Among these, benzyl acrylate, ethyl oxetanyl methyl acrylate, and trimethoxysilylpropyl (meth) acrylate are preferable, and ethyl oxetanyl methyl acrylate and trimethoxysilylpropyl (meth) acrylate are more preferable.

  In addition, as the (meth) acrylic acid ester monomer in the present invention, a polyfunctional (meth) acrylic acid ester monomer having at least one acryloyl group and two or more ethylenically unsaturated bond-containing groups in total can be preferably used. . First, examples of the bifunctional (meth) acrylic acid ester monomer include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated 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, allyloxy polyethylene 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 Nord 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 diacrylate, propylene oxide "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-tetra Methylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) 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, tricyclodecane dimethanol (di) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di (meth) acrylate, triglycerol di ( (Meth) acrylate, dipropylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl Meth) acrylate, dicyclopentanyl di (meth) acrylate, 4-allyloxycarbonyl-phenyl acrylate, 2,3-bis acryloyloxypropyl allyl ether are 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, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate and the like are preferably used in the present invention. Neopentyl glycol di (meth) acrylate, 4-allyloxycarbonylphenyl acrylate, and 2,3-bisacryloyloxypropyl allyl ether are particularly preferable.

Examples of tri- or higher functional (meth) acrylic acid ester monomers include ECH modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, PO modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO modified Phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tris (acrylic) Roxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipen Erythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol Examples thereof include 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.

  In addition, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Compounds having a fluorine atom such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate and tetrafluoropropyl (meth) acrylate are also used in the present invention. It can be used or used in combination as a (meth) acrylic acid ester monomer.

  Further, for the purpose of imparting flexibility to the cured product, urethane acrylate may be used as long as it is not contrary to the spirit of the present invention, that is, within a range in which the surface hardness of the cured product is not excessively flexible. When used for such a purpose, the mass ratio in the composition is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of suppressing the increase in viscosity of the composition.

As such urethane acrylate, NK oligo series U-2PPA, U-4HA, U-6HA, U-15HA, UA-32P, U-108A, U-4100, UA-5201 made by Shin-Nakamura Chemical Co., Ltd. Can be used.
In the composition of the present invention, it is preferable to use a (meth) acrylic acid ester monomer other than urethane acrylate from the viewpoint of improving the surface hardness.

  Monofunctional (meth) acrylic acid ester monomers are usually used as reactive diluents and are effective in reducing the viscosity of the composition of the present invention. The monofunctional (meth) acrylic acid ester monomer is preferably 0 to 80% by mass, more preferably 0 to 60%, from the viewpoint of suppressing increase in the composition viscosity and improving adhesion to the substrate, with respect to the composition of the present invention. It is added in the range of mass%.

  In the composition of the present invention, a vinyl ether compound, a styrene derivative, a propenyl ether, and a butenyl ether may be used in addition to the (meth) acrylic acid ester monomer. The content ratio of these monomer components in the composition of the present invention is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and particularly preferably 0% by mass.

  The vinyl ether compound can be appropriately selected from known ones such as 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, tri Methylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, Raethylene 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 Tris [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 the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

  Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like.

  Examples of other styrene derivatives include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, p -Hydroxystyrene etc. can be mentioned. Furthermore, in the present invention, vinyl naphthalene derivatives can also be used. For example, 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene. 4-methoxy-1-vinylnaphthalene and the like.

  Examples of the propenyl ether or butenyl ether include 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene Carbonate or the like can be suitably applied.

(D) Mold release agent A mold release agent is mix | blended with the composition of this invention in order to improve peelability. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the composition of the present invention to be peeled cleanly without causing the resin layer to become rough or take off the plate. In particular, the composition of the present invention is excellent in pattern accuracy when a pattern is repeatedly formed by including a release agent. Examples of the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used. Moreover, these mold release agents can be adhered to the mold.

  The silicone-based release agent has particularly good releasability from the mold when combined with the photo-curable resin used in the present invention, and the phenomenon that the plate is taken off hardly occurs. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, and examples thereof include unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicate, and silicone acrylic resin. Further, it is possible to apply a silicone leveling agent generally used in a hard coat composition.

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

  It is preferable that the modified silicone oil has appropriate compatibility with the composition components. In particular, when using a reactive silicone oil that is reactive with other coating film forming components blended as necessary in the composition, it is chemically bonded in the cured film obtained by curing the composition of the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step.

Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeded out to the surface, and excellent adhesion to metal deposition and overcoat layer. This is preferable.
The release agent can be added alone or in combination of two or more.

  When a release agent is added to the curable composition for nanoimprints of the present invention, it is preferably added in a proportion of 0.001 to 10% by mass in the total amount of the composition, and is added in a range of 0.01 to 5% by mass. More preferably. When the content of the release agent is in the range of 0.01 to 5% by mass, the effect of improving the peelability between the mold and the curable composition layer for nanoimprinting is improved, and further due to the repelling at the time of coating the composition. The problem of surface roughness of the coating film occurs, the adhesion of the substrate itself or the adjacent layer, for example, the deposited layer in the product, or the destruction of the film during transfer (film strength becomes too weak) occurs. Can be suppressed.

(E) Surfactant The curable composition for optical nanoimprinting of the present invention may contain a surfactant. The surfactant used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass in the entire composition. It is. When using 2 or more types of surfactant, the total amount becomes the said range. 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 preferably includes at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant, and includes both a fluorine-based surfactant and a silicone-based surfactant. Alternatively, it preferably contains a fluorine / silicone surfactant, and most preferably contains a fluorine / silicone surfactant. The fluorine-based surfactant and the silicone-based surfactant are preferably nonionic surfactants.
Here, the “fluorine / silicone surfactant” refers to one having both requirements of a fluorine surfactant and a silicone 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 nanoimprint curable composition of the present invention is applied to a substrate on which various films are formed, such as an amorphous silicone film, an indium oxide (ITO) film doped with tin oxide, and a tin oxide film, It becomes possible to solve the problem of poor coating 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 nanoimprint composition of the present invention can significantly improve the coating uniformity by adding the surfactant, and in a coating using a spin coater or a slit scan coater, good coating suitability regardless of the substrate size. 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 (both OMNOVA Solutions, Inc.), trade names FT250, FT251, DFX18 (both manufactured by Neos Co., Ltd.), 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 (all are Dainichi) Ink and Chemicals Co., Ltd.) and the like.
Examples of the nonionic silicone 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 / silicone 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.).

  As the surfactant used in the composition of the present invention, a nonionic (nonionic) surfactant is preferable from the viewpoint of imparting suitability for slit coating.

(F) Antioxidant Furthermore, it is preferable that the curable composition for optical nanoimprints of the present invention contains an antioxidant. Content of the antioxidant used for this invention is 0.01-10 mass% in the whole composition, for example, Preferably it is 0.2-5 mass%. When using 2 or more types of antioxidant, the total amount becomes the said range.
The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NO _x , SO _x (X is an integer). In particular, in the present invention, 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. Such antioxidants include hydrazide antioxidants, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto antioxidants, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate. , Thiocyanates, thiourea derivatives, saccharides, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, more preferred are hindered phenol antioxidants, thioether antioxidants, hindered amine (HALS) antioxidants, and more preferred are hindered phenol antioxidants and hindered amine antioxidants. is there. By adopting such an antioxidant, coloring of the cured film can be reduced, and the film thickness can be reduced.

  Commercially available products of the antioxidants include trade names Irganox 1010, 1035, 1076, 1222, TINUVIN144 (above, manufactured by Ciba Geigy Co., Ltd.), trade names Antigene P, 3C, FR, Sumilyzer S, Sumilyzer GA80 (Sumitomo Chemical ( Product name) ADK STAB AO70, AO80, AO503, LA series (manufactured by ADEKA) and the like. These may be used alone or in combination.

(Other ingredients)
In addition to the above-described components, the composition of the present invention includes a polymer component, a release agent, an organometallic coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and an adhesive. Accelerators, thermal polymerization initiators, photobase generators, colorants, elastomer particles, other monomer components other than (meth) acrylate monomers, photoacid proliferators, basic compounds, and other flow modifiers, You may add a foaming agent, a dispersing agent, etc.

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 polyfunctional (meth) acrylic acid ester monomer may be blended within a range that achieves the object of the present invention. it can. Examples of the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as ester acrylate, polyether acrylate, and epoxy acrylate, and hydrolysis condensates of trimethoxysilylpropyl acrylate. As addition amount of an oligomer component, 0-30 mass% is preferable with respect to the component except the solvent of a composition, More preferably, it is 0-20 mass%, More preferably, it is 0-10 mass%, Most preferably, it is 0-5. % By mass.
The curable composition for nanoimprinting of the present invention may further contain a polymer component from the viewpoint of improving imprintability and curability. 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. Further, from the viewpoint of pattern formability, it is preferable that the resin component is as few as possible, and it is preferable that the resin component is not included except for surfactants and trace amounts of additives.

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

  Examples of the silane coupling agent that can be used in the composition of the present invention include vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; γ-methacryloxypropyl Trimethoxysilane; epoxy silane such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane; N-β- (amino Aminosilanes such as ethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane ;and, Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane.

  Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacryliso Stearoyl titanate, isopropyl isostearoyl diacryl titanate, Propyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate. Examples thereof include bis (ethyl acetoacetate).

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkyl Examples thereof include acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetoacetate) and the like.

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

  In order to improve storage stability etc., you may mix | blend a polymerization inhibitor with the curable composition for nanoimprint of this invention. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; copper and the like. The polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the composition of the present invention.

  An ultraviolet absorber can also be used for the curable composition for nanoimprints of the present invention. Commercially available UV absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Co., Ltd.) and the like. It is preferable to mix | blend an ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of the curable composition for optical nanoimprints.

  A light stabilizer can also be used in the curable composition for nanoimprinting of the present invention. Commercially available products of the light stabilizer include Tinuvin 292, 144, 622LD (manufactured by Ciba Geigy Corp.), Sanol LS-770, 765, 292, 2626, 1114, 744 (manufactured by Sankyo Kasei Kogyo Co., Ltd.). ) And the like. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

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

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

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

  When hardening the composition of this invention, a thermal-polymerization initiator can also be added as needed. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. The thermal polymerization initiator in the composition is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and still more preferably 4.0% by mass or less. In order to obtain the effect, the addition of the thermal polymerization initiator is preferably 3.0% by mass or more.

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

  In the curable composition for nanoimprints of the present invention, a colorant may be optionally added for the purpose of improving the visibility of the coating film. As the colorant, pigments and dyes used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like can be used as long as the object of the present invention is not impaired. As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And metal complex oxides. Organic pigments include CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139,151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, CIPigment Violet 19, 23, 32, 39, CIPigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36 37, CIPigment Brown 25, 28, CIPigment Black 1, 7 and carbon black. The colorant is preferably blended at a ratio of 0.001 to 2% by mass with respect to the total amount of the composition.

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

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

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

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

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

  Moreover, a solvent can also be used for the curable composition for nanoimprints of the present invention. The content of the organic solvent is preferably 3% by mass or less in the entire composition. That is, since the composition of the present invention preferably contains 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 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 particularly preferably not contained. As described above, the composition of the present invention does not necessarily contain an organic solvent. However, in the case of dissolving a compound that does not dissolve in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. Any of these may be added. The organic solvent that can be preferably used in the composition of the present invention is a solvent generally used in curable compositions for optical nanoimprints and photoresists, which dissolves and uniformly disperses the compound used in the present invention. There is no particular limitation as long as it does not react with these components.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as rumethyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 Ketones such as pentanone and 2-heptanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2- Methyl hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, acetic acid Chill, methyl lactate, and the like esters such as lactic acid esters such as ethyl lactate.
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added. These may be used alone or in combination of two or more.
Among these, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, 2-heptanone and the like are particularly preferable.

The curable composition for nanoimprints of the present invention preferably has a surface tension in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, the effect of improving surface smoothness is acquired.
In addition, the moisture content at the time of preparation of the curable composition for nanoimprinting of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, and further preferably 1.0% by mass or less. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the composition of the present invention can be made more stable.

(Viscosity of curable composition for nanoimprinting of the present invention)
The viscosity of the curable composition for nanoimprints of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. The curable composition for nanoimprints of the present invention preferably has a viscosity at 25 ° C. of 3 to 30 mPa · s, more preferably 5 to 20 mPa · s, and particularly preferably 7 to 12 mPa · s. By setting the viscosity of the composition of the present invention to 3 mPa · s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa · s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. A composition having a viscosity of 3 mPa · s or more is also easier to prepare than a composition having a viscosity of less than 3 mPa · s. On the other hand, by setting the viscosity of the composition of the present invention to 30 mPa · s or less, even when a mold having a fine concavo-convex pattern is brought into close contact with the composition, it is also applied to the cavity of the concave portion of the mold by a load of about 3 atm. This is preferable because the composition flows in and hardly causes bubble defects. Furthermore, by setting the viscosity to 20 mPa · s or less, even if the mold load is about atmospheric pressure, bubble defects are less likely to occur, which is more preferable.

  Generally, the viscosity of the composition can be adjusted by blending various monomers, oligomers and polymers having different viscosities. In order to design the viscosity of the curable composition for nanoimprints of the present invention within the above range, it is preferable to adjust the viscosity by adding a composition having a single viscosity of 5.0 mPa · s or less.

(Light transmittance of cured product)
The nanoimprint curable composition of the present invention preferably has a 400 nm light transmittance of 95% or more when a thin film (cured product) having a thickness of 3.0 μm is formed by exposure and heating. Here, the light transmittance at 400 nm means the light transmittance at a wavelength of 400 nm. The 400 nm light transmittance is more preferably 97% or more.
The 400 nm light transmittance can be measured by, for example, “UV-2400PC” manufactured by Shimadzu Corporation.

  The light transmittance (400 nm light transmittance) can also be improved by adding the above-mentioned antioxidant to the composition of the present invention.

[Method for producing cured product]
Next, the formation method of the hardened | cured material (especially fine uneven | corrugated pattern) using the curable composition for nanoimprints of this invention is demonstrated. Applying (usually applying) the curable composition for nanoimprinting of the present invention onto a substrate or support (base material) to form a pattern forming layer, and pressing a mold against the surface of the pattern forming layer; A fine concavo-convex pattern can be formed by curing the composition of the present invention through the 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. That is, the curable composition for nanoimprints of the present invention is preferably cured by light and heat.
The cured product obtained by the method for producing a cured product of the present invention is excellent in pattern precision, curability, and light transmittance, and is particularly suitable as a protective film for liquid crystal color filters, spacers, and other liquid crystal display device members. Can be used.

  Specifically, a layer (pattern forming layer) consisting of the composition of the present invention is applied on a base material (substrate or support) by applying at least a pattern forming layer consisting of the composition of the present invention 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 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.

  As an application of the curable composition for nanoimprints of the present invention, the composition of the present invention is applied on a substrate or a support, and a layer comprising the composition is exposed, cured, and dried (baked) as necessary. Thus, a permanent film such as an overcoat layer or an insulating film can be produced.

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

Below, the manufacturing method (pattern formation method (pattern transfer method)) of the hardened | cured material using the curable composition for nanoimprints 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 apply | coated on a base material, and a pattern formation layer is formed.
As a method for applying the curable composition for nanoimprinting of the present invention onto a substrate, generally well-known methods such as dip coating, air knife coating, curtain coating, wire bar coating, and gravure are used. It can be formed by applying by a coating method, an extrusion coating method, a spin coating method, a slit scanning method, or 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, 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.

  The substrate (substrate or support) for applying the curable composition for nanoimprinting of the present invention can be selected depending on various applications, for example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (spin on glass glass), polymer film such as polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, glass or transparent There are no particular restrictions on 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. Further, the shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. Furthermore, as described later, as the substrate, a light transmissive or non-light transmissive material can be selected according to the combination with the mold or the like.

  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 (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.

In optical nanoimprint lithography using the curable composition for nanoimprinting of the present invention, a light-transmitting material is selected for at least one of a molding material and / or a substrate. In optical imprint lithography applied to the present invention, a curable composition for optical nanoimprinting of the present invention is applied on a substrate to form a pattern forming layer, 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 optical nanoimprint can be apply | coated on a transparent base material, a mold can be pressed, light can be irradiated from the back surface of a base material, and the curable composition for optical nanoimprint 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.

  The non-light transmissive mold material used in the case of using the transparent substrate of the present invention is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicone, silicone nitride, polysilicon, silicone oxide, and amorphous silicone. There are no particular restrictions. 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 subjected to a release treatment in order to improve the peelability between the curable composition for optical nanoimprint 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, it is usually preferable to perform the mold pressure at 10 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 not easily 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 remaining film of the curable composition for optical nanoimprinting on the mold convex portion is reduced.

In the manufacturing method of the hardened | cured material of this invention, the irradiation amount of the light irradiation in the process of irradiating light to the said pattern formation layer should just be sufficiently larger than the irradiation amount required for hardening. The irradiation amount necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint and the tackiness of the cured film.
Moreover, in the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but 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 optical nanoimprinting. It may be irradiated with light. Moreover, in the manufacturing method of the hardened | cured material of this invention, the preferable vacuum degree at the time of light irradiation is the range of 1 kPa to 1 atmosphere.

  The light used for curing the curable composition for optical nanoimprinting 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 5 mJ / cm ² or more, the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold can be prevented. Also. When the exposure amount is 1000 mJ / cm ² or less, deterioration of the permanent film due to decomposition of the composition can be suppressed.
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.

  In the present invention, the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint lithography 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 reactivity decrease due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprint lithography. It may be irradiated with light. In the present invention, the preferred degree of vacuum is in the range of 1 kPa to normal pressure.

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

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 curable composition for optical nanoimprinting of the present invention can also be applied as an etching resist for semiconductor integrated circuits, recording materials, flat panel displays, and the like.
When using the curable composition for optical nanoimprinting of the present invention as an etching resist, first, for example, a silicon wafer on which a thin film such as SiO ₂ is formed as a substrate, and the cured product of the present invention is formed on the substrate. A fine pattern of nano order is formed by the manufacturing 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 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.

(Preparation of curable composition for optical nanoimprint)
According to the composition described in the table, curable compositions for optical nanoimprints of Examples and Comparative Examples were prepared by adding a polymerizable monomer, a photopolymerization initiator, an antioxidant, a surfactant, a release agent, and the like. . The unit in the table is mass%.

<Polymerizable monomer>
M-1 to M-4: The compounds M-1 to M-4 exemplified as the exemplified compound of the general formula (1) were employed.
S-1: Neopentyl glycol diacrylate (KAYARD NPGDA, manufactured by Nippon Kayaku Co., Ltd.). It is a polyfunctional acrylate monomer.
S-2: benzyl acrylate (Biscoat # 160, manufactured by Osaka Organic Chemical Co., Ltd.). It is a monofunctional acrylate monomer.
S-3: Trimethylolropane triacrylate (KAYARD M309, manufactured by Nippon Kayaku Co., Ltd.). It is a polyfunctional monomer.
S-4: γ-acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.). It is a silane coupling group-containing monomer.
S-5: Ethylene glycol dimethacrylate (NK ester 1G, manufactured by Shin-Nakamura Chemical Co., Ltd.) is a bifunctional methacrylic acid ester monomer.

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

<Antioxidant>
B-1: Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)
B-2: ADK STAB AO503 (manufactured by ADEKA Corporation)
B-3: TINUVIN 144 (Ciba Specialty Chemicals)

<Surfactant>
W-1: Fluorosurfactant (manufactured by DIC Corporation, MegaFuck F780F)
W-2: Non-fluorinated surfactant (manufactured by Takemoto Yushi Co., Ltd., Pionin D6315)

<Release agent>
X-1: Modified silicone oil X-22-3710 (Shin-Etsu Chemical Co., Ltd.)

<Others>
Y-1: Polybenzyl methacrylate-methacrylic acid copolymer (weight average molecular weight 18000)

[Evaluation of curable composition for optical nanoimprint]
About the composition of each Example and the comparative example, it measured and evaluated according to the following evaluation method about the viscosity, pattern precision, heat resistance, pencil hardness, and an elastic recovery factor. Here, Comparative Example 1 corresponds to the composition described in Patent Document 3.

<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 100 rpm for 0.5 mPa · s or more and less than 5 mPa · s, 50 rpm for 5 mPa · s or more and less than 10 mPa · s, 20 rpm for 10 mPa · s or more and less than 30 mPa · s, and 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.

<Observation of pattern accuracy>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The spin-coated coated base film was set in a nanoimprint 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 (vacuum degree: 10 Torr, about 1.33 kPa), the mold was pressed onto the substrate, and nitrogen purge (1.5 atm: mold pressing pressure) was performed to replace the inside of the apparatus with nitrogen. This was exposed from the back surface of the mold at an illuminance of 10 mW / cm ² and an exposure amount of 300 mJ / cm ² . After the exposure, the mold was released to obtain a resist pattern.
The pattern preparation operation was repeated 10 times using the same mold, and the resist pattern obtained at the 10th time was heated in an oven at 230 ° C. for 30 minutes to be completely cured.
The transferred pattern shape was observed with a scanning electron microscope and an optical microscope, and the pattern shape was evaluated according to the following criteria.
A: It is almost the same as the pattern of the original plate from which the pattern shape of the mold is based.
B: There is a part (a range of less than 10% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern.
C: There is a part (a range of 10% or more and less than 20% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern shape.
D: The pattern pattern of the mold is clearly different from the original pattern, or the film thickness of the pattern is 20% or more different from the original pattern.

<Evaluation of heat resistance>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not pressure-bonded, exposed in an atmosphere of nitrogen at an illuminance of 10 mW / cm ² and an exposure amount of 240 mJ / cm ² , and then in an oven It was cured by heating at 230 ° C. for 270 minutes. About the obtained cured film, the light transmittance in 400 nm was measured by UV-2400PC by Shimadzu Corporation.
A: The transmittance was 98% or more.
B: The transmittance was 90% or more and less than 98%.
C: The transmittance is less than 90%, which is problematic in practical use.

<Measurement of pencil hardness>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not pressure-bonded, exposed in an atmosphere of nitrogen at an illuminance of 10 mW / cm ² and an exposure amount of 240 mJ / cm ² , and then in an oven It was cured by heating at 230 ° C. for 30 minutes. With respect to the obtained cured film, the surface hardness was measured using a pencil applied with a load force of 500 g. The pencil hardness was evaluated from a total of five levels, starting from 2H and up to 6H.
The contact surface of the pencil was observed with an optical microscope, and 1H minus the pencil hardness at which a plurality of shavings began to be observed on the surface was defined as the surface hardness of the cured product.
As a permanent film application, a pencil hardness of 2H or less has a practical problem.

<Evaluation of elastic recovery rate>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not pressure-bonded, exposed in an atmosphere of nitrogen at an illuminance of 10 mW / cm ² and an exposure amount of 240 mJ / cm ² , and then in an oven It was cured by heating at 230 ° C. for 30 minutes. An indentation test was performed with a micro hardness tester manufactured by Shimadzu Corporation. The measurement conditions were a triangular pyramid indenter, a load of 3 mN, and a holding time of 1 second.
Elastic recovery rate = [(displacement at maximum load [μm]) − (return displacement at unloading [μm])} ÷ (displacement at maximum load [μm]) × 100 and evaluated as follows: did.
Elastic recovery rate [%]
A: 60% or more B: 50% or more, less than 60% C: 40% or more, less than 50% D: less than 40% An elastic recovery of less than 40% is problematic in practice.

The results are shown in the table below. As is clear from the results in the following table, the composition of the present invention was found to be excellent in all of the viscosity, pattern accuracy, heat resistance and mechanical strength of the composition.
Moreover, in the comparative example 3, it turned out that the hardened | cured material of a composition partially adheres to the mold surface, and has deteriorated the pattern precision.

Claims (20)

(A) A curable composition for optical nanoimprint, which comprises a (meth) acrylate compound represented by the following general formula (1), (B) a photopolymerization initiator, and (D) a release agent.

(In General Formula (1), R ¹ and R ⁴ each represent a hydrogen atom or a methyl group, X represents a divalent organic group, R ² and R ³ represent a hydrogen atom, methyl group, or a halogen atom, R ² and R ³ may be bonded to each other to form a ring, when n is an integer of 1 to 3 .n is 2 or more, respectively, R ² And R ³ may be the same or different. The curable composition for optical nanoimprint according to claim 1, wherein at least one of R ^{1 to} R ^{4 in} the general formula (1) is a hydrogen atom. 2. The curable composition for optical nanoimprinting according to claim 1, wherein all of R ^{1 to} R ^{4 in} the general formula (1) are hydrogen atoms. The curable composition for optical nanoimprints according to any one of claims 1 to 3, wherein X in the general formula (1) is a hydrocarbon group. The curable composition for optical nanoimprints according to any one of claims 1 to 3, wherein X in the general formula (1) is an alkylene group. The curable composition for optical nanoimprints according to any one of claims 1 to 5, wherein X in the general formula (1) is an organic group having 1 carbon atom. The curable composition for optical nanoimprints according to any one of claims 1 to 6, wherein X in the general formula (1) is a substituted or unsubstituted methylene group. N of general formula (1) is 1, The curable composition for optical nanoimprints of any one of Claims 1-7. The optical nanoimprint according to any one of claims 1 to 8, further comprising (C) a polymerizable monomer (excluding the (meth) acrylate compound represented by (A) the general formula (1)). Curable composition. (A) The total content of the (meth) acrylate compound represented by the general formula (1) and the polymerizable monomer (C) is 70% by mass or more, 10. Curable composition for optical nanoimprint. Furthermore, the curable composition for optical nanoimprints of any one of Claims 1-10 containing (E) surfactant. Furthermore, the curable composition for optical nanoimprints of any one of Claims 1-11 containing (F) antioxidant. (F) The curable composition for optical nanoimprints of Claim 12 containing at least 1 sort (s) chosen from a hindered phenolic antioxidant and a hindered amine antioxidant as antioxidant. The curable composition for optical nanoimprints according to any one of claims 1 to 13, wherein the content of the compound having a molecular weight exceeding 2000 is 2% by mass or less. The curable composition for optical nanoimprints according to any one of claims 1 to 14, wherein the curable composition for optical nanoimprints has a viscosity of 30 mPa · s or less. Hardened | cured material which hardened the curable composition for optical nanoimprints of any one of Claims 1-15. The manufacturing method of hardened | cured material characterized by using the curable composition for optical nanoimprints of any one of Claims 1-15. Applying the curable composition for optical nanoimprints according to any one of claims 1 to 15 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 process of heating the said pattern formation layer irradiated with light is included, The manufacturing method of the hardened | cured material of Claim 18 characterized by the above-mentioned. The member for liquid crystal display devices containing the hardened | cured material of Claim 16.