JP2010070586A - Curable composition, cured product, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition suitable for making a so-called permanent film for applications such as fine processing of a member for a liquid crystal display, such as a thin film transistor of a liquid crystal display, a protective film for a liquid crystal color filter, a spacer, or the like. <P>SOLUTION: The curable composition including a modified inorganic fine particle (A) is obtained by mixing a liquid dispersion including the modified inorganic fine particle, which is obtained by linking an inorganic fine particle having an average particle size of 100 nm or less with an organic binder, with a silica gel particle having a particle size of 10 μm or more and then removing the silica gel particle having the particle size of 10 μm or more. The inorganic fine particle is colloidal silica, and further, the curable composition includes a polymerizable monomer (B) and a photoinitiator (C), wherein the polymerizable monomer (B) is a (meth)acrylic acid ester monomer. The cured product is also obtained by curing the curable composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable composition, a cured product using the same, a method for producing the same, and a liquid crystal display device member using the cured product. More specifically, a curable composition suitable for production of a so-called permanent film, such as a thin film transistor for a liquid crystal display, a protective film for a liquid crystal color filter, a spacer, and other fine processing applications for liquid crystal display device members, and the like are used. The present invention relates to a cured product, a method for producing the cured product, and a liquid crystal display member using the cured product.

  There are two types of nanoimprint methods: 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 using a photocurable composition (for example, see Non-Patent Document 2). The technology has been proposed. In the case of the thermal nanoimprint method, the mold is pressed on a polymer resin heated to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer the fine structure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, it is expected to be applied to various fields. For example, Patent Documents 1 and 2 below disclose thermal nanoimprinting methods that form 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, a radical polymerization type curable composition is generally used (for example, non-patent literature). 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.

  As performance necessary for pattern formation by the photo nanoimprint method, 1) a low-viscosity curable composition for filling the concavo-convex portion of the mold with a curable composition, 2) having curability, and 3) mold. The mold and the pattern are peeled off at the time of releasing, and the pattern is not peeled off from the substrate (mold releasability, substrate adhesion).

  On the other hand, when a curable composition for nanoimprint is used as a member for a permanent film of a liquid crystal display, it is necessary to ensure mechanical strength (surface hardness) and transparency of the cured product.

  As a curable composition for nanoimprinting for permanent films of liquid crystal displays, a curable composition comprising a copolymer of styrene / methyl methacrylate, dipentaerythritol pentaacrylate and a photopolymerization initiator has been reported. (Patent Document 2).

  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 (up to several atmospheric pressures) using an inexpensive resin mold, the composition viscosity needs to be 30 mPa · s or less, but there is no description about this. In addition, there is no description about high sensitivity.

  On the other hand, as a method for increasing the mechanical strength of a cured film, it has been proposed to include inorganic fine particles in a curable composition (Patent Document 3). However, the patent does not describe application to a curable composition for nanoimprints, and does not describe any technique relating to low viscosity dispersion.

  On the other hand, a nanoimprint curable composition containing inorganic fine particles has been invented (Patent Document 4). However, the surface hardness of the cured film does not have sufficient hardness, and there is no description of the improvement policy.

US Pat. No. 5,772,905 JP 2008-83336 A JP 2006-63244 A JP 2007-177194 A S.Chou et al.:Appl.Phys.Lett.Vol.67,3114 (1995) M.Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999)

  The object of the present invention is to solve the above-mentioned problems, and provides a nanoimprinting composition capable of forming a hard coat layer excellent in surface hardness while maintaining a suitable viscosity as a nanoimprinting composition. The purpose is to do.

  Based on the above problems, the inventors of the present application have made extensive studies, and as a result, modified inorganic fine particles in which an organic binder is bonded to inorganic fine particles having an average particle diameter of 100 nm or less are treated with silica gel particles having a particle diameter of 10 μm or more. It has been found that by using inorganic fine particles, the composition has a composition viscosity suitable as a curable composition for nanoimprint, and can impart mechanical strength (surface hardness) necessary for a hard coat layer. Moreover, it turned out that the cured film peeling at the time of mold release which is a subject of a nanoimprint system can be improved. Specifically, it has been found that the above problems can be solved by the following means.

(1) A dispersion containing modified inorganic fine particles obtained by binding an organic binder to inorganic fine particles having an average particle size of 100 nm or less is mixed with silica gel particles having a particle size of 10 μm or more, and silica gel particles having a particle size of 10 μm or more are removed. A curable composition containing the modified inorganic fine particles (A).
(2) The curable composition according to (1), wherein the organic binder is a silane coupling agent.
(3) The curable composition according to (1) or (2), wherein the organic binder is represented by the following general formula (1).

（一般式（１）中、Ｒ¹は総炭素数６以上のアルキル基を表し、Ｒ²は総炭素数１〜３のアルコキシ基またはクロロ原子を表し、ｎは１〜３の整数を表す。Ｒ¹および／またはＲ²が複数存在するとき、それぞれのＲ¹およびＲ²は、同一であっても良いし、異なっていても良い。）
（４）前記平均粒径１００ｎｍ以下の無機微粒子がコロイダルシリカである、（１）〜（３）のいずれか１項に記載の硬化性組成物。
（５）前記平均粒径１００ｎｍ以下の無機微粒子の平均粒径が５０ｎｍ以下である、（１）〜（４）のいずれか１項に記載の硬化性組成物。
（６）前記修飾無機微粒子（Ａ）の無機粒子部分の平均粒径が１００ｎｍ以下である、（１）〜（５）のいずれか１項に記載の硬化性組成物。
（７）前記修飾無機微粒子（Ａ）が５０質量％以下の範囲で含まれる、（１）〜（６）のいずれか１項に記載の硬化性組成物。
（８）さらに、（Ｂ）重合性単量体および（Ｃ）光重合開始剤を含む、（１）〜（７）のいずれか１項に記載の硬化性組成物。
（９）前記（Ｂ）重合性単量体が（メタ）アクリル酸エステルモノマーである、（８）に記載の硬化性組成物。
（１０）前記（Ｂ）重合性単量体を６０質量％以上含む、（８）または（９）に記載の硬化性組成物。
（１１）さらに、界面活性剤を含む（１）〜（１０）のいずれか１項に記載の硬化性組成物。
（１２）さらに、酸化防止剤を含む（１）〜（１１）のいずれか１項に記載の硬化性組成物。
（１３）さらに、離型剤を含む（１）〜（１２）のいずれか１項に記載の硬化性組成物。
（１４）有機溶剤を含まない状態での前記硬化性組成物の粘度が３０ｍＰａ・ｓ以下である、（１）〜（１３）のいずれか１項に記載の硬化性組成物。
（１５）（１）〜（１４）のいずれか１項に記載の硬化性組成物を硬化させた硬化物。
（１６）（１）〜（１４）のいずれか１項に記載の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。
（１７）（１）〜（１４）のいずれか１項に記載の硬化性組成物を基材上に塗布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。
（１８）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（１７）に記載の硬化物の製造方法。

(In General Formula (1), R ¹ represents an alkyl group having 6 or more carbon atoms in total, R ² represents an alkoxy group having 1 to 3 carbon atoms or a chloro atom, and n represents an integer of 1 to 3). When a plurality of R ¹ and / or R ² are present, each R ¹ and R ² may be the same or different.)
(4) The curable composition according to any one of (1) to (3), wherein the inorganic fine particles having an average particle diameter of 100 nm or less are colloidal silica.
(5) The curable composition according to any one of (1) to (4), wherein an average particle diameter of the inorganic fine particles having an average particle diameter of 100 nm or less is 50 nm or less.
(6) The curable composition according to any one of (1) to (5), wherein an average particle size of the inorganic particle portion of the modified inorganic fine particles (A) is 100 nm or less.
(7) The curable composition according to any one of (1) to (6), wherein the modified inorganic fine particles (A) are contained in a range of 50% by mass or less.
(8) The curable composition according to any one of (1) to (7), further comprising (B) a polymerizable monomer and (C) a photopolymerization initiator.
(9) The curable composition according to (8), wherein the polymerizable monomer (B) is a (meth) acrylic acid ester monomer.
(10) The curable composition according to (8) or (9), comprising 60% by mass or more of the polymerizable monomer (B).
(11) The curable composition according to any one of (1) to (10), further comprising a surfactant.
(12) The curable composition according to any one of (1) to (11), further comprising an antioxidant.
(13) The curable composition according to any one of (1) to (12), further including a release agent.
(14) The curable composition according to any one of (1) to (13), wherein a viscosity of the curable composition in a state not containing an organic solvent is 30 mPa · s or less.
(15) A cured product obtained by curing the curable composition according to any one of (1) to (14).
(16) A method for producing a cured product, wherein the curable composition according to any one of (1) to (14) is used.
(17) A step of applying the curable composition according to any one of (1) to (14) on a substrate to form a pattern forming layer;
Pressing the mold against the surface of the pattern forming layer;
Irradiating the pattern forming layer with light;
The manufacturing method of the hardened | cured material characterized by including.
(18) The method for producing a cured product according to (17), further comprising a step of heating the pattern forming layer irradiated with light.

  By treating the modified inorganic fine particles, in which an organic binder is bonded to inorganic fine particles having an average particle size of 100 nm or less, with silica gel particles having a particle size of 10 μm or more, the surface has excellent surface hardness while maintaining a suitable viscosity as a nanoimprint composition. It has become possible to provide a composition for nanoimprinting capable of forming a hard coat layer.

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 the present specification, “polymerizable group” refers to a group involved in polymerization.
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.

  The curable composition of the present invention includes a modified inorganic fine particle (A), and is usually a curable composition containing (B) a polymerizable monomer, (C) a photopolymerization initiator, and the like, for nanoimprinting. Preferably used.

(A) Modified inorganic fine particles The modified inorganic fine particles in the present invention are obtained by mixing a dispersion containing modified inorganic fine particles obtained by binding an organic binder to inorganic fine particles having an average particle size of 100 nm or less with silica gel particles having a particle size of 10 μm or more. The silica gel particles having a particle diameter of 10 μm or more are removed. The average particle size of the inorganic fine particle portion of the obtained modified inorganic fine particles is 100 nm or less when inorganic fine particles having an average particle size of 100 nm or less are used, and can be obtained by changing the size of the average particle size of the employed inorganic fine particles. The average particle diameter of the modified inorganic fine particles can be adjusted.

Inorganic fine particles having an average particle size of 100 nm or less The average particle size of the inorganic fine particles in the present invention is 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less. By setting it as such a range, the raise of the viscosity of the curable composition of this invention can be suppressed, and when this cured film is created using the curable composition of this invention, this cured film The strength of is improved. The lower limit of the average particle size of the inorganic fine particles is not particularly defined, but can be set to 1 nm or more, for example.
The kind of inorganic fine particles in the present invention is not particularly defined, and widely known inorganic fine particles can be used. For example, colloidal silica, titania, alumina, zirconia and the like can be employed, and colloidal silica is preferable.
Specific examples of colloidal silica include those manufactured by Nissan Chemical Industries, Snowtex (methanol silica sol: those having an average particle size of 10-15 nm, IPA-ST: those having an average particle size of 10-15 nm, IPA- ST-L: average particle size in the range of 40-50 nm, IPA-ST-ZL: average particle size in the range of 70-100 nm, MEK-ST: average particle size in the range of 10-15 nm), Fuso Chemical Examples include Quartron PL series (PL-1-MA: those having an average particle diameter of 10 to 15 nm, PL-1-Tol: those having an average particle diameter of 10 to 15 nm), and the like, manufactured by Kogyo Co., Ltd.

Organic Binder The organic binder to be bonded to the inorganic fine particles is not particularly defined, but preferably includes a silane coupling agent, an epoxy compound, and an isocyanate compound, and a silane coupling agent is preferable.
The molecular weight of the silane coupling agent is preferably 100 to 1000, more preferably 150 to 600.

  Examples of the silane coupling agent used in the present invention include compounds represented by the following general formula (1).

（一般式（１）中、Ｒ¹は総炭素数１以上のアルキル基を表し、Ｒ²は総炭素数１〜３のアルコキシ基またはクロロ原子を表し、ｎは１〜３の整数を表す。Ｒ¹および／またはＲ²が複数存在するとき、それぞれのＲ¹およびＲ²は、同一であっても良いし、異なっていても良い。）

(In the general formula (1), R ¹ represents a total carbon number of 1 or more alkyl groups, R ² represents an alkoxy group containing a total or chloro atoms carbon atoms 1-3, n represents an integer of 1 to 3. When a plurality of R ¹ and / or R ² are present, each R ¹ and R ² may be the same or different.)

Formula (1) Total alkyl group having 1 or more atoms represented by R ¹ in the remaining on the surface of the inorganic fine particles such as colloidal silica, which functions as a dispersion stabilizing group. For such purposes, R ¹ is preferably an alkyl group having 3 or more carbon atoms, more preferably an alkyl group having 6 or more carbon atoms, and particularly preferably an alkyl group having 10 or more carbon atoms. By making R ¹ have a total carbon number of 3 or more, it becomes easy to form a steric repulsion layer necessary for stabilizing the dispersion. The upper limit of the total carbon number of the alkyl group represented by R ¹ is not particularly defined, but is usually 40 or less.
Moreover, the alkyl group represented by R ¹ may have various substituents. Examples of the substituent include an alkoxy group, an aryloxy group, an alkylthio group, an alkoxycarbonyl group, an alkenylcarbonyloxy group ((meth) acryloyl group), a vinyl group, and the like. By selecting the substituent, the solubility parameter with the dispersion medium in which the modified inorganic fine particles are dispersed can be adjusted. Among these substituents, an unsubstituted alkyl group, an alkoxy-substituted alkyl group, an alkylthio-substituted alkyl group, and an alkoxycarbonyl-substituted alkyl group are preferable from the viewpoint of suppressing the increase in viscosity of the composition because the solubility parameters with the dispersion medium can be easily adjusted. In addition, when these substituents contain a carbon atom, the carbon number of the carbon atom is included in the total carbon number of the alkyl group.

As represented by R ² in the general formula (1), a methoxy group, an ethoxy group, and a chloro atom are preferable, and a methoxy group is more preferable from the viewpoint of reactivity with the surface of the inorganic fine particles and handleability.
In general formula (1), n is preferably 1.

  Specific examples of the general formula (1) include those shown below, but the organic binder in the present invention is not limited thereto.

Bonding of inorganic fine particles and organic binder As a method of bonding inorganic fine particles and an organic binder, known methods can be widely adopted. Usually, a modified inorganic fine particle dispersion is prepared by reacting inorganic fine particles and an organic binder in an organic solvent.
Various organic solvents can be used as the solvent. In particular, when used for a curable composition for nanoimprinting, it may be necessary to remove the solvent. In such a case, the reaction is preferably carried out in a solvent having a boiling point of 120 ° C. or lower, which can be easily distilled off. More preferably, the reaction is carried out in a solvent at 50 to 120 ° C. Specific examples of such solvents include alcohol solvents such as methanol, ethanol and isopropyl alcohol (IPA), ketone solvents such as acetone and methyl ethyl ketone (MEK), and other solvents such as ethyl acetate and toluene. Can be mentioned. The temperature at the time of making it react can be performed under reflux from room temperature, for example, can be room temperature (for example, 25 degreeC) -120 degreeC, and can also be 60-100 degreeC. The reaction time can be, for example, 1 to 8 hours, and further can be 2 to 6 hours. The reaction concentration can be performed, for example, in the range of 0.1 to 40% by mass as the solid content concentration, and further in the range of 5 to 30% by mass.

The addition ratio of the silane coupling agent to be reacted is preferably added 0.05 to 2 times by weight, more preferably 0.5 times by weight based on the weight of the colloidal silica. By adding 0.05 times by weight or more of the silane coupling agent, the surface of the colloidal silica can be effectively coated with the silane coupling agent, and the viscosity of the resulting photosensitive composition can be further reduced. . Moreover, an unreacted silane coupling agent can be reduced by setting it as 2 times weight or less.
For the purpose of promoting the reaction between the silane coupling agent and colloidal silica, acetic acid, acidic water, neutral water, alkaline water, or the like can be added to the reaction solvent.

Silica gel particles having a particle diameter of 10 μm or more As the silica gel particles used in the present invention, known silica gel particles can be used. Examples include Wako Pure Chemical Industries, Wakosil series (particle diameter: 10 μm), Kanto Chemical Co., Ltd. silica gel 60 series, silica gel 60N series (particle diameter: 40 to 210 μm). In the present invention, the use of silica gel particles having a particle diameter of 10 μm or more facilitates separation of the modified inorganic fine particles and the silica gel particles.
The particle size of the silica gel particles is preferably 10 μm or more, and more preferably 100 μm or more. The upper limit is not particularly defined, but is, for example, 10,000 μm or more.

A method of mixing a dispersion containing modified inorganic fine particles obtained by binding an organic binder to inorganic fine particles with silica gel particles and a method of removing silica gel particles having a particle size of 10 μm or more. There is a way.
As a first method, there is a method in which silica gel particles are mixed and stirred in a dispersion containing modified inorganic fine particles in which an organic binder is bonded to inorganic fine particles, and the silica gel particles in the dispersion are separated. Examples of the separation method include filtration separation and centrifugal separation, but filtration separation is preferred for simplicity. Methods such as cotton plug filtration can be employed.
As a second method, there is a method in which a column filled with silica gel particles is prepared in advance, and the dispersion is mixed with and removed from the silica gel particles by passing through the column.
Both the first method and the second method can be diluted and washed with an appropriate organic solvent during mixing and removal.

Method for preparing curable composition containing modified inorganic fine particles It may be preferable that the curable composition is a solventless type. Since the above-described dispersion of modified inorganic fine particles usually contains an organic solvent as a dispersion medium, the solvent needs to be distilled off. As a method of distilling off the solvent, a method of distilling off under reduced pressure can be used. There are two methods for distilling off the solvent of the dispersion.
The first method is a method in which the solvent of the dispersion liquid itself is distilled off to obtain a powder of modified fine particles, and the powdered modified fine particles are redispersed in the curable composition.
As a second method, the monomer components used in the curable composition are added in advance to the dispersion of the modified inorganic fine particles, and the solvent contained in the dispersion is removed from the mixture to create a curable composition. It is a method to do.

  For the particle diameter in the present invention, the particle diameter was calculated from the surface area measured by the specific surface area measurement method (BET method). Here, in the present invention, the calculation is performed assuming that the particles are true spheres.

Curable composition The curable composition of this invention contains a modified inorganic fine particle (A). The content of the modified inorganic fine particles is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less from the viewpoint of improving the strength of the cured film and suppressing the increase in the viscosity of the curable composition. preferable. Moreover, it is preferable to use 3% by mass or more because adhesion between the cured film resin and the substrate can be improved.

  The curable composition of the present invention usually contains (B) a polymerizable monomer and (C) a photopolymerization initiator in addition to the modified inorganic fine particles (A), and further includes a surfactant, an antioxidant, and the like. These components may be included. Hereinafter, these components will be described in detail.

Polymerizable monomer (B)
The polymerizable monomer used in the present invention is not particularly defined as long as it is a photopolymerizable polymerizable monomer, but a (meth) acrylic acid ester monomer is preferable.

(Meth) acrylic acid ester monomer The curable composition of the present invention preferably contains a (meth) acrylic acid ester monomer. The composition of this invention can obtain a 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 (meth) acrylic acid ester monomer used in the present invention is appropriately selected for the purpose of adjusting the viscosity of the composition and the 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.

  Further, from the viewpoint of imparting mechanical properties to the cured film, the (meth) acrylic acid ester monomer is preferably bifunctional or more. 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 of the present invention, the content of the (meth) acrylic acid ester monomer in the entire composition is 60% by mass or more from the viewpoint of imparting mechanical properties of the cured film. The content is preferably 60 to 99% by mass, and more preferably 80 to 99% by mass. However, the content of the (meth) acrylic acid ester monomer in the present invention is determined in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention as described above.

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-methoxy Ethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanediol mono (meth) a Relate, 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, phenoxytetrae Tylene glycol (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 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 present invention, the polyfunctional (meth) acrylate monomer having at least one acryloyl group and two or more ethylenically unsaturated bond-containing groups in total is 15% by mass with respect to the composition of the present invention. Added. The amount added to the curable composition of the present invention is preferably 15 to 99% by mass, more preferably 30 to 99% by mass, and particularly preferably 50 to 99% by mass. The ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 15 to 99% by mass, more preferably 50 to 99% by mass, and particularly preferably 60 to 99% by mass of the total polymerizable unsaturated monomer. It is added in the range of mass%. The ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more ethylenically unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably, based on the composition of the present invention. Preferably, it is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered | hung by making the ratio of the polymerizable unsaturated monomer which has 3 or more of polymerizable unsaturated bond containing groups into 80 mass% or less, it is preferable.

Photopolymerization initiator The curable composition of the present invention usually contains a photopolymerization initiator. The composition of the present invention preferably contains a photoradical polymerization initiator that initiates a radical polymerization reaction by light irradiation, and by including a photoradical polymerization initiator, the pattern accuracy after light irradiation should be good. Can do. The content of the radical photopolymerization initiator used in the present invention is preferably 0.1 to 15% by mass, more preferably 0.2 to 12% by mass, and particularly preferably in the total composition. 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 radical 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 radical 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 radical 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 radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. 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® OXE01: (1,2-octanedione, 1- [4- (phenylthio)) Phenyl] -2- (O-benzoyloxime), Daro ur® 1173: (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 and 1020, CGI 242: (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 Siber Hegner, Japan: (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl -2- (4-Methylphenol Rusulfonyl) 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 Type), Adekaoptomer (registered trademark) N-1606: (triazine type), TFE-triazine made 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 made by Sanwa Chemical: (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-tria ), 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-methylthio Xanthone, 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 dibenzo Suberon, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4-benzoyldiphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenyl Thio) phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ', 5'-tetrakis (3,4,5-to Methoxyphenyl) 1,2'-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, tris (4-dimethylaminophenyl) Examples include methane, ethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

  Furthermore, in addition to the radical photopolymerization initiator, a photosensitizer may be added to the curable composition 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.

Surfactant The curable composition 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. In addition, as said fluorine-type surfactant and silicone type surfactant, a nonionic surfactant is preferable.
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 Florard FC-430 and FC-431 (manufactured by Sumitomo 3M Limited), trade names Surflon S-382 (Asahi Glass ( EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (manufactured by Tochem Products), trade names PF-636, PF-6320, PF -656, PF-6520 (all OMNOVA Solutions, Inc.), trade names FT250, FT251, DFX18 (all manufactured by Neos), trade names Unidyne DS-401, DS-403, DS-451 ( All are manufactured by Daikin Industries, Ltd.), trade names Megafuk F780F, 171, 172, 173, 178K, 178A, (I The deviation is also made by DIC Corporation.
Examples of the nonionic silicone surfactant include trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), Pionin D6315 (manufactured by Takemoto Yushi Co., Ltd.), MegaFuck Paintad 31 (DIC) And 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 DIC Corporation).

  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.

Antioxidant Furthermore, it is preferable that the curable composition of this invention contains 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. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants, thioether antioxidants, and hindered amine (HALS) antioxidants are particularly preferable from the viewpoint of coloring of the cured film and reduction in film thickness.

  Commercially available products of the antioxidants include trade names Irganox 1010, 1035, 1076, 1222, TINUVIN 144 (above, manufactured by Ciba Specialty Chemicals), trade names Antigene P, 3C, FR, Sumilyzer S, Sumilyzer GA80 (Sumitomo Chemical Industries ( Product name) ADK STAB AO70, AO80, AO503, LA series (manufactured by ADEKA) and the like. These may be used alone or in combination.

Other components In addition to the above-described components, the composition of the present invention contains, as necessary, 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. Agent, adhesion promoter, thermal polymerization initiator, photobase generator, colorant, elastomer particles, other monomer components other than (meth) acrylate monomer, photoacid multiplier, basic compound, and other flow control An agent, an antifoaming agent, a dispersing agent and the like may be added.

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 of the present invention may further contain a polymer component from the viewpoint of improving imprint suitability 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.

  For the purpose of further improving the peelability, a release agent can be arbitrarily blended in the composition of the present invention. Specifically, it is added for the purpose of enabling the mold pressed against the layer of the composition of the present invention to be peeled cleanly without causing the resin layer to become rough or take off the plate. Examples of the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, Teflon powder (Teflon is a registered trademark), fluorine-based, 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 of the present invention, it is preferably blended in a proportion of 0.001 to 10% by mass in the total amount of the composition, and added in a range of 0.01 to 5% by mass. Is more preferable. When the content of the release agent is in the range of 0.01 to 5% by mass, the effect of improving the releasability between the mold and the curable composition layer is improved, and the coating film is formed by repelling when the composition is applied. The problem of surface roughness occurs, the product itself may interfere with the adhesion of the substrate itself or the adjacent layer, for example, the deposited layer, or the film may be destroyed during transfer (film strength becomes too weak). Can be suppressed.

  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 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.

  A polymerization inhibitor may be blended with the curable composition of the present invention in order to improve storage stability and the like. 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 of this 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 a ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of a photocurable composition.

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

  An adhesion promoter may be added to the curable composition 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 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.

  A colorant may be optionally added to the curable composition of the present invention for the purpose of improving the visibility of the coating film. As the colorant, pigments and dyes used in UV inkjet compositions, color filter compositions, CCD image sensor compositions, and the like can be used as long as the object of the present invention is not impaired. As the pigment that can be used in the present invention, 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 of the present invention, elastomer particles may be added as optional components for the purpose of improving mechanical strength, flexibility, and the like.
The elastomer particles that can be added as an optional component to the composition of the present invention preferably have an average particle size of 10 nm to 700 nm, more preferably 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / Particles of elastomer such as polyene copolymer, acrylic rubber, butadiene / (meth) acrylic ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer. Further, core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

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

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

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

In the composition of the present invention, other monomer components other than the (meth) acrylic acid ester monomer may be used. As other monomer components, epoxy compounds, oxetane compounds, vinyl ether compounds, styrene derivatives, propenyl ethers and butenyl ethers may be used. The content ratio of other 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.
As the epoxy compound, known compounds can be appropriately selected, and examples thereof include glycidyl-2-ethylhexyl, limonene oxide, and trimethylolpropane triglycidyl ether.
As the oxetane compound, known compounds can be appropriately selected. Examples thereof include 3-ethyl-3-hydroxyethyloxetane and 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene. .

  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.

  In addition, the water content at the time of preparation of the curable composition 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.

  Moreover, a solvent can also be used for the curable composition of this 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. Organic solvents that can be preferably used in the composition of the present invention include those generally used in photocurable compositions and photoresists, and those that dissolve and uniformly disperse the compounds used in the present invention. It is not particularly limited 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 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 water content at the time of preparation of the curable composition 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 The viscosity of the curable composition of this invention is demonstrated. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. The curable composition of the present invention preferably has a viscosity at 25 ° C. of 3 to 18 mPa · s, more preferably 5 to 15 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 18 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for residues to remain after photocuring in the mold convex portion. Further, when the viscosity of the composition of the present invention is 18 mPa · s or less, the viscosity hardly affects the formation of a fine pattern.
Moreover, it is preferable that it is 30 mPa * s or less in the state which does not contain a solvent, and, as for the viscosity of the curable composition of this invention, it is more preferable that it is 5-18 mPa * s.

  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 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 curable composition of the present invention has a 400 nm light transmittance of 95% or more when a 3.0 μm-thick thin film (cured product) is formed by exposure and heating. preferable. 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 concavo-convex pattern) using the curable composition of this invention is demonstrated. A step of applying the curable composition of the present invention on a substrate or a support (base material) to form a pattern forming layer; a step of pressing a mold against the surface of the pattern forming layer; A fine uneven | corrugated pattern can be formed by hardening the composition of this invention through the process of irradiating. 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 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 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 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 coating method when coating the curable composition of the present invention on a substrate, generally well-known coating methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure, etc. It can be formed by coating 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 of the present invention can be selected depending on various applications, for example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection Film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (spin on glass glass), polyester film, polycarbonate film, polymer film such as polyimide film, TFT array substrate, PDP electrode plate, glass and transparent plastic substrate There are no particular restrictions on conductive substrates such as ITO and metals, insulating substrates, semiconductor fabrication substrates such as silicone, silicon 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 of the present invention, a light transmissive 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 of the present invention is applied onto a substrate to form a pattern forming layer, a light-transmitting mold is pressed onto this surface, and the back surface of the mold Then, the pattern forming layer is cured by irradiating light. Moreover, a photocurable composition is apply | coated on a transparent base material, a mold is pressed, light can be irradiated from the back surface of a base material, and a photocurable composition can also be hardened.
The light irradiation may be performed with the mold attached or after the mold is peeled off. In the present invention, the light irradiation is preferably performed with the mold in close contact.

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

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

During exposure is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By making the exposure time 1 mW / cm ² or more, the exposure time can be shortened so that productivity is improved, and by making the exposure time 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure dose is desirably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . If it is 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 of the present invention can be prepared as a solution by mixing each of the above components and then filtering with a filter having a pore size of 0.05 μm to 5.0 μm, for example. Mixing and dissolution of the curable composition 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 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 nanoimprinting composition of the present invention as an etching resist, first, a method for producing a cured product of the present invention on a substrate using, for example, a silicon wafer on which a thin film such as SiO ₂ is formed as a substrate. To form a nano-order fine pattern. 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.

[Example 1]
<Adjustment of modified inorganic fine particles G-1>
Silane coupling to a mixed solution of colloidal silica isopropyl alcohol solution (IPA-ST) 60 g (manufactured by Nissan Chemical Co., Ltd., average particle size 10 nm, 30 mass% IPA solution), methyl ethyl ketone (MEK) 300 ml, acetic acid 8.8 g Agent (A-1) 9.6 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and reacted under reflux for 2.5 hours. Next, 30 g of silica gel (manufactured by Kanto Chemical Co., Inc., 60 N, particle size: 60 to 210 μm) was added. The silica gel suspension was filtered through a cotton plug and then filtered again through a glass filter to remove silica gel particles having a particle diameter of 10 μm or more.
After filtration, MEK was added to adjust the solid content concentration to 30% by mass.

[Example 2]
<Adjustment of modified inorganic fine particles G-2>
Modified inorganic fine particles were prepared in the same manner as in Example 1 except that 9.6 g of the silane coupling agent (A-1) was changed to 4.2 g of the silane coupling agent (A-2).

Example 3
<Adjustment of modified inorganic fine particles G-3>
Modified inorganic fine particles were prepared in the same manner as in Example 1 except that 9.6 g of the silane coupling agent (A-1) was changed to 8.2 g of the silane coupling agent (A-3).

Example 4
<Adjustment of modified inorganic fine particles G-4>
Modified inorganic fine particles were prepared in the same manner as in Example 1 except that 9.6 g of the silane coupling agent (A-1) was changed to 8.2 g of the silane coupling agent (A-4).

Example 5
<Adjustment of modified inorganic fine particles G-5>
Modified inorganic fine particles were prepared in the same manner as in Example 1 except that 9.6 g of the silane coupling agent (A-1) was changed to 12.6 g of the silane coupling agent (A-5).

Example 6
<Adjustment of modified inorganic fine particles G-6>
Modified inorganic fine particles were prepared in the same manner as in Example 1 except that 9.6 g of the silane coupling agent (A-1) was changed to 15.2 g of the silane coupling agent (A-6).

Example 7
<Adjustment of modified inorganic fine particles G-7>
In Example 1, colloidal silica IPA-ST was changed to IPA-ST-L (manufactured by Nissan Chemical Co., Ltd., average particle size 45 nm, 30% by mass IPA solution) in the same manner as in Example 1, except that colloidal silica IPA-ST was changed. The modified inorganic fine particles were prepared by the method described above.

Example 8
(Preparation of curable composition)
The modified inorganic fine particles G-1 (66.7 parts by mass, 20% by mass to the composition) and the polymerizable monomer S-1 (74.9% by mass) are mixed, and the solvent contained in the modified inorganic fine particles under reduced pressure is mixed. Distilled off. The addition amount of the modified inorganic fine particles and the polymerizable monomer after removal of the solvent is as shown in the following table. Furthermore, photoinitiator P-1 (2 mass%), antioxidant B-1 (1 mass%), antioxidant B-2 (2 mass%), surfactant W-1 (0.05 mass) %) And surfactant W-2 (0.1 mass%) were added to prepare the curable composition of Example 8.

[Examples 9-15, Comparative Examples 1-3]
The compositions of Examples 9 to 15 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 8, except that the composition was changed as shown in the following table. In addition, the addition amount of the modified inorganic fine particle in the following table is the addition amount of solid content after the solvent is distilled off.
X-1 used in Comparative Example 2 uses modified inorganic fine particles that were not treated with silica gel in preparation of the modified inorganic fine particles G-3.
In addition, in the adjustment of the modified inorganic fine particles G-3, when silica gel having a particle size of 10 μm or more is mixed and then used as a curable composition without removing silica gel having a particle size of 10 μm or more (Comparative Example 3), curing is performed. The surface roughness of the film (unevenness derived from silica gel), white turbidity and cracks in the cured film were observed, and evaluation was difficult.

<Silane coupling agent>
A-1: Normal hexyl trimethoxysilane, manufactured by Tokyo Chemical Industry Co., Ltd. A-2: Normal octadecyltrimethoxysilane, manufactured by Tokyo Chemical Industry Co., Ltd. A-3: γ-acryloyloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. KBM-5103, manufactured by
A-4: γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403
A-5: γ-methacryloyloxypropylmethyldiethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBE-502
A-6: Butyloxycarbonylethylthiopropyltrimethoxysilane

<Polymerizable monomer>
S-1: Neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARD NPGDA). It is a polyfunctional (meth) acrylic acid ester monomer.
S-2: benzyl acrylate (Osaka Organic Chemical Co., Ltd., Biscoat # 160). It is a monofunctional acrylate monomer.
S-3: Trimethylolropane triacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARD M309). It is a polyfunctional monomer.
S-4: γ-acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.). It is a silane coupling group-containing monomer.

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

<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)

[Evaluation of curable composition]
About the composition of each Example and the comparative example, it measured and evaluated in accordance with the following evaluation method about the viscosity, the transcription | transfer precision, surface hardness, board | substrate adhesiveness, and heat resistance. The results are shown in the table below.

<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 transfer 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 (made by Toray Dow Corning Co., Ltd., “SILPOT184” 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 against 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 under the conditions of an illuminance of 10 mW / cm ² and an exposure amount of 50 mJ / cm ² . After the exposure, the mold was released to obtain a resist pattern.
Further, the obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes.
The pattern shape after the transfer was observed with a scanning electron microscope 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.

<Measurement of pencil hardness of cured film>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3 μm, and set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power 2000 mW / cm ² ) as a light source. Next, without setting the mold, the inside of the apparatus was evacuated (the degree of vacuum was 10 Torr (about 1.33 kPa)), the mold was pressed against the substrate, and the nitrogen purge (1.5 atm: mold pressing pressure) was performed. The inside of the apparatus was replaced with nitrogen. Further, the mold was not pressed and exposed to light at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere, and then heated in an oven at 230 ° C. for 30 minutes to cure the film.
Evaluation was performed by changing the load to 500 g using a 4H pencil with reference to the test method of JIS-K5400.
The cured film after the test was evaluated by observing the degree of scratches on the surface of the cured film with an optical microscope.
A: No scratches were observed on the cured film surface.
B: Scratches were observed on the surface of the cured film, but there is no practical problem.
C: Scratches where the cured film surface is scraped off are observed, and there is a problem in practical use.
D: Scratches enough to peel the cured film from the glass substrate were observed.

<Evaluation of substrate adhesion>
The adhesion between the cured resin and the substrate was measured by the following method. The larger the value, the better the adhesion with the substrate.
Each composition was spin-coated on a substrate previously coated with a blue resin composition for a color filter on a glass substrate so as to have a film thickness of 3 μm. It was set in a nanoimprint apparatus using a high pressure mercury lamp (lamp power: 2000 mW / cm ² ) manufactured by ORC as a light source. Next, without setting the mold, the inside of the apparatus was evacuated (vacuum degree: 10 Torr (about 1.33 kPa)), the mold was pressed against the substrate, and nitrogen purge (1.5 atm: mold pressing pressure) was performed. The inside of the apparatus was replaced with nitrogen. Further, a cured film was formed by exposing the mold at an exposure amount of 240 mJ / cm ² under a nitrogen atmosphere without pressing the mold.
A cellophane tape (manufactured by Nitto Denko Corporation, cellophane tape, width 12 mm) was affixed on the obtained cured film, and the tape was peeled in a direction of 90 ° with respect to the substrate surface. The peeling force at that time was measured with a force gauge.
In all measurements, it was confirmed that peeling occurred at the substrate interface and the cured product interface.

<Evaluation of heat resistance>
Each composition was spin-coated so that the film thickness was 3 μm. The high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC was set in the nanoimprint apparatus using the light source. Next, without setting the mold, the inside of the apparatus was evacuated (the degree of vacuum was 10 Torr (about 1.33 kPa)), the mold was pressed against the substrate, and the nitrogen purge (1.5 atm: mold pressing pressure) was performed. The inside of the apparatus was replaced with nitrogen. A cured film was formed by exposing the mold at a light exposure amount of 240 mJ / cm 2 without applying pressure to the mold. The cured film was heated at 230 ° C. for 270 minutes using a blast oven. 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.

  By using modified inorganic fine particles obtained by treating modified inorganic fine particles obtained by binding an organic binder to inorganic fine particles having an average particle size of 100 nm or less with silica gel particles having a particle diameter of 10 μm or more, a composition viscosity suitable as a curable composition can be obtained. And mechanical strength (surface hardness) necessary for the hard coat layer can be imparted. Moreover, it turned out that the cured film peeling at the time of mold release which is a subject of a nanoimprint system can be improved.

Claims (18)

  A dispersion comprising modified inorganic fine particles in which an organic binder is bonded to inorganic fine particles having an average particle diameter of 100 nm or less is mixed with silica gel particles having a particle diameter of 10 μm or more, and the silica gel particles having a particle diameter of 10 μm or more are removed. A curable composition containing inorganic fine particles (A).   The curable composition according to claim 1, wherein the organic binder is a silane coupling agent. The curable composition according to claim 1 or 2, wherein the organic binder is represented by the following general formula (1).

(In General Formula (1), R ¹ represents an alkyl group having 6 or more carbon atoms in total, R ² represents an alkoxy group having 1 to 3 carbon atoms or a chloro atom, and n represents an integer of 1 to 3). When a plurality of R ¹ and / or R ² are present, each R ¹ and R ² may be the same or different.)   The curable composition according to any one of claims 1 to 3, wherein the inorganic fine particles having an average particle size of 100 nm or less are colloidal silica.  The curable composition according to any one of claims 1 to 4, wherein an average particle size of the inorganic fine particles having an average particle size of 100 nm or less is 50 nm or less.   The curable composition of any one of Claims 1-5 whose average particle diameter of the inorganic particle part of the said modified inorganic fine particle (A) is 100 nm or less.   The curable composition according to any one of claims 1 to 6, wherein the modified inorganic fine particles (A) are contained in an amount of 50% by mass or less.  The curable composition according to any one of claims 1 to 7, further comprising (B) a polymerizable monomer and (C) a photopolymerization initiator.   The curable composition according to claim 8, wherein the polymerizable monomer (B) is a (meth) acrylic acid ester monomer.   The curable composition according to claim 8 or 9, comprising 60% by mass or more of the polymerizable monomer (B).   Furthermore, the curable composition of any one of Claims 1-10 containing surfactant.   Furthermore, the curable composition of any one of Claims 1-11 containing antioxidant.   Furthermore, the curable composition of any one of Claims 1-12 containing a mold release agent.   The curable composition of any one of Claims 1-13 whose viscosity of the said curable composition in the state which does not contain an organic solvent is 30 mPa * s or less.   Hardened | cured material which hardened the curable composition of any one of Claims 1-14.   The manufacturing method of hardened | cured material characterized by using the curable composition of any one of Claims 1-14. The process of apply | coating the curable composition of any one of Claims 1-14 on a base material, and forming a pattern formation 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 17 characterized by the above-mentioned.