JP2010209250A - Photocurable composition, cured product using the same, method for producing the cured product, and member for liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable composition excellent in adhesion after exposure to light, while holding low viscosity and high transcription pattern accuracy. <P>SOLUTION: This photocurable composition includes at least one of compounds expressed by formula (1) and/or formula (2) and at least one of compounds expressed by formula (3), in a mass ratio of 20:80 to 80:20. In the formulas (1) and (2), X represents an organic group; and n denotes an integer of 1-4. In the formula (3), Y represents an organic group; m denotes an integer of 1-4; and R represents hydrogen or a methyl group. The compound expressed by formula (1), the compound expressed by formula (2), and the compound expressed by formula (3) each have a molecular weight of 150-400. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photocurable composition, in particular, a curable composition used for optical nanoimprint, and a cured product obtained by curing the composition. Moreover, it is related with the manufacturing method of hardened | cured material, and the member for liquid crystal display devices using this hardened | cured material.

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

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

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

  First, an application example of the first technique for creating a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the fine processing. On the other hand, the use of a nanoimprint lithography technique (optical nanoimprint method) proposed as a technique for performing fine pattern formation at low cost has been studied. For example, Patent Document 1 below discloses a nanoimprint technique in which a silicon wafer is used as a stamper and a fine structure of 25 nm or less is formed by transfer. Along with this trend, in order to apply nanoimprint lithography to the production of semiconductor integrated circuits, studies on properties such as mold-resin peelability and pattern transfer accuracy have begun to become active. On the other hand, studies for applying nanoimprint lithography to semiconductor integrated circuit fabrication, such as mold releasability from resin, pattern transfer accuracy, and substrate adhesion, have begun to be active.

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

  As a permanent film to which a conventional photolithography technique is applied, for example, a protective film provided on a TFT substrate of a liquid crystal panel, a step between R, G, B layers is reduced, and a high temperature process at the time of sputtering of an ITO film is performed. For example, a protective film provided on the color filter in order to impart resistance. In the formation of these protective films (permanent films), the uniformity of the coating film, adhesion to the substrate, high light transmittance after heat treatment exceeding 200 ° C., planarization characteristics, solvent resistance, scratch resistance Various characteristics such as these are required.

  In the field of spacers used in liquid crystal displays, photocurable compositions comprising a resin, a photopolymerizable monomer, and an initiator have generally been widely used in conventional photolithography methods. The spacer generally forms a pattern having a size of about 10 μm to 20 μm by photolithography using a photocurable composition on the color filter substrate after forming the color filter or after forming the color filter protective film. Further, it is formed by heat curing by post-baking. The spacer used in such a liquid crystal display is required to have high mechanical characteristics against external pressure, hardness, developability, pattern transfer accuracy, adhesion and the like. For this reason, development of the photocurable composition suitable for formation of permanent films (permanent resist), such as the said transparent protective film and spacer using a nanoimprint method, is calculated | required.

  Although the required characteristics of materials used for optical nanoimprint lithography are often different depending on the application to which they are applied, the demands on process characteristics are common regardless of the application. For example, the main requirement items shown in Non-Patent Document 3 below are applicability, substrate adhesion, low viscosity (<5 mPa · s), peelability, low curing shrinkage, fast curability, and the like. The key to material design is how to control these required characteristics and balance them. For this reason, at least the process material and the permanent film have greatly different required characteristics, so the material must be developed according to the process and application.

  As described above, the main technical problems as a permanent film include pattern accuracy, adhesion, transparency after heat treatment exceeding 200 ° C., high mechanical properties (strength against external pressure), scratch resistance, and flattening properties. There are many problems such as solvent resistance and reduction of outgas during heat treatment. Even when the curable composition for optical nanoimprint is applied as a permanent film, it is important to provide uniformity of the coating film, transparency after heat treatment, and scratch resistance, as in the case of conventional resists using acrylic resins. It is.

  At the same time, as a problem peculiar to the curable composition for optical nanoimprint, in addition to the above-mentioned problem, it is necessary to ensure the fluidity of the resist to the concave portion of the mold and to reduce the viscosity without using a solvent or a small amount of solvent. It is necessary to consider that it is easily peeled off from the mold after photocuring and no adhesion to the mold occurs, and the technical difficulty of designing the composition is further increased.

  As described above, although various materials are disclosed for the curable composition for optical nanoimprint, there is no sufficient design guideline for the curable composition suitable for producing a permanent film. It is.

  Patent Document 3 describes a photocurable composition containing an allyl compound and an acrylate compound. Here, as described in the Examples, the composition actually requires a resin. However, since it contains a resin, it is difficult to use as a curable composition for nanoimprint.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 JP 2001-183825 A

S.Chou et al.:Appl.Phys.Lett.Vol.67,3114 (1995) M.Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999) Latest resist material handbook, P1, 103-104 (2005, published by the Information Organization)

  The present invention has been accomplished in view of the above circumstances, and is a photocurable composition excellent in photocurability, in particular, a photocurable composition for photo-nanoimprinting suitable for producing a permanent film such as a flat panel display. The purpose is to provide.

（一般式（１）および一般式（２）中、Ｘは、それぞれ、有機基を表し、ｎは、それぞれ、１〜４の整数を表す。一般式（３）中、Ｙは有機基を表し、ｍは１〜４の整数を表し、Ｒは水素またはメチル基を表す。但し、一般式（１）で表される化合物、一般式（２）で表される化合物および一般式（３）で表される化合物は、それぞれ、分子量が１５０〜４００である。）
（２）前記一般式（１）で表される化合物を含む、（１）に記載の光硬化性組成物。
（３）一般式（１）または一般式（２）におけるＸ、および一般式（３）におけるＹが、それぞれ、炭化水素基である、（１）または（２）に記載の光硬化性組成物。
（４）一般式（３）において、Ｒが水素原子である、（１）〜（３）のいずれか１項に記載の光硬化性組成物。
（５）一般式（１）または一般式（２）におけるｎが、２または３である、（１）〜（４）のいずれか１項に記載の光硬化性組成物。
（６）一般式（１）で表される化合物、一般式（２）で表される化合物および一般式（３）で表される化合物の合計量が、光硬化性組成物の８０質量％以上である、（１）〜（５）のいずれか１項に記載の光硬化性組成物。
（７）（１）〜（６）のいずれか１項に記載の光硬化性組成物を硬化させてなる硬化物。
（８）（７）に記載の硬化物を含む液晶表示装置用部材。
（９）（１）〜（６）のいずれか１項に記載の光硬化性組成物を基板上に適用してパターン形成する工程と、前記パターン形成層にモールドに押圧する工程と、前記パターン形成層に光照射する工程を含むことを特徴とする硬化物の製造方法。 Under such circumstances, as a result of intensive studies by the present inventor, by adding a specific amount of an allyl ester compound or allyl ether compound having a specific structure in addition to a polymerizable monomer such as (meth) acrylate. The inventors have found that a photocurable composition having excellent adhesion after light irradiation can be obtained, and have completed the present invention. Specifically, it was achieved by the following means.
(1) At least one of the compound represented by the following general formula (1) and / or the compound represented by the following general formula (2) and at least one of the compounds represented by the following general formula (3) are included in mass. A photocurable composition comprising a ratio of 20:80 to 80:20.

(In General Formula (1) and General Formula (2), X represents an organic group, and n represents an integer of 1 to 4. In General Formula (3), Y represents an organic group. , M represents an integer of 1 to 4, and R represents hydrogen or a methyl group, provided that the compound represented by the general formula (1), the compound represented by the general formula (2), and the general formula (3) Each of the represented compounds has a molecular weight of 150 to 400.)
(2) The photocurable composition as described in (1) containing the compound represented by the said General formula (1).
(3) The photocurable composition according to (1) or (2), wherein X in general formula (1) or general formula (2) and Y in general formula (3) are each a hydrocarbon group. .
(4) The photocurable composition according to any one of (1) to (3), wherein R in formula (3) is a hydrogen atom.
(5) The photocurable composition according to any one of (1) to (4), wherein n in the general formula (1) or the general formula (2) is 2 or 3.
(6) The total amount of the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) is 80% by mass or more of the photocurable composition. The photocurable composition according to any one of (1) to (5), wherein
(7) A cured product obtained by curing the photocurable composition according to any one of (1) to (6).
(8) A member for a liquid crystal display device comprising the cured product according to (7).
(9) A step of applying a pattern by applying the photocurable composition according to any one of (1) to (6) onto a substrate, a step of pressing the pattern forming layer against a mold, and the pattern The manufacturing method of the hardened | cured material characterized by including the process of light-irradiating a formation layer.

  According to the present invention, it has become possible to provide a curable composition for nanoimprint lithography that has low viscosity and high transfer pattern accuracy and excellent adhesion after light irradiation.

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

The present invention is described in detail below. In the present specification, (meth) acrylate represents acrylate and methacrylate, (meth) acryl represents acryl and methacryl, and (meth) acryloyl represents acryloyl and methacryloyl. Moreover, in this specification, a monomer and a monomer are the same. The monomer in the present invention is a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers. In the present specification, the functional group refers to a group involved in polymerization.
The nanoimprint referred to in the present invention refers to pattern transfer having a size of about several μm to several tens of nm, and it goes without saying that the nanoimprint is not limited to a nano-order.

（一般式（１）および一般式（２）中、Ｘは、それぞれ、有機基を表し、ｎは、それぞれ、１〜４の整数を表す。一般式（３）中、Ｙは有機基を表し、ｍは１〜４の整数を表し、Ｒは水素またはメチル基を表す。但し、一般式（１）で表される化合物、一般式（２）で表される化合物および一般式（３）で表される化合物は、それぞれ、分子量が１５０〜４００である。） [Photocurable composition]
The photocurable composition of the present invention is represented by at least one of a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), and the following general formula (3). It is characterized by including at least one compound in a mass ratio of 20:80 to 80:20.

(In General Formula (1) and General Formula (2), X represents an organic group, and n represents an integer of 1 to 4. In General Formula (3), Y represents an organic group. , M represents an integer of 1 to 4, and R represents hydrogen or a methyl group, provided that the compound represented by the general formula (1), the compound represented by the general formula (2), and the general formula (3) Each of the represented compounds has a molecular weight of 150 to 400.)

In the present invention, by using an allyl ester compound or an allyl ether compound having a specific structure in combination, the storage stability is high before curing and the fine irregular pattern forming ability is excellent. Further, after curing, the pattern accuracy is excellent, and furthermore, the coating film properties can be comprehensively improved in other respects. Therefore, the photocurable composition of the present invention can be widely used for optical nanoimprint lithography. In a particularly preferred embodiment, the substrate adhesion of the photocurable composition of the present invention can also be significantly improved.

That is, the photocurable composition of the present invention can have the following characteristics when used in optical nanoimprint lithography.
(1) Since the solution fluidity at room temperature is excellent, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. Residues hardly remain after curing.
(2) Since the storage stability of the composition is high and problems such as thickening and gelation do not easily occur over time, no deterioration in pattern accuracy is observed over a long period of time after the composition is prepared.
(3) The cured film after curing has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peeling properties between the coating film and the mold. Since pulling does not cause surface roughness, a good pattern can be formed.
(4) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.

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

（一般式（１）および一般式（２）中、Ｘは、それぞれ、有機基を表し、ｎは、それぞれ、１〜４の整数を表す。一般式（３）中、Ｙは有機基を表し、ｍは１〜４の整数を表し、Ｒは水素またはメチル基を表す。但し、一般式（１）で表される化合物、一般式（２）で表される化合物および一般式（３）で表される化合物は、それぞれ、分子量が１５０〜４００である。） (Compound represented by general formula (1), compound represented by general formula (2), compound represented by general formula (3))
The compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) will be described.

(In General Formula (1) and General Formula (2), X represents an organic group, and n represents an integer of 1 to 4. In General Formula (3), Y represents an organic group. , M represents an integer of 1 to 4, and R represents hydrogen or a methyl group, provided that the compound represented by the general formula (1), the compound represented by the general formula (2), and the general formula (3) Each of the represented compounds has a molecular weight of 150 to 400.)

X in the general formulas (1) and (2) is preferably a hydrocarbon group, and more preferably a hydrocarbon group having 2 to 6 carbon atoms. X may be linear, branched or cyclic, and is preferably linear or branched.
In the general formulas (1) and (2), n is preferably 2 or 3, respectively.

Y in the general formula (3) is preferably a hydrocarbon group, more preferably a hydrocarbon group having 2 to 10 carbon atoms. Y may be linear, branched or cyclic, and is preferably linear or branched.
R in the general formula (3) is preferably a hydrogen atom. By using hydrogen atoms, the sensitivity during exposure increases.
Moreover, it is preferable that the curable composition of this invention contains the compound whose m in General formula (3) is 2 or more.

  Specific examples of the compound represented by the general formula (1) include diallyl maleate, diallyl fumarate, diallyl succinate, diallyl adipate, triallyl citrate, allyl phenylacetate, allyl heptanoate, diallyl isophthalate, and the like. It is done.

  Specific examples of the compound represented by the general formula (2) include trimethylolpropane diallyl ether, tetraallyloxyethane, trimethylolpropane monoallyl ether, trimethylolpropan triallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl. Examples include ether, allyl n-octyl ether, glycerol α, α′-diallyl ether, and the like.

  Specific examples of the compound represented by the general formula (3) include 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate. 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, benzyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, Cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, isooctyl ( Acrylate), cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, urethane acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (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, octyl (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxy ethyl (Meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tribromophenyl (meth) ) Acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxy Propyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, 4- (meth) acryloyloxy-benzoic acid allyl ester, 3- (meth) acryloyloxy Benzoic acid allyl ester, p-isopropenylphenol, 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, 1,9-nonanediol di ( (Meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexa Dorofutaru acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO". ) Modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene Glycol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, Propylene glycol di (meth) acrylate, (meth) acrylic acid-2- (meth) acryloyloxy-3-allyloxy-propyl ester, ECH modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, PO modified glycerol Examples include tri (meth) acrylate, pentaerythritol triacrylate, EO-modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, and the like.

The mass ratio of at least one compound represented by the following general formula (1) and / or at least one compound represented by the following general formula (2) and at least one compound represented by the following general formula (3) is: It is 20: 80-80: 20, Preferably, it is 25: 75-75: 20, More preferably, it is 30: 70-70: 30. By setting it as such a range, the low viscosity of a composition and the high adhesiveness of the cured film after light irradiation are compatible.
In the present invention, at least one compound represented by the general formula (1) and / or a compound represented by the general formula (2) and at least one compound represented by the general formula (3) are included. Needless to say, each may contain two or more types.
In particular, the compound represented by the general formula (3) preferably includes two or more kinds. Further, at least one of the compounds represented by the general formula (3) is bifunctional, trifunctional or tetrafunctional. More preferably, it is a compound.

The molecular weight of the compound represented by the general formula (1), the compound represented by the general formula (2) and the compound represented by the general formula (3) is 150 to 400, preferably 160 to 380, 170-360 is more preferable. By setting the molecular weight to 150 or more, volatilization can be prevented and better applicability can be imparted, and by setting the molecular weight to 400 or less, an increase in viscosity can be further suppressed.

  The total amount of the compound represented by the general formula (1), the compound represented by the general formula (2) and the compound represented by the general formula (3) is the total composition of the photocurable composition of the present invention. It is preferable to occupy 80% by mass or more, and more preferably 90% by mass or more.

  The photocurable composition of the present invention may contain other polymerizable monomers other than those described above without departing from the spirit of the present invention.

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

  Examples of the epoxy compound that can be preferably used include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S. Diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin tri Glycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Glycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; aliphatic long-chain dibasic acids Diglycidyl esters of aliphatic higher alcohols; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids, etc. can do.

  Among these components, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo ( Product)). These can be used alone or in combination of two or more.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocyclespart3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura , Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like.

As other polymerizable monomer used in the present invention, a vinyl ether compound may be used in combination.
The vinyl ether compound may be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2- Propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, Trimethylolethane trivinyl ether, hexanediol divinyl ether, tetraethyleneglycol Rudivinyl 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, triethylene glycol Methylolpropane 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.

  In addition, as another polymerizable monomer used in the present invention, an N-vinyl compound can be used as the vinyl compound. Examples of the N-vinyl compound include N-vinyl-2-pyrrolidone, N-vinylcaprolactone, N-vinylsuccinimide, N-vinylformamide, and the like.

  Moreover, a styrene derivative can also be employ | adopted as another polymerizable monomer used by this invention. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like.

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

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

(Polyfunctional oligomers and polymers)
In the photocurable composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer or polymer having a molecular weight higher than that of the other polyfunctional polymerizable monomer is within the range of achieving the object of the present invention. Can be blended. Examples of the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, and polyepoxy acrylate. In the present invention, the content of the polymer having a molecular weight of 1000 or more is preferably 5% by mass or less in the composition. By setting it as such a range, the viscosity of the photocurable composition of this invention can be lowered | hung, and when using as a photocurable composition for nanoimprints, it is more useful.

(B) Photoinitiator A photoinitiator is used for the photocurable composition of this invention. The photoinitiator used for this invention contains 0.1-15 mass% in all the compositions, for example, Preferably it is 0.2-12 mass%, More preferably, it is 0.3-10 mass %. When using 2 or more types of photoinitiators, the total amount becomes the said range.
It is preferable that the ratio of the photopolymerization initiator is 0.1% by mass or more because sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved. On the other hand, when the ratio of the photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable. So far, various addition amounts of preferred photopolymerization initiators and / or photoacid generators have been studied for ink jet compositions and dye display / color pigment compositions for liquid crystal display color filters. The addition amount of a preferable photopolymerization initiator and / or photoacid generator for a photocurable composition such as the above has not been reported. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the photocurable composition of the present invention, dyes and / or pigments are not essential components, and the optimum range of the photopolymerization initiator is in the fields of inkjet compositions, liquid crystal display color filter compositions, and the like. May be different.

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

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

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

  The photopolymerization initiator used in the present invention needs to be selected in a timely manner with respect to the wavelength of the light source to be used, but is preferably one that does not generate gas during mold pressurization / exposure. When the gas is generated, the mold is contaminated, so it is necessary to frequently clean the mold, and the photocurable composition of the present invention is deformed in the mold and deteriorates the transfer pattern accuracy. Produce. Those that do not generate gas are less likely to contaminate the mold, reduce the frequency of cleaning of the mold, and the photocurable composition of the present invention is less likely to be deformed in the mold, so it is difficult to deteriorate transfer pattern accuracy. Is preferable.

(Surfactant)
The photocurable composition of the present invention can 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. If the surfactant is less than 0.001 in the composition, the effect of coating uniformity is insufficient. On the other hand, if it exceeds 5% by mass, the mold transfer characteristics are deteriorated, which is not preferable.
The surfactant preferably contains at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant. Both the fluorine-based surfactant and the silicone-based surfactant or fluorine -More preferably, a silicone-based surfactant is included, and most preferably, a fluorine-silicone-based surfactant is included.
Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, the photocurable composition of the present invention can be applied to a silicon wafer for manufacturing a semiconductor device, a glass square substrate for manufacturing a liquid crystal device, a chromium film, a molybdenum film, a molybdenum alloy film, or tantalum. Striations and scales that occur during coating, such as various films, such as films, tantalum alloy films, silicon nitride films, amorphous silicone films, tin oxide-doped indium oxide (ITO) films and tin oxide films For the purpose of solving the problem of poor coating such as pattern (unevenness of drying of resist film), and improving the fluidity of the composition into the cavity of the mold recess, improving the peelability between the mold and the resist, It becomes possible to improve the adhesion between the substrates and to lower the viscosity of the composition.

Examples of the nonionic fluorosurfactant used in the present invention include trade names Florard FC-430 and FC-431 (Sumitomo 3M), trade names Surflon “S-382” (Asahi Glass Co., Ltd.), 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 are OMNOVA), brand names FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), brand names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.) ), Trade names Megafuk 171, 172, 173, 178K, 178A, F780F (all manufactured by Dainippon Ink & Chemicals, Inc.) Examples of nonionic silicon-based surfactants include the trade name SI-10 series, Pionine D6315 (both manufactured by Takemoto Yushi Co., Ltd.), Megafuck Paintad 31 (manufactured by Dainippon Ink & Chemicals, Inc.), KP -341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.). Manufactured), and trade names Megafuk R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

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

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

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

(Other ingredients)
In addition to the above components, the photocurable composition of the present invention may include a mold release agent, an organometallic coupling agent, an ultraviolet absorber, a light stabilizer, an antiaging agent, a plasticizer, an adhesion promoter, and thermal polymerization. Initiators, colorants, elastomer particles, photosensitizers, photoacid generators, photobase generators, basic compounds, chain transfer agents, and polymerization inhibitors can be added. These will be described below. Other flow modifiers, antifoaming agents, dispersing agents, etc. may be added.

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

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

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

  The modified silicone oil is preferably compatible with the composition components. In particular, in the case of using a reactive silicone oil that is reactive with other coating-forming components blended as necessary in the composition, in the cured film obtained by curing the photocurable composition of the present invention. Since these are fixed by chemical bonding, problems such as adhesion inhibition, contamination, and deterioration of the cured film hardly occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone, vinyl-modified silicone, etc., since it crosslinks with the photocurable composition of the present invention, it has excellent properties after curing. .

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 said mold release agent can be added only in 1 type or in combination of 2 or more types.

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

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

  Examples of the silane coupling agent used in the photocurable 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 that Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) 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, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, isop Pirutori (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 bis. (Ethyl acetoacetate) and the like.

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.

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

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

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

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

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

  When hardening the photocurable 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.

For the purpose of improving the visibility of the coating film, a colorant may be optionally added to the photocurable composition of the present invention. 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 colorant that can be used in the present invention, for example, those described in paragraph No. 0121 of JP-A No. 2008-105414 can be preferably employed.
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 photocurable composition of the present invention, elastomer particles may be added as an optional component for the purpose of improving mechanical strength, flexibility and the like.
The elastomer particles that can be added as an optional component to the photocurable 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 photocurable 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.

  Furthermore, in addition to the photopolymerization initiator, a photosensitizer may be added to the photocurable 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.

  The content of the photosensitizer in the photocurable composition of the present invention is preferably 15% by mass or less, more preferably 8% by mass or less, and particularly preferably 5% by mass or less in the composition. . Although the minimum of a photosensitizer content rate is not specifically limited, In order to express an effect, the minimum of a photosensitizer content rate is about 0.1 mass%.

  For the purpose of accelerating the photocuring reaction, a photoacid generator that initiates photopolymerization by receiving energy rays such as ultraviolet rays may be added to the photocurable composition of the present invention.

  Examples of the photoacid generator include thiobililium salts, iron / allene complexes, aluminum complexes / photolytic silicon compound-based initiators described in US Pat. No. 4,139,655, and halides that generate hydrogen halide. , O-nitrobenzyl ester compounds, imide sulfonate compounds, bissulfonyldiazomethane compounds, and oxime sulfonate compounds.

  As a photoacid generator that can be used in the present invention, for example, a chemical amplification type photoresist or a compound used for photocationic polymerization can be widely employed (imaging organic materials, edited by Organic Electronics Materials Research Group, Bunshin Publishing (1993), see pages 187-192). These compounds are the same as the photoacid generators described in THE CHEMICAL SOCIETY OF JAPAN Voi.71 No.11 (1998) and organic materials for imaging (Organic Electronics Materials Research Group, Bunshin Publishing (1993)). Can be easily synthesized by a known method.

  Examples of commercially available photoacid generators include IRGACURE261, IRGACURE OXE01, IRGACURE CGI-1397 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like. The above photoacid generators can be used alone or in combination of two or more.

  Moreover, the said acid generator can be used in combination as the said photoinitiator. In this case, the photoacid generator is preferably used in the range of 0.05 to 3.0% by mass, and the photopolymerization initiator and the photoacid generator are preferably used in the range of 0.5 to 15.0% by mass. .

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

  A basic compound may be optionally added to the photocurable composition of the present invention for the purpose of suppressing cure 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 photocurable composition of the present invention in order to improve photocurability. Specifically, 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate).

(Organic solvent)
In the photocurable composition of the present invention, the content of the organic solvent is preferably 3% by mass or less in the entire composition. That is, since the photocurable composition of the present invention can preferably contain a specific monofunctional or bifunctional monomer as a reactive diluent, the components of the photocurable composition of the present invention are dissolved. Therefore, it is not always necessary to contain the organic solvent. In addition, if an organic solvent is not included, a baking process for the purpose of volatilization of the solvent is not necessary, so that there is a great merit that it is effective for simplifying the process. Therefore, in the photocurable 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 photocurable composition of the present invention does not necessarily contain an organic solvent. However, in a reactive diluent, a compound that does not dissolve can be dissolved as the photocurable composition of the present invention. You may add arbitrarily, when adjusting a viscosity finely. The organic solvent that can be preferably used in the photocurable composition of the present invention is a solvent generally used in a photocurable composition or a photoresist, and dissolves and uniformly disperses the compound used in the present invention. Any material can be used 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.

(viscosity)
The viscosity of the photocurable composition of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. ± 0.2 ° C. unless otherwise specified. In the photocurable composition of the present invention, the viscosity of the composition excluding the solvent at 25 ° C. ± 0.2 ° C. is 3 mPa · s or more and less than 18 mPa · s, preferably 5 to 15 mPa · s, more preferably Is 7 mPa · s or more and less than 12 mPa · s. By setting the viscosity of the photocurable composition of the present invention to 3 mPa · s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa · s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. On the other hand, by setting the viscosity of the photocurable composition of the present invention to less than 18 mPa · s, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition is also present in the cavity of the concave portion of the mold. Since it becomes difficult to flow in and air | atmosphere is taken in, it becomes difficult to cause a bubble defect, and since a residue does not remain easily after photocuring in a mold convex part, it is preferable.

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

(amount of water)
In addition, the water content at the time of preparation of the photocurable 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 preservability of the photocurable composition of the present invention can be made more stable.

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

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

  Further, by applying the photocurable composition of the present invention on a substrate or a support and exposing, curing, and drying (baking) the layer made of the composition as necessary, an overcoat layer or an insulating film A permanent film such as can be produced.

  In permanent films (resist for structural members) used in liquid crystal displays (LCDs), it is possible 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. Preferably, the concentration needs to be 1000 ppm or less, desirably 100 ppm or less.

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

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

[Method for producing cured film]
Below, the manufacturing method of the cured film using the photocurable composition of this invention is described.
The photocurable composition of the present invention is preferably cured by light or light and heat. Specifically, the pattern forming layer comprising at least the photocurable composition of the present invention is applied (usually applied) on the substrate or the support, and the solvent is dried to form the photocurable composition of the present invention. A pattern receptor is formed by forming a layer (pattern forming layer), the mold is pressed against the surface of the pattern receiving layer of the pattern receptor, the mold pattern is transferred, and the fine uneven pattern forming layer is irradiated with light. Cured by heating. Usually, light irradiation and heating are performed a plurality of times. Nanoimprint lithography according to the method for producing a cured film of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

  The cured product of the present invention is generally applied by well-known application methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scanning. It can form by apply | coating the photocurable composition of this invention by a method etc. Although the film thickness of the layer which consists of a photocurable composition of this invention changes with uses to be used, it is 0.05 micrometer-30 micrometers. In addition, the photocurable composition of the present invention may be applied multiple times.

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

  The light for curing the photocurable 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 light, or may be a plurality of lights having different wavelengths (mixed light).

During exposure is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By setting it to 1 mW / cm ² or more, the exposure time can be shortened, so that productivity is improved. By setting it to 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 amount is desirably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . If it is less than 5 mJ / cm ² , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur. On the other hand, when it exceeds 1000 mJ / cm ² , there is a risk of deterioration of the permanent film due to decomposition of the composition.
Further, during exposure, in order to prevent radical polymerization from being inhibited by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

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

Next, the molding material that can be used in the present invention will be described. In optical nanoimprint lithography using the photocurable composition of the present invention, it is necessary to select a light transmissive material for at least one of the mold material and / or the substrate. In the photoimprint lithography applied to the present invention, a photocurable composition is applied onto a substrate, a light-transmitting mold is pressed, light is irradiated from the back surface of the mold, and the photocurable composition is cured. . Moreover, a photocurable composition is apply | coated on a transparent substrate, a mold is pressed, light can be irradiated from the back surface of a mold, and a photocurable composition can also be hardened.
The light irradiation may be performed in a state where the mold is attached, or may be performed after the mold is peeled off, but in the present invention, it is preferably performed in a state where the mold is adhered.

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

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

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

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

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

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

[Example 1]
(Preparation of photocurable composition)
The following polymerizable monomer AL-1 (50 mass%), the following polymerizable monomer R-1 (10 mass%), the following polymerizable monomer S-1 (40 mass%), the following photopolymerization initiator P-1 (2% by mass with respect to the total amount of polymerizable monomers), the following antioxidant A-1 (1% by mass with respect to the total amount of polymerizable monomers), the following surfactant W- 1 (0.1% by mass with respect to the total amount of polymerizable monomers) and the following surfactant W-2 (0.04% by mass with respect to the total amount of polymerizable monomers) The photocurable composition of Example 1 was prepared.

[Examples 2 to 8]
In Example 1, the composition of Examples 2-8 was prepared like Example 1 except having changed each component of the photocurable composition to the compound of the following table | surface, respectively.

<Allyl ester compound>
AL-1: diallyl maleate (manufactured by Tokyo Chemical Industry), molecular weight 196.20
AL-2: diallyl fumarate (manufactured by ALFA), molecular weight 196.20
AL-3: diallyl succinate (manufactured by Tokyo Chemical Industry), molecular weight 198.22
AL-4: diallyl adipate (manufactured by Tokyo Chemical Industry), molecular weight 226.27
AL-5: triallyl citrate (manufactured by Tokyo Chemical Industry), molecular weight 312.32.

<Allyl ether compound>
AL-6: trimethylolpropane diallyl ether (manufactured by Aldrich), molecular weight 214.30
AL-7: Tetraallyloxyethane (manufactured by Tokyo Chemical Industry), molecular weight 254.32
AL-8: Allyl phenylacetate (manufactured by Tokyo Chemical Industry), molecular weight 176.21
AL-9: Allyl acetate (manufactured by Tokyo Chemical Industry), molecular weight 100.12
AL-10: 1,2,4,6-tetra-O-acetyl-3-O-allyl-β-D-glucopyralose (manufactured by Tokyo Chemical Industry), molecular weight 444.43

<Monofunctional (meth) acrylate>
R-1: 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), molecular weight 234.32
R-2: benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.), molecular weight 162.19

<Bifunctional (meth) acrylate>
S-1: Neopentyl glycol diacrylate (manufactured by Nippon Kayaku Co., Ltd.), molecular weight 212.24
S-2: 1,4-butanediol diacrylate (Biscoat # 195: manufactured by Osaka Organic Chemical Co., Ltd.), molecular weight 198.22

<Trifunctional (meth) acrylate>
T-1: trimethylolpropane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd.), molecular weight 296.32
T-2: Urethane acrylate (UA-306H: manufactured by Kyoeisha),

<Tetrafunctional (meth) acrylate>
F-1: Pentaerythritol tetraacrylate (NK ester A-TMMT: manufactured by Shin-Nakamura Chemical), molecular weight 352.34

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

<Nonionic surfactant>
W-1: Non-fluorinated surfactant (manufactured by Takemoto Yushi Co., Ltd .: Pionin D6315)
W-2: Fluorosurfactant (Dainippon Ink & Chemicals, Inc .: MegaFuck F780F)

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

[Comparative Examples 1 to 7]
In Example 1, the composition of Comparative Examples 1-7 was prepared like Example 1 except having changed each component of the photocurable composition into the compound of the following table | surface.

<Evaluation of optical nanoimprint lithography>
About each of the composition obtained by Examples 1-8 and Comparative Examples 1-7, it measured and evaluated in accordance with the following evaluation method.

<Measurement of viscosity of photocurable composition>
The viscosity of the photocurable composition (before curing) was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotation speed during measurement is 100 rpm for 0.5 mPa · s to less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for 10 mPa · s to less than 30 mPa · s, and 30 mPa · s to less than 60 mPa · s. Were performed at 10 rpm, and classified and evaluated as follows according to the viscosity range.
A: 3 mPa · s or more and less than 12 mPa · s B: 12 mPa · s or more and less than 18 mPa · s C: 18 mPa · s or more

<Curing property>
Each photocurable composition was prepared and 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 10 μm line / space pattern and a groove depth of 4.0 μm (“SILPOT184” manufactured by Toray Dow Corning Co., Ltd., cured at 80 ° C. for 60 minutes) ) Was used. After the inside of the apparatus was evacuated (vacuum degree: 10 Torr (about 1.33 kPa)), the mold was pressed onto the substrate, and nitrogen purge (1.5 atm: mold pressing pressure) was performed to replace the inside of the apparatus with nitrogen. This was exposed from the back surface of the mold under the conditions of an illuminance of 10 mW / cm ² and an exposure amount of 400 mJ / cm ² . After the exposure, the mold was released to obtain a resist pattern. The resist pattern was checked for stickiness and evaluated for curing failure.
A: There was no stickiness and cured well.
B: Although there was no stickiness, poor curing was observed at a part of the pattern corners. When exposed again from the back surface of the mold under the conditions of an illuminance of 10 mW / cm ² and an exposure amount of 200 mJ / cm ² , it cured well.
C: There was stickiness and the entire pattern was poorly cured. It was not cured even when exposed from the back surface of the mold again under the conditions of an illuminance of 10 mW / cm ² and an exposure amount of 200 mJ / cm ² .

<Observation of pattern accuracy>
Each photocurable composition was prepared and 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 10 μm line / space pattern and a groove depth of 4.0 μm (“SILPOT184” manufactured by Toray Dow Corning Co., Ltd., cured at 80 ° C. for 60 minutes) ) Was used. After the inside of the apparatus was evacuated (vacuum degree: 10 Torr (about 1.33 kPa)), the mold was pressed onto the substrate, and nitrogen purge (1.5 atm: mold pressing pressure) was performed to replace the inside of the apparatus with nitrogen. This was exposed from the back surface of the mold under the conditions of an illuminance of 10 mW / cm ² and an exposure amount of 400 mJ / cm ² . After the exposure, the mold was released to obtain a resist pattern. The pattern shape of the resist pattern was observed with a scanning electron microscope or an optical microscope, and the pattern shape was evaluated as follows.
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold. B: There is a portion that is partially different from the pattern shape of the original plate that is the basis of the pattern shape of the mold (the range of the original pattern is less than 10%). 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: Clearly different from the original pattern of the mold pattern shape. Or the film thickness of the pattern differs from the original pattern by 20% or more.

<Adhesion of cured film after exposure>
After the photocurable composition was spin-coated on a silicon nitride substrate, ultraviolet rays were irradiated using a high-pressure mercury lamp so that the exposure amount was 240 mJ / cm ² to form a cured film having a thickness of 3 μm. Judging by visual observation whether the photocured resist pattern photocured on the tape side is attached to the cured film immediately after UV irradiation (within 30 minutes) and after 24 hours after irradiation And evaluated as follows. The results are shown in the table below. In addition, as an adhesive tape, a product name cellophane tape No. 29 was used.
A: There was no pattern adhesion on the tape side. (Adhesion rate less than 5%)
B: A part of the pattern was peeled off on the tape. (Adhesion rate 5% or more and less than 50%)
C: More than half of the pattern was peeled off on the tape. (Adhesion rate 50% or more and less than 95%)
D: The pattern was completely peeled off on the tape. (Adhesion rate 95% or more)

In all of Examples 1 to 8, the photocurable composition (before curing) has a low viscosity and good photocurability, and has a very high transfer pattern accuracy, but relatively excellent adhesion. It was found that it was excellent overall. Moreover, the unexpected effect that the adhesiveness of the cured film which passed 24 hours after ultraviolet irradiation improved rather than immediately after ultraviolet irradiation was seen. This unexpected effect is extremely significant from the viewpoint of preventing peeling due to deterioration with time of the cured film, that is, extending the life of the cured film.
The compositions of Comparative Example 1 and Comparative Example 4 had poor adhesion compared to the photocurable composition of the present invention, and the effect of improving adhesion after aging was small.
The compositions of Comparative Examples 2 and 3 were inferior in photocurability as compared with the photocurable composition of the present invention, and a pattern could not be formed.
The composition of Comparative Example 5 had poor adhesion compared to the photocurable composition of the present invention, and the effect of improving adhesion after time was small.
The composition of Comparative Example 6 was higher in viscosity than the photocurable composition of the present invention, resulting in poor pattern accuracy.
The composition of Comparative Example 7 had a higher viscosity than the photocurable composition of the present invention, and both the pattern accuracy and the adhesion were inferior.

  According to the present invention, it is possible to provide a curable composition for nanoimprint lithography that has low viscosity and high transfer pattern accuracy and is excellent in adhesion after light irradiation, particularly adhesion after aging.

Claims (9)

At least one compound represented by the following general formula (1) and / or a compound represented by the following general formula (2) and at least one compound represented by the following general formula (3) are in a mass ratio of 20: A photocurable composition comprising 80-80: 20.

(In General Formula (1) and General Formula (2), X represents an organic group, and n represents an integer of 1 to 4. In General Formula (3), Y represents an organic group. , M represents an integer of 1 to 4, and R represents hydrogen or a methyl group, provided that the compound represented by the general formula (1), the compound represented by the general formula (2), and the general formula (3) Each of the represented compounds has a molecular weight of 150 to 400.) The photocurable composition of Claim 1 containing the compound represented by the said General formula (1). The photocurable composition according to claim 1 or 2, wherein X in the general formula (1) or the general formula (2) and Y in the general formula (3) are each a hydrocarbon group. The photocurable composition according to any one of claims 1 to 3, wherein, in the general formula (3), R is a hydrogen atom. The photocurable composition of any one of Claims 1-4 whose n in General formula (1) or General formula (2) is 2 or 3. The total amount of the compound represented by the general formula (1), the compound represented by the general formula (2) and the compound represented by the general formula (3) is 80% by mass or more of the photocurable composition. The photocurable composition of any one of Claims 1-5. Hardened | cured material formed by hardening | curing the photocurable composition of any one of Claims 1-6. The member for liquid crystal display devices containing the hardened | cured material of Claim 7. Applying the photocurable composition according to any one of claims 1 to 6 on a substrate to form a pattern, pressing the pattern forming layer against a mold, and irradiating the pattern forming layer with light The manufacturing method of the hardened | cured material characterized by including the process to do.