JP5306903B2 - Curable composition for imprint, cured product using the same, method for producing the same, and member for liquid crystal display device - Google Patents

Abstract

The present invention provides curing combination for stamping, having characters of good stamping and photo-curing, mechanical features and various durability, wherein the photo-curing character, heat resisting property and elastic restitution rate are excellent, condensate using the combination and a method for producing the same, and members for a liquid crystal display device. The curing combination contains optical polymeric monomer, optical polymerization initiator and anti-oxidant, characterized in that a content of the optical polymerism monomer is 80-99% by weight, a content of the anti-oxidant is 0.3-7% by weight, and the anti-oxidant is one of only hindered phenol series anti-oxidant, only semi hindered phenol series anti-oxidant, mixture of hindered phenol series anti-oxidant and semi hindered phenol series anti-oxidant, or only hindered amine series anti-oxidant.

Description

  The present invention relates to a curable composition for imprints, a cured product using the same, a method for producing the same, and a member for a liquid crystal display device using the cured product.

  The imprint method includes a thermal imprint method using a thermoplastic resin as a material to be processed (for example, see Non-Patent Document 1), and an optical imprint using a photocurable composition (for example, see Non-Patent Document 2). The following two techniques have been proposed. In the case of the thermal imprint method, 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 fine structure to the resin on the substrate. Since this method can be applied to various resin materials and glass materials, it is expected to be applied to various fields. For example, Patent Documents 1 and 2 listed below disclose thermal imprinting methods for forming nanopatterns at low cost using a thermoplastic resin.

  On the other hand, in the photoimprint method in which light is irradiated through a transparent mold or a transparent substrate to photocure the photocurable composition, it is not necessary to heat the material to which the pattern is transferred when the mold is pressed. Is 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 an imprint method, the following nanoscale 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 other technologies, a multilayer structure is constructed by simultaneous integral molding of microstructures and nanostructures, and simple interlayer alignment, and is applied to the production of μ-TAS (Micro-Total Analysis System) and biochips. It is something to try. As a third technique, there is an attempt to apply high-precision alignment and high integration to the production of a high-density semiconductor integrated circuit instead of the conventional lithography, the production of a liquid crystal display in a transistor, or the like. . In recent years, efforts to put imprint methods relating to these applications into practical use, including the aforementioned technologies, have become active.

  An application example of the first technique for manufacturing a high-density semiconductor integrated circuit will be described. 2. Description of the Related Art In recent years, semiconductor integrated circuits have been miniaturized and integrated, and photolithography apparatuses have been improved in accuracy as a pattern transfer technique for realizing the fine processing. However, it has become difficult to satisfy the three requirements of fine pattern resolution, apparatus cost, and throughput in response to further miniaturization requirements. On the other hand, it has been proposed to use an imprint lithography technique, particularly a nanoimprint lithography technique (optical nanoimprint method) as a technique for performing fine pattern formation at low cost. For example, Patent Document 1 below discloses a nanoimprint technique that uses a silicon wafer as a stamper and forms a fine structure of 25 nm or less by pattern transfer. Along with this trend, in order to apply nanoimprint lithography to the fabrication of semiconductor integrated circuits, studies on properties such as mold-resin peelability, imprint uniformity, and pattern transfer accuracy have begun to be activated.

  An application example of the optical imprint method to a flat display such as a liquid crystal display (LCD) or a plasma display (PDP) in the second technique will be described. Imprint lithography has recently attracted attention as an inexpensive alternative to conventional photolithography methods used in the manufacture of thin film transistors (TFTs) and electrode plates, as LCD and PDP substrates become larger and more precise. Therefore, it has become necessary to develop a photo-curable resist that replaces the etching photoresist used in the conventional photolithography method. Also, the application of the imprint method is 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 above-described etching resist, such a resist for a structural member is finally left in a display such as a flat display panel, and is therefore 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, or a high temperature process during sputtering of an ITO film by reducing a step between R, G and B layers. For example, a protective film provided on the color filter in order to impart resistance. In the formation of these protective films (permanent films), various properties such as uniformity of the coating film, high light transmittance after heat treatment exceeding 200 ° C., and scratch resistance are required. Development of a curable composition for imprints that satisfies the above has been demanded. The spacer used in the liquid crystal display is generally 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. A pattern having a size is formed, and further heated and cured by post-baking. Such a spacer used in the liquid crystal display is required to have a particularly high elastic recovery rate in addition to hardness, pattern accuracy, etc., and development of a curable composition for imprints that satisfies these characteristics is required. Yes.

  Furthermore, in the imprint method, it is necessary to improve the fluidity of the curable composition for imprints in the cavity of the concave portion of the mold surface where the pattern is formed. Moreover, it is necessary to improve the adhesiveness between a resist and a base material (a board | substrate, a support body), improving the peelability between a mold and a resist.

  As described above, the required characteristics of materials used for imprint lithography often vary depending on the application used. However, with regard to the composition for imprinting, for example, although there has been a description of a request regarding viscosity, there has been no report on a material design guideline for adapting to each application.

  Therefore, as a main technical problem as a permanent film, there are many problems such as pattern accuracy, heat resistance, and hardness. Even when the curable composition for imprints is applied as a permanent film, (1) pattern transfer accuracy (imprintability in imprint lithography) and (2) heat resistance, similar to conventional resists using acrylic resin and the like. And (3) imparting curability are important.

  As a problem peculiar to the curable composition for photoimprint, in addition to the performances of (1) to (3) above, (4) high elastic recovery that can withstand use as a permanent film as one of the mechanical properties Giving rate is important. Furthermore, when designing the composition of the curable composition for imprints, in addition to the above points (1) to (4), at the same time, (5) ensuring the fluidity of the resist to the concave portion of the mold, no solvent Or it is necessary to take into account the need to reduce the viscosity under the use of a small amount of solvent (preferably 5 mPa.s or less) and (6) to improve the voltage characteristics for use as a structural member of an electric circuit. Yes, the technical difficulty of designing the composition is further increased.

  In recent years, for the purpose of suppressing fading, proposals have been made to use an antioxidant for an imprint curable composition (see Patent Document 3 and Patent Document 4). However, the present situation is that the examination which actually uses antioxidant for the curable composition for imprints is not yet made.

  In addition, it has been studied to add an antioxidant to a photocurable composition for other uses. For example, there is an example for the purpose of preventing the oxidation of the metal surface to be bonded in the optical disk adhesive composition and increasing the adhesive strength of the adhesive (Patent Document 5). In this document, an example in which an antioxidant is used in an amount of less than 0.2% by mass is described in the photocurable composition, but imprintability, heat resistance, photocurability, high elastic recovery rate, and low viscosity. There is no description which suggests satisfying the characteristics required for the curable composition for imprints, such as conversion and voltage characteristics. In particular, in an example using an antioxidant of less than 0.2% by mass, the viscosity of the composition is 380 mPa.s. s (25 ° C.), and the composition described in Patent Document 5 cannot be applied to a curable composition for imprints that require low viscosity.

  In addition, an example of adding 0.15% by mass of an antioxidant to an actinic ray curable inkjet ink composition has been reported for the purpose of improving viscosity (Patent Document 6). However, although there is a description regarding improvement in viscosity in the same document, there is no description regarding imprintability, heat resistance, photocurability, high elastic recovery rate and voltage characteristics.

  As described in Patent Document 5 and Patent Document 6, the purpose of the known literature for adding an antioxidant to the photocurable resin composition is to prevent oxidation by oxygen in the air and to lower the viscosity. In the past, no further detailed investigation has been made. Also, the purpose of the known literature for adding an antioxidant to a thermosetting resin was to suppress the discoloration of the resin due to oxidation during heating.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 JP 2008-105414 A JP 2008-92099 A JP 2002-256228 A JP 2006-124636 A

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

  In view of the above problems, when the composition described in Patent Document 6 is used for imprinting as it is, it has been found that it is inferior in terms of heat resistance, elastic recovery rate and voltage characteristics. .

  An object of the present invention is to provide a curable composition for imprints having good imprintability and photocurability, and excellent mechanical properties and various durability properties, among which photocurability, heat resistance and elastic recovery rate, It is providing the hardened | cured material using this, its manufacturing method, and the member for liquid crystal display devices. A more specific object of the present invention is to provide a curable composition for imprints particularly suitable for transparent protective films such as flat panel displays and permanent films such as spacers.

  As a result of intensive studies by the inventors of the present invention under the above-mentioned problems, by incorporating a specific amount of an antioxidant in the curable composition for imprints, the characteristics (1) to (6) described above are obtained. It has been found that a composition satisfying all of them, in particular, (4) a composition capable of obtaining a high elastic recovery rate can be designed. That is, it has been found that the above problems can be solved by the following means.

[1] A composition for photoimprinting comprising A) a photopolymerizable monomer, B) a photopolymerization initiator, C) an antioxidant, and A) containing the photopolymerizable monomer The amount is 80 to 99% by mass, the content of the C) antioxidant is 0.3 to 7% by mass, and the C) antioxidant is only a hindered phenol antioxidant, semi-hindered A curable composition for imprints characterized in that it is only a phenolic antioxidant, a mixture of a hindered phenolic antioxidant and a semi-hindered phenolic antioxidant, or only a hindered amine antioxidant. object.
[2] The curable composition for imprints according to [1], wherein the antioxidant comprises only a semi-hindered phenolic antioxidant.
[3] A composition for photoimprinting comprising A) a photopolymerizable monomer, B) a photopolymerization initiator, C) an antioxidant, and A) containing the photopolymerizable monomer. The amount is 80 to 99% by mass, and the content of the C) antioxidant is 0.3 to 7% by mass, and the C) antioxidant is a hindered phenol antioxidant and a thioether antioxidant. A curable composition for imprints, which is a mixture of agents or a mixture of a semi-hindered phenolic antioxidant and a thioether antioxidant.
[4] The curable composition for imprints according to [3], wherein the antioxidant is a mixture of semi-hindered phenol and thioether.
[5] The imprinting composition according to any one of [1] to [4], wherein the content of the antioxidant is 0.5 to 5% by mass.
[6] The imprinting composition according to any one of [1] to [5], wherein an elastic recovery rate is 70% or more.
[7] A cured product obtained by curing the curable composition for imprints according to any one of [1] to [6].
[8] A liquid crystal display member comprising the cured product according to [7].
[9] A step of applying a curable composition for imprints according to any one of [1] to [7] onto a substrate to form a pattern forming layer;
Pressing the mold against the surface of the pattern forming layer;
Irradiating the pattern forming layer with light;
The manufacturing method of the hardened | cured material characterized by including.
[10] The method for producing a cured product according to [9], further comprising a step of heating the pattern forming layer irradiated with light.

  According to the present invention, a curable composition for imprints excellent in pattern accuracy, surface hardness, light transmittance and heat resistance after heat curing, a cured product using the same, a method for producing the same, and a liquid crystal display device A member can be provided.

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

In the present specification, “(meth) acrylate” represents “acrylate” and “methacrylate”, “(meth) acryl” represents “acryl” and “methacryl”, and “(meth) acryloyl” represents “ Represents “acryloyl” and “methacryloyl”. Further, in the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 1,000 or less. In this specification, “functional group” refers to a group involved in polymerization.
Further, the imprint referred to in the present invention refers to pattern transfer having a size of about several tens of nanometers to several tens of micrometers, and includes nanoimprints, but is not limited to nano-order ones.
Further, in the present specification, “hindered phenol-based antioxidant” and “semi-hindered phenol-based” are concepts that do not overlap and are clearly distinguished.

[Curable composition for imprints]
The curable composition for imprints of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) is a light containing a photopolymerizable monomer, a photopolymerization initiator, and an antioxidant. The composition for imprinting, the content of the photopolymerizable monomer is 80 to 99% by mass, and the content of the antioxidant is 0.3 to 7% by mass. Furthermore, in the first aspect of the curable composition for imprints of the present invention, the antioxidant is only a hindered phenol antioxidant, only a semi-hindered phenol antioxidant, or a hindered phenol antioxidant. And a hindered amine antioxidant, or a mixture of a semi-hindered phenol antioxidant and a hindered amine antioxidant. On the other hand, in the second aspect of the curable composition for imprints of the present invention, the antioxidant is a mixture of a hindered phenol antioxidant and a thioether antioxidant, or a semi-hindered phenol antioxidant. It is a mixture of thioether-based antioxidants.
The composition of the present invention contains a specific range of an amount of an antioxidant in addition to a specific range of a photopolymerizable monomer and a photopolymerization initiator, thereby imprintability and photocurability. At the same time, the heat resistance and voltage characteristics can be achieved at a high level, and the elastic recovery rate can be increased to a high level. Since the effect of increasing the elastic recovery rate cannot be predicted from the function of the conventional antioxidant, it was surprising that the elastic recovery rate was particularly increased.

Moreover, the curable composition for imprints of the present invention can be widely used for photoimprint lithography (including photonanoimprint lithography), and can have the following characteristics.
(1) Since the composition of the present invention is excellent in solution fluidity at room temperature, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. In any of the recesses, it is difficult for residues to remain after photocuring.
(2) The cured film after curing the composition of the present invention has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peelability between the coating film and the mold. A good pattern can be formed because the pattern is not broken when the film is peeled off, and the surface of the coating film is not drawn and the surface is not roughened (good imprintability).
(3) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.
(4) Since the mechanical properties such as photocurability, heat resistance, and elastic recovery rate are high, it can be suitably used as various permanent films. (5) Since it has excellent voltage characteristics, it is suitable for materials for electronic circuits. And the like.

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

(Photopolymerizable monomer)
The curable composition for imprints of the present invention contains a photopolymerizable monomer. Since the composition of the present invention contains a photopolymerizable monomer, good pattern accuracy (imprintability) can be obtained after light irradiation. In the present invention, the “photopolymerizable monomer” means a monomer capable of causing a polymerization reaction by light irradiation to form a high molecular weight product.

  The main function of the photopolymerizable monomer used in the present invention is appropriately selected for the purpose of adjusting the viscosity of the composition and the mechanical properties of the cured film. From the viewpoint of adjusting the viscosity of the composition, it is preferable to use a photopolymerizable monomer having a low viscosity. In order to improve the pattern accuracy of the cured product, the viscosity of the composition is usually preferably 18 mPa · s or less, and for that purpose, a polymerizable monomer having a viscosity as low as possible is used. preferable. Since the viscosity of the photopolymerizable monomer is related to the molecular weight, intermolecular interaction, etc., the reduction of the viscosity of the photoradical polymerizable monomer can be achieved by considering the low molecular weight and the low intermolecular interaction. can do.

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

  Examples of the photoradically polymerizable functional group that the photopolymerizable monomer in the present invention has include a functional group having an ethylenically unsaturated bond, such as a (meth) acryl group, a vinyl group, an allyl group, and a styryl group. Is preferred. 1 type may be sufficient as the photopolymerizable monomer contained in the composition of this invention, and 2 or more types may be sufficient as it. The composition of the present invention includes a photopolymerizable monomer having a photoradically polymerizable functional group and a photopolymerizable monomer having no photopolymerizable functional group (for example, a polymerizable monomer having a cationic polymerizable group). ) May be used in combination.

  From the viewpoint of imparting mechanical properties to the cured film, it is preferable to use a bifunctional or higher polyfunctional monomer. Such a polyfunctional monomer inevitably has a high molecular weight and thus has a high viscosity, and the pattern accuracy may be lowered by increasing the viscosity of the composition. Therefore, the polymerizable monomer used in the present invention is a combination of a low-viscosity monomer for adjusting viscosity and a polyfunctional monomer for imparting mechanical properties of a cured film, or an oxetane compound or a functional acid anhydride in the present invention. It is selected comprehensively considering the combination of objects.

  In the curable composition for imprints of the present invention, the content of the photopolymerizable monomer in the entire composition is preferably 20 to 90 mass%, and preferably 30 to 70 mass% from the viewpoint of pattern accuracy after light irradiation. % Is more preferable. However, the content of the photopolymerizable monomer in the present invention is determined in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention as described above.

  In the present invention, only one kind of silsesquioxane compound may be contained, or two or more kinds thereof may be contained. Moreover, it is preferable that the silsesquioxane compound is contained in the ratio of 1-40 mass% in the composition of this invention, and it is more preferable that it is contained in the ratio of 1-20 mass%. By setting it as such a range, the composition viscosity and the mechanical characteristic of a cured film can be made compatible.

Examples of the photopolymerizable monomer in the present invention include a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer). Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanediol mono (meth) acrylate Rate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) ) Acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclo Pentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate Methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene Glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meta ) Acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, ethyl oxetanylmethyl acrylate, Is exemplified.
Furthermore, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and other vinylsilanes, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxy (Meth) acryloxysilane such as propyltrimethoxysilane is exemplified.
Among these, acrylate monomers are particularly preferably used in the present invention.

  Moreover, as a photopolymerizable monomer in this invention, the bifunctional polymerizable unsaturated monomer which has two ethylenically unsaturated bond containing groups can also be used preferably. Examples of the bifunctional polymerizable unsaturated monomer include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol. Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol Acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meta) Acrylate, ECH-modified hexahydrophthalic acid diacrylate, hydroxypivalate 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, poly (ethylene glycol-tetramethylene glycol) di (meta ) Acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, polyester (di) acrylate, poly Tylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Tricyclodecane dimethanol (di) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, divinylethyleneurea, divinylpropyleneurea, dicyclopentenyl (meth) acrylate, di Black pentenyl oxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate, are exemplified.

  Among these, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate and the like are preferably used in the present invention. It is done.

  As the photopolymerizable monomer in the present invention, a polyfunctional polymerizable unsaturated monomer having three or more ethylenically unsaturated bond-containing groups can also be preferably used. Examples of the polyfunctional polymerizable unsaturated monomer include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, and EO-modified phosphorus. Acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tris (acryloxy) Ethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol Roxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (Meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. are mentioned.

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

As the photopolymerizable monomer used in the present invention, a vinyl ether compound may be used.
The vinyl ether compound can be appropriately selected from known ones such as 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether. 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, tri Methylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, Raethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene Vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1 Tris [4- (2-vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

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

  Other examples of styrene derivatives that can be used in combination with the monofunctional polymer of the present invention include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, Examples thereof include p-methoxy-β-methylstyrene and p-hydroxystyrene. Furthermore, in the present invention, vinyl naphthalene derivatives can also be used. For example, 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, 4-methyl-1-vinylnaphthalene. 4-methoxy-1-vinylnaphthalene and the like.

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

  Furthermore, as the photopolymerizable 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.

The curable composition for imprints of the present invention is a compound having an oxetane ring having a radical photopolymerizable functional group (hereinafter simply referred to as “oxetane compound” or “oxetane monomer” as the photopolymerizable monomer used in the present invention. May be included as a photopolymerizable monomer. When the composition of the present invention contains a compound having an oxetane ring, it is preferable because excellent hardness can be obtained by heating.
The number of oxetane ring structures (oxetanyl groups) contained in the compound having an oxetane ring in the present invention is preferably 1 to 4, and more preferably 1 to 3, from the viewpoint of curing speed and cured film properties.
Moreover, as a total carbon number of the compound which has an oxetane ring in this invention, 5-50 are preferable from a viewpoint of the viscosity reduction of a composition, and 5-20 are more preferable.
As a molecular weight of the compound which has an oxetane ring in this invention, 100-1000 are preferable from a viewpoint of the viscosity reduction of a composition, and 100-400 are further more preferable.

  Moreover, the oxetane compound as a photopolymerizable monomer in the present invention has a photoradically polymerizable functional group. Examples of the radical photopolymerizable functional group include a functional group having an ethylenically unsaturated bond, and a (meth) acryl group, a vinyl group, an allyl group, and a styryl group are preferable. The number of photoradically polymerizable groups contained in the compound having an oxetane ring in the present invention is preferably 1 to 4, more preferably 1 to 2, from the viewpoint of pattern accuracy during light irradiation and adhesion to the substrate. The compound having an oxetane ring contained in the composition of the present invention may be one type or two or more types. In the composition of the present invention, an oxetane compound having a photoradically polymerizable functional group and an oxetane compound not having this may be used in combination. When using together the compound (x) which has a photoradically polymerizable functional group, and the oxetane compound (y) which does not have this, as the content ratio (x: y, x reference | standard), pattern accuracy after light irradiation and From the viewpoint of suppression of volatilization of unreacted components during heating, 1/2 to 5/1 is preferable, and 1/1 to 2/1 is more preferable.

  In addition, the curable composition for imprints of the present invention may contain a compound having an oxetane ring other than the photopolymerizable monomer as long as it does not contradict the gist of the present invention.

  In the curable composition for imprints of the present invention, the content of the oxetane compound in the entire composition is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, from the viewpoint of pattern accuracy after light irradiation. . However, when the compound having an oxetane ring in the present invention has a photo-radical polymerizable functional group, the content thereof, as described above, considers the content of the compound having a radical polymerizable functional group in the composition of the present invention. Can be determined. At this time, the content of the oxetane compound having a photoradically polymerizable functional group is related to the content of the compound having another radical polymerizable functional group or the content of the oxetane compound having no photoradically polymerizable functional group. It is determined appropriately from the relationship.

  Examples of the compound having an oxetanyl group in the present invention include 3-ethyl-3-hydroxymethyloxetane (trade name: OXT-101, manufactured by Toagosei Co., Ltd.), 1,4-bis [[(3-ethyl- 3-Oxetanyl) methoxy] methyl] benzene (trade name: OXT-121, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (phenoxymethyl) oxetane (trade name: OXT-211, manufactured by Toagosei Co., Ltd.) ), Di [1-ethyl (3-oxetanyl)] methyl ether (trade name: OXT-221, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name: OXT-212, manufactured by Toagosei Co., Ltd.), 4,4′-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl (trade name: ETERRNACOLL OX BP, manufactured by Ube Industries, Ltd.), silsesquioxane modified oxetane (trade name: OX-SQ, manufactured by Toagosei Co., Ltd.), oxetane (meth) acrylate (trade name: OXE-10, 30, Osaka Organic) Chemical Co., Ltd.).

The curable composition for imprints of the present invention may contain a functional acid anhydride. The acid anhydride compound in the present invention has a function as a curing agent for the oxetane compound. When the composition of this invention contains a functional acid anhydride, since high surface hardness can be obtained after heat-hardening, it is preferable.
In the present invention, the “functional acid anhydride” means a compound obtained by dehydration condensation of two molecules of oxo acid and chemically bonded to other functional groups by heating or the like.
Examples of the functional acid anhydride include phthalic anhydrides, citraconic anhydrides, succinic anhydrides, propionic anhydrides, maleic anhydrides, acetic anhydrides, etc., from the viewpoint of viscosity reduction and composition stability. Phthalic anhydrides and maleic anhydrides are preferred.

Moreover, as a total carbon number of the functional acid anhydride in this invention, 10-100 are preferable from a viewpoint of the viscosity reduction of a composition, and 10-50 are more preferable.
The molecular weight of the functional acid anhydride in the present invention is preferably from 100 to 1,000, more preferably from 100 to 500, from the viewpoint of reducing the viscosity of the composition.

  Moreover, it is preferable that the said functional acid anhydride has a radical photopolymerizable functional group from a viewpoint which makes a photopolymerizable monomer into the said range. Examples of the photoradical polymerizable functional group include a functional group having an ethylenically unsaturated bond, and a (meth) acryl group, a vinyl group, an allyl group, and a styryl group are preferable. The number of photoradically polymerizable groups contained in the functional acid anhydride in the present invention is preferably 1 to 3, more preferably 1 to 2, from the viewpoint of pattern accuracy during light irradiation and adhesion to the substrate. 1 type may be sufficient as the functional acid anhydride contained in the composition of this invention, and 2 or more types may be sufficient as it. Moreover, the composition of this invention may use together the functional acid anhydride which has a photoradically polymerizable functional group, and the functional acid anhydride which does not have this. When using together the compound (q) which has a radical photopolymerizable functional group, and the functional acid anhydride (w) which does not have this, as the content ratio (q: w, q reference | standard), after light irradiation From the viewpoint of pattern accuracy and suppression of volatilization of unreacted components during heating, 1/2 to 5/1 is preferable, and 1/1 to 2/1 is more preferable.

  In the curable composition for imprints of the present invention, the content of the functional acid anhydride in the entire composition is preferably 5 to 50% by mass, and 10 to 30% by mass from the viewpoint of pattern accuracy after light irradiation. Is more preferable. However, when the functional acid anhydride in the present invention has a photo-radical polymerizable functional group, the content thereof, as described above, considers the content of the compound having a radical polymerizable functional group in the composition of the present invention. Can be determined. At this time, the content of the functional acid anhydride having a photoradically polymerizable functional group is related to the content of a compound having another radical polymerizable functional group or a functional acid having no photoradically polymerizable functional group. It is determined appropriately from the relationship with the anhydride content.

  In the curable composition for imprints of the present invention, the content ratio (a: b, a standard) of the oxetane compound (a) and the functional acid anhydride (b) in the present invention is an unreacted functional group. 3/1 to 1/3 is preferable from the viewpoint of minimizing the amount of A, and 2/1 to 1/2 is more preferable.

  Examples of the functional acid anhydride in the present invention include methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: Epiklone B570, manufactured by Dainippon Ink & Chemicals, Inc.), methyl-hexahydrophthalic anhydride. Acid (trade name: Epicron B650, manufactured by Dainippon Ink & Chemicals, Inc.), methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (trade name: MHAC-P, Hitachi Chemical) Kogyo Co., Ltd.), 4-methylhexahydrophthalic anhydride (trade name: Ricacid MH-700, manufactured by Shin Nippon Rika Co., Ltd.), citraconic anhydride, dodecene succinic anhydride (trade name: Ricacid DDSA, Shin Nippon Rika Co., Ltd.), glycerol bis (anhydrous trimellitate) monoacetate (trade name: Ricacid MTA-10, Shin Nippon Rika Co., Ltd.), Nippon Zeo QUINHARD-200 (trade name) manufactured by NON Co., Ltd., EpiCure YH-306 (trade name) manufactured by Japan Epoxy Resin Co., Ltd., Aldrich reagent (P25205, 294152, B9750, B4600, 41287, N818, N1607, 3307376 ) And the like.

  Next, the preferable blend form of the photopolymerizable monomer in this invention is demonstrated.

  In the curable composition for imprints of the present invention, the total content of photopolymerizable monomers in the composition is 80 to 99% by mass. The “photopolymerizable monomer” is a compound having a radically polymerizable functional group having an ethylenically unsaturated bond such as a (meth) acryl group, a vinyl group, or an allyl group. For example, the oxetane (meth) acrylate of the compound having an oxetane ring corresponds to the photopolymerizable monomer because the (meth) acryl group is a radical polymerizable functional group.

  When the total content of the photopolymerizable monomer in the composition of the present invention is less than 80% by mass, it cannot be sufficiently cured even by light irradiation, and the mold pattern cannot be accurately transferred. Physical properties such as hardness of the cured film are also insufficient. Moreover, when the total content of the compound having a radical polymerizable functional group in the composition of the present invention exceeds 99% by mass, additives such as a radical photopolymerization initiator and a surfactant do not function sufficiently, and the pattern Accuracy and physical properties of the cured film will deteriorate. From the viewpoint of pattern accuracy and cured film properties, the total content of the compound having a radical polymerizable functional group in the composition of the present invention is preferably 60 to 99% by mass, and more preferably 80 to 98% by mass.

The monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent and is effective in reducing the viscosity of the composition of the present invention. More than mass% is added. Preferably, it is added in the range of 20 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass.
Since the monofunctional polymerizable unsaturated monomer is better as a reactive diluent, it is preferable to add 10% by mass or more of the total polymerizable unsaturated monomer.
The monomer having two unsaturated bond-containing groups (bifunctional polymerizable unsaturated monomer) is preferably 90% by mass or less, more preferably 80% by mass or less of the total polymerizable unsaturated monomer, Especially preferably, it adds in 70 mass% or less. The ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 1 to 95% by mass, more preferably 3 to 95% by mass, and particularly preferably 5 to 90% by mass of the total polymerizable unsaturated monomer. It is added in the range of mass%. The ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, particularly preferably 70% by mass or less, based on the total polymerizable unsaturated monomer. Preferably, it is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered | hung by making the ratio of the polymerizable unsaturated monomer which has 3 or more of polymerizable unsaturated bond containing groups into 80 mass% or less, it is preferable.

(Photo radical polymerization initiator)
The curable composition for imprints of the present invention contains a radical photopolymerization initiator. The composition of this invention can make the pattern precision after light irradiation favorable by including the radical photopolymerization initiator which starts radical polymerization reaction by light irradiation. Photo radical polymerization initiator The content of the photo radical polymerization initiator used in the present invention is preferably, for example, 0.1 to 15% by mass, more preferably 0.2 to 12% by mass in the entire composition. Especially preferably, it is 0.3-10 mass%. When using 2 or more types of photoinitiators, the total amount becomes the said range.
When the ratio of the radical photopolymerization initiator is 0.1% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved, which is preferable. On the other hand, when the ratio of the radical photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable. Up to now, 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. No preferred photopolymerization initiator and / or photoacid generator addition amount has been reported for curable compositions for photoimprint lithography. That is, in a system containing dyes and / or pigments, these may act as radical trapping agents, affecting the photopolymerizability and sensitivity. In consideration of this point, the amount of the photopolymerization initiator added is optimized in these applications. On the other hand, in the composition of the present invention, the dye and / or pigment is not an essential component, and the optimum range of the photopolymerization initiator is different from that in the field of an ink jet composition or a liquid crystal display color filter composition. There is.

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

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

(Antioxidant)
The curable composition for imprints of the present invention contains an antioxidant.
In the first aspect of the curable composition for imprints of the present invention, the antioxidant is only a hindered phenol antioxidant, only a semi-hindered phenol antioxidant, hindered phenol antioxidant and semi It is either a mixture of hindered phenolic antioxidants or only a hindered amine antioxidant.
On the other hand, in the second aspect of the curable composition for imprints of the present invention, the antioxidant is a mixture of a hindered phenol antioxidant and a thioether antioxidant, or a semi-hindered phenol antioxidant. It is a mixture of thioether-based antioxidants.
A feature of the present invention is that the use of an antioxidant in the two aspects of the present invention described above improves the photocurability, heat resistance, and elastic recovery rate. In particular, the addition of an antioxidant in the above two aspects of the present invention improves the elastic recovery rate of the cured film after the effect of the composition of the present invention. It was surprising in view of the technology in the photocurable resin composition field in which the agent was added.
It should be noted that phenolic antioxidants other than hindered phenolic or semi-hindered phenolic antioxidants are not preferred because polymerization inhibition is large.

  Content of the antioxidant used for the curable composition for imprints of this invention is 0.3-7 mass% in all the compositions, Preferably it is 0.5-5 mass%, More preferably Is 1.5-5 mass%. When using 2 or more types of antioxidant, the total amount becomes the said range. When the content of the antioxidant is 0.3% by mass or more, heat resistance and elastic recovery are improved, and when it is 7% by mass or less, photocurability is improved. Further, when the content of the antioxidant is 0.5% by mass or more, the heat resistance and the elastic recovery rate are further improved, and when it is 5% by mass or less, the photocurability is further improved. preferable. Furthermore, since the heat resistance and the elastic recovery rate are further improved when the content of the antioxidant is 1.5% by mass or more, the content is particularly preferably 1.5 to 5% by mass.

  The hindered phenol antioxidant in the present invention is a substance having a structure represented by the following general formula (1).

In the general formula (1), R ¹ and R ² each independently represents a tert-butyl group or —C (R ⁴ R ⁵ ) —R ⁶ , and R ³ is a hydrogen atom or having 1 to 6 carbon atoms. An alkyl group which may have a branched or straight chain substituent is represented, and L ¹ represents a monovalent substituent. R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ represents a substituent having a structure represented by the following general formula (2).

In general formula (2), X ¹ represents a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group, or a carboxyl group. When X ¹ is a hydroxyl group, R ⁷ represents a tert-butyl group, and X ¹ represents In a case other than a hydroxyl group, R ⁷ represents a hydrogen atom, an alkyl group which may have a branched or straight chain substituent having 1 to 6 carbon atoms, and R ⁸ represents a hydrogen atom or 1 to 6 carbon atoms. Represents an alkyl group which may have a branched or straight-chain substituent, L ² represents a monovalent substituent, and * represents a binding site.

In the general formula (1), R ¹ and R ² are preferably a tert-butyl group.
R ³ is preferably a hydrogen atom.
R ⁴ and R ⁵ are preferably hydrogen atoms.
L ¹ is preferably a hydrogen atom, an alkyl group or an alkoxy group which may have a branched or straight chain substituent having 1 to 6 carbon atoms. More preferably, it is a C1-C4 alkyl group which has a methyl group, an alkoxy group, or an amino group as a substituent.
When said R ⁶ have multiple, even different plurality of R ⁶ may each be the same.

In the general formula (2), X ¹ is preferably a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group, or a carboxyl group, and more preferably a hydroxyl group.
When X ¹ is other than a hydroxyl group, R ⁷ is preferably a hydrogen atom, a methyl group, or a tert-butyl group, and more preferably a tert-butyl group.
R ⁸ is preferably a hydrogen atom.
L ² is the same as the preferred range of L ¹ .

  Specific examples of the hindered phenol antioxidant include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis (6-tert-butyl). -4-methylphenol) and the like. These specific examples are not intended to limit the present invention.

  The semi-hindered phenol antioxidant in the present invention is a substance having a structure represented by the following general formula (3).

In General Formula (3), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a tert-butyl group or —C (R ¹⁴ R ¹⁵ ) —R ¹⁶ , and R ¹³ represents a hydrogen atom or a carbon number. It represents an alkyl group which may have 1 to 6 branched or straight chain substituents, and L ¹¹ represents a monovalent substituent. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a methyl group, and R ¹⁶ represents a substituent having a structure represented by the following general formula (4).

In the general formula (4), X ¹¹ represents a hydrogen atom, an alkyl group, a hydroxyl group, (meth) acrylate group, a carboxyl group, if X ¹¹ is a hydroxyl radical R ¹⁷ represents a hydrogen atom or a methyl group, X ¹¹ R ¹⁷ represents a hydrogen atom, an alkyl group which may have a branched or straight chain substituent having 1 to 6 carbon atoms, and R ¹⁸ represents a hydrogen atom or 1 to carbon atoms. 6 represents an alkyl group which may have a branched or straight chain substituent, L ¹² represents a monovalent substituent, and * represents a binding site.

In the general formula (3), R ¹¹ is preferably a methyl group.
R ¹² is preferably a tert-butyl group.
R ¹³ is preferably a hydrogen atom.
R ¹⁴ and R ¹⁵ are preferably hydrogen atoms.
L ¹¹ is the same as the preferred range of L ¹ .

In the general formula (4), X ¹¹ is preferably a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group, or a carboxyl group, and more preferably a hydroxyl group.
When X ¹¹ is a hydroxyl group, R ¹⁷ is preferably a tert-butyl group.
When X ¹¹ is other than a hydroxyl group, R ¹⁷ is preferably a hydrogen atom, a methyl group, or a tert-butyl group, and more preferably a methyl group.
R ⁸ is preferably a hydrogen atom.
L ² is the same as the preferred range of L ¹ .

  Specific examples of the semi-hindered phenol antioxidant include 2-methyl-6-tert-butylphenol, 2-methyl-6-tert-butyl-4-methylphenol, 6-tert-butyl-4-methylphenol, Examples include 6-tert-butyl-4-methylphenol, 2,2'-methylenebis (4,6-dimethylphenol) and the like. These specific examples are not intended to limit the present invention.

  Although it does not specifically limit as a hindered amine type antioxidant in this invention, The compound which has a structure represented by following General formula (5) as a partial structure is illustrated.

In the general formula (5), R ²¹ represents a monovalent substituent, and L ²¹ represents a monovalent substituent.

R ²¹ is preferably a hydrogen atom, an alkyl group or an alkoxy group which may have a branched or straight chain substituent having 1 to 6 carbon atoms, and preferably a hydrogen atom or an alkoxy group. More preferred.
The preferred range of L ^{21 is the same as} the preferred range of L ¹ .

  Specific examples of the hindered amine antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl). ) Sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetra Methyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2 , 3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2, 6,6-tetramethyl-4- Peridyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2 , 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) Polycondensate with -4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2, 2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like. The illustrations limit the invention No.

The thioether-based antioxidant in the present invention is a compound represented by the general formula R—S—R ′. Here, R and R ′ are each an alkyl group or an alkyl ester group, and an alkyl ester group is preferable.
Examples of the thioether-based antioxidant include ditridecyl-thiodipropionate. These specific examples are not intended to limit the present invention.

  In addition, the phenolic antioxidant outside the scope of the present invention is a substance having a structure represented by the following general formula (6).

In the general formula (6), R ³¹ and R ³² represent a hydrogen atom or a methyl group, and R ³³ and L ³¹ represent a monovalent substituent.

In the first aspect of the curable composition for imprints of the present invention, the antioxidant consists only of a semi-hindered phenol-based antioxidant, which further enhances the antioxidant ability, reduces polymerization inhibition, and is photocured. From the viewpoint of improving the property, it is more preferable.
Further, in the second aspect of the curable composition for imprints of the present invention, the antioxidant is a mixture of a semi-hindered phenol type and a thioether type to further improve the antioxidant ability and reduce polymerization inhibition. From the viewpoint of improving photocurability, it is more preferable.

  The antioxidant suppresses fading caused by heat or light irradiation and fading caused by various oxidizing gases such as ozone, active oxygen, NOx, and SOx (X is an integer). In particular, in the present invention, by adding an antioxidant, there is an advantage that coloring of a cured film can be prevented and a reduction in film thickness due to decomposition can be reduced.

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

(Surfactant)
The curable composition for imprints of the present invention may contain a surfactant. The surfactant used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 3% by mass in the entire composition. It is. When using 2 or more types of surfactant, the total amount becomes the said range. When the surfactant is in the range of 0.001 to 5% by mass in the composition, the effect of coating uniformity is good, and deterioration of mold transfer characteristics due to excessive surfactant is unlikely to occur.
The surfactant preferably includes at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant, and includes both a fluorine-based surfactant and a silicone-based surfactant. Alternatively, it preferably contains a fluorine / silicone surfactant, and most preferably contains a fluorine / silicone surfactant. The fluorine-based surfactant and the silicone-based surfactant are preferably nonionic surfactants.
Here, the “fluorine / silicone surfactant” refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, a silicon wafer for manufacturing a semiconductor element, a glass square substrate for manufacturing a liquid crystal element, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, The striations that occur when the imprint curable composition of the present invention is applied to a substrate on which various films such as an amorphous silicone film, an indium oxide (ITO) film doped with tin oxide, and a tin oxide film are formed. In addition, it is possible to solve the problem of poor coating such as a scale-like pattern (unevenness of drying of the resist film). In addition, the fluidity of the composition of the present invention into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, the adhesion between the resist and the substrate is improved, the viscosity of the composition is decreased, etc. Is possible. In particular, the imprint composition of the present invention can significantly improve the coating uniformity by adding the surfactant, and can be satisfactorily applied regardless of the substrate size in coating using a spin coater or slit scan coater. Aptitude is obtained.

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

(Other ingredients)
In addition to the above components, the composition of the present invention includes a non-polymerizable molecule, a polymer component, a release agent, an organometallic coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, and an anti-aging agent as necessary. , Plasticizers, adhesion promoters, thermal polymerization initiators, photobase generators, colorants, elastomer particles, photosensitizers, basic compounds, and other flow regulators, antifoaming agents, dispersants, etc. May be.
The non-polymerizable molecule can be added to the composition of the present invention for the purpose of imparting adhesion and controlling physical properties of the cured film. The addition amount of such a non-polymerizable molecule can be determined within a range in which the addition amount of the photopolymerizable molecule can be controlled within the range of the present invention. Examples of such non-polymerizable molecules include alkyl esters such as dioctyl sebacate, (thio) urea compounds, organic fine particles, and inorganic fine particles.

In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer having a molecular weight higher than that of the other polyfunctional polymerizable monomer may be blended within a range that achieves the object of the present invention. it can. Examples of the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as ester acrylate, polyurethane acrylate, polyether acrylate, and epoxy acrylate, and hydrolysis condensation products of trimethoxysilylpropyl acrylate. As addition amount of an oligomer component, 0-30 mass% is preferable with respect to the component except the solvent of a composition, More preferably, it is 0-20 mass%, More preferably, it is 0-10 mass%, Most preferably, it is 0-5. % By mass.
The curable composition for imprints of the present invention may further contain a polymer component from the viewpoint of improving imprint suitability and curability. The polymer component is preferably a polymer having a polymerizable functional group in the side chain. As a weight average molecular weight of the said polymer component, 2000-100000 are preferable from a compatible viewpoint with a polymeric compound, and 5000-50000 are more preferable. The addition amount of the polymer component is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, and most preferably 2% by mass or less, relative to the component excluding the solvent of the composition. It is. Further, from the viewpoint of pattern formability, it is preferable that the resin component is as few as possible, and it is preferable that the resin component is not included except for surfactants and trace amounts of additives.

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

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

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, 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 modification methods as described above may be performed on one polysiloxane molecule.

  It is preferable that the modified silicone oil has appropriate compatibility with the composition components. In particular, when using a reactive silicone oil that is reactive with other coating film forming components blended as necessary in the composition, it is chemically bonded in the cured film obtained by curing the composition of the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. In addition, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone or vinyl-modified silicone, it is excellent in characteristics after curing because it is crosslinked with the composition of the present invention.

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

  When a release agent is added to the curable composition for imprints 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, in a range of 0.01 to 5% by mass. More preferably, it is added. When the content of the release agent is in the range of 0.01 to 5% by mass, the effect of improving the peelability between the mold and the curable composition layer for imprinting is improved, and the repelling at the time of coating the composition is further improved. May cause surface roughness due to coating, may interfere with the adhesion of the substrate itself or adjacent layers in the product, for example, the deposited layer, or may cause film destruction during transfer (film strength becomes too weak). It can be suppressed from occurring.

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

  Examples of the silane coupling agent that can be used in the composition of the present invention include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyl. Epoxy silanes such as methyldiethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane Aminosilanes such as N-phenyl-γ-aminopropyltrimethoxysilane; and other silane coupling agents such as γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane Etc.

  Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tridodecyl benzene sulfonyl 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, isopropyldimethacryliso Stearoyl titanate, isopropyl isostearoyl diacryl titanate, Propyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Furthermore, in addition to the radical photopolymerization initiator, a photosensitizer can be added to the curable composition for imprints 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 Crivello [JV Crivello, Adv. In Polymer Sci, 62, 1 (1984)]. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

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

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

  In the curable composition for imprints of the present invention, the amount of water at the time of preparation is preferably 2.0% by mass or less, more preferably 1.5% by mass, and further preferably 1.0% by mass or less. By making the water content at the time of preparation 2.0% by mass or less, the storage stability of the composition of the present invention can be made more stable.

  Moreover, a solvent can also be used for the curable composition for imprints of the present invention. The content of the organic solvent is preferably 3% by mass or less in the entire composition. That is, since the composition of the present invention preferably contains other monofunctional and / or bifunctional monomers as described above as reactive diluents, the organic solvent for dissolving the components of the composition of the present invention is It is not always necessary to contain. In the composition of the present invention, the content of the organic solvent is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably not contained. As described above, the composition of the present invention does not necessarily contain an organic solvent. However, in the case of dissolving a compound that does not dissolve in the reactive diluent as the composition of the present invention, or when finely adjusting the viscosity. Any of these may be added. The organic solvent that can be preferably used in the composition of the present invention is a solvent that is generally used in curable compositions for photoimprints and photoresists, 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.

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

The viscosity of the curable composition for imprints of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. The curable composition for imprints of the present invention preferably has a viscosity at 25 ° C. of 3 to 18 mPa · s, more preferably 5 to 15 mPa · s, and particularly preferably 7 to 12 mPa · s. . By setting the viscosity of the composition of the present invention to 3 mPa · s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa · s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. A composition having a viscosity of 3 mPa · s or more is also easier to prepare than a composition having a viscosity of less than 3 mPa · s. On the other hand, by setting the viscosity of the composition of the present invention to 18 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for residues to remain after photocuring in the mold convex portion. Further, when the viscosity of the composition of the present invention is 18 mPa · s or less, the viscosity hardly affects the formation of a fine pattern.
Generally, the viscosity of the composition can be adjusted by blending various monomers, oligomers and polymers having different viscosities. In order to design the viscosity of the curable composition for imprints of the present invention within the above range, it is preferable to adjust the viscosity by adding a composition having a single viscosity of 5.0 mPa · s or less.

[Method for producing cured product]
Next, the formation method of the hardened | cured material (especially fine concavo-convex pattern) using the curable composition for imprints of this invention is demonstrated. A step of applying a curable composition for imprints of the present invention on a substrate or a support (base material) to form a pattern forming layer, a step of pressing a mold against the surface of the pattern forming layer, and the pattern forming layer A fine concavo-convex pattern can be formed by curing the composition of the present invention through the step of irradiating light. In particular, in the present invention, in order to improve the degree of curing of the cured product, it is preferable to further include a step of heating the pattern forming layer after light irradiation. That is, the curable composition for imprints of the present invention is preferably cured by light and heat.
The cured product obtained by the method for producing a cured product of the present invention is excellent in pattern precision, curability, and light transmittance, and is particularly suitable as a protective film for liquid crystal color filters, spacers, and other liquid crystal display device members. Can be used.

  Specifically, a layer (pattern forming layer) consisting of the composition of the present invention is applied on a base material (substrate or support) by applying at least a pattern forming layer consisting of the composition of the present invention and drying as necessary. To form a pattern receptor (with a pattern-forming layer provided on the substrate), press the mold against the surface of the pattern-receiving layer of the pattern receptor, and transfer the mold pattern. The concavo-convex pattern forming layer is cured by light irradiation and heating. Light irradiation and heating may be performed a plurality of times. The optical imprint lithography according to the pattern forming method (a method for producing a cured product) of the present invention can be laminated and multiple patterned, and can be used in combination with ordinary thermal imprint.

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

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

Below, the manufacturing method (pattern formation method (pattern transfer method)) of the hardened | cured material using the curable composition for imprints of this invention is described concretely.
In the manufacturing method of the hardened | cured material of this invention, first, the composition of this invention is apply | coated on a base material, and a pattern formation layer is formed.
As a coating method when the curable composition for imprints of the present invention is coated on a substrate, generally known coating methods such as a dip coating method, an air knife coating method, a curtain coating method, and a wire bar coating are used. It can be formed by coating by a method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, or the like. Moreover, although the film thickness of the pattern formation layer which consists of a composition of this invention changes with uses to be used, it is about 0.05 micrometer-30 micrometers. Further, the composition of the present invention may be applied by multiple coating. In addition, you may form other organic layers, such as a planarization layer, for example between a base material and the pattern formation layer which consists of a composition of this invention. Thereby, since the pattern formation layer and the substrate are not in direct contact with each other, it is possible to prevent adhesion of dust to the substrate, damage to the substrate and the like.

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

  Subsequently, in the manufacturing method of the hardened | cured material of this invention, in order to transcribe | transfer a pattern to a pattern formation layer, a mold is pressed (pressed) on the pattern formation layer surface. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.

In the optical imprint lithography using the curable composition for imprints of the present invention, a light transmissive material is selected for at least one of the mold material and / or the substrate. In the optical imprint lithography applied to the present invention, a curable composition for imprints of the present invention is applied on a substrate to form a pattern forming layer, and a light-transmitting mold is pressed on this surface, Light is irradiated from the back surface of the mold to cure the pattern forming layer. Alternatively, the curable composition for imprints of the present invention may be applied on a light transmissive substrate, pressed against a mold, and irradiated with light from the back surface of the substrate to cure the curable composition for imprints. it can.
The light irradiation may be performed with the mold attached or after the mold is peeled off. In the present invention, the light irradiation is preferably performed with the mold in close contact.

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

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

  The mold used in the method for producing a cured product of the present invention may be a mold that has been subjected to a release treatment in order to improve the peelability between the curable composition for imprints and the mold surface. Examples of such molds include those that have been treated with a silane coupling agent such as silicone or fluorine, such as Optool DSX manufactured by Daikin Industries, Ltd. or Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. Commercially available release agents can also be suitably used.

  When photoimprint lithography is performed using the composition of the present invention, it is usually preferable to perform the mold pressure at 10 atm or less in the method for producing a cured product of the present invention. By setting the mold pressure to 10 atm or less, the mold and the substrate are not easily deformed and the pattern accuracy tends to be improved. Further, it is preferable from the viewpoint that the apparatus can be reduced because the pressure is low. As the mold pressure, it is preferable to select a region in which the uniformity of mold transfer can be ensured within a range in which the residual film of the curable composition for imprints on the mold convex portion is reduced.

In the manufacturing method of the hardened | cured material of this invention, the irradiation amount of the light irradiation in the process of irradiating light to the said pattern formation layer should just be sufficiently larger than the irradiation amount required for hardening. The irradiation amount necessary for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprints and the tackiness of the cured film.
Moreover, in the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprinting. It may be irradiated with light. Moreover, in the manufacturing method of the hardened | cured material of this invention, the preferable vacuum degree at the time of light irradiation is the range of 10-1 Pa to a normal pressure.

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

During exposure is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By making the exposure time 1 mW / cm ² or more, the exposure time can be shortened so that productivity is improved, and by making the exposure time 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure dose is desirably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . If it is 5 mJ / cm ² or more, the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold can be prevented. Also. When the exposure amount is 1000 mJ / cm ² or less, deterioration of the permanent film due to decomposition of the composition can be suppressed.
Further, during exposure, in order to prevent inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

  In the manufacturing method of the hardened | cured material of this invention, after making a pattern formation layer harden | cure by light irradiation, it is preferable to include the process (post-baking process) which adds and heats the hardened pattern. The heating may be performed either before or after the mold is peeled from the pattern forming layer after light irradiation, but it is preferable to heat the pattern forming layer after the mold is peeled off. As heat which heat-hardens the composition of this invention after light irradiation, 150-280 degreeC is preferable and 200-250 degreeC is more preferable. In addition, the time for applying heat is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes.

  In the present invention, the light irradiation in the photoimprint lithography may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for imprint lithography and the tackiness of the cured film.

  In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but the light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is kept in a vacuum state, it is effective in preventing bubble mixing, suppressing the decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprint lithography. It may be irradiated with light. In the present invention, the preferred degree of vacuum is 10-1 Pa to normal pressure.

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

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

  The elastic recovery rate of the cured product of the present invention is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more, from the viewpoint of being suitably used as a member for a liquid crystal display device. preferable.

[Components for liquid crystal display devices]
Further, the curable composition for imprints of the present invention can be applied as a member for a semiconductor integrated circuit, a recording material, and a liquid crystal display device, and among them, a member for a liquid crystal display device is preferable, and a flat panel display or the like It is more preferable to apply as an etching resist.
When the composition for imprints of the present invention is used as an etching resist, first, a silicon wafer or the like on which a thin film such as SiO2 is formed as a substrate, and the method for producing a cured product of the present invention on the substrate To form a nano-order fine pattern. Thereafter, a desired pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.

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

[ Reference Example 1]
In the composition shown in the following Table 2, the photopolymerizable monomers M1 to M3 described in the following Table 1, the following photo-radical polymerization initiator P-1, the following surfactants W-1 and W-2, the following antioxidant The curable composition for imprints of Reference Example 1 was prepared by adding the agent AO1. The numerical values in Table 2 are mass%.

[ Reference Examples 1-7 and 15-21, Examples 8-14 and 22-66, Comparative Examples 1-21 and 25-37]
These compositions were obtained in the same manner as the composition of Reference Example 1 except that the compositions shown in Tables 2 to 6 below were used.

[Comparative Examples 22-24]
No. described in Table 18 of JP-A-2006-124636. 8, no. 9 and no. 11, compositions of Comparative Examples 22 to 24 except the pigment were prepared. No. No. 8 contains no antioxidant, and No. 9 contains 0.15% by mass of Sumilizer MDP-S (manufactured by Sumitomo Chemical Co., Ltd.) as a hindered phenol-based antioxidant. No. 11 contains 0.15% by mass of hostabine N-24 (manufactured by Clariant) as a hindered amine antioxidant.

[Evaluation of curable composition for imprints]
The compositions of each reference example, each example and comparative example were measured and evaluated according to the following evaluation methods for imprintability, photocurability, heat resistance, elastic recovery rate and voltage characteristics. The results are shown in Tables 2 to 6 below.

<Imprintability>
It was evaluated how much the pattern transferred to the resist could reproduce the shape of the mold. Specifically, each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The spin-coated coated base film was set in an imprint apparatus using a high-pressure mercury lamp (lamp power 2000 mW / cm ² ) manufactured by ORC as a light source. The mold pressure was 0.8 kN and the degree of vacuum during exposure was 10 Torr ((about 1 .33 × 10 ⁴ Pa) As a mold, polydimethylsiloxane having a line / space pattern of 10 μm and a groove depth of 4.0 μm (“SILPOT184” manufactured by Toray Dow Corning Co., Ltd.) is 80 The product was pressed with a material made of a material cured at 60 ° C. for 60 minutes, and further exposed from the surface of the mold under the condition of 240 mJ / cm ^2. After the exposure, the mold was released to obtain a resist pattern.
Further, the obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes. The pattern shape after the transfer was observed with a scanning electron microscope and an optical microscope, and the pattern shape was evaluated according to the following criteria.
5: The mold shape transfer rate was 95% or more.
4: The mold shape transfer rate was 90% or more and less than 95%.
3: The mold shape transfer rate was 80% or more and less than 90%.
2: The mold shape transfer rate was 70% or more and less than 80%.
1: The transfer rate of the mold shape was less than 70%.

<Evaluation of photocurability>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not subjected to pressure bonding, and was exposed under conditions of 10 mW and 300 mJ / cm ^{2 in} a nitrogen atmosphere. Thereafter, a plastic film was pressed against the surface of the film, and the remaining degree (tack property) of the marks when the plastic film was peeled off was evaluated, and photocurability was measured.
5: No trace is left.
4: Traces remain, but disappear in a few seconds.
3: Traces remain, but disappear in a few minutes.
2: Traces remain and do not disappear over time.
1: The film is not cured.

<Heat resistance>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not subjected to pressure bonding, and was exposed under conditions of 10 mW and 300 mJ / cm ^{2 in} a nitrogen atmosphere. Then, it was cured by heating in an oven at 230 ° C. for 15 minutes. The film thickness before and after baking in an oven was measured, the reduction rate was determined, and the reduction rate (film reduction) of the film due to heating was evaluated according to the following criteria.
5: Film loss before and after baking at 230 ° C. for 150 minutes was 5% or less.
4: The film loss before and after baking at 230 ° C. for 150 minutes was 5% or more and less than 10%.
3: The film loss before and after baking at 230 ° C.-150 min was 10% or more and less than 15%.
2: The film loss before and after baking at 230 ° C.-150 min was 15% or more and less than 20%.
1: Film loss before and after baking at 230 ° C.-150 min was 20% or more.

<Evaluation of elastic recovery rate>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not pressed and exposed at 10 mW-200 mJ in a nitrogen atmosphere. Thereafter, the film cured by heating at 230 ° C. for 30 minutes in an oven was formed into a column shape of 20 × 30 × 4 μm, and the elastic recovery rate was measured with DUH-W201 manufactured by Shimadzu Corporation.
5: Elastic recovery rate was 80% or more.
4: Elastic recovery was 75% or more and less than 80%.
3: The elastic recovery was 70% or more and less than 75%.
2: Elastic recovery was 60% or more and less than 75%.
1: The elastic recovery rate was less than 60%.

<Evaluation of voltage characteristics>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and the mold was not pressed and exposed at 10 mW-200 mJ in a nitrogen atmosphere. Thereafter, the volume resistance of the film cured by heating at 230 ° C. for 30 minutes in an oven was measured by a double ring method, and voltage characteristics were measured. The obtained voltage characteristics were evaluated according to the following evaluation.
5: Volume resistance was 1 × 10E15 Ω · m or more.
4: The volume resistance was 5 × 10E14Ω · m or more and less than 1 × 10E15Ω · m.
3: The volume resistance was 1 × 10E14Ω · m or more and less than 5 × 10E14Ω · m.
2: The volume resistance was 1 × 10E13 Ω · m or more and less than 1 × 10E14 Ω · m.
1: Volume resistance was less than 1 × 10E13 Ω · m.

Here, the reference examples 1-7 and the comparative example 26 change the addition amount of antioxidant in the aspect using only a hindered phenolic antioxidant. Examples 8 to 14 and Comparative Example 27 are comparisons in which only the semi-hindered phenol antioxidant is used and the amount of addition of the antioxidant is changed. Reference Example 15-21 and Comparative Example 28 is a comparison by changing the added amount of the antioxidant in a manner using only Semihindado amine antioxidant. Examples 22 to 28 and Comparative Example 29 are comparisons in which the addition amount of the antioxidant is changed in a mode using a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant. Examples 29 to 35 and Comparative Example 30 are comparisons in which the addition amount of the antioxidant is changed in a mode in which a mixture of a semi-hindered phenolic antioxidant and a thioether antioxidant is used. In Examples 36 and 37 and Comparative Examples 17 to 21 in which only a semi-hindered phenolic antioxidant was used, a comparison was made when the non-polymerizable molecule C1 was further added to increase the addition amount. It is. In Examples 38 to 44, Comparative Example 25, and Comparative Example 31, in which only a semi-hindered phenol antioxidant is used, the photopolymerizable monomers M1 to M3 of Examples 8 to 14 are changed to photopolymerizable oxetane. Comparison is made when the amount of addition is changed by changing to compounds M4 to M6. In Comparative Example 1, a comparison was made when no antioxidant was added. The comparative example 2 compared with the case where a photoinitiator is not added. In Comparative Examples 3 to 8, the amount of addition was changed using a phenol-based antioxidant and compared with the effect of the specific antioxidant of the examples of the present invention. Comparative Examples 9 and 10 are comparative examples when the addition amount of the photopolymerization initiator is increased using a phenolic antioxidant. In Comparative Examples 11 to 16, only the thioether-based antioxidant was used alone to change the addition amount, and compared with the effect of the specific antioxidant of the examples of the present invention. No. described in Table 18 of JP-A-2006-124636. 8, no. 9 and no. The comparative examples 22-24 which excluded the pigment among 11 were compared generally with Examples 8-14 and 22-44 of this application.

  In Table 4 above, the heat resistance, elastic recovery rate, and voltage characteristics of Comparative Example 2 were not measurable.

As can be seen from the above Tables 2 to 4, No. 1 described in Table 18 of JP-A-2006-124636. 8, no. 9 and no. In contrast to Comparative Examples 22 to 24, in which the pigment was removed, the compositions of the Examples all had good imprintability, photocurability, heat resistance, elastic recovery rate, and voltage characteristics. In Examples 38 to 44 using the oxetane compound, the effect of improving the voltage characteristics was low as compared with the other examples.
On the other hand, since Comparative Example 1 did not contain an antioxidant, the heat resistance and the elastic recovery rate were low. Since Comparative Example 2 did not contain a photopolymerization initiator, the evaluation was very low. From Comparative Examples 3 to 10, it was found that when only the phenolic antioxidant was used, the evaluation of photocurability was clearly lowered, and this added the amount of photopolymerization agent at the expense of heat resistance and elastic recovery rate. Even in the increased Comparative Examples 9 and 10, a cured film having properties required by the present invention could not be obtained. From Comparative Examples 11 to 16, when only the thioether-based antioxidant was used, the heat resistance and the elastic recovery rate were clearly low. From the comparison of Examples 36 and 37 and Comparative Examples 17 to 21, even if only the semi-hindered phenol antioxidant is used, the amount of the photopolymerizable monomer added is within the range of the present invention (80 Mass% to 99 mass%), it was found that photocurability, heat resistance and elastic recovery rate were simultaneously improved, and this was a remarkable effect. In Comparative Examples 19 to 21 in which the blending amounts of monofunctional, bifunctional and trifunctional monomers were finely adjusted, the heat resistance and the elastic recovery rate could not be improved. The quantity was found to be an important factor. From the comparison of Examples 38 to 44, Comparative Example 25 and Comparative Example 31, if the added amount of the antioxidant is within the range of the present invention (0.3 to 7% by mass), the heat resistance and the elastic recovery rate are remarkable. It turned out to be improved.
Also, from Tables 5 and 6, it was found that the heat resistance and the elastic recovery rate of the examples of the present invention having a high antioxidant content were remarkably improved as compared with the comparative examples having a low antioxidant content. did.

Claims (10)

A) a photopolymerizable monomer;
B) a photopolymerization initiator;
C) an antioxidant,
A composition for photoimprinting comprising: A) the content of the photopolymerizable monomer is 80 to 99% by mass;
The content of the C) antioxidant is 0.3 to 7% by mass,
Wherein C) antioxidant, Se Mi hindered phenolic antioxidant alone, Hindadofu phenol system for imprint curing, characterized in that either a mixture of antioxidants and semi hindered phenol antioxidant Sex composition.     The curable composition for imprints according to claim 1, wherein the antioxidant comprises only a semi-hindered phenol-based antioxidant. A) a photopolymerizable monomer;
B) a photopolymerization initiator;
C) an antioxidant,
A composition for photoimprinting containing A), wherein the content of the photopolymerizable monomer is 80 to 99% by mass,
The content of the C) antioxidant is 0.3 to 7% by mass,
C) The antioxidant is a mixture of a hindered phenol antioxidant and a thioether antioxidant, or a mixture of a semi-hindered phenol antioxidant and a thioether antioxidant. A curable composition for printing.     The curable composition for imprints according to claim 3, wherein the antioxidant is a mixture of semi-hindered phenol and thioether.     The imprinting composition according to any one of claims 1 to 4, wherein the content of the antioxidant is 0.5 to 5% by mass.     The composition for imprints according to any one of claims 1 to 5, wherein an elastic recovery rate is 70% or more.     A cured product obtained by curing the curable composition for imprints according to any one of claims 1 to 6.     A member for a liquid crystal display device, comprising the cured product according to claim 7. Applying the curable composition for imprints according to any one of claims 1 to 7 on a substrate to form a pattern forming layer;
Pressing the mold against the surface of the pattern forming layer;
Irradiating the pattern forming layer with light;
The manufacturing method of the hardened | cured material characterized by including.     Furthermore, the process of heating the said pattern formation layer irradiated with light is included, The manufacturing method of the hardened | cured material of Claim 9 characterized by the above-mentioned.