TWI438235B - Curable composition for imprint, curing object using the same, manufacturing method thereof and member for liquid crystal display device - Google Patents

Description

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

The present invention relates to a curable composition for imprint, 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.

In the embossing method, a thermal imprint method using a thermoplastic resin as a material to be processed (for example, refer to Non-Patent Document 1) and photo-imprinting using a photocurable composition (for example, refer to Non-Patent Document 2) 2 technologies. In the case of the hot stamping method, a mold is pressed against a polymer resin heated to a temperature higher than the glass transition temperature, and after cooling, the mold is released to transfer the fine structure to the resin on the substrate. Since this method can also be applied to various resin materials and glass materials, application in various aspects is expected. For example, Patent Documents 1 and 2 below disclose a hot stamping method in which a nano pattern is inexpensively formed using a thermoplastic resin.

On the other hand, a photoimprint method in which light is cured by a transparent mold or a transparent substrate to photoharden the photocurable composition does not require heating of the material of the transfer pattern when the mold is pressed, and can be imprinted at room temperature. Recently, there have been reports of new developments such as the nano-casting method and the reverse imprinting method of a three-dimensional laminated structure combining the advantages of both.

In this imprint method, the following application techniques on the nanometer scale have been proposed. The first technique is applied to the fabrication of a high-density semiconductor integrated circuit or the fabrication of a transistor for a liquid crystal display by high-precision position blending and high integration, instead of the prior lithography. The shape (pattern) formed by the second technique has its own function and can be applied as an elemental part of various nano technologies or as a structural member, and examples thereof include various micro-nano optical elements or high-density recording media, and opticals. Thin film, structural members in flat displays, and the like. Further, as another technique, it is applied to a μ-TAS (Micro-Total Analysis System) or a bio-wafer by integrally molding a micro-structure and a nanostructure at the same time, or by simply blending between layers to form a laminated structure. Production. The third technique utilizes high-precision position blending and high-combination, and is suitable for fabrication of a high-density semiconductor integrated circuit or a transistor for a liquid crystal display, instead of the prior lithography. Including the foregoing techniques, practical combinations of imprint methods for such applications are becoming increasingly active.

An application example of the fabrication of the high-density semiconductor integrated circuit in the first technique described above will be described. In recent years, the semiconductor integrated circuit has progressed in miniaturization and integration, and the precision of the photolithography apparatus as a pattern transfer technique for realizing microfabrication has progressed. However, it is difficult to satisfy the fine pattern resolution, the device cost, and the throughput in comparison with the requirements of additional miniaturization. In view of this, as a technique for performing fine pattern formation at low cost, it has been proposed to use an imprint lithography technique, in particular, a nanoimprint lithography technique (photon nanoimprint method). For example, Patent Document 1 listed below discloses a nanoimprint technique in which a tantalum wafer is used as a rigid printhead to form a fine structure of 25 nm or less by pattern transfer. With this trend, in order to apply nanoimprint lithography to the fabrication of semiconductor integrated circuits, active properties such as mold-resin peelability, imprint uniformity, and pattern transfer precision have been actively developed. Review.

An application example of the photoimprint method of a flat panel display such as a liquid crystal display (LCD) or a plasma display (PDP) in the second technique described above will be described. With the increase in size and high-definition of LCD substrates and PDP substrates, in recent years, attention has been paid to the replacement of the previous photolithography method used in the manufacture of thin film transistors (TFTs) or electrode plates. As a cheap lithography, shadows must develop photocurable photoresists that replace the etch photoresist used in previous photolithography. Further, as a structural member such as an LCD, the application of the imprint method has been reviewed for a transparent protective film material to be used or a spacer for a cell gap of a liquid crystal display. The photoresist for such a structural member is different from the above-described etching resist, and is eventually referred to as a "permanent photoresist" or a "permanent film" because it eventually remains in a display such as a flat panel display panel.

As a permanent film to which the prior photolithography technique is applied, for example, a protective film provided on a TFT substrate of a liquid crystal panel, or a step of reducing the gap between the R, G, and B layers and imparting a film to the ITO film during sputtering can be used. A protective film or the like provided on a color filter for resistance to high-temperature treatment. In the formation of such a protective film (permanent film), since various properties such as uniformity of the coating film, high light transmittance after heat treatment exceeding 200 ° C, and scratch resistance are required, it is required to perform imprinting for satisfying such characteristics. Development of a hardenable composition. Further, the spacer used in the liquid crystal display is usually formed after the color filter is formed or after the protective film for the color filter is formed, and a photocurable composition is used on the color filter substrate by light micro The shadow formed a pattern having a size of about 10 μm to 20 μm, and was further formed by post-baking heat hardening. In addition to hardness and pattern precision, the spacer used in the liquid crystal display device described above requires a high elastic recovery ratio, and development of a hardenable composition for imprint which satisfies these characteristics has been sought.

Further, in the imprint method, it is necessary to improve the fluidity of the curable composition for imprinting in the cavity in which the concave portion of the mold surface is formed. Further, it is necessary to improve the peeling property between the mold and the photoresist while improving the adhesion between the photoresist and the substrate (substrate, support).

As noted above, the required characteristics of the materials used in embossing lithography vary widely depending on the application. However, there has been a description of the expectation of viscosity, for example, regarding the composition for imprint, but there have been no reports of design guidelines for materials suitable for each application.

Therefore, various problems such as pattern accuracy, heat resistance, and hardness have been cited as main technical problems of the permanent film. The case where the curable composition for imprint is used as the permanent film is also the same as that of the conventional acrylic resin, (1) pattern transfer precision (imprinting of imprint lithography), and (2) heat resistance. (3) The imparting of the hardening property is important.

As a problem specific to the curable composition for photoimprint, in addition to the properties (1) to (3) above, one of the mechanical properties can withstand the use of a high elastic recovery rate (4) which is used as a permanent film. . Further, when designing the composition of the curable composition for imprinting, in addition to the above points (1) to (4), it is necessary to ensure (5) the fluidity of the photoresist in the concave portion of the mold, and it is necessary to have no solvent or a small amount. The low viscosity (preferably 5 mPa.s or less) under the use of a solvent, and (6) must be improved in consideration of voltage characteristics for use as a structural member of an electric circuit, and the technical difficulty in designing the composition is further improved.

In recent years, in order to suppress discoloration, it has been proposed to use an antioxidant in a curable composition for imprint (see Patent Document 3 and Patent Document 4). However, in actuality, the use of antioxidants for the hardening composition for imprinting has not been reviewed.

Further, a photocurable composition in which a conventional antioxidant is added to other uses is reviewed. For example, in order to prevent oxidation of the metal surface to be bonded to the adhesive composition for a disc, and to improve the adhesion of the adhesive (Patent Document 5). An example in which less than 0.2% by mass of an antioxidant is used in the photocurable composition is described in the same document, but it is not suggested to satisfy imprintability, heat resistance, photocurability, high elastic recovery, low viscosity, voltage characteristics, and the like. Description of the characteristics required for the curable composition for imprint. In particular, in the case of using an antioxidant of less than 0.2% by mass, the viscosity of the composition is 380 mPa·s (25 ° C), and it is not applicable to the imprint of the low-viscosity composition described in Patent Document 5. Use a hardening composition.

Further, an example of adding 0.15 mass% of an antioxidant to the active light-curing inkjet composition has been reported for the purpose of improving the viscosity (Patent Document 6). However, although there is a description about the improvement of viscosity in the same literature, there is no description about imprintability, heat resistance, photocurability, high elastic recovery rate, and voltage characteristics.

As disclosed in Patent Document 5 and Patent Document 6, a known document in which an antioxidant is added to a photocurable resin composition is intended to prevent oxidation by oxygen in the air or to lower the viscosity. Detailed review. Further, the purpose of the known literature in which an antioxidant is added to a thermosetting resin is to suppress discoloration of the resin caused by oxidation upon heating.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] U.S. Patent No. 5,772,905

[Patent Document 2] U.S. Patent No. 5,956,216

[Patent Document 3] JP-A-2008-105414

[Patent Document 4] JP-A-2008-92099

[Patent Document 5] JP-A-2002-256228

[Patent Document 6] JP-A-2006-124636

[Non-patent literature]

[Non-Patent Document 1] S. Chou et al.: Appl. Phys. Lett. Vol. 67, 3114 (1995)

[Non-Patent Document 2] M. Colbun et al.: Proc. SPIE, Vol. 3676, 379 (1999)

In view of the above-described problems, the composition described in Patent Document 6 is used as it is for imprinting, and it is understood that the heat resistance, the elastic recovery rate, and the voltage characteristics are poor.

An object of the present invention is to provide a hardenable composition for embossing which has good embossability and photocurability, and which is excellent in mechanical properties, various durability, photohardness, heat resistance and elastic recovery, and hardening thereof. And a method for producing the same, and a member for a liquid crystal display device. More specifically, an object of the present invention is to provide a curable composition for imprint which is particularly suitable for a permanent film such as a transparent protective film or a spacer of a flat panel display or the like.

Based on the above-mentioned problems, the inventors of the present invention conducted a drill collar investigation and found that a composition satisfying the above characteristics (1) to (6) can be designed by including a specific amount of an antioxidant in the curable composition for imprint. Among them, (4) a composition having a high elastic recovery ratio is particularly available. That is, it has been found that the above problems can be solved by the following means.

[1] A curable composition for imprinting comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition of an antioxidant, wherein the aforementioned A The content of the photopolymerizable monomer is from 80 to 99% by mass, the content of the above C) antioxidant is from 0.3 to 7% by mass, and the above-mentioned C) antioxidant is only a hindered phenol-based antioxidant, and only a semi-hindered phenolic resistance Any of an oxidizing agent, a mixture of a hindered phenol-based antioxidant and a semi-hindered phenol-based antioxidant, or only a hindered amine-based antioxidant.

[2] The curable composition for imprint according to [1], wherein the antioxidant is composed only of a semi-hindered phenol-based antioxidant.

[3] A curable composition for embossing, comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an antioxidant photo-imprint composition, wherein the aforementioned A The content of the photopolymerizable monomer 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 mixture of a hindered phenol antioxidant and a thioether antioxidant, or A mixture of a semi-hindered phenolic antioxidant and a thioether antioxidant.

[4] The curable composition for imprint according to [3], wherein the antioxidant is a mixture of a semi-hindered phenol system and a thioether system.

[5] The composition for imprint according to any one of [1] to [4] wherein the content of the antioxidant is from 0.5 to 5% by mass.

[6] The composition for imprint according to any one of [1] to [5], wherein the elastic recovery ratio is 70% or more.

[7] A cured product obtained by curing the curable composition for imprint according to any one of [1] to [6].

[8] A member for a liquid crystal display device, characterized by comprising the cured product according to [7].

[9] A method of producing a cured product, comprising the step of applying a curable composition for imprint according to any one of [1] to [7] on a substrate to form a pattern forming layer. And a step of pressing the mold on the surface of the pattern forming layer and a step of irradiating the pattern forming layer with light.

[10] The method for producing a cured product according to [9], which further comprises the step of heating the pattern forming layer of the irradiated light.

According to the present invention, it is possible to provide a curable composition for imprint, which is 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 member for a liquid crystal display device.

[Formation of the Invention]

The contents of the present invention are described in detail below. The use of "~" in the present specification means that the numerical values listed before and after are referred to as the lower limit and the upper limit.

In the present specification, "(meth)acrylate" means "acrylic acid ester" and "methacrylic acid ester", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid", "( "Methyl) acrylonitrile" means "acryloyl" and "methacryl". In addition, in this specification, "monomer" is synonymous with "single molecule". The single system in the present invention is different from the oligomer and the polymer, and means a compound having a weight average molecular weight of 1,000 or less. In the present specification, "functional group" means a group related to polymerization.

Further, the imprinting system according to the present invention may comprise a pattern transfer of a size of about several tens of nanometers to several tens of micrometers, and also includes nanoimprinting, not limited to a nanoscale.

Further, in the present specification, the concept of "hindered phenolic antioxidant" and "semi-hindered phenolic" are not clearly distinguished.

[Sclerosing composition for imprint]

The curable composition for imprint of the present invention (hereinafter, simply referred to as "the composition of the present invention") is a photoimprint composition containing a photopolymerizable monomer, a photopolymerization initiator, and an antioxidant, and the photopolymerization is carried out. The content of the monomer is 80 to 99% by mass, and the content of the antioxidant is 0.3 to 7% by mass. Further, the first aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is only a hindered phenol-based antioxidant, only a semi-hindered phenol-based antioxidant, a hindered phenol-based antioxidant, and a semi-blocked A mixture of phenolic antioxidants or only one of hindered amine antioxidants. On the other hand, the second aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, or a semi-hindered phenol-based antioxidant and a thioether system. a mixture of antioxidants.

The composition of the present invention contains a specific range of amounts of the antioxidant in addition to a photopolymerizable monomer and a photopolymerization initiator in a specific range, thereby achieving high level of imprintability and photocurability at the same time. Heat resistance and voltage characteristics, in addition, can also make the elastic recovery rate a high level. Increasing the elastic recovery rate is a particularly surprising effect since the effect of increasing the elastic recovery rate cannot be expected from the function of the previous antioxidant.

Further, the curable composition for imprint of the present invention can be widely used for photoimprint lithography (including photon lithography), and can have the following features.

(1) Since the composition of the present invention is excellent in fluidity at a solution at room temperature, the composition can easily flow into the cavity of the concave portion of the mold, and it is difficult to inhale the atmosphere to cause bubble defects, which is difficult in the convex portion or the concave portion of the mold. The residue remains after photohardening.

(2) The cured film obtained by curing the composition of the present invention is excellent in mechanical properties, excellent in adhesion between the coating film and the substrate, and excellent in peeling property between the coating film and the mold, so that pattern peeling is not caused when the mold is peeled off. Or a stringness is generated on the surface of the coating film to cause surface cracking, so that a good pattern (good embossability) can be formed.

(3) Because of uniform coating, it is suitable for coating of large substrates, fine processing, and the like.

(4) Since it has high mechanical properties such as photocurability, heat resistance, and elastic recovery, it is suitable as a permanent film.

(5) Since it is excellent in voltage characteristics, it is suitable for materials for electronic circuits and the like.

Therefore, the curable composition for imprint of the present invention can be suitably applied to, for example, a semiconductor integrated circuit or a member for a liquid crystal display device which has hitherto been difficult to develop (especially a thin film transistor of a liquid crystal display, a protective film of a liquid crystal color filter) , spacers, and other micro-processing applications for liquid crystal display devices, etc.), can also be widely used in other applications, such as partition walls for plasma display panels, flat screens, micro electromechanical systems (MEMS), sensing elements, Optical components such as magnetic recording media such as optical disks and high-density memory disks, optical components such as diffraction gratings or embossed holograms, nanodevices, optical devices, optical films or polarizing elements, organic transistors, color filters, and watches Coating, column, liquid crystal alignment rib, microlens array, immunoassay wafer, DNA separation wafer, microreactor, nano biochemical device, optical waveguide, filter, photonic liquid crystal, etc. Production.

(photopolymerizable monomer)

The photopolymerizable monomer is contained in the curable composition for imprint of the present invention. The composition of the present invention can provide good pattern precision (imprint property) after light irradiation by containing a photopolymerizable monomer. In the present invention, the "photopolymerizable monomer" means a monomer which can initiate a polymerization reaction by light irradiation to form a high molecular weight body.

As the main function of the photopolymerizable monomer used in the present invention, the viscosity of the composition or the mechanical properties of the cured film can be appropriately selected depending on the purpose. From the viewpoint of viscosity adjustment of the composition, it is preferred to use a photopolymerizable monomer having a low viscosity. Further, in order to improve the pattern accuracy of the cured product, the viscosity of the composition is usually preferably 18 mPa ‧ or less, and the purpose is preferably to use a polymerizable monomer having a viscosity as low as possible. The viscosity of the photopolymerizable monomer is related to the molecular weight, the intermolecular interaction, and the like. Therefore, a single amount of low-viscosity of photoradical polymerization can be achieved by considering low molecular weight and low intermolecular interaction.

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, and 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.

In addition, the photoradical polymerizable functional group which the photopolymerizable monomer has in the present invention may, for example, be a functional group having an ethylenically unsaturated bond, and may be a (meth)acrylic group, a vinyl group or an allyl styrene. The base is preferred. The photopolymerizable monomer contained in the composition of the present invention may be one type or two or more types. Further, the composition of the present invention may be used in combination with a photopolymerizable monomer having a photoradical polymerizable functional group or a photopolymerizable monomer (for example, a polymerizable monomer having a cationic polymerizable group).

Further, from the viewpoint of imparting mechanical properties to the cured film, it is preferred to use a difunctional or higher polyfunctional monomer. Such a polyfunctional monomer is inevitably increased in viscosity due to an increase in molecular weight, and the pattern viscosity is lowered due to high viscosity of the composition. Therefore, the polymerizable single system used in the present invention considers a combination of a low-viscosity single molecule for viscosity adjustment and a polyfunctional single molecule imparted to impart mechanical properties to the cured film, or an oxetane of the present invention (oxetane) A combination of a compound or a functional anhydride is selected in a comprehensive manner.

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

In the present invention, only one type of silsesquioxane compound may be contained, or two or more types may be contained. Further, in the composition of the present invention, the sesquioxane compound is preferably contained in an amount of from 1 to 40% by mass, more preferably from 1 to 20% by mass. By being in this range, it is possible to combine both the viscosity of the composition and the mechanical properties of the cured film.

In the photopolymerizable monomer of the present invention, a polymerizable unsaturated monomer (monofunctional polymerizable unsaturated monomer) having one group containing an ethylenically unsaturated bond may be mentioned. Specifically, 2-propenyloxyethyl terephthalate, 2-propenyloxy 2-hydroxyethyl terephthalate, 2-propenyloxyethyl hexahydroterephthalate, p-benzene 2-propenyl propyl propyl dicarboxylate, 2-ethyl-2-butyl propylene glycol 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, (methyl) ) 3-methoxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, acrylate acid dimer, benzyl (meth) acrylate, butane diol mono (meth) acrylate, (methyl) Butyloxyethyl acrylate, butyl (meth) acrylate, hexadecyl (meth) acrylate, ethylene oxide modification (hereinafter referred to as "EO") cresyl (meth) acrylate, ( Dipropylene glycol (meth)acrylate, phenyl ethoxylate (meth)acrylate, ethyl (meth)acrylate, isoamyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) Isooctyl acrylate, cyclohexyl (meth)acrylate, (meth) propyl Isobornyl enoate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate, (A) (meth) propylene dipropylene glycol acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, Methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, decyl phenoxy polyethylene glycol (meth) acrylate, decyl phenoxy poly(meth) acrylate Propylene glycol ester, octyl (meth) acrylate, p-cumyl phenoxy glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate, (methyl Benzyl acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, Poly(ethylene glycol) (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, stearyl (meth)acrylate, EO modified (methyl) Acetic acid succinic acid , tert-butyl (meth)acrylate, tribromophenyl (meth)acrylate, EO modified tribromophenyl (meth)acrylate, tri-dodecyl (meth)acrylate, p-isopropene Phenolic, styrene, α-methylstyrene, acrylonitrile, vinylcarbazole, ethyl oxetanemethyl acrylate.

Further, vinyl vinyl hydride, 3-methyl group such as vinyl trichloromethane, vinyl stilbene (β-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trimethoxy decane, etc., may be exemplified. (Methyl) propylene oxime such as propylene methoxy propyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3- propylene methoxy propyl trimethoxy decane Base decane.

Among these, the present invention is particularly suitable for the use of acrylate single molecules.

Further, as the photopolymerizable monomer of the present invention, a difunctional polymerizable unsaturated monomer having two groups containing an ethylenically unsaturated bond can be preferably used. As an example of the aforementioned difunctional polymerizable unsaturated monomer, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di(meth) acrylate, di(methyl) can be exemplified. Acrylic cyanurate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, EO modified di(meth)acrylic acid 1, 6-hexanediol ester, ECH modified 1,6-hexanediol di(meth)acrylate, allyloxypolyethylene 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 II Methyl) acrylate, ECH modified hexahydrofurfurate diacrylate, hydroxytrimethyl acetic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, EO modified Neopentyl glycol acrylate, propylene oxide (hereinafter referred to as "PO".) modified neopentyl glycol diacrylate, caprolactone modified hydroxytrimethyl acetate neopentyl glycol, stearic acid Ethylene pentaerythritol (meth) acrylate, ECH modified di(meth)acrylic acid Phthalate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propylene glycol-butanediol) di(meth)acrylate, polyester (di)acrylate, di(methyl) Polyethylene glycol acrylate, polypropylene glycol di(meth)acrylate, ECH modified propylene glycol di(meth)acrylate, fluorenone di(meth)acrylate, triethylene glycol di(meth)acrylate Ester, tetraethylene glycol di(meth)acrylate, (b) tricyclodecane dimethanol acetate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, di(methyl) Tripropylene glycol acrylate, EO modified tripropylene glycol di(meth)acrylate, triglycerol di(meth)acrylate, dipropylene glycol di(meth)acrylate, divinylethylene urea, divinyl propylene Urea, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl di(meth)acrylate.

Among these, neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethyl bis(meth)acrylate Glycol ester, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Cyclopentenyloxyethyl ester, dicyclopentyl di(meth)acrylate, and the like are particularly suitable for use in the present invention.

As the photopolymerizable monomer in the present invention, a polyfunctional polymerizable unsaturated monomer having three or more groups containing an ethylenically unsaturated bond can also be preferably used. Examples of the polyfunctional polymerizable unsaturated monomer include ECH-modified tris(meth)acrylic acid glycerol ester, EO-modified tris(meth)acrylic acid glycerol ester, and PO-modified tris(A). Glycerol acrylate, neopentyl glycol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri(meth) acrylate, caprolactone modified trimethylolpropane tris Acrylate, EO modified trimethylolpropane tri(meth) acrylate, PO modified trimethylolpropane tri(meth) acrylate, ginseng (propylene oxyethyl) cyanuric acid Ester, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, hydroxyp-pentaerythritol penta(meth)acrylate, alkyl modification R-pentaerythritol penta(meth)acrylate, di-n-pentyl glycol poly(meth)acrylate, alkyl-modified dipentaerythritol tris(meth)acrylate, di-trimethylol Propane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like.

Among these, EO modified tris(meth)acrylic acid glycerol ester, PO modified tris(meth)acrylic acid glycerol ester, trimethylolpropane tri(meth)acrylate, EO modified three Hydroxymethylpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, neopentyl tetra(meth)acrylate Alcohol ethoxylate, neopentyl tetra(meth)acrylate, and the like are particularly suitable for use in the present invention.

As the photopolymerizable monomer used in the present invention, a vinyl ether compound can also be used.

The above vinyl ether compound can be appropriately selected from known ones, for example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol Alcohol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propylene glycol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol Divinyl ether, 1,4-butanediol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane Trivinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, neopentyl alcohol divinyl ether, neopentyl alcohol trivinyl ether, neopentyl alcohol tetravinyl ether, sorbus Sugar alcohol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol divinyl vinyl ether, triethylene glycol divinyl vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene ethylene Ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane divinyl vinyl ether, neopentyl alcohol divinyl vinyl ether, neopentyl alcohol triethylene glycol Ethyl ether, neopentyl alcohol tetravinyl vinyl ether, 1,1,1-gin[4-(2-vinyloxyethoxy)phenyl]ethane, bisphenol A divinyloxyethyl ether, etc. .

These vinyl ether compounds can be used, for example, by the method described in Stephen. C. Lapin, Polymers Paint Colour Journal. 179 (4237), 321 (1988), that is, by reaction of a polyhydric alcohol or a polyhydric phenol with acetylene, or The reaction of the polyol or the polyhydric phenol with the halogenated alkyl vinyl ether is carried out, and these may be used alone or in combination of two or more.

Further, the photopolymerizable monomer used in the present invention may also be a styrene derivative. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, and p-hydroxystyrene.

Other styrene derivatives which can be used in combination with the monofunctional polymer of the present invention include, for example, styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-A. Base-β-methylstyrene, α-methylstyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like. Further, in the present invention, a vinyl naphthalene derivative may be used, and examples thereof include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinylnaphthalene, and 4- Methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, and the like.

Further, in order to improve the peeling property and the coating property with the mold, trifluoroethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, (perfluorobutyl)ethyl (meth)acrylate, Perfluorobutyl-hydroxypropyl (meth)acrylate, (perfluorohexyl)ethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, A compound having a fluorine atom such as tetrafluoropropyl methacrylate is used as the photopolymerizable monomer in the present invention or in combination with the photopolymerizable monomer in the present invention.

Further, the photopolymerizable monomer used in the present invention may be blended with a propenyl ether and a butenyl ether. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butoxymethyl-2-norbornene, 1-4-di(1) -butenyloxy)butane, 1,10-bis(1-butoxy)decane, 1,4-bis(1-butoxymethyl)cyclohexane, diethylene glycol di 1-butenyl)ether, 1,2,3-tris(1-butenyloxy)propane, propylene ether propylene carbonate, or the like can be suitably used.

In the curable composition for imprint of the present invention, the photopolymerizable monomer used in the present invention may further contain a compound having an oxetane ring containing a photoradical polymerizable functional group (hereinafter, simply referred to as " An oxetane compound or an oxetane single molecule is used as a photopolymerizable monomer. When the composition of the present invention contains a compound having an oxetane ring, it is preferred because it can obtain excellent hardness by heating.

The number of the oxetane ring structure (oxetanyl group) contained in the compound having an oxetane ring in the present invention is from 1 to 4 from the viewpoint of the curing rate and the physical properties of the cured film. Preferably, it is preferably from 1 to 3.

Further, the total carbon number of the compound having an oxetane ring in the present invention is preferably from 5 to 50, more preferably from 5 to 20, from the viewpoint of reducing the viscosity of the composition.

The molecular weight of the compound having an oxetane ring in the present invention is preferably from 100 to 1,000, more preferably from 100 to 400, from the viewpoint of reducing the viscosity of the composition.

Moreover, the oxetane compound which is a photopolymerizable monomer in the present invention has a photoradical polymerizable functional group. The photoradical polymerizable functional group may, for example, be a functional group having an ethylenically unsaturated bond, and preferably a (meth)acrylic group, a vinyl group, an allyl group or a styryl group. The number of photoradical polymerizable groups contained in the compound having an oxetane ring in the present invention is preferably from 1 to 4 from the viewpoint of the pattern precision at the time of light irradiation and the adhesion between the substrates. 1 to 2 is better. The compound having an oxetane ring contained in the composition of the present invention may be one type or two or more types. Further, the composition of the present invention may be used in combination with an oxetane compound having a photoradical polymerizable functional group and an oxetane compound not containing the same. When the compound (x) having a photoradical polymerizable functional group and the oxetane compound (y) having no photo-polymerizable functional group are used, the pattern precision after light irradiation and the suppression of suppression of volatilization of unreacted components during heating are suppressed. In view of the above, the content ratio (x:y, reference x) is preferably 1/2 to 5/1, more preferably 1/1 to 2/1.

Further, the curable composition for imprint of the present invention may contain a compound having an oxetane ring in addition to the photopolymerizable monomer, as long as it does not deviate from the gist of the present invention.

In the curable composition for imprint of the present invention, the content of the oxetane compound in the total composition is preferably from 5 to 50% by mass, preferably from 10%, from the viewpoint of pattern accuracy after light irradiation. 30% by mass is more preferred. However, when the compound having an oxetane ring in the present invention has a photoradical polymerizable functional group, the content thereof is as described above, and the content of the compound having a radical polymerizable functional group in the composition of the present invention can be considered. To decide. In this case, the content of the oxetane compound having a photoradical polymerizable functional group is related to the content of the compound having another radical polymerizable functional group or the photoradical polymerizable functional group. The relationship between the content of the oxetane compound is appropriately determined.

The compound having an oxetanyl group in the invention may, for example, be 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 East Asia Synthetic Co., Ltd.), 3-ethyl- 3-(phenoxymethyl)oxetane (trade name: OXT-211, manufactured by Toagosei Co., Ltd.), bis[1-ethyl(3-oxetanyl)]methyl ether (trade name: OXT-221, manufactured by East Asia Synthetic Co., Ltd.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (trade name: OXT-212, East Asian Synthesis ( (4)-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl (trade name: ETERNACOLLOXBP, Ube Industries, Ltd.) Sesquiterpene oxide modified oxetane (trade name: OX-SQ, manufactured by Toagosei Co., Ltd.), oxetane (meth) acrylate (trade name: OXE-10, 30, Osaka Organic Chemicals Co., Ltd.).

The curable composition for imprint of the present invention may further contain a functional acid anhydride. The acid anhydride compound of the present invention has a function as a curing agent for the aforementioned oxetane compound. When the composition of the present invention contains a functional acid anhydride, it is preferred because a high surface hardness can be obtained after heat curing.

In the present invention, the "functional acid anhydride" is a compound obtained by dehydrating and condensing two molecules of keto acid, and is chemically bonded to other functional groups by heating or the like.

Examples of the functional anhydride anhydride include phthalic anhydride, citraconic anhydride, succinic anhydride, propionic anhydride, maleic anhydride, and acetic anhydride, and the viscosity is lowered and the stability of the composition is considered. It is preferred to use phthalic anhydride or maleic anhydride.

Further, in the present invention, the total carbon number of the functional acid anhydride is preferably from 10 to 100, more preferably from 10 to 50, from the viewpoint of reducing the viscosity of the composition.

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.

Further, the functional acid anhydride is preferably a photoradical polymerizable functional group from the viewpoint that the photopolymerizable monomer is in the above range. The photoradical polymerizable functional group may, for example, be a functional group having an ethylenically unsaturated bond, and preferably a (meth)acrylic group, a vinyl group, an allyl group or a styryl group. In the present invention, the number of photo-radical polymerizable groups contained in the functional acid anhydride is preferably from 1 to 3, more preferably from 1 to 2, from the viewpoint of pattern accuracy at the time of light irradiation and adhesion to a substrate. good. The functional acid anhydride contained in the composition of the present invention may be one type or two or more types. Further, the composition of the present invention may be a functional acid anhydride having a photoradical polymerizable functional group or a functional acid anhydride having no such functionality. When the compound (q) having a photoradical polymerizable functional group and the functional acid anhydride (w) having no functional group are used, the pattern precision after light irradiation and the suppression of volatilization of unreacted components during heating are considered. The content ratio (q:w, reference q) is preferably 1/2 to 5/1, more preferably 1/1 to 2/1.

In the curable composition for imprint of the present invention, the content of the functional acid anhydride in the total composition is preferably from 5 to 50% by mass, preferably from 10 to 30% by mass, from the viewpoint of pattern accuracy after light irradiation. For better. However, when the functional acid anhydride of the present invention has a photoradical polymerizable functional group, the content thereof is as described above, and can be determined in consideration of the content of the compound having a radical polymerizable functional group in the composition of the present invention. In this case, the content of the functional acid anhydride having a photoradical polymerizable functional group is a relationship with the content of a compound having another radical polymerizable functional group or a functional anhydride having no photoradical polymerizable functional group. The relationship between the content is appropriately determined.

Further, in the curable composition for imprint of the present invention, the content ratio (a: b, reference a) of the oxetane compound (a) of the present invention to the functional acid anhydride (b) is reduced as much as possible. From the viewpoint of the amount of the unreacted functional group, it is preferably 3/1 to 1/3, more preferably 2/1 to 1/2.

The functional anhydride in the present invention may, for example, be methyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: EPICLON B570, manufactured by Dainippon Ink Chemicals Co., Ltd.), methyl-hexahydrogen Anthraquinone anhydride (trade name: EPICLON B650, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), methyl-3,6-endomethyl-1,2,3,6-tetrahydrophthalic anhydride (trade name: MHAC- P, Hitachi Chemical Co., Ltd.), 4-methylhexahydrophthalic anhydride (trade name: RIKACID M H-700, manufactured by Nippon Chemical and Chemical Co., Ltd.), anhydrous citraconic acid, dodecene succinic anhydride (commercial product) Name: RIKACID DDSA, New Japan Physical and Chemical Co., Ltd.), glycerol bis(benzenetricarboxylic anhydride) monoacetate (trade name: RIKACID MTA-10, New Japan Physical and Chemical Co., Ltd.), Japan Zeon (share) It is manufactured by Quinhard-200 (trade name), EPICURE YH-306 (trade name) manufactured by Nippon Epoxy Resin Co., Ltd., Aldrich reagent (P25205, 294152, B9750, B4600, 412287, N818, N1607, 330736).

Next, a preferred blending form of the photopolymerizable monomer in the present invention will be described.

The total content of the photopolymerizable monomer in the curable composition for imprint of the present invention is from 80 to 99% by mass. The "photopolymerizable monomer" means a compound having a radical polymerizable functional group having an ethylenically unsaturated bond such as a (meth)acrylic group, a vinyl group or an allyl group. For example, the oxetane (meth) acrylate having a compound having an oxetane ring is a photopolymerizable monomer because the (meth)acrylic 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, the film can not be sufficiently cured even by light irradiation, and the mold pattern cannot be transferred accurately, and the physical properties such as the hardness of the cured film are not improved. full. Further, when the total content of the compound having a radical polymerizable functional group in the composition of the present invention is more than 99% by mass, an additive such as a photoradical polymerization initiator or a surfactant is not sufficiently effective, pattern precision, physical properties of the cured film deterioration. The total content of the compound having a radical polymerizable functional group in the composition of the present invention is preferably from 60 to 99% by mass, more preferably from 80 to 98% by mass, from the viewpoint of pattern accuracy and physical properties of the cured film.

The monofunctional polymerizable unsaturated monomer is usually used as a reactive diluent, and the viscosity of the composition of the present invention is effectively lowered, and usually 10% by mass or more of the total polymerizable unsaturated monomer is added. It is preferably added in an amount of from 20 to 80% by mass, more preferably from 25 to 70% by mass, even more preferably from 30 to 60% by mass.

Since the monofunctional polymerizable unsaturated monomer is more preferably a reactive diluent, it is preferably 10% by mass or more of the total polymerizable unsaturated monomer.

The monomer having two groups containing an unsaturated bond (difunctional polymerizable unsaturated monomer) is preferably 90% by mass or less, more preferably 80% by mass or less, based on the total polymerizable unsaturated monomer. It is added in the range of 70% by mass or less. The ratio of the monofunctional and difunctional polymerizable unsaturated monomers is preferably from 1 to 95% by mass, more preferably from 3 to 95% by mass, even more preferably from 5 to 90% by mass based on the total of the polymerizable unsaturated monomers. Add it. The proportion of the polyfunctional polymerizable unsaturated monomer having three or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total polymerizable unsaturated monomer. It is added in the range of 60 mass% or less. When the ratio of the polymerizable unsaturated monomer having three or more polymerizable unsaturated bond-containing groups is 80% by mass or less, the viscosity of the composition can be lowered, which is preferable.

(Photoradical polymerization initiator)

The curable composition for imprint of the present invention contains a photoradical polymerization initiator. The composition of the present invention can make the pattern precision after light irradiation good by including a radical polymerization which can be initiated by light irradiation and a photoradical polymerization initiator. The content of the photoradical polymerization initiator used in the present invention is, for example, 0.1 to 15% by mass, more preferably 0.2 to 12% by mass, particularly preferably 0.3, based on the total composition. ～10% by mass. When two or more types of photopolymerization initiators are used, the total amount thereof is in the above range.

When the ratio of the photoradical polymerization initiator is 0.1% by mass or more, sensitivity (speed hardenability), resolution, line edge roughness, and coating film strength tend to be improved. On the other hand, when the ratio of the photoradical polymerization initiator is 15% by mass or less, light permeability, colorability, handleability, and the like tend to be improved. In the inkjet composition containing a dye and/or a pigment or a composition for a color filter of a liquid crystal display, various evaluations have been made on the addition amount of a preferred photopolymerization initiator and/or photoacid generator. However, the amount of the preferred photopolymerization initiator and/or photoacid generator added to the curable composition for photoimprint lithography for imprinting or the like is not reported. That is, in a system containing a dye and/or a pigment, these have a function as a radical trapping agent, and have an influence on photopolymerizability and sensitivity. In view of this, the amount of the photopolymerization initiator added in these applications is optimized. On the other hand, in the composition of the present invention, the dye and/or the pigment are not essential components, and the optimum range of the photopolymerization initiator may be in the field of an inkjet composition or a liquid crystal display color filter composition or the like. Different.

The photoradical polymerization initiator used in the present invention is blended to be active at the wavelength of the light source used and used to produce an appropriate active species.

The photoradical polymerization initiator used in the present invention may be, for example, a commercially available initiator. Examples of such an example include Irgacure (registered trademark) 2959 available from Ciba Corporation: (1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1- Ketone, 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 (registered trademark) 369: (2-benzyl-2-dimethylamino-1-(4) - morpholinyl phenyl) butanone-1), Irgacure (registered trademark) 907: (2-methyl-1[4-methylthiophenyl]-2- morpholinopropan-1-one, Irgacure ( Registered trademark) 819: (bis(2,4,6-trimethylbenzylidene)-phenylphosphine, Irgacure (registered trademark) 1800: (bis(2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine, 1-hydroxy-cyclohexyl-phenyl-one), Irgacure (registered trademark) 1800: (bis(2,6-dimethoxybenzamide) )-2,4,4-trimethyl-pentylphosphine, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure (registered trademark) OXE01: (1, 2 - Octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzylidenehydrazine), Darocur (registered trademark) 1173: (2-hydroxy-2- 1-phenyl-1-propan-1-one), Darocur (registered trademark) 1116, 1398, 1174 and 1020, CGI242: (ethanone, 1-[9-ethyl-6-(2-methyl) Benzyl hydrazino)-9H-carbazol-3-yl]-1-(O-ethenyl hydrazine); Lucirin TPO available from BASF: (2,4,6-trimethylbenzoguanidinyl) Phenylphosphine), Lucirin TPO-L: (2,4,6-trimethyl benzhydrylethoxyphenylphosphine); ESACURE can be obtained by Siber Hegner, Japan, ESACURE 1001M: (1-[4-benzamide] Aphenyl fluorenyl]phenyl]-2-methyl-2-(4-methylphenylindenyl)propan-1-one, Adeka Optomer (registered trademark) N-1414 available from N-1414 Asahi Chemical Co., Ltd. : (carbazole benzophenone), Adeka Optomer (registered trademark) N-1717: (acridine), Adeka Optomer (registered trademark) N-1606: (three Department); Sanhe Chemical TFE-three :(2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), three and chemical TME-three :(2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), Sanhe Chemical MP-III :(2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI Chemical TAZ-113: (2-[2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three ), MIDORI Chemical TAZ-108 (2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three ), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide , 4-phenylbenzophenone, ethyl acesulfame, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-Diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxy Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-three Chloroacetophenone, diethoxyacetophenone and dibenzocycloheptanone, methyl o-benzylidene benzoate, 2-benzylidene naphthalene, 4-benzylidenebiphenyl, 4- Benzyl decyl diphenyl ether, 1,4-benzylidene benzene, benzyl, 10-butyl-2-chloroacridone, [4-(methylphenylthio)phenyl]phenylmethane ), 2-ethyl hydrazine, 2,2-bis(2-chlorophenyl) 4,5,4',5'-fluorene (3,4,5-trimethoxyphenyl) 1,2'- Biimidazole, 2,2-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-biimidazole, ginseng (4-dimethylaminophenyl)methane Ethyl-4-(dimethylamino)benzoate 2- (dimethylamino) ethyl benzoate, butoxyethyl 4- (dimethylamino) benzoate and the like.

(Antioxidants)

The curable composition for imprint of the present invention may also contain an antioxidant.

The first aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is only a hindered phenol-based antioxidant, only a semi-hindered phenol-based antioxidant, a hindered phenol-based antioxidant, and a semi-hindered phenolic anti-oxidant. A mixture of oxidizing agents, or only one of the hindered amine-based antioxidants.

On the other hand, the second aspect of the curable composition for imprint of the present invention is characterized in that the antioxidant is a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, or a semi-hindered phenol-based antioxidant and a thioether system. a mixture of antioxidants.

The present invention is characterized in that the antioxidants used in the above-described two aspects of the present invention are used to enhance photocurability, heat resistance, and elastic recovery. In view of the technique of adding a photo-curable resin composition of a conventional antioxidant, an antioxidant is added in the above two aspects of the present invention, and the elastic recovery rate of the cured film is improved after the effect of the composition of the present invention is achieved. Particularly amazing results.

Further, the phenol-based antioxidant other than the hindered phenol-based or semi-hindered phenol-based antioxidant is not preferable because of a large polymerization inhibition.

The content of the antioxidant used in the curable composition for imprint of the present invention is 0.3 to 7% by mass, preferably 0.5 to 5% by mass, and more preferably 1.5 to 5% by mass based on the total composition. When two or more types of antioxidants are used, the total amount thereof is in the above range. When the content of the antioxidant is 0.3% by mass or more, the heat resistance and the elastic recovery ratio are preferably improved, and when the content is 7% by mass or less, the photocurability is improved. In addition, when the content of the antioxidant is 0.5% by mass or more, the heat resistance and the elastic recovery ratio are further improved, and when the content is 5% by mass or less, the photocurability is further improved. In addition, when the content of the antioxidant is 1.5% by mass or more, the heat resistance and the elastic recovery ratio can be further improved, and therefore it is particularly preferably 1.5 to 5% by mass.

The hindered phenol-based antioxidant of the present invention has a structure represented by the following general formula (1).

In the general formula (1), R ¹ and R ² each independently represent tert-butyl or -C(R ⁴ R ⁵ )-R ⁶ , and R ³ represents a hydrogen atom or a branch having a carbon number of 1 to 6 or A linear alkyl group which may have a substituent, 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 of the structure represented by the following general formula (2).

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

In the general formula (1), the above R ¹ and the above R ^{2 are} preferably tert-butyl.

The above R ^{3 is} preferably a hydrogen atom.

The above R ⁴ and R ^{5 are} preferably a hydrogen atom.

The above L ^{1 is} preferably a hydrogen atom or a branched or linear alkyl group or alkoxy group having a carbon number of 1 to 6. More preferably, it is an alkyl group having 1 to 4 carbon atoms which has a methyl group, an alkoxy group or an amine group as a substituent.

When the above R ⁶ is a complex number, the plurality of R ⁶ systems may be different from each other or the same.

In the general formula (2), the above 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, more preferably a tert-butyl group.

The above R ^{8 is} preferably a hydrogen atom.

The aforementioned L ² system is the same as the preferred range of the above L ¹ .

Specific examples of the hindered phenol-based antioxidant include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,2'-methylenebis (6). -tert-butyl-4-methylphenol) and the like. Further, the present invention is not limited to the examples of the specific examples.

The semi-hindered phenol-based antioxidant of the present invention has a structure represented by the following general formula (3).

In the general formula (3), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents tert-butyl or -C(R ¹⁴ R ¹⁵ )-R ¹⁶ , and R ¹³ represents a hydrogen atom or a carbon number of 1 to 6 A branched or straight chain alkyl group which may have a substituent, 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 of the 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, a (meth) acrylate group or a carboxyl group, and when X ¹¹ is a hydroxyl group, R ¹⁷ represents a hydrogen atom or a methyl group, and when X ¹¹ is a hydroxyl group, R ¹⁷ represents a hydrogen atom, a branched group having 1 to 6 carbon atoms or a linear alkyl group which may have a substituent, and R ¹⁸ represents a hydrogen atom, or a branched or straight chain having a carbon number of 1 to 6 may have a substituent. Alkyl groups, L ¹² represents a monovalent substituent, and * represents a bond site.

In the general formula (3), the above R ^{11 is} preferably a methyl group.

The aforementioned R ^{12 is} preferably a tert-butyl group.

The above R ^{13 is} preferably a hydrogen atom.

The above R ¹⁴ and R ^{15 are} preferably a hydrogen atom.

The aforementioned L ¹¹ system is the same as the preferred range of the above L ¹ .

In the general formula (4), the above X ^{11 is} preferably a hydrogen atom, an alkyl group, a hydroxyl group, a (meth) acrylate group, a carboxyl group, or 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, more preferably a methyl group.

The above R ^{8 is} preferably a hydrogen atom.

The aforementioned L ² system is the same as the preferred range of the above L ¹ .

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

The hindered amine-based antioxidant of the present invention is not particularly limited, and a compound having a structure represented by the following general formula (5) as a partial structure can be exemplified.

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 or a branched or straight-chain alkyl group or alkoxy group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkoxy group.

The preferred range of the aforementioned L ^{21 is} the same as the preferred range of the aforementioned L ¹ .

Specific examples of the hindered amine-based antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and bis(N-methyl-2,2,6). ,6-tetramethyl-4-piperidinyl) sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexa Methyldiamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4 - piperidinyl) propylamine, hydrazine (2,2,6,6-tetramethyl-4-piperidinyl) (1,2,3,4-butane tetracarboxylate, poly[{6- (1,1,3,3-tetramethylbutyl)imido-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethyl{(2,2,6,6-tetramethyl-4) -piperidinyl)imido}], poly[(6-morpholinyl-1,3,5-three -2,4-diyl){(2,2,6,6-tetramethyl-4-piperidinyl)imide}}hexamethine{(2,2,6,6-tetramethyl-4- Piperidinyl)imine}], dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, N, N '-4,7-肆[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3, 5-three -2-yl]-4,7-diazadecane-1,10-diamine, and the like. Further, the present invention is not limited to the examples of the specific examples.

The thioether-based antioxidant of 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 preferred.

Examples of the thioether-based antioxidant include di-tridecyl thiodipropionate and the like. Further, the present invention is not limited to the examples of the specific examples.

Further, the phenol-based antioxidant other than the range of the present invention has 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 imprint of the present invention, the antioxidant is composed only of a semi-hindered phenol-based antioxidant, and is improved from the viewpoint of further improving oxidation resistance, reducing polymerization inhibition, and improving photocurability. Better.

Further, in the second aspect of the curable composition for imprint of the present invention, the antioxidant is a mixture of a semi-hindered phenol system and a thioether system, and the viewpoint of further improving oxidation resistance, reducing polymerization inhibition, and improving photocurability Look at it better.

The antioxidant can suppress discoloration due to heat or light irradiation, and various oxidizing gases such as ozone, active oxygen, NOx, SOx (x is an integer), and the like to discoloration. In particular, the present invention has an advantage of preventing the coloration of the cured film and reducing the film thickness due to decomposition by adding an antioxidant.

Commercial products of the above-mentioned antioxidants include Irganox 1010, 1035, 1076, and 1222 (manufactured by Ciba Geigy Co., Ltd.), trade names Antigene P, 3C, FR, Sumilizer S, and Sumilizer GA80 (Sumitomo Chemical Industries Co., Ltd.) )), the product name is ADK STAB AO7O, AO80, AO503 (made by Adeka). These may be used alone or in combination.

Further, the antioxidant can be synthesized by a known method.

(surfactant)

The curable composition for imprint of the present invention may also contain a surfactant. The total surfactant composition used in the present invention contains, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, more preferably 0.005 to 3% by mass. When two or more types of surfactants are used, the total amount thereof is in the above range. When the surfactant is in the range of 0.001 to 5% by mass of the composition, the effect of uniformity of coating is good, and deterioration of mold transfer characteristics due to excessive surfactant is less likely to occur.

As the surfactant, at least one of a fluorine-containing surfactant, an anthrone-based surfactant, and a fluoro-ketone-based surfactant is preferable, and a surfactant of a fluorine-containing surfactant and an anthrone is used. It is more preferable to use a two-component or fluorine-containing ketone-based surfactant, and a fluorine-containing ketone-based surfactant is preferred. Further, the fluorine-based surfactant and the anthrone-based surfactant are preferably a nonionic surfactant.

Here, the "fluoro-ketone-based surfactant" means a component having both a fluorine-based surfactant and an anthrone-based surfactant.

By using such a surfactant, it is possible to solve the problem that the imprint-curable composition of the present invention is applied to a wafer for manufacturing a semiconductor element, a prismatic glass substrate for producing a liquid crystal element, a chromium film, a molybdenum film, or a molybdenum alloy film. a crepe film, a bismuth alloy film, a tantalum nitride film, an amorphous fluorene film, an indium oxide (ITO) film doped with tin oxide, or a tin oxide film, etc. There is a problem of poor coating such as a scaly appearance (drying unevenness of the photoresist film). Moreover, the fluidity of the composition of the present invention in the cavity of the concave portion of the mold can be improved, the peeling property between the mold and the photoresist can be improved, the adhesion between the photoresist and the substrate can be improved, and the viscosity of the composition can be reduced. In particular, the imprint composition of the present invention can greatly improve coating uniformity by adding the above-mentioned surfactant, and good coating suitability irrespective of substrate size can be obtained in coating using a spin coater or a slit sweep coater. .

Examples of the nonionic fluorine-based surfactant which can be used in the present invention include the trade names Fluorad FC-430, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), and the trade name Surflon S-382 (Asahi Glass Co., Ltd.). ), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (TOCHEM PRODUCTS), trade name PF-636, PF-6320, PF-656, PF -6520 (both OMNOVA Solutions, Inc.), trade names FUTAGENT FT250, FT251, DFX18 (both NEOS), trade names UNIDAIN DS-401, DS-403, DS-451 (both DAIKIN Industries) Co., Ltd.), trade names MEGAFAC 171, 172, 173, 178K, 178A, (all manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

In addition, examples of the nonionic ketone-based surfactants include the product name SI-10 series (made by Takeshi Oil Co., Ltd.), MEGAFAC PEINTAD 31 (made by Dainippon Ink Chemical Industry Co., Ltd.), KP-341 (Shin-Etsu Chemical Industry Co., Ltd.).

Moreover, examples of the fluorine fluorenone-based surfactant include trade names X-70-090, X-70-091, X-70-092, and X-70-093 (all of Shin-Etsu Chemical Industries ( Co., Ltd.), trade name MEGAFAC R-08, XRB-4 (both manufactured by Dainippon Ink Chemical Industry Co., Ltd.).

(other ingredients)

In addition to the above components, the composition of the present invention may optionally contain a non-polymerizable molecule, a polymer component, a release agent, an organic metal coupling agent, a polymerization inhibitor, an ultraviolet absorber, a photo-stabilizer, an anti-aging agent, and a plasticizer. , adhesion promoter, thermal polymerization initiator, photobase generator, colorant, elastomer particles, photosensitizer, basic compound, and other flow regulators, antifoaming agents, dispersants, and the like.

In the composition of the present invention, the non-polymerizable molecule may be added for the purpose of imparting adhesion and controlling the physical properties of the cured film. The amount of such a non-polymerizable molecule to be added can be determined in accordance with the range in which the amount of the photopolymerizable molecule can be controlled within the range of the present invention. Examples of such a non-polymerizable molecule include an alkyl ester such as dioctyl sebacate, a (sulfur) urea compound, organic fine particles, and inorganic fine particles.

In the composition of the present invention, in order to further increase the crosslinking density, a polyfunctional oligomer having a molecular weight larger than that of the above-mentioned polyfunctional other polymerizable monomer may be blended in the range in which the object of the present invention is attained. 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 the top three. A hydrolysis condensate of oxonium propyl acrylate. The amount of the oligomer component added is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, even more preferably from 0 to 10% by mass, based on the component other than the solvent from which the composition is removed. The optimum is 0 to 5 mass%.

The curable composition for imprint of the present invention may further contain a polymer component from the viewpoint of improving the embossability and the curability. The polymer component is preferably a polymer having a polymerizable functional group in a side chain. The weight average molecular weight of the polymer component is preferably from 2,000 to 100,000, more preferably from 5,000 to 50,000, from the viewpoint of compatibility with the polymerizable compound. The amount of the polymer component added is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, even more preferably from 0 to 10% by mass, most preferably from 0 to 10% by mass, based on the component of the solvent from which the composition is removed. 2% by mass or less. Further, from the viewpoint of pattern formability, the resin component is preferably as small as possible, and it is preferred that the resin component is not contained in addition to the surfactant and the trace additive.

In order to further improve the peelability, the composition of the present invention may optionally incorporate a release agent. Specifically, the purpose of the addition is that the mold which is pressed against the layer of the composition of the present invention can be peeled off perfectly without causing surface cracking or residue of the resin layer. As the release agent, a previously known release agent such as an anthrone-based release agent, a polyethylene wax, a guanamine wax, a Teflon powder (Teflon is a registered trademark), or the like, a solid wax, a fluorine-based, or a phosphoric acid may be used. Any of ester compounds and the like. Further, these release agents may be attached to the mold.

When the fluorenone-based release agent is combined with the photocurable resin used in the present invention, the release property from the mold is particularly excellent, and the residual phenomenon is less likely to occur. The above-mentioned anthrone-based release agent is a release agent having a basic structure of an organic polyoxymethane, for example, a polyoxane or an anthrone having an unmodified or modified eucalyptus oil, trimethylphosphonium decanoic acid. It is compatible with an acrylic resin or the like, and an anthrone-based leveling agent which is usually used for a composition for a hard coat layer is also applicable.

The modified eucalyptus oil is obtained by modifying the side chain and/or the terminal of the polyoxyalkylene, and is classified into a reactive eucalyptus oil and a non-reactive eucalyptus oil. Examples of the reactive eucalyptus oil include amine group modification, epoxy group modification, carboxyl group modification, methanol modification, methacrylic acid modification, thiol modification, phenol modification, single terminal reactivity, and heterogeneous functional group modification. Quality and so on. Examples of the non-reactive eucalyptus oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, and higher fatty acid modification. Fluorine modification.

It is also possible to carry out two or more modification methods as described above for one polyoxyalkylene molecule.

The modified eucalyptus oil preferably has a moderate compatibility with the composition component. In particular, when a reactive eucalyptus oil which is reactive with other coating film forming components blended as needed in the composition is used, since the composition of the present invention is fixed by chemical bonding in the cured cured film, it is difficult to cause the The adhesion of the cured film is hindered, contaminated, deteriorated, and the like. It is particularly effective in improving the adhesion to the vapor-deposited layer in the vapor deposition step. Further, in the case of an anthrone having a photocurable functional group such as a (meth) acrylonitrile-based fluorenone or a vinyl modified fluorenone, it is crosslinked with the composition of the present invention. Therefore, the properties after hardening are excellent.

The polyoxyalkylene containing trimethylphosphonium decanoic acid is excellent in peeling property on the surface, and is excellent in peelability, and is excellent in adhesion to the surface of the exudation surface, and is excellent in adhesion to metal vapor deposition or surface coating. It is better.

The above-mentioned release agent may be added alone or in combination of two or more.

When the release agent is added to the curable composition for imprint of the present invention, it is preferably blended in a ratio of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the composition. When the content of the release agent is in the range of 0.01 to 5% by mass, the peeling property-improving effect of the mold and the hardenable composition layer for imprinting is improved, and the shrinkage at the time of coating of the composition can be suppressed to cause the coating film surface. The surface cracking problem occurs, and the adhesion of the vapor deposition layer, the destruction of the film at the time of transfer, and the like (the film strength becomes too weak) occurs in the substrate itself or in the adjacent layer.

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

The decane coupling agent which can be used in the composition of the present invention may, for example, be β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane or γ-glycidoxypropyltrimethoxydecane. An epoxy decane such as γ-glycidoxypropylmethyldiethoxy decane; N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β-( Amino group such as aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane The decane; and other decane coupling agents may, for example, be γ-mercaptopropyltrimethoxydecane, γ-chloropropylmethyldimethoxydecane, or γ-chloropropylmethyldiethoxydecane.

The titanium coupling agent may, for example, be isopropyl triisostearate titanate, isopropyl tri-dodecylphenylphosphonium titanate or isopropyl sulfonate (dioctyl pyrophosphate). Ester) titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctylbis(di-tridecylphosphite) titanate, tetrakis(2,2-diene) Propyloxymethyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene Titanate, isopropyl trioctyl decyl titanate, isostearyl isopropyl methacrylate, isopropyl isostearyl bis acrylate, isopropyl tris(dioctyl) Phosphate) titanate, isopropyl triisopropylphenyl phenyl titanate, isopropyl tris(N-aminoethyl ‧ aminoethyl) titanate, diisopropyl phenyl phenyl Oxyacetate titanate, diisostearate vinyl titanate, and the like.

The zirconium coupling agent may, for example, be tetra-n-propoxy zirconium, tetra-butoxy zirconium, zirconium tetraethanopyruvate, zirconium dibutoxy bis(ethylmercaptopyruvate), or the like. Zirconium butoxide, zirconium butoxide, bis(ethylacetonitrile acetate), zirconium, and the like.

Examples of the aluminum coupling agent include aluminum isopropylate, aluminum sec-butoxydiisopropylate, aluminum sec-butyrate, aluminum acetate, and ethyl acetoacetate aluminum diisopropylate. Refractory (ethyl acetoacetate) aluminum, alkyl acetoacetate aluminum diisopropylate, acetoacetate bis(ethyl acetonitrile) aluminum, ginseng (ethylene acetonitrile) aluminum Wait.

The organometallic coupling agent can be arbitrarily blended in a proportion of 0.001 to 10% by mass based on the total solid content of the curable composition for imprint of the present invention. When the ratio of the organic metal coupling agent is 0.001% by mass or more, the heat resistance, the strength, and the adhesion to the vapor-deposited layer are more effectively promoted. On the other hand, when the ratio of the organic metal coupling agent is 10% by mass or less, it is preferable to suppress the stability of the composition and the defect of the film formability.

The curable composition for imprint of the present invention may be blended with a polymerization inhibitor in order to improve storage stability and the like. As the polymerization inhibitor, for example, a phenol such as hydroquinone, tert-butylhydroquinone, catechol or hydroquinone monomethyl ether; an anthracene such as benzoquinone or diphenylphenylhydrazine; Class; copper, etc. The polymerization inhibitor is preferably blended at a ratio of 0.001 to 10% by mass based on the total amount of the composition of the present invention.

An ultraviolet absorber can also be used for the curable composition for imprint of the present invention. Commercial products of the ultraviolet absorber 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 (above, Sumitomo Chemical Industry Co., Ltd.) and so on. The ultraviolet absorber is preferably blended at a ratio of 0.01 to 10% by mass based on the total amount of the curable composition for imprint.

A light stabilizer can also be used for the curable composition for imprint of the present invention. Commercial products of the above-mentioned light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, and 744 (above, Sankyo Chemical Industry Co., Ltd. ( Stock system) and so on. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass based on the total amount of the curable composition for imprint.

An anti-aging agent can also be used for the curable composition for imprint of the present invention. The commercial product of the anti-aging agent may, for example, be Antigene W, S, P, 3C, 6C, RD-G, FR, AW (above, Sumitomo Chemical Industries Co., Ltd.). The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass based on the total amount of the curable composition for imprint.

In the curable composition for imprint of the present invention, a plasticizer may be added in order to adjust the adhesion to the substrate, the flexibility of the film, the hardness, and the like. Specific examples of preferred plasticizers, for example, dioctyl terephthalate, behenyl terephthalate, triethylene glycol dioctanoate, dimethyl glycol terephthalate, tricresol Phosphate, dioctyl adipate, dibutyl sebacate, triethylene glyceryl triglyceride, dimethyl adipate, diethyl adipate, di(n-butyl) adipate The ester, the dimethyl suberate, the diethyl dioctate, the di(n-butyl) suberate, and the like can be arbitrarily added in an amount of 30% by mass or less of the composition. It is preferably 20% by mass or less, more preferably 10% by mass or less. In order to obtain the effect of adding a plasticizer, it is preferably 0.1% by mass or more.

In the curable composition for imprint of the present invention, an adhesion promoter may be added in order to adjust the adhesion to the substrate or the like. As the adhesion promoter, benzimidazoles or polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or sulfur urea, organophosphorus compounds, 8-hydroxyquinoline, 4 can be used. -hydroxyacridine, 1,10-phenanthroline, 2,2'-bipyridine derivative, benzotriazole, organophosphorus compound and phenylenediamine compound, 2-amino-1-phenylethanol, N - phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanolamine and derivatives, benzothiazole derivatives, and the like. The adhesion promoter is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, based on the composition. In order to obtain the effect of adding the adhesion promoter, it is preferably 0.1% by mass or more.

When the composition of the present invention is hardened, a thermal polymerization initiator may be added as needed. As a preferable thermal polymerization initiator, a peroxide and an azo compound are mentioned, for example. Specific examples thereof include benzammonium peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. The thermal polymerization initiator is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, still more preferably 4.0% by mass or less. The effect of adding the thermal polymerization initiator is preferably 3.0% by mass or more.

The curable composition for imprint of the present invention may be added with a photobase generator as needed for the purpose of adjusting the shape, sensitivity, and the like. The photobase generator may, for example, be 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-amine formazan hydroxyguanamine, O-amine formazan, [[ (2,6-Dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methyl Thiobenzylidene)-1-methyl-1-tyrosolinylethane, (4-morpholinylbenzylidene)-1-benzyl-1-dimethylaminopropane, N-(2 -Nitrobenzyloxycarbonyl)pyrrolidine, hexaammine cobalt(III) ginseng (triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2,6-dimethyl-3,5-diethylindol-4-(2'-nitrophenyl)-1,4-dihydropyridine, 2,6-di Methyl-3,5-diethylinden-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine or the like.

In the curable composition for imprint of the present invention, a coloring agent may be arbitrarily added for the purpose of improving the visibility of the coating film and the like. In the range which does not impair the object of the present invention, a pigment or a dye used for a UV inkjet composition, a color filter composition, a CCD image sensing application composition, or the like can be used as the colorant. As the pigment which can be used in the present invention, various inorganic pigments or organic pigments previously known can be used. Examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, lanthanum, and the like. Metal oxide, metal composite oxide. As the organic pigment, CI Pigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139, 151, 154, 167, CI Pigment Orange 36, 38, 43, CI Pigment Red 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, CI Pigment Violet 19, 23, 32, 39, CI Pigment Blue 1 can be exemplified. , 2, 15, 16, 22, 60, 66, CI Pigment Green 7, 36, 37, CI Pigment Brown 25, 28, CI Pigment Black 1, 7 and carbon black. The colorant is preferably blended in a ratio of 0.001 to 2% by mass based on the total amount of the composition.

Further, in the curable composition for imprint of the present invention, elastomer particles which are optional components may be added for the purpose of improving mechanical strength and flexibility.

The average particle size of the elastomer particles to be added as an optional component in the composition of the present invention is preferably from 10 nm to 700 nm, more preferably from 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene/acrylonitrile copolymer, styrene/butadiene copolymer, styrene/isoprene copolymer, ethylene/propylene copolymer, ethylene/α- Olefin-based copolymer, ethylene/α-olefin/polyene copolymer, acrylic rubber, butadiene/(meth)acrylate copolymer, styrene/butadiene block copolymer, styrene/isoprene Elastomer particles such as an alkyl block copolymer. Further, core/shell type particles in which the 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 also have a crosslinked structure.

For example, Resinous Bond RKB (manufactured by Resinous Chemical Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like are mentioned.

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

Further, in addition to the photoradical polymerization initiator, the curable composition for imprint of the present invention may be added with a photosensitizer to adjust the wavelength in the UV region. Typical sensitizers which can be used in the present invention are disclosed in Crivello [JV Crivello, Adv. in Polymer Sci, 62, 1 (1984)], specifically, hydrazine, hydrazine, acridine orange, thioxanthone. , 2-chlorothioxanthone, benzoxanthin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, thiophene Derivatives, etc.

In the composition of the present invention, a basic compound may be arbitrarily added for the purpose of suppressing the curing shrinkage and improving the thermal stability. As a basic compound, an amine, a quinoline, and a quinine are mentioned. A nitrogen-containing heterocyclic compound, a basic alkali metal compound, a basic alkaline earth metal compound, or the like. Among these, an amine is preferable in terms of compatibility with photopolymerization into a single molecule, and examples thereof include octylamine, naphthylamine, xylenediamine, dibenzylamine, and diphenyl. Amine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, trioctylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylene Diamine, hexamethylenetetramine and triethanolamine.

The composition of the present invention may be added with a chain shifting agent in order to enhance photocurability. Specific examples of the chain shifting agent include 4-bis(3-mercaptobutyloxy)butane and 1,3,5-gin(3-mercaptobutyloxyethyl) 1,3,5. -three -2,4,6(1H,3H,5H)-trione, pentaerythritol bismuth (3-mercaptobutyrate).

Moreover, the moisture content at the time of preparation of the curable composition for imprint of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, still more preferably 1.0% by mass or less. When the water content at the time of preparation is 2.0% by mass or less, the preservability of the composition of the present invention can be made more stable.

Further, a solvent may be used as the curable composition for imprint of the present invention. The content of the organic solvent is preferably 3% by mass or less based on the total composition. That is, the composition of the present invention preferably contains, as a reactive diluent, a monofunctional and/or difunctional monomer as described above, and therefore does not necessarily contain an organic solvent for dissolving the components of the composition of the present invention. . 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 is not necessarily an organic solvent-free one, and may be arbitrarily added when the compound in which the reactive diluent is dissolved or the like is dissolved in the composition of the invention or when the viscosity is finely adjusted. The type of the organic solvent which can be preferably used in the composition of the present invention is a solvent which is usually used for a photocurable hardenable composition or a photoresist, as long as the compound used in the present invention can be dissolved and uniformly dispersed, and does not The component reaction is not particularly limited.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene a glycol ether such as an alcohol monoethyl ether; a glycol alkyl ether acetate such as methyl stilbene acetate or ethyl stilbene acetate; diethylene glycol monomethyl ether; Diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. Alcohols; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone, methyl Ketones such as butanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, 2-heptanone, etc.; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate , 2-hydroxy-2-methylpropionic acid ethyl ester, ethoxyethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate esters, etc., etc. esters.

Further, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N -methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, acetic acid High boiling point solvent such as benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl racelus acetate. These may be used alone or in combination of two or more.

Among them, particularly preferred are methoxypropylene glycol acetate, ethyl 2-hydroxypropynoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and a ring. Hexanone, methyl isobutyl ketone, 2-heptanone, and the like.

The surface tension of the curable composition for imprint of the present invention is preferably in the range of 18 to 30 mN/m, more preferably in the range of 20 to 28 mN/m. By becoming such a range, the effect of improving surface smoothness can be obtained.

Moreover, the moisture content at the time of preparation of the curable composition for imprint of the present invention is preferably 2.0% by mass or less, more preferably 1.5% by mass, still more preferably 1.0% by mass or less. When the water content at the time of preparation is 2.0% by mass or less, the preservability of the composition of the present invention can be made more stable.

The viscosity of the curable composition for imprint 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 imprint 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. When the viscosity of the composition of the present invention is 3 mPa ‧ s or more, there is a problem that substrate coating suitability is less likely to occur or the mechanical strength of the film tends to decrease. Specifically, by setting the viscosity to 3 mPa ‧ s or more, it is possible to suppress surface unevenness during coating of the composition or to flow out of the substrate from the substrate during coating. Further, the composition having a viscosity of 3 mPa ‧ or more is also easily modulated than the composition having a viscosity of less than 3 mPa ‧ s. On the other hand, when the viscosity of the composition of the present invention is 18 mPa‧s, even if the mold having the fine uneven pattern is adhered to the composition, the composition can flow into the cavity of the concave portion of the mold, and it is not easy to bring in Atmospheric, it is not easy to cause bubble defects, and it is preferable that the mold convex portion is less likely to remain after the photocuring. Further, when the viscosity of the composition of the present invention is 18 mPa·s or less, the viscosity does not affect the formation of the fine pattern.

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

[Method for producing cured product]

Next, a method of forming a cured product (particularly, a fine uneven pattern) using the curable composition for imprint of the present invention will be described. a step of forming a pattern forming layer by applying the curable composition for imprint of the present invention onto a substrate or a support (substrate), a step of pressing a mold on the surface of the pattern forming layer, and irradiating the pattern forming layer with light The step of hardening the composition of the present invention can form a fine concavo-convex pattern. In particular, in the present invention, in order to increase the degree of hardening of the cured product, it is preferred to further include a step of heating the pattern forming layer after light irradiation. That is, it is preferable that the curable composition for imprint of the present invention is 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 suitably used for a protective film for a liquid crystal color filter, a spacer, and other members for a liquid crystal display device.

Specifically, a pattern forming layer composed of at least a composition of the present invention is applied onto a substrate (substrate or support), and a layer (pattern forming layer) composed of the composition of the present invention is formed as necessary to form a pattern. The receiving body (the pattern forming layer is provided on the substrate), and the mold is crimped to the surface of the pattern forming layer of the pattern receiving body, and the transfer mold pattern is processed, and the fine concave and convex pattern is made by light irradiation and heating. The layer is hardened. Light irradiation and heating can also be carried out several times. The photoimprint lithography by the pattern forming method (the method for producing a cured product) of the present invention may be laminated or multi-patterned, or may be used in combination with usual hot stamping.

Further, as the application of the curable composition for imprint of the present invention, the composition of the present invention may be applied onto a substrate or a support, and a layer composed of the composition may be exposed, hardened, and dried (baked) as necessary. To make a permanent film such as a surface coating or an insulating film.

In a permanent film (photoresist for a structural member) used in a liquid crystal display (LCD) or the like, in order not to hinder the operation of the display, it is preferable to prevent ionic impurities of metal or organic substances from being mixed into the photoresist, and the concentration thereof is preferably 1000 ppm or less. It is 100 ppm or less.

Hereinafter, a method of producing a cured product (pattern forming method (pattern transfer method)) using the curable composition for imprint of the present invention will be specifically described.

In the method for producing a cured product of the present invention, the composition of the present invention is first applied onto a substrate to form a pattern forming layer.

As a coating method when the curable composition for imprint of the present invention is applied onto a substrate, a conventional coating method such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, or the like can be used. A gravure coating method, an extrusion coating method, a spin coating method, a quilting scanning method, or the like is formed by coating. Further, the film thickness of the pattern forming layer composed of the composition of the present invention varies depending on the intended use, and is about 0.05 μm to 30 μm. Further, the composition of the present invention may be applied by multiple coating. Further, another organic layer such as a planarization layer may be formed between the substrate and the pattern forming layer composed of the composition of the present invention. Thereby, since the pattern forming layer does not directly contact the substrate, dust adhesion to the substrate, damage to the substrate, and the like can be prevented.

The substrate (substrate or support) for applying the curable composition for imprint of the present invention can be selected according to various uses, for example, quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film. , metal substrate of Ni, Cu, Cr, Fe, etc., polymer substrate of paper, SOG (spin on glass), polyester film, polycarbonate film, polyimide film, etc., TFT array substrate , PDP electrode plate, glass or transparent plastic substrate, conductive substrate such as ITO or metal, insulating substrate, fluorenone, fluorenone, fluorenone, fluorenone, amorphous fluorenone, etc. There is no particular limitation on the production of a substrate or the like. Further, the shape of the substrate is not particularly limited, and may be a plate shape or a cylindrical shape. Further, as described above, the substrate may be selected to have light transmittance or non-light transmittance in accordance with a combination with a mold or the like.

Next, in the method for producing a cured product of the present invention, in order to transfer the pattern to the pattern forming layer, the mold is pressed (pressed) on the surface of the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.

Photoimprint lithography using the curable composition for imprint of the present invention requires selection of a light transmissive material in at least one of a mold material and/or a substrate. In the photoimprint lithography suitable for the present invention, the curable composition for imprint of the present invention is applied onto a substrate to form a pattern forming layer, and a light transmissive mold is pressed on the surface thereof, and is irradiated from the inner surface of the mold. Light causes the aforementioned pattern forming layer to harden. Further, the curable composition for imprint of the present invention may be applied onto a light-transmitting substrate, and a mold may be pressed thereon to irradiate light from the inner surface of the substrate to cure the curable composition for imprint.

The light irradiation may be performed in a state in which the mold is attached, or may be performed after the mold is peeled off. In the present invention, it is preferable to carry out the state in which the mold is adhered.

A mold which can be used in the present invention uses a mold having a pattern to be transferred. The pattern on the mold can be patterned according to a desired processing precision by, for example, photolithography or electron beam drawing. However, in the present invention, the mold pattern forming method is not particularly limited.

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 or polycarbonate resin, a transparent metal deposition film, a soft film such as polydimethyl siloxane or a photocured film, a metal film, or the like can be exemplified.

When the transparent substrate is used in the present invention, the non-light transmitting type mold material to be used is not particularly limited as long as it has a predetermined strength. Specific examples thereof include a ceramic material, a vapor deposited film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, and Fe, SiC, anthrone, fluorenone, fluorenone, fluorenone, and amorphous. The substrate such as an anthrone or the like is not particularly limited. Further, the shape of the mold is not particularly limited, and a plate mold or a cylindrical mold may be used. The cylindrical mold is suitable for the case where continuous productivity of transfer is particularly required.

The mold used in the method for producing a cured product of the present invention may be subjected to a release treatment in order to improve the peeling property between the curable composition for imprint and the surface of the mold. As such a mold, those which are subjected to a decane coupling agent such as an anthrone or a fluorine-based one may be, for example, an OPTOOL DSX manufactured by DAIKIN Industries Co., Ltd. or a Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd. And other commercially available release agents.

When photoimprint lithography is carried out using the composition of the present invention, the method for producing a cured product of the present invention is usually carried out at a mold pressure of 10 atm or less. When the mold pressure is 10 atm or less, the mold or the substrate is less likely to be deformed and the pattern accuracy tends to be improved. Further, since the applied pressure is low, there is a tendency to reduce the size of the device, and this is also preferable. The mold pressure is preferably selected in a range in which the residual film of the curable composition for imprinting of the mold is reduced, and the uniformity of transfer of the mold can be ensured.

In the method for producing a cured product of the present invention, the amount of irradiation of the light in the step of irradiating the pattern forming layer with light may be sufficiently larger than the amount of irradiation required for curing. The amount of irradiation required for the hardening is appropriately determined depending on the consumption of the unsaturated bond of the curable composition for imprint or the adhesiveness of the cured film.

Further, in the photoimprint lithography which is applied to the present invention, the substrate temperature at the time of light irradiation is usually carried out at room temperature, but it is also possible to perform light irradiation while heating in order to improve the reactivity. In the pre-light irradiation stage, if it is controlled to be in a vacuum state, it is possible to prevent the bubble from entering and suppress the decrease in reactivity due to oxygen incorporation, and to improve the adhesion between the mold and the hardenable composition for imprinting, so vacuum can be used. The state is illuminated by light. Further, in the method for producing a cured product of the present invention, the preferred degree of vacuum at the time of light irradiation is in the range of 10 ^-1 Pa to normal pressure.

The light for curing the curable composition for imprint of the present invention is not particularly limited, and examples thereof include light or radiation having a wavelength in a range of high-energy ionizing radiation, near-ultraviolet light, far ultraviolet light, visible light, and infrared light. As a high-energy ionizing radiation source, the electron beam accelerated by an accelerator such as a Krokoff type accelerator, a Vandergrave type accelerator, a linear accelerator, a betatron, a cyclotron, etc. is most convenient for industrial use. Further, it is also economical to use other radiation such as gamma rays, X-rays, alpha rays, neutron rays, proton wires, or the like which are emitted by a radioisotope or an atomic furnace. Examples of the ultraviolet light 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 sun lamp. Radiation includes, for example, microwaves, EUV. Further, laser light for microfabrication of semiconductors such as LEDs, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser light can also be applied to the present invention. These light systems can use monochromatic light, or a plurality of different wavelengths of light (mixed light) can be used.

At the time of exposure, the exposure illuminance is preferably in the range of 1 mW/cm ² to 50 mW/cm ² . When the thickness is 1 mW/cm ² or more, the productivity can be improved by shortening the exposure time, and when it is 50 mW/cm ² or less, it is preferable to suppress deterioration of permanent film characteristics due to side reactions. Exposure amount is suitably 5mJ / cm range of ² ~ ^1000mJ / cm ² of. When it is 5 mJ/cm ² or more, it is possible to prevent the exposure margin from becoming narrow, and the problem of insufficient photohardening and adhesion of unreacted materials to the mold occurs. Moreover, 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, at the time of exposure, in order to prevent the oxygen from causing the inhibition of radical polymerization, an inert gas such as nitrogen or argon may be passed to control the oxygen concentration to be less than 100 mg/L.

In the method for producing a cured product of the present invention, after the pattern forming layer is cured by light irradiation, it is preferred to include a step of heating the hardened pattern to further harden (post-baking step). Further, heating may be performed at any point before and after the pattern forming layer is peeled off from the light after the light is irradiated, and it is preferable to heat the pattern forming layer after the mold is peeled off. The heat of the composition of the present invention after heating and hardening after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. Further, the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

In the present invention, the light irradiation by photoimprint lithography may be sufficiently larger than the amount of irradiation required for hardening. The amount of irradiation required for hardening is determined in accordance with the consumption of the unsaturated bond of the hardenable composition by imprint lithography or the adhesiveness of the cured film.

Further, in the photoimprint lithography used in the present invention, the substrate temperature at the time of light irradiation is usually performed at room temperature, but it is also possible to perform light irradiation while heating in order to improve the reactivity. In the pre-stage of light irradiation, if it is controlled to be in a vacuum state, it is possible to prevent the bubble from entering and suppress the decrease in reactivity due to oxygen incorporation, and to improve the adhesion between the mold and the hardenable composition for imprint lithography. Therefore, it is preferable to perform light irradiation in a vacuum state. In the present invention, it is preferred that the degree of vacuum is in the range of from 10 ^-1 Pa to atmospheric pressure.

The curable composition for imprint of the present invention is prepared by mixing the above components, and then filtering by, for example, a filter having a pore diameter of 0.05 μm to 5.0 μm to prepare a solution. The mixing of the curable composition for imprinting and the dissolution are usually carried out in the range of 0 °C to 100 °C. Filtration can be done in multiple stages or repeated many times. Alternatively, the filtered liquid can be refiltered. A polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, or the like can be used as the material used for the filtration, and is not particularly limited.

[hardened material]

The cured product of the present invention formed by the above-described method for producing a cured product of the present invention can be used as a permanent film (photoresist for a structural member) or an etching photoresist for a liquid crystal display (LCD) or the like. Further, the permanent film is bottled in a container such as a gallon bottle or a quart bottle after being manufactured, and transported and stored. In this case, in order to prevent deterioration, the inside of the container may be replaced with inert nitrogen or argon. Further, in transportation and storage, the temperature may be normal temperature, and in order to prevent deterioration of the permanent film, the temperature may be controlled within a range of -20 ° C to 0 ° C. Of course, it is preferred to be light-shielded to the extent that no reaction is carried out.

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

[Member for liquid crystal display device]

Further, the curable composition for imprint of the present invention can be suitably used as a semiconductor integrated circuit, a recording material, and a member for a liquid crystal display device. Among them, a member for a liquid crystal display device is preferably used as an etching resist for a flat display or the like. For better.

When the composition for imprint of the present invention is used as an etching resist, first, a germanium wafer or the like on which a thin film such as SiO _{2 is} formed is used as a substrate, and a nanoscale is formed on the substrate by the method for producing a cured product of the present invention. Fine pattern. Then, hydrogen etching or the like is used for wet etching, and etching is performed using an etching gas such as CF ₄ during dry etching, whereby a desired pattern can be formed on the substrate.

[Examples]

The invention will be more specifically described below by way of examples. The materials, the amounts, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Example 1]

The photopolymerizable monomers M1 to M3 described in the following Table 1 and the following photoradical polymerization initiator P-1 and the following surfactants W-1 and W-2 were added to the composition shown in the following Table 2. The curable composition for imprint of Example 1 was prepared by the following antioxidant AO1. Further, the numerical values in Table 2 are mass%.

[Examples 2 to 66, Comparative Examples 1 to 21, and 25 to 37]

These compositions were obtained in the same manner as the product of Example 1 except that they were changed to the compositions of the following Tables 2 to 6.

[Comparative Examples 22 to 24]

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

[Evaluation of hardenable composition for imprint]

With respect to the compositions of the respective examples and comparative examples, the embossability, photocurability, heat resistance, elastic recovery ratio, and voltage characteristics were measured and evaluated according to the following evaluation methods. The results are shown in Tables 2 to 6 below.

<embossing>

The pattern transferred to the photoresist evaluates to what extent the shape of the mold can be reproduced. Specifically, each of the compositions was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm. The spin-coated base film was placed in an imprinting apparatus made of a high-pressure mercury lamp (lamp power of 2000 mW/cm ² ) made by ORC, with a mold pressing pressure of 0.8 kN and an exposure vacuum of 10 Torr (about 1.33×). The condition of 10 ⁴ Pa) was pressed by a mold, and the mold was made of a material having a line/space pattern of 10 μm and a groove depth of 4.0 μm as a polydimethyl siloxane (made by Toray ‧ Dow Corning Co., Ltd.) SILPOT 184" was cured at 80 ° C for 60 minutes, and then exposed from the surface of the mold at 240 mJ/cm ² . After the exposure, the mold was removed to obtain a photoresist pattern.

Then, the obtained photoresist pattern was heated in an oven at 230 ° C for 30 minutes to completely harden. The shape of the pattern after the transfer was observed by a scanning electron microscope and an optical microscope, and the pattern shape was evaluated in accordance with the following criteria.

5: The transfer rate of the mold shape was 95% or more.

4: The transfer rate of the mold shape was 90% or more and less than 95%.

3: The transfer rate of the mold shape is 80% or more and less than 90%.

2: The transfer rate of the mold shape was 70% or more and less than 80%.

1: The transfer rate of the mold shape is less than 70%.

<Evaluation of light hardenability>

Each of the compositions was spin-coated on a glass substrate so that the film thickness was 3.0 μm, and the film was exposed to a condition of 10 mW and 300 mJ/cm ² under a nitrogen atmosphere without pressing the mold. Then, the plastic film was pressed on the surface of the film, and the residual trace (adhesiveness) at the time of peeling off the plastic film was evaluated, and the photocurability was measured.

5: There are no traces at all.

4: Although there are residual marks, they disappear within a few seconds.

3: Although there are residual marks, they disappear within a few minutes.

2: Residual traces, and the passage of time has not disappeared.

1: The film is not hardened.

<heat resistance>

Each of the compositions was spin-coated on a glass substrate so that the film thickness was 3.0 μm, and the film was exposed to a condition of 10 mW and 300 mJ/cm ² under a nitrogen atmosphere without pressing the mold. Then, it was hardened by heating in an oven at 230 ° C for 15 minutes. The film thickness before and after baking in the oven was measured, and the rate of reduction was determined, and the film reduction rate (film reduction) by heating was evaluated according to the following criteria.

The film reduction before and after baking at 5:230 ° C - 150 min was 5% or less.

The film reduction before and after baking at 4:230 ° C - 150 min is 5% or more and less than 10%.

The film reduction before and after baking at 3:230 ° C - 150 min is 10% or more and less than 15%.

2: The film reduction before and after baking at 230 ° C - 150 min is 15% or more and less than 20%.

The film reduction before and after baking at 1:230 ° C - 150 min is 20% or more.

<Evaluation of elastic recovery rate>

Each of the compositions was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and was exposed to light at 10 mW to 200 mJ in a nitrogen atmosphere without pressing the mold. Thereafter, the film was cured by heating in an oven at 230 ° C for 30 minutes, and the film obtained by hardening was formed into a column shape of 20 x 30 x 4 μm, and the elastic recovery ratio was measured by DUH-W201 manufactured by Shimadzu Corporation.

5: The elastic recovery rate is 80% or more.

4: The elastic recovery rate is 75% or more and less than 80%.

3: The elastic recovery rate is 70% or more and less than 75%.

2: The elastic recovery rate is 60% or more and less than 75%.

1: The elastic recovery rate is less than 60%.

<Evaluation of voltage characteristics>

Each of the compositions was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, and was exposed to light at 10 mW to 200 mJ in a nitrogen atmosphere without pressing the mold. Thereafter, the film was cured by heating in an oven at 230 ° C for 30 minutes, and the volume resistance of the film obtained by the hardening was measured according to the concentric ring method, and the voltage characteristics were measured. The obtained voltage characteristics were evaluated in accordance with the following evaluation.

5: The volume resistance is 1 × 10E15 Ω or more.

4: The volume resistance is 5 × 10 E14 Ω ‧ m or more and less than 1 × 10 E15 Ω ‧ m.

3: The volume resistance is 1×10E14 Ω··m or more and less than 5×10E14 Ω·m.

2: The volume resistance is 1 × 10 E13 Ω ‧ m or more and less than 1 × 10 E14 Ω ‧ m.

1: Volume resistance is less than 1 × 10E13 Ω ‧ m.

Here, in Examples 1 to 7 and Comparative Example 26, only the hindered phenol-based antioxidant was used, and the amount of the antioxidant added was changed. In Examples 8 to 14 and Comparative Example 27, only the semi-hindered phenol-based antioxidant was used, and the amount of the antioxidant added was changed for comparison. In Examples 15 to 21 and Comparative Example 28, only the semi-hindered phenol-based antioxidant was used, and the amount of the antioxidant added was changed for comparison. Examples 22 to 28 and Comparative Example 29 were compared using a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, and the amount of the antioxidant added was changed. In Examples 29 to 35 and Comparative Example 30, a mixture of a semi-hindered phenol-based antioxidant and a thioether-based antioxidant was used, and the amount of the antioxidant added was changed for comparison. In Examples 36 and 37 and Comparative Examples 17 to 21, in the case where only the semi-hindered phenol-based antioxidant was used, the addition amount of the non-polymerizable molecule C1 was further increased. In Examples 38 to 44, Comparative Example 25, and Comparative Example 31, the photopolymerizable monomers M1 to M3 of Examples 8 to 14 were changed to photopolymerizable oxygen in the case of using only the semi-hindered phenol-based antioxidant. The heterocyclic butane compounds M4 to M6 were compared and the amount of addition was changed. Further, Comparative Example 1 was compared when no antioxidant was added. Comparative Example 2 was a comparison when no photopolymerization initiator was 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 in which the amount of the photopolymerization initiator added is increased by using a phenol-based antioxidant. In Comparative Examples 11 to 16, the addition amount was changed by using only the thioether-based antioxidant alone, and compared with the effect of the specific antioxidant of the examples of the present invention. Comparative Examples 22 to 24 in which the pigments in No. 8, No. 9, and No. 11 described in Table 18 of JP-A-2006-124636 were completely compared with Examples 1 to 44 of the present invention.

The heat resistance, the elastic recovery ratio, and the voltage characteristics of the above Table 4 and Comparative Example 2 were not measured.

From the above-mentioned Tables 2 to 4, the comparative examples 22 to 24 in which the pigments in No. 8, No. 9, and No. 11 described in Table 18 of JP-A-2006-124636 are removed are described. Each of the compositions of the examples was excellent in embossability, photocurability, heat resistance, elastic recovery, and voltage characteristics. Further, in Examples 38 to 44 in which the oxetane compound was used, the effect of improving the voltage characteristics was lower than that of the other examples.

On the other hand, since Comparative Example 1 does not contain an antioxidant, heat resistance and elastic recovery rate were low. In Comparative Example 2, since the photopolymerization initiator was not contained, the evaluation was extremely low. In Comparative Examples 3 to 10, it was found that when only a phenol-based antioxidant was used, the evaluation of photocurability was remarkably lowered, and Comparative Examples 9 and 10 in which the amount of the photopolymerization agent was increased at the expense of heat resistance and elastic recovery were not obtained. A cured film of the nature sought for by the present invention. As is apparent from Comparative Examples 11 to 16, when only the thioether-based antioxidant was used, the heat resistance and the elastic recovery ratio were remarkably low. From the comparison of Examples 36 and 37 and Comparative Examples 17 to 21, it is understood that even when only a semi-hindered phenol-based antioxidant is used, the amount of the photopolymerizable monomer added is within the range of the present invention (80 mass) When the amount is from % to 99% by mass, the photocurability, heat resistance and elastic recovery ratio can be simultaneously improved, which is a remarkable effect. Further, in Comparative Examples 19 to 21 in which the blending amount of the monofunctional, difunctional, and trifunctional single molecules was finely adjusted, the heat resistance and the elastic recovery ratio could not be improved. Therefore, it was found that the amount of the photopolymerizable monomer added was important. Elements. As is clear from the comparison of Examples 38 to 44, Comparative Example 25, and Comparative Example 31, when the amount of the antioxidant added is within the range of the present invention (0.3 to 7 mass%), the heat resistance and the elastic recovery ratio can be remarkably improved.

Further, as can be understood from Tables 5 and 6, the examples of the present invention having a high antioxidant content are remarkably improved in heat resistance and elastic recovery ratio as compared with the comparative examples having a small antioxidant content.

Claims (10)

A curable composition for embossing, comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition of an antioxidant, wherein A) photopolymerization The content of the monomer is 80 to 99% by mass, and the content of the above C) antioxidant is 0.3 to 7% by mass, and the above C) is a mixture of a hindered phenol-based antioxidant and a semi-hindered phenol-based antioxidant. The curable composition for imprint of claim 1, wherein the antioxidant is composed only of a semi-hindered phenol-based antioxidant. A curable composition for embossing, comprising: A) a photopolymerizable monomer, B) a photopolymerization initiator, and C) an optical imprint composition of an antioxidant, wherein A) photopolymerization The content of the monomer is 80 to 99% by mass, and the content of the above-mentioned C) antioxidant is 0.3 to 7% by mass, and the above-mentioned C) antioxidant is a mixture of a hindered phenol-based antioxidant and a thioether-based antioxidant, or a semi-hindered phenol. It is a mixture of an antioxidant and a thioether antioxidant. The curable composition for imprint of claim 3, wherein the antioxidant is a mixture of a semi-hindered phenol system and a thioether system. The curable composition for imprint according to any one of claims 1 to 4, wherein the content of the antioxidant is from 0.5 to 5% by mass. The curable composition for imprint according to any one of claims 1 to 4, which has an elastic recovery ratio of 70% or more. A cured product obtained by curing the curable composition for imprint according to any one of claims 1 to 6. A member for a liquid crystal display device, characterized by comprising a cured product as in claim 7 of the patent application. A method for producing a cured product, comprising the step of applying a curable composition for imprint according to any one of claims 1 to 6 to a substrate to form a pattern forming layer, and a step of pressing the mold against the surface of the pattern forming layer and a step of irradiating the pattern forming layer with light. The method for producing a cured product according to claim 9, which further comprises the step of heating the pattern forming layer of the irradiated light.