KR101790350B1 - Curable composition for imprints and method for manufacturing a cured product using the same - Google Patents

Abstract

Provided is a curable composition for optical imprint capable of providing a pattern having excellent adhesion with a substrate, imprinting property, releasability to a mold, and high surface hardness. The curable composition for optical imprint of the present invention contains (A) a photopolymerizable monomer, (B) a photopolymerization initiator and (C) a tertiary amino group-containing compound.

Description

TECHNICAL FIELD The present invention relates to a curable composition for optical imprinting, and a method for producing a cured product using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a curable composition for optical imprinting and a process for producing a cured product using the same.

The imprint method develops a well-known embossing technique in optical disk manufacturing, mechanically deforms a mold tool (generally called a mold, a stamper, or a template) having a concavo-convex pattern formed thereon by pressing it on a resist to finely pattern the fine pattern It is a technology to transfer. Since the nano structure can be easily and repeatedly formed by molding the mold once, it is economical and has a nano processing technology with few harmful disposal and emission. Therefore, application to various fields is expected in recent years.

In the imprint method, in particular, in the optical imprinting method of irradiating light through a transparent mold and light curing the curable composition for imprint, it is useful in that imprinting at room temperature becomes possible (Japanese Unexamined Patent Application Publication No. 2007-91816) . In recent years, in place of conventional lithography, it is applied to manufacture of a high-density semiconductor integrated circuit, a transistor of a liquid crystal display, a protective film in a cell, and so on.

 Under such circumstances, there is a demand for a curable composition for optical imprint that is more excellent in optical imprint characteristics.

One of the properties required for the composition for optical imprint is the adhesion to the substrate (substrate adhesion). The substrate adhesion is not limited to the optical imprint, but has been studied in various fields. For example, in a resist material or the like, a resist material and a substrate are brought into close contact with each other by using a chemical reaction by frequent heat. However, when used for imprinting, the adhesion between the composition and the substrate is required to be immediate from the viewpoint of the imprinting property in which the composition is applied onto the substrate, immediately exposed to the mold and cured, and then the mold is peeled off. That is, it is preferable that the composition is applied to a substrate and exposed to light to exhibit adhesion.

 SUMMARY OF THE INVENTION The present invention aims at solving such problems and aims to provide a composition having an excellent substrate adhesion. In addition, a curable composition for imprint is obtained which is excellent in both substrate adhesion, imprinting property and mold releasing property, and also capable of obtaining a pattern having a high surface hardness.

Under the above-mentioned problems, the present inventors have intensively studied and, as a result, surprisingly found that immediate substrate adhesion can be improved by adding a (C) tertiary amino group-containing compound to the curable composition for optical imprint. In general, if the immediate substrate adhesion is to be improved, the adhesion with the mold is improved, and this is often a problem. However, in the present invention, it is very significant in that the substrate adhesion can be improved while maintaining the mold releasability.

Specifically, the problem of the present invention has been solved by the following means.

(1) A curable composition for optical imprinting comprising (A) a photopolymerizable monomer, (B) a photopolymerization initiator, and (C) a tertiary amino group-containing compound.

(2) The curable composition for optical imprinting according to (1), wherein the (C) tertiary amino group-containing compound is a photopolymerizable monomer.

(3) The curable composition for optical imprinting according to (1), wherein the (C) tertiary amino group-containing compound has a crosslinkable group.

(4) The curable composition for optical imprinting according to (1), wherein the (C) tertiary amino group-containing compound is a (meth) acrylate-based monomer containing a tertiary amino group.

(5) The curable composition for optical imprinting according to any one of (1) to (4), wherein the content of the (C) tertiary amino group-containing compound in the composition is 1.0% by mass or more.

(6) The curable composition for optical imprinting according to any one of (1) to (5), wherein the content of the (C) tertiary amino group-containing compound in the composition is 25 mass% or less.

(7) The curable composition for optical imprinting according to any one of (1) to (6), wherein the (C) tertiary amino group-containing compound has a viscosity at 25 ° C of 1.0 to 20,000 mPa · s.

(8) The curable composition for optical imprinting according to any one of (1) to (7), wherein the monofunctional monomer (A) in the composition is 15 mass% or less in the composition.

(9) The curable composition for optical imprinting according to any one of (1) to (8), wherein the content of the photopolymerizable oligomer is 1% by mass or less.

(10) The curable composition for optical imprinting according to any one of (1) to (9), further comprising a releasing agent.

(11) The curable composition for optical imprinting according to any one of (1) to (10), further comprising an antioxidant.

(12) The photocurable composition according to any one of (1) to (11), wherein 50 to 99% by mass of the curable composition for optical imprinting is a (A) photopolymerizable monomer and 0.5 to 32% Wherein the curable composition for optical imprinting is a curable composition for optical imprint.

(13) The curable composition for optical imprinting according to any one of (1) to (11), wherein 60 to 98% by mass of the curable composition for optical imprinting is a (A) photopolymerizable monomer and 1.5 to 25% Wherein the curable composition for optical imprinting is a curable composition for optical imprint.

(14) The curable composition for optical imprinting according to any one of (1) to (13), which is used for application to a substrate containing an acidic functional group.

(15) A method for forming a fine pattern, which comprises using the curable composition for optical imprinting according to any one of (1) to (14).

(16) A method for producing a pattern-forming layer, comprising the steps of forming a pattern-forming layer by applying the curable composition for optical imprinting described in any one of (1) to (14) on a substrate, pressing the mold onto the surface of the pattern- And a step of irradiating light onto the substrate.

(17) The method for producing a fine pattern according to (16), wherein the application of the curable composition for optical imprint to a substrate is carried out by application.

(18) The method for producing a fine pattern according to (16) or (17), wherein the substrate is a substrate containing an acidic functional group.

(19) The method for producing a fine pattern according to (16) or (17), wherein the substrate is a color filter resin.

According to the present invention, it has become possible to provide a curable composition for optical imprint capable of immediately increasing the adhesion with a substrate. Further, in the present invention, surface treatment of the substrate and the like are unnecessary for increasing the adhesion between the substrate and the curable composition for optical imprint, and the work process can be reduced.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, " ~ " is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

In the present specification, "(meth) acrylate" refers to "acrylate" and "methacrylate", "(meth) acrylic" refers to "acryl" and "methacryl" Acryloyl "and" methacryloyl ". In the present specification, the terms "monomer" and "monomer" have the same meaning. The monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 1,000 or less. In the present specification, the term "functional group" refers to a group involved in polymerization.

The term "imprint " in the present invention refers to pattern transfer of a size of preferably 1 nm to 10 mm, more preferably pattern transfer of a size of 10 nm to 100 μm (nanoimprint).

[Curable composition for optical imprint]

The curable composition for optical imprint of the present invention (hereinafter sometimes simply referred to as " composition of the present invention ") is a composition comprising (A) a photopolymerizable monomer, (B) a photopolymerization initiator, and (C) . By employing such a means, the adhesion with the substrate can be improved while maintaining the mold releasability. Particularly, in the present invention, adhesion to a substrate having an acidic group such as a color filter tends to be further improved.

The curable composition for optical imprint of the present invention can be widely used for optical imprint lithography and has the following characteristics.

(1) Since the composition of the present invention is excellent in fluidity at room temperature, the composition tends to flow into the cavity of the mold recess, the atmosphere is not introduced well, and there is no case of bubble defect, In any of the concave portions, the residue does not remain well after the light curing,

(2) Since the cured film obtained by curing the composition of the present invention has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peeling property of the coating film and the mold, A good pattern can be formed because there is no case where the surface of the coating film is subjected to thread dragging and the surface is roughened (good imprinting property)

(3) Since it is excellent in coating uniformity, it is suitable for application to a large substrate, fine processing field,

(4) Since it has high mechanical properties such as light curing property, heat resistance and elastic recovery rate, it can be preferably used as various permanent films.

(5) Since it has excellent voltage characteristics, it is suitable for electronic circuit materials and the like,

And the like.

Therefore, the curable composition for optical imprinting of the present invention can be used for a semiconductor integrated circuit or a member for a liquid crystal display (for example, a thin film transistor of a liquid crystal display, a protective film of a liquid crystal color filter, a spacer, For example, a plasma display panel, a flat screen, a microelectromechanical system (MEMS), a sensor element, an optical disk, a liquid crystal display device, An optical device such as a diffraction grating or a relief hologram, a nano device, an optical device, an optical film or a polarizing element, an organic transistor, a color filter, an overcoat layer, a column material, A micro-lens array, an immunoassay chip, a DNA separation chip, a microreactor, a nano-bio device, In production, such as, optical filters, photonic crystal can be widely applied.

The viscosity of the curable composition for optical imprint of the present invention will be described. The viscosity in the present invention refers to the viscosity at 25 캜 unless otherwise specified. The curable composition for optical imprint of the present invention preferably has a viscosity at 25 ° C of 3 to 20 mPa · s, more preferably 3 to 15 mPa · s, particularly preferably 3 to 10 mPa · s to be. By setting the viscosity of the composition of the present invention to 3 mPa.s or more, it is possible to further improve the substrate application suitability and the mechanical strength of the film. Specifically, by setting the viscosity to 3 mPa · s or more, surface irregularities can be generated at the time of applying the composition, or the composition can be prevented from flowing out from the substrate at the time of application. The composition having a viscosity of 3 mPa s or more is easier to prepare than a composition having a viscosity of less than 3 mPa.. On the other hand, by setting the viscosity of the composition of the present invention to 20 mPa · s or less, the composition flows into the cavity of the mold concave portion even when the mold having a fine uneven pattern is brought into close contact with the composition, The bubble defect does not occur well, and the residue of the convex portion of the mold does not remain well after the photo-curing. In addition, when the viscosity of the composition of the present invention exceeds 20 mPa · s, the viscosity affects the formation of a fine pattern.

(A) a photopolymerizable monomer

The curable composition for optical imprint of the present invention contains a photopolymerizable monomer. Since the composition of the present invention contains a photopolymerizable monomer, good pattern accuracy (imprinting property) can be obtained after light irradiation. In the present invention, the "photopolymerizable monomer" means a monomer capable of forming a high molecular weight by causing a polymerization reaction by light irradiation. In the present invention, the polymerizable monomer (A) refers to a compound other than the tertiary amino group-containing compound.

The photopolymerizable monomer used in the present invention is preferably a compound having a viscosity of 300 mPa 占 퐏 or less, more preferably 100 mPa 占 퐏 or less, and particularly preferably 20 mPa 占 퐏 or less, desirable.

The photopolymerizable monomer in the present invention is preferably one having a photo-radically polymerizable functional group, and examples thereof include a functional group having an ethylenic unsaturated bond, and a (meth) acrylate group, a vinyl group, an allyl group , And a styryl group is preferable, and a (meth) acrylate group is more preferable. The photopolymerizable monomers contained in the composition of the present invention may be one kind or two or more kinds. In addition, the composition of the present invention may contain other photopolymerizable monomers (for example, a polymerizable monomer having a cationic polymerizable group), but preferably does not.

From the viewpoint of imparting the mechanical properties of the cured film, it is preferable to use a polyfunctional monomer having two or more functional groups. Such a multifunctional monomer necessarily has a high molecular weight because of its high molecular weight, and the pattern accuracy may be lowered by increasing the viscosity of the composition. Therefore, the photopolymerizable monomer used in the present invention is preferably a combination of a low-viscosity monomer for adjusting viscosity and a multifunctional monomer for imparting mechanical properties to the cured film, or a combination of an oxetane compound or a functional acid anhydride in the present invention And are collectively selected.

In the curable composition for optical imprint of the present invention, the content of the (A) photopolymerizable monomer in the whole composition is preferably 30 to 99% by mass, more preferably 50 to 95% by mass , More preferably from 60 to 90 mass%.

First, as the polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer), a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer) . Specific examples thereof include 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, Acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide Meth) acrylate, (Meth) acrylates such as propyleneglycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, isopropyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol , Neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, epichlorohydrin (hereinafter referred to as " ECH ") modified phenoxy acrylate, (Meth) acrylates such as ethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol- (Meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl (meth) acrylate, EO-modified tribromo (Meth) acrylate, p-isopropenylphenol, styrene,? -Methylstyrene, acrylonitrile, vinylcarbazole, The tilok theta carbonyl methyl acrylate and the like.

Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used in the present invention include diethylene glycol monoethyl ether (meth) acrylate, dimethyloldicyclopentane di (meth) acrylate, di (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO modified 1,6-hexanediol di 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 di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxypivalic neopentyl glycol di Acrylate, neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, caprolactone- Poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di Di (meth) acrylate, polyester diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH modified propylene glycol di (meth) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclode (Meth) acrylate, trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, triglycerol di Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethylene urea, divinylpropylene urea, Meth) acrylate are exemplified.

Among these, preferred are neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) (Meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentanyl di (meth) Rate and the like are preferably used in the present invention.

Examples of the multifunctional polymerizable unsaturated monomer having three or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) (Meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol (Meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipenta (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Methacrylate, and the like.

Among them, EO modified glycerol tri (meth) acrylate, PO modified glycerol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, EO modified trimethylol propane tri (meth) acrylate, PO modified trimethylol Propane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.

U-2PPA, U-4HA, U-6HA, UA-100H and U-2PPA available from Shin Nakamura Chemical Co., Ltd. can be used as the photopolymerizable monomer in the present invention. UA-340P, UA-2235PE, UA-2200PE, UA-32P, UA-32P, U-324A, U-4H, U-6H, U-108A, U-200PA, U-412A, UA- UA-7200 (all registered trademark) and Kyoeisha Chemical Co., Ltd., all of which are commercially available from Kyoeisha Chemical Co., Ltd., UA-160TM, UA-122P, UA-5201, UA-512, UA-W2A, UA-W2, UA- UA-306A, UA-510H, UF-8001G, and the like. In addition, urethane (meth) acrylates having any structure can be selected.

In the composition of the present invention, when a (meth) acrylate compound is used as the photopolymerizable monomer, an acrylate compound is preferable from the viewpoint of curability.

Next, preferred blend forms of the photopolymerizable monomers in the present invention will be described.

The monofunctional polymerizable unsaturated monomer is effective for lowering the viscosity of the composition and is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 2% by mass or less, in the photopolymerizable monomer (A) % Or less.

The monomer having two or more unsaturated bond-containing groups (multifunctional polymerizable unsaturated monomer) is effective for improving the mechanical properties of the cured film, and is preferably 70% by mass or more, more preferably 70% by mass or more, Is added in the range of 85% by mass or more, particularly preferably 90% by mass or more. The upper limit of the content of the polyfunctional polymerizable unsaturated monomer is not particularly limited, but is usually 100 mass% or less.

In the present invention, the content of the photopolymerizable oligomer is preferably 1% by mass or less.

(B) a photopolymerization initiator

The curable composition for optical imprint of the present invention contains a photopolymerization initiator. The photopolymerization initiator is usually a photoradical polymerization initiator. The composition of the present invention contains a photopolymerization initiator that initiates a polymerization reaction by light irradiation, so that pattern accuracy after light irradiation can be improved. The content of the photopolymerization initiator is, for example, preferably 0.1 to 15 mass%, more preferably 0.2 to 12 mass%, and particularly preferably 0.3 to 10 mass% in the total composition. When two or more types of photopolymerization initiators are used, the total amount is in the above range.

When the ratio of the photopolymerization initiator is 0.1% by mass or more, the sensitivity (fast curability), resolution, line edge roughness, and film strength tend to be improved, which is preferable. On the other hand, when the proportion of the photopolymerization initiator is 15 mass% or less, light transmittance, coloring property, handling property and the like tend to be improved.

The photocradical polymerization initiator used in the present invention is one which is blended with one having an activity with respect to the wavelength of a light source to be used and generates a suitable active species.

(C) a compound having a tertiary amino group

In the present invention, a tertiary amino group-containing compound is contained. The compound having a tertiary amino group can be widely employed without specifying its kind or the like. That is, it may be a tertiary amino group-containing polymer, a tertiary amino group-containing photopolymerizable monomer or other tertiary amino group-containing compound. Preferably a tertiary amino group-containing photopolymerizable monomer. Since amine has high reactivity, it is feared that deterioration of the stability over time can be avoided by selecting tertiary amine having low reactivity in the present invention. In particular, in the system containing the silane coupling agent, hydrolysis, condensation reaction, and the like are promoted to cause concern about stability, but this point can also be avoided in the present invention.

The tertiary amino group-containing compound preferably has a crosslinkable group, more preferably a (meth) acrylate-based monomer or an allyl-based monomer, and more preferably a (meth) acrylate-based monomer. In particular, the use of the (meth) acrylate monomer in both the polymerizable monomer (A) and the tertiary amino group-containing compound (C) tends to exert more effectively the effect of the present invention.

The (meth) acrylate as the (C) tertiary amino group-containing compound may be a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate, preferably a monofunctional (meth) acrylate.

Specific examples of the tertiary amino compound having a crosslinkable group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropylacrylamide, and acryloylmorpholine. Examples of the compound having no crosslinkable group include BYK-4500, DISPERBYK 160, 162, 163, 164, 166, 167, 168, 182, 184, 185, 2155, 2163 and 2164 (all manufactured by BYK Chemie).

The molecular weight of the tertiary amino group-containing compound is preferably 100 to 30000, more preferably 100 to 500.

The number of tertiary amino groups in one molecule of the tertiary amino group-containing compound is preferably 1 to 10, more preferably 1 to 3.

The viscosity of the tertiary amino group-containing compound at 25 캜 is preferably 1.0 to 20,000 mPa s, more preferably 1.0 to 200 mPa..

The tertiary amino group-containing compound is contained in the composition of the present invention in an amount of usually 0.5% by mass or more, preferably 1.0% by mass or more, and more preferably 6% by mass or more. The upper limit value is not particularly limited but is usually 32 mass% or less, preferably 25 mass% or less, and more preferably 15 mass% or less.

In the present invention, it is particularly preferable that 50 to 99% by mass of the curable composition for optical imprinting is the (A) photopolymerizable monomer and 0.5 to 32% by mass is the (C) tertiary amino group- (A) is a photopolymerizable monomer, and 1.0 to 25 mass% is (C) a tertiary amino group-containing compound.

(Silane coupling agent)

The composition of the present invention preferably contains a silane coupling agent. The kind of the silane coupling agent used in the present invention is not specifically defined, but may be selected from vinyl silane, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, aminosilane, ureide silane, chloropropyl silane, mercaptosilane, Polysulfide silane, and isocyanate silane. When (meth) acrylate is used as the photopolymerizable monomer, it is preferable to use methacryloxy silane and / or acryloxy silane. By using such a silane coupling agent, it becomes possible to exhibit excellent substrate adhesion.

Examples of the silane coupling agent usable in the composition of the present invention include vinyl trichlorosilane, vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane,? -Methacryl (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Mercapto Propyltrimethoxysilane,? -Chloropropylmethyldimethoxysilane,? -Chloropropylmethyldiethoxysilane, and the like.

The silane coupling agent used in the present invention preferably has a molecular weight of 150-400.

The silane coupling agent is preferably blended at a ratio of 5% by mass or more, and more preferably 8% by mass or more, based on the total solid content of the curable composition for optical imprint of the present invention. The upper limit is not specifically defined, but is usually 20 mass% or less, preferably 15 mass% or less.

(Antioxidant)

Further, the curable composition for optical imprint of the present invention preferably contains an antioxidant. The content of the antioxidant used in the present invention is, for example, 0.01 to 10% by mass, preferably 0.2 to 5% by mass, in the total composition. When two or more kinds of antioxidants are used, the total amount is in the above range.

The antioxidant suppresses discoloration caused by heat or light irradiation and fading due to various oxidizing gases such as ozone, active oxygen, NO _x , and SO _x (X is an integer). Particularly, in the present invention, addition of an antioxidant has the advantage of preventing coloring of the cured film or reducing film thickness reduction due to decomposition. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates , A thiourea derivative, a saccharide, a nitrite, a sulfite, a thiosulfate, and a hydroxylamine derivative. Among them, a hindered phenol-based antioxidant and a thioether-based antioxidant are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness.

Antigene P, 3C, FR, watertight riser S, watertight riser GA80 (manufactured by Sumitomo Chemical Co., Ltd.), trade name Irganox 1010, 1035FF, 1076 and 1222 AO80, AO503, LA52, LA57, LA62, LA63, LA67, LA68LD, and LA77 (manufactured by ADEKA Corporation). These may be used alone or in combination.

(Releasing agent)

The curable composition for optical imprint of the present invention may contain a release agent. The release agent to be used in the present invention is contained in an amount of, for example, 0.001 to 5 mass%, preferably 0.002 to 4 mass%, and more preferably 0.005 to 3 mass% in the total composition. When two or more kinds of release agents are used, the total amount is in the above range. When the mold release agent is in the range of 0.001 to 5 mass% in the composition, the uniformity effect of coating is good and it is difficult to cause deterioration of the mold transfer characteristics due to excessive release agent. Particularly, in the present invention, it is advantageous in that mold releasability can be ensured when a mold having a hydroxy group on its surface is used.

Examples of the mold release agent include a surfactant and at least one of a fluorine surfactant, a silicone surfactant and a fluorine silicon surfactant. The fluorine surfactant and the silicon surfactant may be contained in the fluorine- More preferably contains an activator, and most preferably contains a fluorine-silicon surfactant. As the fluorine-based surfactant and the silicon-based surfactant, a nonionic surfactant is preferred.

Here, the term "fluorine-silicon surfactant" refers to both fluorine surfactant and silicone surfactant.

By using such a surfactant, a silicon wafer for manufacturing semiconductor devices, a rectangular glass substrate for producing liquid crystal devices, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, a tantalum alloy film, a silicon nitride film, an amorphous silicon film, (Irregular dryness of the resist film) or the like which occurs when the imprint curable composition of the present invention is applied onto a substrate on which various films such as indium oxide (ITO) film or tin oxide film doped with tin are formed The problem of coating failure can be solved. Further, it is possible to improve the fluidity of the composition of the present invention in the cavity of the mold recess, to improve the peelability between the mold and the resist, to improve the adhesion between the resist and the substrate, and to lower the viscosity of the composition. In particular, the imprint composition of the present invention can significantly improve the coating uniformity by adding the above-mentioned surfactant, and in coating with a spin coater or a slit scan coater, good coating applicability can be obtained regardless of the substrate size.

Examples of the nonionic fluorosurfactant that can be used in the present invention include Furorado FC-430 and FC-431 (manufactured by Sumitomo 3M Ltd.), Saffron S-382 (manufactured by Asahi Glass Co., Ltd.) PF-6320, PF-6320, PF-6520, and PF-6520 (trade names, manufactured by TOKEM PRODUCTS CO., LTD.), EF-122A, 122B, 122C, EF-121, EF- DSD-401, DS-403, and DS-451 (all manufactured by Daikin Industries, Ltd.)), trade names: Futanoto FT250, FT251 and DFX18 (all manufactured by Neos Co., Ltd.), trade names: OMNOVA Solutions, 172, 173, 178K and 178A (all manufactured by Dainippon Ink and Chemicals, Inc.).

Examples of the nonionic silicone-based surfactants include KP-341, KF-341, KP-341, KP- 352A, and KF-6012 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Examples of the fluorine-silicon surfactants include trade names X-70-090, X-70-091, X-70-092 and X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.) Park R-08, and XRB-4 (all manufactured by Dainippon Ink and Chemicals, Inc.).

(Other components)

The composition of the present invention may contain, in addition to the above components, a non-polymerizable molecule, a polymer component, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an antioxidant, a plasticizer, an adhesion promoter, a thermal polymerization initiator, , A photosensitizer, a basic compound, and a flow control agent, a defoaming agent, a dispersant, and the like may be added.

The above-mentioned non-polymerizable molecules may be added to the composition of the present invention for the purpose of imparting adhesiveness and controlling physical properties of the cured film. The addition amount of such a non-polymerizable molecule can be determined within a range in which the addition amount of the photopolymerizable molecule can be controlled within the range of the present invention. Examples of such non-polymerizable molecules include alkyl esters such as sebacodioctyl, (thio) urea compounds, organic fine particles, and inorganic fine particles.

In the curable composition for optical imprint of the present invention, a polymerization inhibitor may be added in order to improve storage stability and the like. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; Can be used. The polymerization inhibitor is preferably blended in a proportion of 0.001 to 10 mass%, based on the total amount of the composition of the present invention.

An ultraviolet absorber may be used for the curable composition for optical imprint of the present invention. The ultraviolet absorber is commercially available as Tinuvin P, 234, 320, 326, 327, 328 and 213 (manufactured by Chiba Kagi K.K.), Sumisorb 110,130,140,220,250,300,320,340 , 350, 400 (manufactured by Sumitomo Chemical Co., Ltd.), and the like. The ultraviolet absorber is preferably blended in a proportion of 0.01 to 10% by mass, based on the total amount of the curable composition for optical imprint.

In the curable composition for optical imprint of the present invention, a light stabilizer may be used. Examples of commercially available light stabilizers include Tinuvin 292, 144 and 622 LD (manufactured by Chiba Chemical Industry Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114 and 744 (manufactured by Sankyo Chemical Industry Co., ) And the like. The light stabilizer is preferably blended in a proportion of 0.01 to 10% by mass based on the total amount of the composition.

An antioxidant may be used in the curable composition for optical imprint of the present invention. Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Co., Ltd.) can be used as a commercially available antioxidant. The antioxidant is preferably blended in a proportion of 0.01 to 10% by mass with respect to the total amount of the composition.

In the curable composition for optical imprint of the present invention, a plasticizer may be added to adjust adhesiveness to the substrate, flexibility of the film, and hardness. Specific examples of the preferable plasticizer include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl Di (n-butyl) adipate, di (n-butyl) adipate, dimethylsuberate, diethylsuberate, di . Preferably 20 mass% or less, and more preferably 10 mass% or less. In order to obtain the effect of adding the plasticizer, 0.1 mass% or more is preferable.

An adhesion promoter may be added to the curable composition for optical imprint of the present invention in order to adjust the adhesion to the substrate. Examples of the adhesion promoter include benzimidazoles, polybenzimidazoles, lower hydroxyalkyl substituted pyridine derivatives, nitrogenous heterocyclic compounds, urea or thiourea, organic phosphorus compounds, 8-oxyquinoline, 4-hydroxyphthyridine , 1,10-phenanthroline, 2,2'-bipyridine derivatives, benzotriazoles, organic phosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, Ethanolamine, N-ethyldiethanolamine, N-ethylethanolamine and derivatives, benzothiazole derivatives and the like can be used. The adhesion promoter is preferably 20 mass% or less, more preferably 10 mass% or less, and most preferably 5 mass% or less, in the composition. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain an effect.

When the composition of the present invention is cured, a thermal polymerization initiation system may be added if necessary. Preferred examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, and azobisisobutyronitrile. The thermal polymerization initiator is preferably 8.0 mass% or less, more preferably 6.0 mass% or less, and still more preferably 4.0 mass% or less in the composition. The addition of the thermal polymerization initiator is preferably 3.0% by mass or more in order to obtain an effect.

In the curable composition for optical imprint of the present invention, a photobase generator may be added as needed for the purpose of adjusting the pattern shape, sensitivity, and the like. Examples of the photobase generators include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) (Methylthiobenzoyl) -1-methyl-1-morpholinoethane, ((2-nitrobenzyl) oxy] carbonyl] Benzyl-1-dimethylaminopropane, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexamammine cobalt (III) tris (triphenylmethyl borate) (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine , 2,6-dimethyl-3,5-diacetyl-4- (2 ', 4'-dinitrophenyl) -1,4-dihydropyridine, and the like.

In the curable composition for optical imprint of the present invention, a colorant may be optionally added for the purpose of improving the visibility of the coating film, but it is preferable that the colorant is not contained. In the present invention, it is preferable that the content of the pigment or dye is 1% by mass or less.

In the curable composition for optical imprint of the present invention, elastomer particles may be added as optional components for the purpose of improving mechanical strength, flexibility and the like.

The elastomer particles which can be optionally added to the composition of the present invention have an average particle size of preferably 10 nm to 700 nm, more preferably 30 to 300 nm. Butylene copolymer, a styrene / isoprene copolymer, an ethylene / propylene copolymer, an ethylene /? - olefin copolymer, an ethylene /? - olefin / isoprene copolymer, a polyisoprene, a polyisoprene, a butadiene / acrylonitrile copolymer, Styrene / butadiene block copolymer, and styrene / isoprene block copolymer. The styrene / butadiene block copolymer is a copolymer of styrene and isoprene. Further, core / shell type particles obtained by coating these elastomer particles with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

Commercially available products of the elastomer particles include, for example, Resinus bond RKB (manufactured by REGINAS HASUNG CO., LTD.), TECHNO MBS-61 and MBS-69 (manufactured by TECHNO POLYMER CO., LTD.).

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

In addition to the photo-radical polymerization initiator, the photo-sensitizer may be added to the curable composition for optical imprint of the present invention to adjust the wavelength of the UV region. Typical sensitizers that can be used in the present invention include, but are not limited to, V. Crivello, Adv. in Polymer Sci, 62, 1 (1984), and specific examples thereof include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, Vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphaquinone, phenothiazine derivatives and the like.

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

Further, the moisture content of the curable composition for optical imprint of the present invention at the time of preparation is preferably 2.0 mass% or less, more preferably 1.5 mass%, further preferably 1.0 mass% or less. When the water content at the time of preparation is 2.0 mass% or less, the storage stability of the composition of the present invention can be more stabilized.

A solvent may be used in the curable composition for optical imprint of the present invention, and it is preferably 5 mass% or less, more preferably 3 mass% or less, and further preferably 1 mass% or less. That is, since the composition of the present invention can contain monofunctional and / or bifunctional monomers as a reactive diluent, it is not necessary to necessarily contain a solvent for dissolving the components of the composition of the present invention. As described above, the composition of the present invention does not necessarily contain an organic solvent, but may be optionally added, for example, when dissolving a compound or the like which is insoluble in the reactive diluent as the composition of the present invention or when finely adjusting the viscosity. Examples of the organic solvent that can be preferably used in the composition of the present invention include a solvent generally used in a curable composition for optical imprinting or a photoresist and a compound which dissolves and uniformly disperses the compound used in the present invention, Is not particularly limited.

Examples of the solvent that can be used in the present invention include those described in the identification number 0066 of Japanese Laid-Open Patent Publication No. 2009-73078.

The content of the compound having a molecular weight of 1000 or more is preferably 5 mass% or less, and more preferably 3 mass% or less.

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

[Production method of cured product]

Next, a method for producing a cured product (particularly a fine concavo-convex pattern) using the curable composition for optical imprint of the present invention will be described. A step of forming a pattern forming layer by applying the curable composition for optical imprinting of the present invention on a substrate or a support (substrate), a step of pressing the mold on the surface of the pattern forming layer, and a step of irradiating light onto the pattern forming layer By curing the composition of the present invention, a fine uneven pattern can be formed. Particularly in the present invention, in order to improve the degree of curing of the cured product, it is preferable to further include a step of heating the pattern forming layer after light irradiation. That is, the curable composition for optical imprint of the present invention is preferably cured by light, light, and heat.

The cured product obtained by the process for producing a cured product of the present invention is excellent in pattern precision, curability and light transmittance, and can be preferably used particularly as a protective film for a liquid crystal color filter, a spacer, and other members for a liquid crystal display device.

Specifically, at least a pattern-forming layer composed of the composition of the present invention is applied onto a substrate (substrate or support) and, if necessary, dried to form a layer (pattern-forming layer) comprising the composition of the present invention, Forming layer is formed on the surface of the pattern-receiving layer of the pattern-receiving layer, the mold is brought into pressure contact with the surface of the pattern-forming layer of the pattern-receiving layer, the mold pattern is transferred, and the fine uneven pattern-forming layer is cured by light irradiation and heating. The light irradiation and heating may be carried out a plurality of times. The optical imprint lithography by the pattern forming method (cured product manufacturing method) of the present invention can be laminated or multi-patterned, and can be used in combination with a conventional thermal imprint.

In addition, as an application of the curable composition for optical imprint of the present invention, the composition of the present invention is applied to a substrate or a support, and the layer comprising the composition is exposed, cured and if necessary dried (baked) A permanent film such as an insulating film can be produced.

In a permanent film (resist for a structural member) used for a liquid crystal display (LCD) or the like, it is preferable to avoid the incorporation of ionic impurities of a metal or an organic material in the resist to the utmost to prevent the operation of the display from being hindered. Is not more than 1000 ppm, preferably not more than 100 ppm.

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

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

As the method for applying the curable composition for optical imprint of the present invention onto a substrate, there can be used generally known application methods such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, An extrusion coating method, a spin coating method, a slit scanning method, or the like. In the present invention, it is preferable to form by coating. The thickness of the pattern-forming layer made of the composition of the present invention varies depending on the intended use, but is in the range of about 0.05 mu m to about 30 mu m. The composition of the present invention may also be applied by multiple application. Further, another organic layer such as a planarization layer may be formed between the substrate and the pattern-forming layer comprising the composition of the present invention. Thereby, since the pattern forming layer and the substrate are not in direct contact with each other, adhesion of dust to the substrate and damage to the substrate can be prevented.

The substrate to which the composition of the present invention is applied may be a substrate made of quartz, glass, an optical film, a ceramic material, a vapor deposition film, a magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, Fe, paper, SOG, a polyester film, Film substrate, a PDP electrode plate, a glass or transparent plastic substrate, a conductive substrate such as ITO or metal, an insulating substrate, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon or the like A semiconductor manufacturing substrate, a color filter, and the like.

The substrate to which the composition of the present invention is applied preferably has an acidic group. Examples of the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group and a phenol group. Specifically, a color filter, an organic insulating film, an organic hard coat film, and an etching resist are preferable.

The shape of the substrate may be a plate shape or a roll shape.

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 (pressurized) onto the surface of the pattern forming layer. As a result, a fine pattern previously formed on the pressing surface of the mold can be transferred to the pattern forming layer.

The optical imprint lithography using the curable composition for optical imprinting of the present invention selects a light-transmitting material on at least one of the mold material and / or the substrate. In the optical imprint lithography applied to the present invention, the curable composition for optical imprinting of the present invention is applied onto a substrate to form a pattern forming layer, a light transmitting mold is pressed on the surface, and light is irradiated from the back surface of the mold, The pattern forming layer is cured. The curable composition for optical imprinting may be cured by applying a curable composition for optical imprinting onto a light-transmitting substrate, pressing the mold, and irradiating light from the backside of the substrate.

The light irradiation may be carried out with the mold attached or after the mold release, but in the present invention, it is preferable to carry out the irradiation with the mold in close contact.

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

The light-transmissive mold material used in the present invention is not particularly limited, but any material having predetermined strength and durability may be used, and excellent releasability is preferable. Specifically, examples thereof include light transparent resins such as glass, quartz, PMMA, polycarbonate resin, fluororesin and urethane resin, transparent metal vapor deposition films, flexible films such as polydimethylsiloxane, light cured films and metal films, It is preferable that the molding material having a hydrophilic surface such as a transparent metal vapor deposition film is subjected to a mold-releasing treatment such as a silicone system or a fluorine system. For example, Offsuru DSX manufactured by Daikin Industries, Ltd., Novec EGC-1720 manufactured by Sumitomo 3M Co., Ltd., and the like can be given.

The non-light-transmitting mold material to be used in the case of using the transparent substrate of the present invention is not particularly limited, but it is preferable that it has a predetermined strength and durability and is excellent in releasability. Specifically, examples of the substrate include ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, It is not constrained. It is preferable that the molding material having a hydrophilic surface such as a vapor deposition film, a metal substrate, a silicon substrate, or the like is subjected to a releasing treatment such as the above-described silicon system or fluorine system.

The shape of the mold is not particularly limited, and either a plate-like mold or a roll-shaped mold may be used. The roll-shaped mold is applied particularly when continuous productivity of the transfer is required.

When the optical imprint lithography is carried out using the composition of the present invention, it is preferable that the mold pressure is usually 10 atm or less in the method for producing a cured product of the present invention. When the mold pressure is 10 atm or less, the mold or the substrate is not deformed well and the pattern accuracy tends to be improved. It is also preferable in that the apparatus is reduced because the pressure is low. It is preferable that the mold pressure is selected in such a range that the uniformity of the mold transfer can be ensured within a range in which the residual film of the curable composition for optical imprint of the convex portions of the mold becomes smaller.

In the method for producing a cured product of the present invention, the irradiation dose of light irradiation in the step of irradiating light to the pattern formation layer may be sufficiently larger than the irradiation dose required for curing. The irradiation amount required for curing is suitably determined by examining the consumption amount of the unsaturated bond of the curable composition for optical imprint or the tackiness of the cured film.

Further, in the optical imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually carried out at room temperature, but light irradiation may be performed while heating to increase the reactivity. If it is kept in a vacuum state as the previous step of light irradiation, light irradiation may be conducted in a vacuum state since it is effective in preventing air bubble mixing, suppressing a decrease in reactivity due to oxygen incorporation, and improving adhesion of a mold and a curable composition for optical imprinting. 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 atmospheric pressure.

The light used for curing the curable composition for optical imprinting of the present invention is not particularly limited and includes, for example, light or radiation having a wavelength in a region of high energy ionizing radiation, extraordinary, extra-atomic, have. As the high energy ionizing radiation source, for example, electron beams accelerated by accelerators such as a cockroach type accelerator, a grape type accelerator, a linear accelerator, a betatron, and a cyclotron are industrially most conveniently used and economically used, X-rays, alpha rays, neutron rays, and proton rays emitted from isotopes or reactors may also be used. Examples of the ultraviolet ray source include ultraviolet fluorescent lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, xenon lamps, carbon arc lamps, and the like. Radiation includes, for example, microwave and EUV. Further, laser light used in microfabrication of semiconductors such as LED, semiconductor laser light, KrF excimer laser light of 248 nm, or 193 nm ArF excimer laser can also be preferably used in the present invention. These lights may be monochrome light, or may be light of different wavelengths (mixed light).

At the time of exposure, the exposure illuminance is preferably set in the range of 1 mW / cm 2 to 50 mW / cm 2. By setting it to 1 mW / cm 2 or more, productivity can be improved because the exposure time can be shortened, and when it is 50 mW / cm 2 or less, deterioration of permanent film characteristics due to occurrence of side reaction can be suppressed . The exposure dose is preferably in the range of 5 mJ / cm 2 to 1000 mJ / cm 2. If it is 5 mJ / cm < 2 > or more, the exposure margin becomes narrow and the photocuring becomes insufficient, thereby preventing occurrence of problems such as adhesion of unreacted materials to the mold. When the exposure dose is 1000 mJ / cm < 2 > or less, deterioration of the permanent film due to decomposition of the composition can be suppressed.

At the time of exposure, an inert gas such as nitrogen or argon may be flown to control the oxygen concentration to less than 100 mg / L in order to prevent inhibition of radical polymerization by oxygen.

In the method for producing a cured product of the present invention, it is preferable to include a step of curing the pattern forming layer by light irradiation and then curing the cured pattern by further heating (post-baking step). The heating may be carried out either before or after the pattern is peeled off from the patterned layer after the light irradiation. It is preferable to heat the patterned layer after peeling off the mold. The heat for curing the composition of the present invention after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

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

In the optical imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually carried out at room temperature, but light irradiation may be performed while heating to increase the reactivity. In the vacuum state before the light irradiation, light irradiation may be performed in a vacuum state since it is effective in preventing air bubble mixing, suppressing decrease of reactivity due to oxygen incorporation, and improving adhesion of the curable composition for a mold and optical imprint lithography. In the present invention, the preferred degree of vacuum is 10 < ^-1 > Pa to atmospheric pressure.

The curable composition for optical imprinting of the present invention can be prepared as a solution by mixing the components described above and then filtering them with a filter having a pore diameter of 0.05 mu m to 5.0 mu m, for example. The mixing and dissolution of the curable composition for optical imprinting is usually carried out in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple steps or repeated several times. In addition, the filtrate may be re-filtered. The material to be used for filtration may be polyethylene resin, polypropylene resin, fluorine resin, nylon resin or the like, but is not particularly limited.

[Cured goods]

As described above, the cured product of the present invention formed by the method for producing a cured product of the present invention can be used as a permanent film (resist for a structural member) or an etching resist used for a liquid crystal display (LCD) or the like. The permanent film is then transported and stored by bottling it into a container such as a gallon bottle or a coat bottle. In this case, for the purpose of preventing deterioration, the inside of the container may be replaced with inert nitrogen, argon or the like. The temperature may be room temperature during transportation and storage, but the temperature may be controlled in the range of -20 캜 to 0 캜 to further prevent deterioration of the permanent film. Of course, it is preferable to shield the light to a level at which the reaction does not proceed.

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

[Member for Liquid Crystal Display Device]

The curable composition for optical imprint of the present invention can be applied to a semiconductor integrated circuit, a recording material, and a member for a liquid crystal display device, and is preferably a member for a liquid crystal display device, and is applicable as an etching resist for a flat panel display .

When the composition for imprints of the present invention is used as an etching resist, first, a silicon wafer or the like having a thin film of, for example, SiO ₂ formed thereon is used as the substrate, Thereby forming a fine pattern. Thereafter, a desired pattern can be formed on the substrate by etching with hydrogen fluoride in the case of wet etching or etching gas such as CF _{4 in} the case of dry etching. Example

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

(Preparation of curable composition for optical imprint)

A photopolymerizable monomer, a tertiary amino group-containing compound, a photopolymerization initiator, a silane coupling agent and, if necessary, an antioxidant and a silicone oil were blended in accordance with the compositions described in the following Tables to obtain curable compositions for optical imprinting of Examples and Comparative Examples Lt; / RTI > The unit in the table is the mass part. The materials used are as follows.

≪ Photopolymerizable monomer >

M-1: n-hexyl methacrylate (hexyl methacrylate, manufactured by Tokuyama Chemical Co., Ltd.)

M-2: 1,6 hexanediol diacrylate (Viscot # 230, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

M-3: 1,9 nonanediol diacrylate (Viscot # 260, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

M-4: Trimethylolpropane triacrylate (Aronix M309, manufactured by TOA Corporation)

M-5: tetrafunctional urethane acrylate (NK Oligo U-4HA, manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Amino group-containing compound>

A-1: Dimethylaminoethyl acrylate (DMAEA, manufactured by Kyojin Kabushiki Kaisha, molecular weight: 43, viscosity: 1.3 mPa 揃 s)

A-2: Dimethylaminopropylacrylamide (DMAPAA, manufactured by Kyojin Kabushiki Kaisha, molecular weight: 156, viscosity: 50.0 mPa s)

A-3: amino group-containing high molecular weight product (DISPERBYK182, manufactured by BYK Chemie, molecular weight: about 20000, viscosity: 100000 mPa.s)

A-4: amino group-containing high molecular weight product (DISPERBYK2155, manufactured by BYK Chemie, molecular weight: 20000, viscosity: 13000 mPa.s)

A-5: trimethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 59, viscosity 0.3 mPa 占 퐏)

A-6: N, N-Dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 121, viscosity 1.2 mPa s)

A-7: 2- (tert-Butylamino) ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 171, viscosity 3.8 mPa s)

A-8: Aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 179, viscosity 2.5 mPa 占 퐏)

&Lt; Photopolymerization initiator &gt;

P-1: Phosphine oxide-based photopolymerization initiator (Luricin TPO-L, manufactured by BASF)

<Silane coupling agent>

S-1: acryloyl-modified trimethoxysilane (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Antioxidant>

AO-1: Semihindered phenol antioxidant (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.)

AO-2: Thioether-based antioxidant (Irganox 1035FF, manufactured by Chiba)

<Silicone oil>

O-1: Polyether-modified silicone oil KF-6012 (manufactured by Shinetsu Silicones)

<Solvent>

Y-1: EEP (ethyl 3-ethoxypropionate, manufactured by Tokyo Chemical Industry Co., Ltd.)

The composition thus obtained was applied to a substrate to evaluate the substrate adhesion and coatability. Here, the following substrates were used.

In Examples 1 to 21, 25 and 26, and Comparative Examples 1 to 4, a color filter (manufactured by FUJIFILM, TRANSOR) was used as a substrate.

In Example 22, an etching resist (FMTR2913, manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD.) Was used as a substrate.

In Example 23, a glass substrate (Eagle 2000, manufactured by Asahi Glass Co., Ltd.) was used as a substrate.

Example 24 was formed on the ITO surface of a substrate (ITO-attached glass 45 Ω manufactured by Nippon Sheet Glass Co., Ltd., having a high temperature) with ITO attached thereto.

&Lt; Substrate adhesion property &

The curable composition for optical imprint was coated on the substrate to a thickness of 3 mu m and cured by UV exposure of 150 mJ. Then, in the 100 mask loss cut test described in JIS K5600, the peeled water was counted as follows .

5: 100/100

4: 51/100 to 99/100

3: 21/100 to 50/100

2: 1/100 to 20/100

1: 0/100

<Imprintability>

It was evaluated to what extent the pattern transferred to the resist can reproduce the shape of the mold. Specifically, each of the compositions was spin-coated on the substrate so as to have a film thickness of 3.0 mu m. The coating film obtained by spin coating was set on an imprint apparatus using a high-pressure mercury lamp (lamp power: 2000 mW / cm2) manufactured by ORC Co., Ltd. as a light source and the mold pressing force was 0.8 kN and the degree of vacuum during exposure was 10 Torr (about 1.33 x 10 ⁴ Pa) Under the condition that the mold was subjected to a NANOS-B mold release treatment of T & K on a mold of NIM-UH100 (manufactured by NTT-AT Nanofabrication Co., Ltd.) having a rectangular hole pattern of 100 nm as a mold, 150 mJ / cm &lt; 2 &gt;. After exposure, the mold was removed and a resist pattern was obtained. Further, the obtained resist pattern was heated in an oven at 230 DEG C for 30 minutes to be completely cured. The pattern shape after transfer was observed with a scanning electron microscope and an optical microscope, and the pattern shape was evaluated according to the following criteria.

5: Transfer rate of mold shape 95% or more

4: Transfer rate of mold shape 90% or more to less than 95%

3: Transfer rate of mold shape 80% or more to less than 90%

2: Transfer rate of the mold shape is 70% or more and less than 80%

1: Transfer rate of mold shape is less than 70%

&Lt; Mold release property &

In the imprint apparatus, the peeling force at the time of peeling the mold from the substrate was measured. (5 占 퐇) for optical imprint was coated on a substrate and exposed to light at a light intensity of 10 mW / cm2 and an exposure dose of 150 mJ / cm2 using a high-pressure mercury lamp (lamp power: 2000 mW / . The substrate and the mold were peeled off at a rate of 20 占 퐉 / sec, and the maximum peeling force at this time was measured to obtain a mold peeling force. The unit is expressed as [N (Newton)].

These results are shown in the following table. As is apparent from the following table, it was found that the curable composition for optical imprinting of the present invention can form a pattern having excellent substrate adhesion, imprint property and mold releasability, and high surface hardness.

Claims (19)

A curable composition for optical imprinting comprising (A) a photopolymerizable monomer, (B) a photopolymerization initiator, and (C) a tertiary amino group-containing polymer. delete The method according to claim 1,
(C) a polymer body having a tertiary amino group has a crosslinkable group. delete The method according to claim 1,
, And the content of the tertiary amino group-containing polymer (C) itself in the composition is at least 1.0% by mass. The method according to claim 1,
, And the content of the tertiary amino group-containing polymer (C) is 25% by mass or less in the composition. The method according to claim 1,
And the viscosity of the (C) tertiary amino group-containing high molecular weight component at 25 캜 is 1.0 to 20,000 mPa s. The method according to claim 1,
Wherein the monofunctional compound in the photopolymerizable monomer (A) is 15 mass% or less in the composition. The method according to claim 1,
Wherein the content of the photopolymerizable oligomer is 1% by mass or less. The method according to claim 1,
Curable composition for optical imprinting further comprising a releasing agent. The method according to claim 1,
Wherein the curable composition further comprises an antioxidant. The method according to claim 1,
Wherein 50 to 99% by mass of the curable composition for optical imprinting is a (A) photopolymerizable monomer and 0.5 to 32% by mass of the polymer is a tertiary amino group-containing polymer. The method according to claim 1,
60 to 98% by mass of the curable composition for optical imprinting is a (A) photopolymerizable monomer, and 1.5 to 25% by mass is a (C) tertiary amino group-containing polymer. The method according to claim 1,
A curable composition for optical imprint used for application to a substrate containing an acidic functional group. A method for forming a fine pattern, which comprises using the curable composition for optical imprinting according to any one of claims 1, 3 and 5 to 14. A process for producing a pattern for optical imprinting, comprising: forming a pattern forming layer by applying the curable composition for optical imprinting according to any one of claims 1, 3 and 5 to a substrate; And a step of irradiating the pattern forming layer with light. 17. The method of claim 16,
Wherein the application of the curable composition for optical imprint onto a substrate is carried out by application. 17. The method of claim 16,
Wherein the substrate is a substrate containing an acidic functional group. 17. The method of claim 16,
Wherein the substrate is a color filter resin.