KR20160125453A - Curable composition for optical imprinting, pattern forming method and pattern - Google Patents

Abstract

A curable composition for optical imprinting excellent in inkjet ejection accuracy and releasability, particularly, a curable composition for optical imprinting excellent in stability with time of inkjet ejection precision and releasability, a pattern forming method and a pattern.
A curable composition for optical imprinting comprising a polymerizable compound, a photopolymerization initiator, and a fluorinated compound, wherein the fluorinated compound is represented by the following formula (I):
In the general formula (I), Rf ¹ represents a fluorinated alkyl group having 1 to 6 carbon atoms and two or more fluorine atoms; R ¹ represents an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 8 carbon atoms; m represents an integer of 0 to 2, and n represents an integer of 1 to 3; When n represents 2 or 3, Rf ¹ may be different from each other.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable composition for optical imprint, a pattern forming method and a pattern,

The present invention relates to a curable composition for optical imprinting. More particularly, the present invention relates to a magnetic recording medium such as a semiconductor integrated circuit, a flat screen, a microelectromechanical system (MEMS), a sensor element, an optical disk and a high density memory disk, optical parts such as a diffraction grating and a relief hologram, An organic transistor, a color filter, an overcoat layer, a column material, a rib material for liquid crystal alignment, a micro lens array, an immunoassay chip, a DNA separation chip A pattern forming method, and a pattern for forming a pattern using light irradiation, which is used for manufacturing a microreactor, a nanobio device, an optical waveguide, an optical filter, a photonic liquid crystal, and the like.

The imprint method is a method of developing an embossing technique well known in optical disk manufacturing and dynamically deforming a mold tool (generally called a mold, a stamper, or a template) having a concavo-convex pattern formed thereon by pressing it onto a resist to finely pattern the fine pattern It is a technology to transfer. When the mold is once fabricated, the microstructure such as the nanostructure can be simply and repeatedly molded, which is economical and has recently been expected to be applied to various fields.

As the imprint method, a thermal imprint method (for example, refer to Non-Patent Document 1) using a thermoplastic resin as a material to be processed and an optical imprint method (for example, see Non-Patent Document 2 and Non-Patent Document 3 ) Has been proposed. In the thermal imprint method, a mold is pressed onto a polymer resin heated to a glass transition temperature or higher, and then the mold is released after cooling to a glass transition temperature or lower, thereby transferring the microstructure to the resin on the substrate. This method is very simple and applicable to various resin materials and glass materials.

On the other hand, in the optical imprint method, the curable composition is photo-cured by light irradiation through a light-transmissive mold or a light-transmissive substrate, and then the mold is peeled to transfer the fine pattern to the light cured product. Since this method enables imprinting at room temperature, it can be applied to the field of precision processing of ultrafine patterns such as the fabrication of semiconductor integrated circuits. Recently, new developments such as a nano-casting method combining the merits of both of them and a reverse imprint method of manufacturing a three-dimensional laminated structure have been reported.

In such an imprint method, the following applications are proposed.

In the first application, the formed shape (pattern) itself has a function and is used as a component part or structural member of the nano-technology. Examples include various micro-nano optical elements, high-density recording media, optical films, structural members in flat panel displays, and the like.

In the second application, a laminated structure is constructed by forming a microstructure and a nanostructure simultaneously or integrally with each other, and then using the laminated structure for manufacturing a micro-total analysis system (μ-TAS) or a biochip.

The third application is used for the purpose of processing a substrate by a method such as etching using the formed pattern as a mask. This technique can be used for high-density semiconductor integrated circuit fabrication, transistor fabrication of a liquid crystal display, and magnetic fabrication of a next-generation hard disk called patterned media, instead of the conventional lithography technique, by high-precision alignment and high integration. Efforts to commercialize the imprint method for these applications have recently become active.

Since the imprint method has a step of peeling the mold, its releasing property has been a problem from the beginning. As an attempt to improve the releasability, a method of incorporating a fluorinated monomer or a non-reactive fluorinated compound into a curable composition is known (Non-Patent Document 4).

On the other hand, an inkjet method has attracted attention (for example, in the use of an etching resist for processing a semiconductor substrate) in which an ultrafine pattern is formed with high accuracy by the imprint method (Patent Document 1).

Patent Document 1: Japanese Published Patent Application No. 2008-502157

Non-Patent Document 1: S. Chou et al., Appl. Phys. Lett. 67, 3114 (1995) Non-Patent Document 2: J. Haisma et al., J. Vac. Sci. Technol. B 14 (6), 4124 (1996) Non-Patent Document 3: M. Colbun et al., Proc. SPIE 3676, 379 (1999) Non-Patent Document 4: M. W. Lin et al., J. Micro / Nanolith. MEMS MOEMS 7 (3), 033005 (2008)

Here, the inkjet method can adjust the coating amount of the curable composition in accordance with the roughness of the pattern, so that the variation in the thickness of the remaining film can be reduced and the pattern quality can be advantageously improved. In addition, compared with the spin coating method, the utilization efficiency of the material is high, and there is also an advantage of reducing the production cost and reducing the environmental load. However, if the inkjet discharge is not stably performed with good precision, problems such as poor filling of the curable composition and variation in thickness of the residual film occur.

On the other hand, the inventors of the present invention have conducted intensive studies on the prior art. When the non-reactive fluorinated compound described in Non-Patent Document 4 is contained in the curable composition for optical imprint, the releasing property is improved to some extent. It was found that the precision and releasability could not be achieved at the same time, and that the inkjet ejection accuracy and releasability of the curable composition deteriorated remarkably with the passage of time. The curable composition for optical imprint containing the fluorine-containing monomer described in Non-Patent Document 4 was not at a level that can satisfy the releasability.

Disclosure of the Invention An object of the present invention is to provide a curable composition for optical imprinting which is excellent in inkjet ejection accuracy and releasability, and in particular, to provide a curable composition for optical imprint that is excellent in stability with time of inkjet ejection precision and releasability . It is also an object of the present invention to provide a pattern forming method and a pattern.

Under these circumstances, the inventors of the present invention have conducted intensive studies, and as a result, they have found that ink-jet ejection accuracy and releasability and stability over time are improved by containing a specific fluorine compound in the curable composition for optical imprint. .

More specifically, according to the following solving means <1>, preferably, the above-mentioned problems are solved by means <2> to <15>.

&Lt; 1 > A photosensitive composition comprising a polymerizable compound, a photopolymerization initiator, and a fluorinated compound,

Wherein the fluorinated compound is represented by the following general formula (I);

The compound of formula (I)

[Chemical Formula 1]

In the general formula (I), Rf ¹ represents a fluorinated alkyl group having 1 to 6 carbon atoms and two or more fluorine atoms; R ¹ represents an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 8 carbon atoms; m represents an integer of 0 to 2, and n represents an integer of 1 to 3; When n represents 2 or 3, Rf ¹ may be different from each other.

&Lt; 2 > The curable composition for optical imprinting according to < 1 >, wherein the fluorinated compound is contained in an amount of 1 to 5 mass% based on the total components excluding the solvent.

<3> The curable composition for optical imprinting according to <1> or <2>, wherein in the general formula (I), Rf ¹ is a perfluoroalkyl group having 4 to 6 carbon atoms.

<4> The curable composition for optical imprinting according to any one of <1> to <3>, wherein R ¹ in the general formula (I) is an alkyl group having 1 to 7 carbon atoms.

<5> The curable composition for optical imprinting according to any one of <1> to <4>, wherein the polymerizable compound is a (meth) acrylate compound.

<6> The optical imprinting method according to any one of <1> to <5>, wherein the polymerizable compound contains 40 to 100% by mass of a polymerizable compound having two (meth) Curable composition.

<7> The curable composition for optical imprinting according to <6>, wherein the polymerizable compound contains a polymerizable compound having one (meth) acrylate group in an amount of 10 to 45 mass% with respect to the total polymerizable compound.

<8> The curable composition for optical imprinting according to any one of <1> to <7>, wherein the curable composition for optical imprint further contains a non-polymerizable compound having a polyalkyleneglycol structure.

<9> The curable composition for optical imprinting according to <8>, wherein the non-polymerizable compound having a polyalkyleneglycol structure is represented by the following formula (II).

In general formula (II)

(2)

In the general formula (II), Rf ² and Rf ³ each independently represent a fluorinated alkyl group having 1 to 6 carbon atoms and at least two fluorine atoms; p ¹ and p ² each independently represent an integer of 1 to 3, q ¹ and q ² each independently represent an integer of 0 to 2, r represents an integer of 2 to 4, s represents an integer of 6 to 20, .

<10> The optical imprint according to <8> or <9>, wherein the mass ratio of the fluorine compound represented by the general formula (I) and the non-polymerizable compound having a polyalkylene glycol structure is 1: 5 to 5: Curable composition;

<11> The curable composition for optical imprinting according to any one of <1> to <10>, wherein the curable composition for optical imprinting contains substantially no solvent.

<12> The curable composition for optical imprinting according to any one of <1> to <11>, wherein the curable composition for optical imprint has a viscosity at 23 ° C. of 15 mPa · s or less and a surface tension of 25 to 35 mN / m.

&Lt; 13 > A curable composition for optical imprinting as described in any one of < 1 > to < 12 >, which is applied onto a mold having a substrate or a pattern and the curable composition for optical imprint is sandwiched between the mold and the substrate, Wherein the pattern forming step comprises:

<14> The pattern forming method according to <13>, wherein the method of applying the composition on a substrate having a pattern or a pattern of the curable composition for optical imprint is an inkjet method.

&Lt; 15 > A pattern obtained by the pattern formation method according to < 13 > or < 14 >.

According to the present invention, it becomes possible to provide a curable composition for optical imprinting which is excellent in inkjet ejection accuracy and releasability, particularly, a curable composition for optical imprint that is excellent in stability with time of inkjet ejection accuracy and releasability. It is also possible to provide a pattern forming method and a pattern.

Hereinafter, the contents of the present invention will be described in detail. Descriptions of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, "~" is used to mean the numerical values described before and after the lower limit and the upper limit.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acryl and methacryl, "(meth) acryloyl" And methacryloyl. In the present specification, the terms "monomer" and "monomer" are synonyms. 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 less than 1,000. In the present specification, the term "functional group" refers to a group involved in the polymerization reaction. The term "imprint" in the present invention refers to pattern transfer of a size of 1 nm to 100 μm, and more preferably, pattern transfer of a size (nanoimprint) of 10 nm to 1 μm.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acryl and methacryl, "(meth) acryloyl" And methacryloyl. In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of less than 1000. In the present specification, the term "functional group" refers to a group involved in the polymerization reaction. The term "imprint" in the present invention refers to pattern transfer of a size of preferably 1 nm to 100 μm, and more preferably, pattern transfer of a size (nanoimprint) of 10 nm to 1 μm.

In the notation of the group (atomic group) in the specification of the present specification, the notation in which substitution and non-substitution are not described includes a group having a substituent and a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, the term "light" includes not only electromagnetic waves but also radiation of wavelengths in the ultraviolet, extinction, non-atomic, visible, and infrared regions. Radiation includes, for example, microwave, electron beam, EUV, and X-ray. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can also be used. These lights may be monochromatic light (single wavelength light) through an optical filter, or light having a plurality of different wavelengths (composite light).

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.

<Curable composition for optical imprint of the present invention>

The curable composition for optical imprint of the present invention (hereinafter occasionally referred to simply as "the curable composition of the present invention" or "the composition of the present invention") comprises a polymerizable compound (A), a photopolymerization initiator (B) Contains the fluorine compound (C) represented by the general formula (I).

The compound of formula (I)

(3)

In the general formula (I), Rf ¹ represents a fluorinated alkyl group having 1 to 6 carbon atoms and two or more fluorine atoms; R ¹ represents an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 8 carbon atoms; m represents an integer of 0 to 2, and n represents an integer of 1 to 3; When n represents 2 or 3, Rf ¹ may be different from each other.

According to the present invention, it is possible to provide a curable composition for optical imprint, which is excellent in inkjet ejection accuracy and releasability, particularly, a curable composition for optical imprint which is excellent in stability with time of inkjet ejection precision and releasability. Although this mechanism is not clear, it is preferable that the carbon atom adjacent to Rf ¹ in the general formula (I) does not have a fluorine atom and that R ¹ in the general formula (I) is an alkyl group having 1 to 7 carbon atoms or an alkyl group having 6 to 8 carbon atoms By being an aryl group, it is possible to suppress the hydrolysis of the fluorinated compound, and the stability of the inkjet discharge accuracy and the releasability over time can be improved.

&Lt; Polymerizable compound (A) >

The polymerizable compound used in the curable composition of the present invention is not particularly limited as long as it does not deviate from the object of the present invention. For example, a polymerizable unsaturated monomer having 1 to 6 groups containing an ethylenic unsaturated bond; Epoxy compounds, oxetane compounds; Vinyl ether compounds; Styrene derivatives; Propenyl ether; View teneters, and the like. Specific examples of the polymerizable compound (A) include those described in paragraphs 0020 to 0098 of Japanese Laid-Open Patent Publication No. 2011-231308, the contents of which are incorporated herein by reference.

Specific examples of the polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, N-vinylpyrrolidinone, Hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate (Meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, 1- or 2-naphthyl (Meth) acrylate (Meth) acrylate, isopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylate, isomyristyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) (Meth) acrylate, methoxy dipropylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy triethylene glycol (Meth) acrylate, neopentylglycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate (Meth) acrylate, phenoxyethyl (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate, phenoxyethyl , Phenoxy diethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, polyethylene glycol (meth) (Meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, ) Acrylate, EO-modified tribromide (meth) acrylate, dodecyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropranylphenol, N-vinylpyrrolidone, The pro-lactam and the like.

Among monofunctional polymerizable monomers containing an ethylenically unsaturated bond, it is preferable in the present invention to use a monofunctional (meth) acrylate compound from the viewpoint of photo-curability. Examples of the monofunctional (meth) acrylate compound include monofunctional (meth) acrylate compounds exemplified as monofunctional polymerizable monomers containing an ethylenic unsaturated bond.

Of the monofunctional (meth) acrylate compounds, monofunctional (meth) acrylates having an aromatic structure and / or an alicyclic hydrocarbon structure are preferable from the viewpoint of dry etching resistance, and monofunctional (meth) acrylates having an aromatic structure The rate is more preferred.

Among these monofunctional (meth) acrylates having an aromatic structure and / or alicyclic hydrocarbon structure, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, benzyl Acrylate, 1- or 2-naphthylmethyl (meth) acrylate (preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group) Acrylate, dicyclopentanyloxy (meth) acrylate, isobornyl (meth) acrylate, isobornyl (meth) acrylate, Adamantyl (meth) acrylate, benzyl (meth) acrylate, benzyl (meth) acrylate having a substituent on the aromatic ring, and monofunctional (meth) acrylate compounds having a naphthalene structure are more preferable, 1- or 2- Butyl (meth) acrylate is particularly preferred, 1 or 2-naphthyl (meth) acrylate.

In the present invention, as the polymerizable monomer, it is also preferable to use a polyfunctional polymerizable unsaturated monomer having two or more ethylenic unsaturated bond-containing groups.

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 monoethylether (meth) acrylate, dimethylol dicyclopentane di (Meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonene diol di (meth) Acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO- rope Neopentylglycol di (meth) acrylate, EO-modified neopentylglycol diacrylate, propylene oxide (hereinafter referred to as "PO (Meth) acrylate, ECH-modified phthalic acid di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, caprolactone-modified hydroxypropionic acid ester neopentyl glycol (Meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) (Meth) acrylate, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, silicone die (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, neopentylglycol modified tri (Meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol (Meth) acrylate, divinylethylene urea, divinylpropylene urea, o-, m-, p-xylylenedi (meth) acrylate, 1,3-adamantane diacrylate, norbornene dimethanol Diacrylate, and m-xylylene bis (meth) acrylate.

Among them, particularly preferred is at least one selected from the group consisting of neopentyl glycol di (meth) acrylate, 1,9-nonene diol di (meth) acrylate, tripropylene glycol di (meth) (Meth) acrylate, hydroxypivalic acid neopentylglycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, o-, m-, , m-, p-xylylene di (meth) acrylate, and the like are suitably used in the present invention.

As the polymerizable compound used in the curable composition of the present invention, a (meth) acrylate compound is preferable, and a (meth) acrylate compound having an alicyclic hydrocarbon group and / or an aromatic group is more preferable from the viewpoint of etching resistance And a (meth) acrylate compound having an aromatic group is more preferable.

The (meth) acrylate compound preferably contains a compound having two (meth) acrylate groups, and preferably includes a compound having one (meth) acrylate group and a compound having two (meth) Is more preferable.

The compound having two (meth) acrylate groups preferably has a molecular weight of 100 to 500, more preferably 170 to 300. The compound having two (meth) acrylate groups is preferably represented by, for example, the formula "A ¹ -LA ² ". In the formula, A ¹ and A ² each independently represent a (meth) acrylate group, and L represents a divalent linking group. The divalent linking group is preferably a group consisting of an alkylene group, an arylene group, or a combination thereof. The carbon number of the divalent linking group is preferably 2 to 20, more preferably 4 to 12, and still more preferably 5 to 10.

The compound having one (meth) acrylate group preferably has a molecular weight of 100 to 500, more preferably 170 to 400, further preferably 200 to 300. The compound having one (meth) acrylate group is preferably represented by, for example, the formula "A ¹ -LH". Here, A ¹ and L in the formula is the (meth) and A ¹ and L and copper in the equation "A ¹ -LA ^2" of the compound having two acrylate groups, are also the same preferable range. H is a hydrogen atom.

The curable composition of the present invention may contain a polymerizable compound having a silicon atom and / or a fluorine atom. Examples of the polymerizable compound having a fluorine atom include a polymerizable compound having a fluorinated alkyl group having 1 to 9 carbon atoms. The polymerizable group includes, for example, a (meth) acrylate group. As the polymerizable compound having a fluorine atom, reference can be made, for example, to the description in paragraphs 0022 to 0023 of International Patent Publication No. 2010/137724, the contents of which are incorporated herein by reference.

In the present invention, on the other hand, it is also preferable to make it not substantially contain a polymerizable compound having a silicon atom and / or a fluorine atom. In the present invention, since the fluorinated compound represented by the general formula (I) is blended, even in the case of not substantially containing the polymerizable compound having a silicon atom and / or a fluorine atom, inkjet discharge accuracy and releasability, The stability can be improved. The term "substantially not containing" means, for example, 1% by mass or less based on the total amount of the fluorine compound represented by formula (I).

The total amount of the polymerizable compound having one (meth) acrylate group in the entire polymerizable compound contained in the curable composition of the present invention is preferably 60% by mass or less, more preferably 45% by mass or less More preferably 35% by mass or less. The lower limit value is preferably 5% by mass or more, and more preferably 10% by mass or more. By blending a polymerizable compound having one (meth) acrylate group, the pattern formability can be further improved. The sum of the polymerizable compounds having two (meth) acrylate groups is preferably 40 to 100 mass%, more preferably 55 to 95 mass%, and still more preferably 65 to 90 mass% %to be.

The total amount of the polymerizable compound having an alicyclic hydrocarbon group and / or aromatic group in the total polymerizable compound contained in the curable composition of the present invention is preferably 30 to 100% by mass of the total polymerizable compound, Preferably 50 to 100% by mass, and more preferably 60 to 100% by mass.

(Meth) acrylate polymerizable compound containing an aromatic group as a polymerizable compound is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and more preferably 60 to 100% by mass of the total polymerizable component Is particularly preferable.

Particularly preferred embodiments are those wherein the amount of the polymerizable compound (A1) is from 0 to 60% by mass, more preferably from 5 to 45% by mass, and still more preferably from 10 to 40% by mass of the total polymerizable component The amount of the polymerizable compound (A2) is 40 to 100% by mass, more preferably 55 to 95% by mass, and more preferably 60 to 90% by mass of the total polymerizable component.

(A1) a polymerizable compound having a linear or branched alkyl group having 10 to 20 carbon atoms and a (meth) acrylate group, or a linear or branched alkyl group-substituted aromatic group having 1 to 12 carbon atoms and (meth) A polymerizable compound having one group

(A2) an aromatic group (preferably a phenyl group, a naphthyl group, a phenylene group, more preferably a phenylene group) and a polymerizable compound having two (meth) acrylate groups

The polymerizable compounds may be used alone or in combination of two or more.

In the pattern inversion method described later, it is preferable not to have etching resistance.

&Lt; Photopolymerization initiator (B) >

The curable composition of the present invention includes a photopolymerization initiator. The photopolymerization initiator used in the present invention may be any compound that generates an active species that polymerizes the above-mentioned polymerizable compound by light irradiation. As the photopolymerization initiator, a radical polymerization initiator and a cation polymerization initiator are preferable, and a radical polymerization initiator is more preferable. In the present invention, a plurality of photopolymerization initiators may be used in combination.

As the radical photopolymerization initiator used in the present invention, for example, commercially available initiators can be used. For example, those described in Japanese Patent Application Laid-Open No. 2008-105414, paragraph number 0091, can be preferably employed. Particularly, among these, an acetophenone compound, an acylphosphine oxide compound, and an oxime ester compound are preferable from the viewpoints of curing sensitivity and absorption characteristics.

The photopolymerization initiator may be used alone or in combination of two or more. When two or more species are used in combination, it is more preferable to use two or more radical polymerization initiators in combination. Concretely, there are listed DERACURE (registered trademark) 1173, IRGACURE (registered trademark) 907, DERACURE 1173 and LUCYRIN (registered trademark) TPO, DERACURE 1173, IRGACURE 819, DERACURE 1173 A combination of Irgacure (registered trademark) OXE01, Irgacure 907, Lucillin TPO, Irgacure 907 and Irgacure 819 are exemplified. With such a combination, the exposure margin can be further widened.

The ratio (mass ratio) is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and more preferably 7: 3 to 3: 7 in the case of using a photopolymerization initiator in combination.

The content of the photopolymerization initiator used in the present invention is preferably from 0.01 to 15% by mass, more preferably from 0.1 to 10% by mass, in the total composition excluding the solvent, i.e., from the total solid content of the curable composition of the present invention , More preferably from 0.5 to 7 mass%. When two or more kinds of photopolymerization initiators are used, the total amount is in the above range. When the content of the photopolymerization initiator is 0.01 mass% or more, the sensitivity (fast curability), resolution, line edge roughness, and film strength tend to be improved, which is preferable. When the content of the photopolymerization initiator is 15 mass% or less, light transmittance, coloring property, handling property and the like tend to be further improved, which is preferable.

&Lt; Fluorine compound (C) >

The curable composition of the present invention includes a fluorine compound (C) represented by the following general formula (I). By using such fluorinated compound (C), the releasability, inkjet ejection accuracy and aging stability of the curable composition of the present invention can be improved.

The compound of formula (I)

[Chemical Formula 4]

In the general formula (I), Rf ¹ represents a fluorinated alkyl group having 1 to 6 carbon atoms and two or more fluorine atoms; R ¹ represents an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 8 carbon atoms; m represents an integer of 0 to 2, and n represents an integer of 1 to 3; When n represents 2 or 3, Rf ¹ may be different from each other.

In the general formula (I), Rf ¹ represents a fluorinated alkyl group having 1 to 6 carbon atoms and two or more fluorine atoms. Rf ¹ may be any of linear, branched and cyclic, but is preferably straight-chain or branched, more preferably straight-chain.

The carbon number of Rf ¹ is more preferably from 3 to 6, still more preferably from 4 to 6, and particularly preferably from 5 or 6.

The structure of the terminal of Rf ¹ is preferably -CF ₃ or -C (HF ₂ ), particularly preferably -CF ₃ .

The substitution ratio of fluorine atoms in Rf ¹ is preferably 80 to 100%, more preferably 90 to 100%, further preferably 100% (perfluoroalkyl group). For example, Rf ¹ is preferably a perfluoroalkyl group having 4 to 6 carbon atoms. The substitution ratio of fluorine atoms means the ratio (%) of the alkyl groups having 1 to 6 carbon atoms in which hydrogen atoms are substituted by fluorine atoms.

Specific examples of Rf _{^1, -CF 3, CF 3 CF 2} -, CF 3 (CF 2) 2 -, CF 3 (CF 2) 3 -, CF 3 (CF 2) 4 -, CF 3 (CF 2) 5 _{-, (CF 3) 2 CH-} , (CF 3) 2 C (CH 3) -, (CF 3) 2 CF (CF 2) 2 -, (CF 3) 2 CF (CF 2) 4 -, H ( CF ₂ ) ₂ -, H (CF ₂ ) ₄ -, H (CF ₂ ) ₆ - and the like. Among them, CF ₃ (CF ₂ ) ₄ -, CF ₃ (CF ₂ ) ₅ - and H (CF ₂ ) ₆ - are more preferable, and CF ₃ (CF ₂ ) ₅ - is particularly preferable.

In the general formula (I), R ¹ represents an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 8 carbon atoms, preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. R ¹ may be any of linear, branched and cyclic, but is preferably straight-chain or branched, more preferably straight-chain.

The carbon number of the aryl group having 6 to 18 carbon atoms is preferably 6 to 8, more preferably 6.

Specific examples of R ¹ include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n- A t-butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, and a benzyl group. Among them, a methyl group, an ethyl group, an n-propyl group and an isopropyl group are more preferable, and a methyl group or an ethyl group is more preferable, and an ethyl group is particularly preferable.

In the general formula (I), m represents an integer of 0 to 2, preferably 1 or 2, and more preferably 1.

n represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

Specific preferred examples of the fluorine compound (C) include the following compounds C-1 to C-15, but the fluorine compound (C) used in the present invention is not limited to these compounds.

[Chemical Formula 5]

The molecular weight of the fluorine compound (C) is preferably from 140 to 550, more preferably from 200 to 500, still more preferably from 400 to 450.

The content of the fluorine-containing compound (C) in the curable composition of the present invention is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and more preferably 1 to 3% by mass desirable. When the content of the fluorine compound (C) is 1% by mass or more, the releasability is further improved. When the content of the fluorine-containing compound (C) is 10 mass% or less, the pattern roughness becomes better. The fluorine compound (C) may be used alone, or two or more thereof may be used in combination. When two or more kinds of fluorine compounds (C) are used, the total amount is in the above range.

<Non-polymerizable compound (D) having a polyalkyleneglycol structure>

The curable composition of the present invention preferably contains a non-polymerizable compound (D) having a polyalkyleneglycol structure in order to improve the releasability. Here, the non-polymer compound means a compound having no polymerizable group.

As the polyalkylene structure, a polyethylene glycol structure, a polypropylene glycol structure, a polybutylene glycol structure, or a mixed structure thereof is more preferable, and a polyethylene glycol structure or a polypropylene glycol structure More preferable. It is also preferable that the polyglycerol such as glycerin or pentaerythritol be a branched core.

The polyalkylene glycol structure preferably has 3 to 30 alkylene glycol constituent units, more preferably 5 to 20, more preferably 7 to 15, and most preferably 9 to 13 It is particularly preferable to have such a structure.

At least one of the terminal hydroxyl groups of the polyalkyleneglycol structure may be substituted with an organic group, and all the hydroxyl groups may be substituted. The organic group to be substituted is preferably an organic group having 1 to 20 carbon atoms, more preferably an oxygen atom, a fluorine atom, or a silicon atom. The substituted organic group is linked to the polyalkylene glycol structure through an ether bond, an ester bond, or a divalent linking group. Specific examples of the substituted organic group include a hydrocarbon group such as a methyl group, an ethyl group, a butyl group, an allyl group, a benzyl group and a phenyl group, a fluorinated alkyl group, a fluorinated alkylether group and a polysyloxetyl group.

The number average molecular weight of the non-polymerizable compound (D) is preferably 300 to 3000, more preferably 400 to 2000, and still more preferably 500 to 1500.

Specific examples of the preferred non-polymerizable compound (D) include polyethylene glycol, polypropylene glycol, polyethylene glycol glyceryl ether, polypropylene glycol glyceryl ether, methyl etherified products thereof, acetylated products thereof , And fluorine compounds represented by the following general formula (II).

In general formula (II)

[Chemical Formula 6]

In the general formula (II), Rf ² and Rf ³ each independently represent a fluorinated alkyl group having 1 to 6 carbon atoms and at least two fluorine atoms; p ¹ and p ² each independently represent an integer of 1 to 3, q ¹ and q ² each independently represent an integer of 0 to 2, r represents an integer of 2 to 4, s represents an integer of 6 to 20, .

The preferable range of Rf ² and Rf ^{3 in} the general formula (II) is the same as the preferable range of Rf ^{1 in} the general formula (I), and the preferable ranges of Rf ² and Rf ³ and the specific examples are also the same.

In the general formula (II), p ¹ and p ² each independently represent an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

q ¹ and q ² each independently represent an integer of 0 to 2, preferably 1 or 2, and more preferably 1.

r represents an integer of 2 to 4, preferably 2 or 3, and more preferably 2.

s represents 6 to 20, preferably 7 to 15, and more preferably 9 to 13.

With respect to the non-polymerizable compound (D), reference can be made to the description in paragraphs 0105 to 0106 of Japanese Laid-Open Patent Publication No. 2013-036027, the contents of which are incorporated herein by reference.

The content of the non-polymerizable compound (D) is preferably from 1 to 10 mass%, more preferably from 2 to 8 mass%, still more preferably from 3 to 7 mass%, and even more preferably from 4 to 6 mass% Is particularly preferable.

In the curable composition of the present invention, the mass ratio of the fluorine compound represented by the formula (I) and the non-polymerizable compound having a polyalkylene glycol structure is preferably 1: 5 to 5: 5, more preferably 1: : 5 to 2: 5 is more preferable. By setting this range, the effect of the present invention can be achieved more effectively.

<Polymerization inhibitor>

The curable composition of the present invention preferably contains a polymerization inhibitor. The content of the polymerization inhibitor is preferably from 0.001 to 0.1% by mass, more preferably from 0.005 to 0.08% by mass, and even more preferably from 0.01 to 0.05% by mass, based on the total polymerizable monomer, The viscosity change due to aging can be suppressed while maintaining high curing sensitivity. The polymerization inhibitor may be added at the time of production of the polymerizable monomer, or may be added later to the curing composition of the present invention. Specific examples of the polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical. Specific examples of other polymerization inhibitors include those described in paragraph [0121] of Japanese Laid-Open Patent Publication No. 2012-169462, which disclosure is incorporated herein by reference.

<Surfactant>

The curable composition of the present invention may contain a surfactant, if necessary. Generally, a surfactant is a substance that has a hydrophobic portion and a hydrophilic portion in a molecule, and remarkably changes the properties of the interface by adding a small amount. The surfactant in the present invention is a substance having a hydrophobic part and a hydrophobic part in the molecule and remarkably lowering the surface tension of the curable composition by the addition of a small amount. For example, the surfactant may be added in an amount of 1% And lowering the surface tension of the curable composition from 40 mN / m to 30 mN / m or lower. When the surfactant is contained in the curable composition of the present invention, the effect of improving uniformity of coating and the effect of improving releasability can be expected.

The surfactant used in the present invention is preferably a nonionic surfactant and preferably contains at least one of a fluorine-based surfactant, a Si-based surfactant and a fluorine-Si-based surfactant, and the fluorine-based nonionic surface- desirable. Here, the term "fluorine-Si surfactant" refers to both fluorine surfactant and Si surfactant.

Examples of the fluorine-based nonionic surfactant that can be used in the present invention include Fluorad (Sumitomo 3M), Megapak (DIC), Surfron (AGC Seimei Chemical), Unidyne (Daikin Kogyo), Fotogen , Poly Fox (OMNOVA), Capstone (DuPont), and the like can be cited as examples of such materials as polytetrafluoroethylene (polytetrafluoroethylene), polytetrafluoroethylene (polytetrafluoroethylene), polytetrafluoroethylene .

The content of the surfactant used in the present invention is, for example, preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, and further preferably 1 to 3% by mass in the total composition. The surfactant may be used alone, or two or more surfactants may be used in combination. When two or more kinds of surfactants are used, the total amount is in the above range. When the surfactant is in the range of 0.01 to 5% by mass in the curable composition of the present invention, the effect of uniformity of application is good and it is difficult to cause deterioration of the mold transfer characteristics due to excessive surfactant.

In the present invention, by mixing the fluorine compound represented by the general formula (I), even when the surfactant is substantially not contained, a low releasing force can be achieved. The term "substantially not containing" means, for example, 1% by mass or less based on the total amount of the fluorine compound represented by formula (I).

<Other ingredients>

The curable composition of the present invention may contain, in addition to the above components, a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antioxidant, a plasticizer, a contact promoter, a thermal polymerization initiator, , An elastomer particle, a basic compound, a photoacid generator, a photo acid generator, a chain transfer agent, an antistatic agent, a flow regulator, a defoaming agent, a dispersing agent and the like. Specific examples of such components include those described in Japanese Patent Application Laid-Open No. 2008-105414, paragraphs 0092 to 0093, and paragraphs 0113 to 0137, the contents of which are incorporated herein by reference.

In the present invention, by blending the fluorinated compound represented by the general formula (I), a fluorinated surfactant, a fluorinated silane coupling agent, a fluorinated monomer, or a non-reactive fluorinated compound described in Non-Patent Document 4 can be substantially Even in the mode not including it, a low releasing force can be achieved. In addition, in the present invention, since the non-reactive fluorinated compound described in Non-Patent Document 4 is not substantially contained, the stability with time of the curable composition can be improved and deterioration of the ink jet discharge accuracy can be suppressed. The term "substantially not containing" means, for example, 1% by mass or less of the compounding amount of the fluorine compound represented by formula (I).

<Solvent>

The curable composition of the present invention may contain a solvent. The content of the solvent in the curable composition of the present invention is preferably 5 mass% or less, more preferably 3 mass% or less, and particularly preferably substantially free of solvent. Here, substantially no solvent means, for example, 1% by mass or less based on the total mass of the curable composition of the present invention. When the curable composition of the present invention is coated on a substrate by an ink-jet method, it is preferable that the blending amount of the solvent is small because the viscosity change of the composition due to the volatilization of the solvent can be suppressed.

As described above, the curable composition of the present invention does not necessarily contain a solvent, but may be optionally added when the viscosity of the composition is finely adjusted. The solvent which can be preferably used in the curable composition of the present invention is a solvent which is generally used in a curable composition for optical imprint or a photoresist and which dissolves and uniformly disperses the compound used in the present invention, Is not particularly limited as long as it does not react with the component. Examples of the solvent that can be used in the present invention include those described in paragraph [0088] of Japanese Laid-Open Patent Publication No. 2008-105414, the contents of which are incorporated herein by reference.

The curable composition of the present invention can be adjusted by mixing the respective components described above. The mixing and dissolution of the curable composition of the present invention is usually carried out in the range of 0 ° C to 100 ° C. Further, it is preferable that the components are mixed and then filtered with a filter having a pore diameter of 0.003 μm to 1.0 μm, for example. The filtration may be performed in multiple steps or repeated a plurality of times. In addition, the filtrate may be re-filtered. As the material of the filter used for filtration, a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, or the like can be used, but it is not particularly limited.

The curable composition of the present invention preferably has a viscosity of 15 mPa · s or less at 23 ° C., more preferably 12 mPa · s or less, further preferably 11 mPa · s or less, particularly preferably 10 mPa · s or less. By setting to such a range, it is possible to improve inkjet ejection accuracy and pattern formation property. In the curable composition of the present invention, it is preferable to blend, as the polymerizable compound (A), which functions as a reaction diluent in order to reduce the blending amount of the solvent and thus reduce the viscosity. As the polymerizable compound serving as a reactive diluent, for example, a polymerizable compound having one (meth) acrylate group is exemplified.

The surface tension of the curable composition of the present invention is preferably 25 to 35 mN / m, more preferably 27 to 34 mN / m, even more preferably 28 to 32 mN / m, still more preferably 29 to 31 mN / m Is particularly preferable. By setting to such a range, the inkjet ejection accuracy and surface smoothness can be improved. In particular, the curable composition of the present invention preferably has a viscosity of 15 mPa · s or less at 23 ° C. and a surface tension of 25 to 35 mN / m, more preferably a viscosity of 11 mPa · s or less and a surface tension of 28 to 32 mN / m More preferably a viscosity of 10 mPa · s or less and a surface tension of 29 to 31 mN / m.

&Lt; Pattern formation method >

Hereinafter, a pattern forming method (pattern transfer method) using the curable composition of the present invention will be described in detail. In the pattern forming method of the present invention, first, the curable composition of the present invention is applied onto a mold having a substrate or pattern, and the curable composition of the present invention is irradiated with light interposed between the mold and the substrate.

As a method of applying the curable composition of the present invention on a substrate, there can be used a known coating method such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, A coating film or a droplet can be arranged on a substrate by using a coating method, a spin coating method, a slit scanning method, or an ink jet method. In particular, since the curable composition of the present invention contains the fluorine compound (C) represented by the above-mentioned general formula (I), even when the inkjet method is used, the inkjet dischargeability can be improved.

When the curable composition of the present invention is sandwiched between a mold and a substrate, helium may be introduced between the mold and the substrate. By using such a method, the permeation of the quartz mold of the gas can be promoted, and the disappearance of the residual bubbles can be promoted. In addition, by inhibiting the dissolved oxygen in the curable composition, inhibition of radical polymerization in exposure can be suppressed. Instead of helium, a condensable gas may be introduced between the mold and the substrate. By using such a method, the disappearance of the residual bubbles can be further promoted by utilizing the fact that the introduced condensable gas is condensed and the volume is reduced. The condensable gas means a gas which is condensed by the temperature or the pressure. For example, trichlorofluoromethane, 1,1,1,3,3-pentafluoropropane and the like can be used. As for the condensable gas, reference can be made, for example, to paragraphs 0023 and 05 of JP-A No. 2004-103817 and paragraph No. 0003 of JP-A No. 2013-254783, the contents of which are incorporated herein by reference.

When exposed, the exposure light intensity is preferably in the range of 1 mW / cm ² to 200 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 200 mW / cm ² or less, deterioration of the properties of the cured film due to occurrence of side reactions tends to be suppressed . The exposure dose is preferably in the range of ⁵ mJ / cm ² to 1000 mJ / cm ² . If it is less than 5 mJ / cm ² , the exposure margin becomes narrow, and the photo-curing becomes insufficient, and problems such as adhesion of unreacted matters to the mold are likely to occur. On the other hand, if it exceeds 1000 mJ / cm ² , there is a fear of deterioration of the cured film due to decomposition of the composition.

It is preferable that an inert gas such as nitrogen, helium, argon, carbon dioxide or the like is allowed to flow to control the oxygen concentration in the atmosphere to 10 kPa or less in order to suppress radical polymerization inhibition by oxygen when exposed. More preferably, the oxygen concentration in the atmosphere is 3 kPa or less, more preferably 1 kPa or less.

The pattern forming method of the present invention may include a step of curing the pattern forming layer (the layer comprising the curable composition of the present invention) by light irradiation, and then curing the pattern by applying heat to the cured pattern, if necessary . The heat for curing the curable 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.

Specific examples of the pattern forming method include those described in paragraphs 0125 to 0136 of Japanese Laid-Open Patent Publication No. 2012-169462, which is incorporated herein by reference.

The pattern forming method of the present invention can be applied to the pattern inversion method. Specifically, a resist pattern is formed on a substrate to be processed having a carbon film (SOC) by a pattern forming method of the present invention. Next, after covering the resist pattern with a Si-containing film (SOG), the top of the Si-containing film is etched back to expose the resist pattern, and the exposed resist pattern is removed by oxygen plasma or the like, . Further, with the use of the inversion pattern of the Si-containing film as an etching mask, the carbon film in the lower layer is etched, and the reverse pattern is transferred to the carbon film. Finally, the substrate is etched using the carbon film transferred with the reversed pattern as an etching mask. As an example of such a method, reference can be made to Japanese Laid-Open Patent Publication Nos. 5-267253, 2002-110510, and 2006-521702, paragraphs 0016 to 0030, do.

The pattern forming method of the present invention is a method of forming a pattern, comprising the steps of forming a lower layer film by applying a lower layer film composition on a substrate, applying the curable composition of the present invention to the surface of the lower layer film, A step of curing the curable composition of the present invention by irradiating light in a state sandwiched between molds having a pattern, and a step of peeling off the mold. The curable composition of the present invention may be applied after a lower layer film composition is applied on a substrate and then a part of the lower layer film composition is cured by heat or light irradiation.

The subbing layer composition includes, for example, a curable main agent. The curable subject may be either thermosetting or photo-curable, preferably thermosetting. The molecular weight of the curable subject is preferably 400 or more, and may be a low molecular weight compound or a polymer, but a polymer is preferable. The molecular weight of the curable subject is preferably 500 or more, more preferably 1000 or more, and still more preferably 3000 or more. The upper limit of the molecular weight is preferably 200,000 or less, more preferably 100000 or less, and even more preferably 50,000 or less. When the molecular weight is 400 or more, the volatilization of the component can be suppressed more effectively. For example, those described in Japanese Patent Application Publication No. 2009-503139, paragraphs 0040 to 0056, which are incorporated herein by reference.

The content of the curable subject matter is preferably 30 mass% or more, more preferably 50 mass% or more, and most preferably 70 mass% or more, of all the components except for the solvent. The curable subject may be two or more kinds, and in this case, the total amount is preferably in the above range.

The lower layer film composition preferably contains a solvent. A preferable solvent is a solvent having a boiling point at normal pressure of 80 to 200 占 폚. The solvent may be any solvent capable of dissolving the lower layer film composition, preferably a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group and an ether structure. Specifically, preferred solvents are a single solvent or a mixed solvent selected from propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, gamma butyrolactone, propylene glycol monomethyl ether and ethyl lactate, A solvent containing propylene glycol monomethyl ether acetate is most preferable in view of coating uniformity.

The content of the above-mentioned solvent in the lower layer film composition is optimally adjusted by the viscosity of the component other than the solvent, the coating property and the intended film thickness. In view of improving the coating property, the content of the solvent is preferably 70% Preferably 90 mass% or more, more preferably 95 mass% or more, and further preferably 99 mass% or more.

The lower layer film composition may contain at least one of a surfactant, a thermal polymerization initiator, a polymerization inhibitor and a catalyst as other components. The blending amount thereof is preferably 50 mass% or less with respect to the total components excluding the solvent.

The lower layer film composition can be adjusted by mixing the respective components described above. Further, it is preferable to mix the above-mentioned components and then filter them with, for example, a filter having a pore diameter of 0.003 μm to 1.0 μm. The filtration may be performed in multiple steps or repeated a plurality of times. In addition, the filtrate may be re-filtered. As the material of the filter used for filtration, a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin, or the like can be used, but it is not particularly limited.

The lower layer film composition is applied on a substrate to form a lower layer film. Examples of the method of applying on the substrate include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, A coating film or a droplet can be disposed on a substrate by a method or the like. From the viewpoint of the uniformity of the film thickness, the spin coat method is more preferable. Thereafter, the solvent is dried. The preferred drying temperature is 70 ° C to 130 ° C. Preferably by further activating energy (preferably heat and / or light). Preferably at a temperature of 150 ° C to 250 ° C. The step of drying the solvent and the step of hardening may be performed at the same time. As described above, it is preferable to apply the curable composition of the present invention after applying the lower layer film composition and then curing a part of the lower layer film composition by heat or light irradiation. When such a means is employed, when the curable composition of the present invention is photo-cured, the lower layer film composition is also completely cured, and the adhesion tends to be further improved.

The thickness of the lower layer film made of the curable composition of the present invention is about 0.1 nm to 100 nm, preferably 1 nm to 20 nm, and more preferably 2 nm to 10 nm, although it varies depending on the intended use. Alternatively, the lower layer film composition may be applied by multiple application. The obtained lower layer film is preferably as flat as possible.

The substrate (substrate or support) may be selected depending on a variety of applications, and examples thereof include quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrate such as Ni, Cu, , A TFT array substrate, an electrode plate of a PDP, a glass or a transparent plastic substrate, a conductive substrate such as ITO or metal, an insulating substrate, a silicon substrate, a silicon substrate, , Silicon nitride, polysilicon, silicon oxide, amorphous silicon, and the like. However, in the case of being used for etching, as described later, a semiconductor fabrication substrate is preferable.

<Pattern>

As described above, the pattern formed by the pattern forming method 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.

In addition, the pattern using the curable composition of the present invention has good solvent resistance. The curable composition of the present invention preferably has a high resistance to various kinds of solvents. When the solvent is used in a general substrate production process, for example, immersing in a solvent of N-methylpyrrolidone at 25 DEG C for 10 minutes It is particularly preferable that the film thickness fluctuation does not occur.

The pattern formed by the pattern forming method of the present invention is also useful as an etching resist. In the case of using the curable composition of the present invention as an etching resist, first, by, for example, as a base material using a silicon wafer, such as a thin film such as SiO ₂ is formed, a fine pattern of a nano order by the pattern forming method of the present invention on a base material . 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. The curable composition of the present invention preferably has good etching resistance against dry etching using fluorocarbon or the like.

<Method of Manufacturing Semiconductor Device>

The method for manufacturing a semiconductor device of the present invention is characterized by using the above-described pattern as an etching mask. Using the above-described pattern as an etching mask, the base material is treated. For example, dry etching is performed using the pattern as an etching mask, and the upper layer portion of the substrate is selectively removed. By repeating this process for the substrate, a semiconductor device can be obtained. The semiconductor device is, for example, an LSI (large scale integrated circuit).

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Also, unless otherwise stated, "%" is on a mass basis.

&Lt; Synthesis of fluorine compound (C) >

The fluorine compounds (C-10) to (C-13) were synthesized by the methods described below.

Synthesis of fluorine compound (C-10)

(7)

18.2 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol (manufactured by Wako Pure Chemical Industries, Ltd.), 18.2 g of acetic anhydride ) And 50 mL of ethyl acetate were stirred and mixed in an ice bath, and 10.1 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise while keeping the internal temperature at 10 ° C or lower. After completion of the dropwise addition, the mixture was reacted at 25 DEG C for 6 hours, 150 mL of ethyl acetate and 100 mL of 2% aqueous sodium bicarbonate were added, and the mixture was stirred for 10 minutes. Thereafter, the organic layer obtained by separating was washed with 100 mL of 0.1N hydrochloric acid and then with 100 mL of pure water, and then concentrated under reduced pressure to obtain 19.1 g (yield 94%) of the desired fluorine compound (C-10) as a colorless liquid.

^{1 H-NMR (400MHz, CDCl} 3, TMS, δ = ppm): δ = 2.22 (s, 3H), 2.49 (m, 2H), 4.38 (t, 2H).

Synthesis of fluorine compound (C-11)

[Chemical Formula 8]

(Yield: 98%) was obtained as a colorless liquid (C-10) in the same manner as in the synthesis of the above fluorinated compound (C-10) except that 13.0 g of propionic acid anhydride .

^{1 H-NMR (400MHz, CDCl} 3, TMS, δ = ppm): δ = 1.15 (t, 3H), 2.35 (q, 2H), 2.47 (m, 2H), 4.38 (t, 2H).

Synthesis of fluorine compound (C-12)

[Chemical Formula 9]

22.6 g (yield: 92%) of the fluorine compound (C-12) was colorless as in the synthesis of the fluorine compound (C-10) except that 9.8 g of octanoic acid chloride (Wako Pure Chemical Industries) Liquid.

^{1 H-NMR (400MHz, CDCl} 3, TMS, δ = ppm): δ = 0.88 (t, 3H), 1.29 (m, 6H), 1.63 (m, 2H), 2.32 (t, 2H), 2.47 (m , &Lt; / RTI &gt; 2H), 4.38 (t, 2H).

Synthesis of fluorine compound (C-13)

[Chemical formula 10]

22.3 g (yield 95%) of a fluorine compound (C-13) was obtained in the same manner as the synthesis of the fluorine compound (C-10) except that 8.4 g of benzoyl chloride (Wako Pure Chemical Industries) was used.

^{1 H-NMR (400MHz, CDCl} 3, TMS, δ = ppm): δ = 2.61 (m, 2H), 4.63 (t, 2H), 7.45 (t, 2H), 7.58 (t, 1H), 8.04 (d , 2H).

&Lt; Preparation of curable composition for optical imprint &

The polymerizable compound (A), the photopolymerization initiator (B) and the fluorinated compound (C) were mixed at the mass ratio shown in the following Table 1, and 4-hydroxy-2,2,6,6-tetra Methylpiperidine-1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added so as to be 200 ppm (0.02 mass%) with respect to the curable composition. The resultant was filtered with a PTFE filter of 0.1 m to prepare curable compositions X-1 to X-10 and comparative curable compositions R-1 to R-4 for optical imprinting of the present invention. The viscosity and surface tension of the adjusted curable composition at 23 캜 were measured. Viscosity and surface tension at 23 占 폚 of the curable composition prepared were measured using an E-type viscometer RE85L (Toki-San bridge) and a surface tension meter CBVP-A3 (Kyowa Kaimengagaku).

[Table 1]

Details of the polymerizable compound (A), the photopolymerization initiator (B), the additive (D), and the comparative compound (S) used in Examples and Comparative Examples are as follows.

&Lt; Polymerizable compound (A) >

A-1: 2-phenoxyethyl acrylate (Viscot # 192, manufactured by Osaka Kikogaku Kogyo Co., Ltd.)

A-2: 4-isobutylbenzyl acrylate (synthesized from 4-isobutylbenzyl alcohol and acrylic acid chloride)

A-3: Dodecyl acrylate (Kyoeisha Chemical Co., Light Acrylate L-A)

A-4: Neopentylglycol diacrylate (Kyoeisha Chemical Co., Light Acrylate NP-A)

A-5: m-xylylene bisacrylate (synthesized with?,? '- dichloro-m-xylene and acrylic acid)

(11)

&Lt; Photopolymerization initiator (B) >

B-1: Irgacure 819 (manufactured by BASF)

B-2: DAROCURE 1173 (BASF)

The non-polymerizable compound (D) having a polyalkyleneglycol structure

D-1: Polypropylene glycol (number average molecular weight 700, manufactured by Wako Pure Chemical Industries, Ltd.)

D-2: A fluorine compound having the following structure (polyethylene glycol biscarboxylic methyl ether (number average molecular weight: 600, manufactured by Sigma-Aldrich) and 3,3,4,4,5,5,6,6,6 - Synthesis by dehydration condensation of nonafluorohexanol (manufactured by Tokyo Kasei Kogyo)

[Chemical Formula 12]

The comparative compound (S)

S-1: Methyl perfluorooctanoate (manufactured by Wako Pure Chemical Industries, Ltd.)

S-2: Acrylic acid 2- (perfluorooctyl) ethyl (manufactured by Tokyo Kasei Kogyo)

[Chemical Formula 13]

&Lt; Preparation of lower layer film composition >

3 g of NK Oligo EA-7140 / PGMAc (manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.) was dissolved in 997 g of propylene glycol monomethyl ether acetate, followed by filtration with a 0.1 μm tetrafluoroethylene filter to obtain a lower layer film composition.

[Chemical Formula 14]

NK Oligo EA-7140 / PGMAc (70% solids)

Average m + n = 4, average n / (m + n) = 0.5

(evaluation)

The following evaluations were performed on each of the obtained curable compositions for imprints of the examples and the comparative examples. The results are shown in Table 2 below.

<Inkjet Discharge Accuracy>

The curable composition for optical imprinting, the temperature of which was adjusted to 23 占 폚, was ejected onto a silicon wafer in an amount of 1 pl per nozzle using an inkjet printer DMP-2831 (manufactured by Fuji Film DYMATICS) The coating was applied so that the enemy was squarely arranged at intervals of 100 mu m.

2500 dots of 5 mm square on the coated substrate were observed and the deviation from the square array was measured to calculate the standard deviation sigma. The inkjet ejection accuracy was evaluated as A to D as follows.

A: σ <3 μm

B: 3 mu m &lt;

C: 5 m &lt;

D: 10 占 퐉?

&Lt; Evaluation of releasing property &

The lower layer film composition was spin-coated on a silicon wafer and heated on a hot plate at 100 占 폚 for 1 minute to dry the solvent. Further, the lower layer film composition was cured by heating on a hot plate at 220 占 폚 for 5 minutes to form a lower layer film. The film thickness of the lower layer film after curing was 3 nm.

The curable composition for optical imprinting, the temperature of which was adjusted to 23 占 폚, was ejected onto the surface of the lower layer film on the silicon wafer using an inkjet printer DMP-2831 (manufactured by Fuji Film DYMATICS) at a droplet amount of 1 pl per nozzle, The droplets were applied on the film so as to have a square arrangement with intervals of about 100 mu m.

A quartz mold (line / space = 1/1, line width of 30 nm, groove depth of 60 nm, line edge roughness of 3.0 nm) was brought into contact with the curable composition applied on the lower layer film under a reduced pressure of 0.1 atm to form a quartz mold And exposed under a condition of 100 mJ / cm ² using a high-pressure mercury lamp. After exposure, the quartz mold was separated, and the release force (F) at that time was measured. The releasing force F was measured in accordance with the method described in [0102] to [0107] of Japanese Laid-Open Patent Publication No. 2011-206977, and evaluated by S to E as follows. Further, C or more is a practical level.

S: F &lt; 12N

A: 12N? F <13N

B: 13N &lt; F &lt; 15N

C: 15N? F <20N

D: 20N? F <30N

E: 30N? F

<Evaluation of stability after 3 months storage>

The curable composition for optical imprint was stored in a material cartridge for an inkjet printer DMP-2831 in a state of being charged for 3 months, and then the inkjet discharge accuracy and releasability were evaluated.

[Table 2]

As is evident from the results of the table, the curable compositions for optical imprinting of Examples 1 to 10 showed no deterioration in ink jet discharge accuracy and releasability in comparison with the aged test before and after 3 months, all showing good performance.

In particular, when R ^{1 in the} general formula (I) is an alkyl group, it was found that the ink jet discharging property was superior to that of the aryl group. Further, by compounding the compound represented by the general formula (II), the ink-jet characteristics and the releasability were improved more effectively.

On the other hand, in the curable compositions for optical imprinting of Comparative Examples 1 and 2, the ink jet ejection accuracy and releasability deteriorated remarkably after 3 months.

The curable compositions for optical imprint of Comparative Example 3 and Comparative Example 4 were not at a level that can satisfy the releasability before the aging test.

As described above, according to the present invention, by containing the polymerizable compound (A), the photopolymerization initiator (B) and the fluorinated compound (C) represented by the general formula (I) in the curable composition for optical imprint, And a curable composition for an optical imprint excellent in releasability, particularly a curable composition for optical imprint which is excellent in stability with time of ink jet discharge precision and releasability.

It was also found that when the viscosity of the curable composition of the present invention is different from 1 mPa 占 퐏, it greatly influences the effect of the present invention. It was also found that the curable composition of the present invention largely influences the effect of the present invention when the surface tension is different, for example, 3 mN / m even if the viscosity is the same.

Claims (15)

A photopolymerizable composition comprising a polymerizable compound, a photopolymerization initiator and a fluorinated compound,
The curable composition for optical imprinting wherein the fluorinated compound is represented by the following general formula (I);
The compound of formula (I)
[Chemical Formula 1]

In the general formula (I), Rf ¹ represents a fluorinated alkyl group having 1 to 6 carbon atoms and two or more fluorine atoms; R ¹ represents an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 8 carbon atoms; m represents an integer of 0 to 2, and n represents an integer of 1 to 3; When n represents 2 or 3, Rf ¹ may be different from each other. The method according to claim 1,
Wherein the fluorine-containing compound is contained in an amount of 1 to 5 mass% with respect to the total components excluding the solvent. The method according to claim 1 or 2,
In the above general formula (I), Rf ¹ is a perfluoroalkyl group having 4 to 6 carbon atoms. The method according to any one of claims 1 to 3,
In the above general formula (I), R ¹ is an alkyl group having 1 to 7 carbon atoms. The method according to any one of claims 1 to 4,
Wherein the polymerizable compound is a (meth) acrylate compound. The method according to any one of claims 1 to 5,
Wherein the polymerizable compound contains a polymerizable compound having two (meth) acrylate groups in an amount of 40 to 100 mass% based on the total polymerizable compound. The method of claim 6,
Wherein the polymerizable compound contains a polymerizable compound having one (meth) acrylate group in an amount of 10 to 45 mass% based on the total polymerizable compound. The method according to any one of claims 1 to 7,
Wherein the curable composition for optical imprint further contains a non-polymerizable compound having a polyalkyleneglycol structure. The method of claim 8,
Wherein the non-polymerizable compound having a polyalkylene glycol structure is represented by the following general formula (II).
In general formula (II)
(2)

In the general formula (II), Rf ² and Rf ³ each independently represent a fluorinated alkyl group having 1 to 6 carbon atoms and at least two fluorine atoms; p ¹ and p ² each independently represent an integer of 1 to 3, q ¹ and q ² each independently represent an integer of 0 to 2, r represents an integer of 2 to 4, s represents an integer of 6 to 20, . The method according to claim 8 or 9,
Wherein the weight ratio of the fluorine compound represented by the general formula (I) to the non-polymerizable compound having the polyalkylene glycol structure is 1: 5 to 5: 5. The method according to any one of claims 1 to 10,
Wherein the curable composition for optical imprint is substantially solvent-free. The method according to any one of claims 1 to 11,
Wherein the curable composition for optical imprint has a viscosity of 15 mPa 占 퐏 or less and a surface tension of 25 to 35 mN / m at 23 占 폚. A curable composition for optical imprinting according to any one of claims 1 to 12 is applied on a mold having a substrate or a pattern and light irradiation is performed in a state that the curable composition for optical imprint is sandwiched between the mold and the substrate / RTI &gt; 14. The method of claim 13,
Wherein the method of applying on a substrate having a pattern or a pattern of a curable composition for optical imprint is an inkjet method. A pattern obtained by the pattern formation method according to claim 13 or 14.