TWI662087B - Curable composition for photo-imprints, method for forming pattern and pattern - Google Patents

Abstract

Provided are a curable composition for photoimprint, a pattern forming method, a pattern, and a fluorine-containing compound, which are excellent in mold release properties and inkjet ejection accuracy.

The curable composition for photoimprint contains a polymerizable compound, a photopolymerization initiator, and a fluorine-containing compound. The fluorine-containing compound is represented by the following general formula (I) or (II); the general formula (I) and ( In II), Rf ¹ to Rf ³ each independently represent a fluorine-containing alkyl group having 1 to 9 carbon atoms having 2 or more fluorine atoms; R represents an alkyl group having 1 to 8 carbon atoms and an olefin having 2 to 8 carbon atoms. And aryl groups having 6 to 8 carbon atoms; 11 to 13 each independently represent 0 to 10; m each independently represents an integer of 2 to 4; n1 and n2 each independently represent 1 to 25.

Description

Curable composition for photoimprint, pattern forming method, and pattern

The present invention relates to a curable composition for photoimprint. In more detail, optical devices such as semiconductor integrated circuits, flat screens, micro-electro-mechanical systems (MEMS), sensor elements, optical disks, high-density memory disks, diffraction gratings, or embossed holograms, etc. Parts, nano-devices, optical devices, optical films or polarizing elements for the production of flat-panel displays, thin-film transistors, organic transistors, color filters, overcoat layers, pillars, and liquid crystal alignment for liquid crystal displays Photoimprinting for the production of ribs, microlens arrays, immunoassay wafers, DNA separation wafers, microreactors, nano biological devices, optical waveguides, filters, photonic liquid crystals, etc. A curable composition, a pattern forming method, a pattern, and a fluorine-containing compound.

The embossing method develops the embossing technology that is well known in the production of optical discs. The prototype of a metal mold (commonly referred to as a mold, a stamper, and a template) formed with an uneven pattern is pressed against the photoresist to mechanically deform it and transfer it accurately. Fine pattern technology. Once the mold is made, The fine structure can be easily and repeatedly molded and economical, and is expected to be applied to various fields in recent years.

As the embossing method, a thermal embossing method using a thermoplastic resin as a material to be processed (for example, see Non-Patent Document 1) and a light embossing method using a hardening composition (for example, see Non-Patent Document 2 and Non-Patent Document) 3). The hot stamping method is a resin that is heated to a temperature higher than the glass transition temperature, presses the mold, cools to the temperature below the glass transition temperature, and then releases the mold to transfer the fine structure to the substrate. This method is extremely simple and can also be applied to a variety of resin materials or glass materials.

On the other hand, the photo-imprint method is a method in which a fine pattern is transferred to a photo-hardened object by light-hardening a hardening composition after light irradiation through a light-transmitting mold or a light-transmitting substrate. Since this method can be embossed at room temperature, it can be applied to the field of precision processing of ultra-fine patterns such as the production of semiconductor integrated circuits. Recently, there have been reported new developments such as a nano casting method combining the advantages of the two or an inverse embossing method for making a three-dimensional laminated structure.

In such an imprint method, there are proposals as follows.

The first application is that the formed shape (pattern) itself has a function and is used as an element part or a structural member of nanotechnology. As an example, various micrometers can be cited. Nano optical elements or high-density recording media, optical films, structural members in flat displays, etc.

The second application is to build a laminated structure through the simultaneous integral molding of microstructures and nanostructures or simple interlayer positioning, and It uses this for production of μ-TAS (Micro-Total Analysis System) or biochip.

The third application is to use the formed pattern as a mask for processing a substrate by a method such as etching. In such technology, by using high-precision positioning and high integration, instead of the conventional lithography technology, it can be used for the production of high-density semiconductor integrated circuits or the production of transistors for liquid crystal displays. Magnetic processing of the next generation hard disk of patterned media. The progress of imprint methods related to these applications toward practical use has been active in recent years.

Since the imprint method has a step of peeling the mold, its release property has been a problem since the beginning. As a method for improving the mold release property, a method for releasing the surface of a mold by using a mold release agent such as a silane coupling agent having a perfluoro group is known. In order to reduce the surface energy of the mold surface, this method has a high effect of improving the mold release property. However, the mold release agent deteriorates with repeated embossing, which has a problem in durability.

As an attempt to improve the durability of the release treatment, a method is known in which a curable composition contains a silane coupling agent having a perfluoro group (Non-Patent Document 4).

In addition, as an attempt to improve the mold release property, a method of including a surfactant having a perfluoro group in the curable composition (Patent Document 1) or a method of containing one or more compounds in the curable composition is known. Method for polymerizable compound of fluorine atom alkyl group (Patent Document 2). These methods ensure the storage stability of the hardenable composition which is a problem due to the silane coupling agent.

On the other hand, the inkjet method has attracted attention for applications in which ultrafine patterns are formed with a high precision by an imprint method (for example, an etching photoresist for semiconductor substrate processing) (Patent Document 3).

Prior art literature Patent literature

Patent Document 1 International Publication WO2005 / 000552

Patent Document 2 Japanese Patent Application Publication No. 2010-239121

Patent Document 3 Japanese Patent Publication No. 2008-502157

Non-patent literature

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. Bender et al., Microelectronic Engineering 61-62, 407 (2002)

Here, the inventors of the present case conducted an intensive review of the known technology. As a result, they learned that the method described in Non-Patent Document 4 has a silane coupling agent that is reactive, so the storage stability of the hardening composition is poor, and there is imprint The problem of increased pattern defects. Also, learn that patents A method of making a curable composition contain a surfactant having a perfluoro group described in Document 1, and a method of polymerizing an alkyl group having two or more fluorine atoms in a curable composition described in Patent Document 2 Although the method of the hard compound improves the releasability of the hardenable composition, the surface tension of the hardenable composition is drastically reduced, so that the discharge accuracy of the inkjet method is deteriorated. If the discharge accuracy is deteriorated, problems such as poor filling of the curable composition or uneven thickness of the residual film occur.

An object of the present invention is to solve the above problems, and an object thereof is to provide a curable composition for photoimprint, which is excellent in mold release properties and inkjet discharge accuracy. Another object is to provide a pattern forming method, a pattern, and a fluorine-containing compound.

Under such circumstances, the inventors of the present case conducted an intensive review. As a result, it was found that by including a specific fluorine-containing compound in the curable composition for photoimprint, the release of the curable composition for photoimprint can be improved. Performance and inkjet discharge accuracy, and finally completed the present invention.

Specifically, the above-mentioned problem is solved by means of the following solution <1>, and more preferably by means of <2> to <13>.

<1> A curable composition for photoimprint comprising a polymerizable compound, a photopolymerization initiator, and a fluorine-containing compound. The fluorine-containing compound includes a compound represented by the following general formula (I) and the following general formula ( II) at least one compound shown;

In the general formulae (I) and (II), Rf ¹ to Rf ³ each independently represent a fluorine-containing alkyl group having 1 to 9 carbon atoms having 2 or more fluorine atoms; R represents an alkyl group having 1 to 8 carbon atoms, Alkenyl with 2 to 8 carbons and aryl with 6 to 8 carbons; l1 to l3 each independently represent 0 to 10, m each independently represent an integer of 2 to 4, n1 and n2 each independently represent 1 to 25 .

<2> The curable composition for photoimprinting according to <1>, which contains 2 to 10% by mass of a fluorine-containing compound with respect to all components other than the solvent.

<3> The curable composition for photoimprinting according to <1> or <2>, wherein m is 2 in the general formula (I) or (II).

<4> The curable composition for photoimprinting according to any one of <1> to <3>, wherein in the general formula (I), R is a methyl group.

<5> The curable composition for photoimprinting according to any one of <1> to <4>, wherein the structure of the terminal of Rf ¹ to Rf ³ in the general formula (I) or (II) is − CF ₃ or -C (HF ₂ ).

<6> The curable composition for photoimprinting according to any one of <1> to <5>, wherein the polymerizable compound is a (meth) acrylate compound.

<7> The curable composition for photoimprinting according to any one of <1> to <6>, wherein the polymerizable compound is a compound having an aromatic group.

<8> The curable composition for photoimprinting according to any one of <1> to <7>, wherein the curable composition for photoimprint does not substantially contain a solvent.

<9> The curable composition for photoimprinting according to any one of <1> to <8>, wherein the viscosity of the curable composition for photoimprint at 23 ° C is 15 mPa. s or less and the surface tension is 25 ~ 35mN / m.

<10> A pattern forming method comprising applying a curable composition for photoimprinting according to any one of <1> to <9> on a substrate or a mold having a pattern, and using the mold and the substrate The light is irradiated while the hardenable composition for photoimprint is sandwiched between the substrates.

<11> The pattern forming method according to <10>, wherein the method of applying the curable composition for photoimprint on a substrate or a mold having a pattern is an inkjet method.

<12> A pattern obtained by the pattern forming method described in <10> or <11>.

<13> a fluorine-containing compound represented by the following general formula (I) or a fluorine-containing compound represented by the following general formula (II);

In the general formulae (I) and (II), Rf ¹ to Rf ³ each independently represent a fluorine-containing alkyl group having 1 to 9 carbon atoms having 2 or more fluorine atoms; R represents an alkyl group having 1 to 8 carbon atoms; l1 to l3 each independently represent 0 to 10, m each independently represents an integer of 2 to 4, and n1 and n2 each independently represent 1 to 25.

According to the present invention, it is possible to provide a curable composition for photoimprint, which is excellent in mold release properties and inkjet discharge accuracy. In addition, a pattern forming method, a pattern, and a fluorine-containing compound can be provided.

[Mode for Carrying Out the Invention]

Hereinafter, the content of the present invention will be described in detail. The description of the constituent elements described below is based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. The "~" used in the specification of this case is used to include the numerical value described before and after it as a lower limit value and an upper limit value.

In the description of this case, "(meth) acrylate" means acrylate and methacrylate, "(meth) acryl" means acrylic and methacrylic acid, and "(meth) acryl" refers to acryl and Methacrylfluorenyl. In the present specification, "monomer" is synonymous with "monomer molecule". Single system is different from oligomers and polymers, and refers to compounds with a weight average molecular weight of less than 1,000. In the description of this case, "functional group" refers to a group participating in a polymerization reaction. The term "imprint" as used in the present invention preferably refers to a pattern transfer with a size of 1 nm to 100 μm, and more preferably refers to a pattern transfer with a size of 10 nm to 1 μm (nano imprint).

In the description of the radical (atomic group) in the description of the present case, the descriptions that are not substituted or unsubstituted include those without a substituent and those with a substituent. For example, the so-called "alkyl" is not only The substituted alkyl group (unsubstituted alkyl group) also includes a substituted alkyl group (substituted alkyl group).

Furthermore, in the description of this case, "light" means not only light or electromagnetic waves with a wavelength in the range of ultraviolet, near ultraviolet, far ultraviolet, visible, infrared, etc., but also includes radiation. The radiation includes, for example, microwaves, electron beams, EUV, and X-rays. Alternatively, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser may be used. These types of light may be monochromatic light (single-wavelength light) that has passed through a filter, or plural kinds of light (composite light) having different wavelengths.

In the present specification, the term “total solid content” refers to the total mass of the components after the solvent is removed from the entire composition of the composition.

<The curable composition for photoimprint of the present invention>

The curable composition for photoimprint of the present invention (hereinafter sometimes referred to simply as "curable composition of the present invention" or "composition of the present invention") contains a polymerizable compound (A) and a photopolymerization initiator (B) with a fluorine-containing compound (C).

The composition according to the present invention can provide a curable composition for photoimprint, which is excellent in mold release properties and inkjet discharge accuracy. Although the mechanism is not clear, it is judged that the composition contains a fluorinated compound having a fluorinated alkyl group and an alkyleneoxy group, and the alkoxyl portion is adsorbed on the mold. The surface energy of the mold is reduced, and the mold release property is improved. In addition, the combination of the ester group of the fluorine-containing compound, the fluorine-containing alkyl group, and the alkoxy group can suppress an increase in the viscosity of the composition or an excessive decrease in surface tension, thereby improving the accuracy of inkjet discharge. As a result, mold releasability and inkjet discharge accuracy can be made compatible.

<< 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 depart from the gist of the present invention, and examples thereof include a polymerizable unsaturated group having 1 to 6 groups containing an ethylenically unsaturated bond. Monomers; epoxy compounds, oxetane compounds; vinyl ether compounds; styrene derivatives; allyl ether or butenyl ether. Specific examples of the polymerizable compound (A) include those described in paragraph numbers 0020 to 0098 of Japanese Patent Application Laid-Open No. 2011-231308, the contents of which are incorporated into the specification of the present application.

A polymerizable unsaturated monomer (1 to 6 functional polymerizable unsaturated monomers) having 1 to 6 ethylenically unsaturated bond-containing groups will be described.

First, as the polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group, specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, N-vinylpyrrolidone, 2-propenyloxyethyl phthalate, 2-propenyloxy-2-hydroxyethyl phthalate, 2-propenyloxyethyl hexahydro Phthalate, 2-propenyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth) acrylate, 2-ethyl Hexylcarbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (methyl) ) 4-hydroxybutyl acrylate, acrylic acid dimer, benzyl (meth) acrylate, 1- or 2-naphthyl (meth) acrylate, butoxyethyl (meth) acrylate, (methyl) Cetyl acrylate, cresol (meth) acrylate modified with ethylene oxide (hereinafter referred to as "EO"), dipropylene glycol (meth) acrylate, ethoxylated benzene (meth) acrylate Ester, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Yl) acrylate Esters, dicyclopentyl (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, (meth) acrylic myristate, lauryl (meth) acrylate, methoxydipropylene glycol ( (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, neopentyl glycol Benzoate (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, para Cumene phenoxyethylene glycol (meth) acrylate, phenoxy acrylate modified with epichlorohydrin (hereinafter referred to as "ECH"), phenoxyethyl (meth) acrylate, benzene Oxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate Ester, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, octadecyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, ( Methacrylate Bromophenyl, EO-modified tribromophenyl (meth) acrylate, tri-dodecyl (meth) acrylate, p-isopropenylphenol, N-vinylpyrrolidone, N-vinylhexano Lactamine.

Among the monofunctional polymerizable monomers containing an ethylenically unsaturated bond, a monofunctional (meth) acrylate compound is preferably used in the present invention from the viewpoint of photocurability. Examples of the monofunctional (meth) acrylate compound include monofunctional (meth) acrylate compounds exemplified in the monofunctional polymerizable monomer containing an ethylenically unsaturated bond.

Furthermore, among monofunctional (meth) acrylate compounds, a monofunctional (meth) acrylate having an aromatic structure and / or an alicyclic hydrocarbon structure is preferred from the viewpoint of dry etching resistance, more preferably A monofunctional (meth) acrylate having an aromatic structure.

Among such monofunctional (meth) acrylates having an aromatic structure and / or an alicyclic hydrocarbon structure, benzyl (meth) acrylate, 2-phenoxyethyl acrylate, and Benzyl (meth) acrylate with substituents on the ring (preferable substituents are alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, cyano), (meth) acrylic acid-1 -Or 2-naphthyl ester, 1- or 2-naphthyl methyl (meth) acrylate, 1- or 2-naphthyl ethyl (meth) acrylate, dicyclopentyl (meth) acrylate, ( Dicyclopentyloxyethyl (meth) acrylate, iso (meth) acrylate Ester, adamantane (meth) acrylate, more preferably benzyl (meth) acrylate, benzyl (meth) acrylate having a substituent on the aromatic ring, monofunctional (meth) acrylate having a naphthalene structure The compound is particularly preferably 1- or 2-naphthyl (meth) acrylate and 1- or 2-naphthyl methyl (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 ethylenically 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 monoethyl ether (meth) acrylate, dihydroxy Methyldicyclopentane di (meth) acrylate, di (meth) acrylated isotricyanate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6-hexanediol di (meth) acrylate, allyl Oxypolyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A bis ( (Meth) acrylates, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate Hydroxytrimethylacetic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, modified with caprolactone Hydroxytrimethylacetate neopentyl glycol, stearic acid-modified pentaerythritol di (meth) acrylate, ECH-modified phthalic acid di (meth) acrylate, poly (ethylene glycol- Tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylic acid Ester, polypropylene glycol di (meth) acrylate, ECH-modified propylene glycol di (meth) acrylate, siloxane di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethyl Diethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, neomethylol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (Meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethylene urea, diethylene glycol Vinylpropion urea, o-, m-, p-xylylene di (meth) acrylate, 1,3-adamantane diacrylate, Alkanedimethanol diacrylate.

Among these, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Base) acrylate, hydroxytrimethylacetic acid neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, o-, m-, p-benzenedi (meth) acrylate Bifunctional (meth) acrylates such as, o-, m-, p-xylylene di (meth) acrylate and the like are particularly suitable for use in the present invention.

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

The curable composition of the present invention may contain a polymerizable compound having a silicon atom and / or a fluorine atom. The polymerizable compound having a silicon atom and / or a fluorine atom preferably contains a fluorine atom, and more preferably a fluorine-containing alkyl group having 1 to 9 carbon atoms.

The substitution rate of fluorine atoms of the fluorine-containing alkyl group having 1 to 9 carbon atoms is preferably 40 to 100%, more preferably 50 to 90%, and even more preferably 65 to 85%. The substitution rate of a fluorine atom means, for example, the ratio (%) of a hydrogen atom to a fluorine atom in an alkyl group having 1 to 9 carbon atoms. The fluorine-containing alkyl group having 1 to 9 carbon atoms preferably contains -C _n F _{2n + 1} or -C _n F _2n H, and more preferably contains -C _n F _{2n + 1} . Here, n represents an integer of 1-9, and more preferably represents an integer of 4-8.

As a polymerizability which the polymerizable compound which has a silicon atom and / or a fluorine atom has, a (meth) acrylate group is preferable. The number of polymerizable groups is preferably 1 or 2, and more preferably 1.

The molecular weight of the polymerizable compound having a silicon atom and / or a fluorine atom is preferably 100 to 600, and more preferably 300 to 500. As the polymerizable compound having a fluorine atom, for example, reference may be made to the descriptions in paragraphs 0022 to 0223 of International Publication No. 2010/137724, and the contents are incorporated into the specification of the present application. Examples of the polymerizable compound having a fluorine atom include 2- (perfluorohexyl) ethyl acrylate.

On the other hand, in this invention, it can also be set as the state which does not contain the polymerizable compound which has a silicon atom and / or a fluorine atom substantially. In the present invention, since at least one of the fluorine-containing compound represented by the general formula (I) and the fluorine-containing compound represented by the general formula (II) is blended, it does not substantially contain silicon atoms and / or fluorine atoms. In the form of a polymerizable compound, a low release force can also be achieved. The term "substantially free" means, for example, that the total amount of the fluorine-containing compound represented by the general formula (I) and the amount of the fluorine-containing compound represented by the general formula (II) is 1% by mass or less .

Among the components of all polymerizable compounds contained in the curable composition of the present invention, the total of the polymerizable compounds having one (meth) acrylate group is preferably 0 to 60 with respect to the total polymerizable compounds. Mass%, more preferably 5 to 45 mass%, and even more preferably 10 to 35 mass%. The total of the polymerizable compounds having two (meth) acrylate groups is preferably 40 to 100% by mass, more preferably 55 to 95% by mass, and even more preferably 65 to 90% by mass, relative to all polymerizable compounds. .

Among the components of all polymerizable compounds contained in the curable composition of the present invention, the total of the polymerizable compounds having an alicyclic hydrocarbon group and / or an aromatic group is preferably 30 to 100% by mass of the total polymerizable compounds. , More preferably 50 to 100% by mass, and even more preferably 60 to 100% by mass.

The amount of the aromatic group-containing (meth) acrylate polymerizable compound as the polymerizable compound is preferably 30 to 100% by mass of the total polymerizable components, more preferably 50 to 100% by mass, and particularly preferably 60 to 100%. quality%.

A particularly preferred embodiment is that the amount of the following polymerizable compound (A1) is 0 to 60% by mass of all polymerizable components, more preferably 5 to 45% by mass, and even more preferably 10 to 40% by mass. The following polymerization The amount of the sexual compound (A2) is 40 to 100% by mass of all polymerizable components, more preferably 55 to 95% by mass, and even more preferably 60 to 90% by mass.

(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 group having 1 to 12 carbon atoms Polymerizable compound of alkyl-substituted aromatic group and (meth) acrylate group

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

The polymerizable compound may be used singly or in combination of two or more kinds.

In the pattern inversion method described later, it is preferable to have no etching resistance.

<Photopolymerization initiator (B)>

The curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator used in the present invention can be used as long as it is a compound that generates an active species that polymerizes the polymerizable compound by light irradiation. As the photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferred, and a radical polymerization initiator is more preferred. 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, a commercially available initiator can be used. As such an example, for example, paragraph number 0091 of Japanese Patent Application Laid-Open No. 2008-105414 may be preferably used. Recorder. Among them, acetophenone-based compounds, fluorenylphosphine oxide-based compounds, and oxime ester-based compounds are particularly preferred from the viewpoint of curing sensitivity and absorption characteristics.

The photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used in combination, it is more preferable to use two or more kinds of radical polymerization initiators in combination. Specifically, Darocure (registered trademark) 1173 and Irgacure (registered trademark) 907, Darocure 1173 and Lucirin (registered trademark) TPO, Darocure 1173 and Irgacure (registered trademark) 819, Darocure 1173 and Irgacure (registered trademark) OXE01, Irgacure Combination of 907 and Lucirin TPO, Irgacure 907 and Irgacure 819. By making such a combination, it is possible to further expand the exposure margin.

The preferred ratio (mass ratio) when combined with a photopolymerization initiator is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, and even more preferably 7: 3 to 3: 7.

The content of the photopolymerization initiator used in the present invention is in all the components other than the solvent, that is, in all the solid components of the curable composition of the present invention. For example, it is preferably 0.01 to 15% by mass, and more preferably 0.1. ~ 10 mass%, particularly preferably 0.5 to 7 mass%. When two or more photopolymerization initiators are used, the total amount thereof falls within the above range. If the content of the photopolymerization initiator is 0.01% by mass or more, the sensitivity (rapid curing), resolution, line edge roughness, and coating film strength tend to be further improved, which is preferable. In addition, if the content of the photopolymerization initiator is 15% by mass or less, the light transmittance, coloring properties, and handling properties tend to be further improved, which is preferable.

<Fluorine compound (C)>

The curable composition of the present invention includes at least one of a fluorine-containing compound represented by the following general formula (I) and a fluorine-containing compound represented by the general formula (II). By using such a fluorine-containing compound (C), the mold release property and inkjet discharge accuracy of the curable composition of the present invention can be improved.

<< Compounds represented by general formula (I) >>

In the general formula (I), Rf ¹ represents a fluorine-containing alkyl group having 1 to 9 carbon atoms having 2 or more fluorine atoms; R represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and carbon. An aryl group of 6 to 8; l1 represents 0 to 10, m each independently represents an integer of 2 to 4, and n1 represents 1 to 25.

In the general formula (I), Rf ¹ represents a fluorine-containing alkyl group having 1 to 9 carbon atoms having two or more fluorine atoms. Rf ¹ represents any of linear, branched, and cyclic, but is preferably linear or branched, and more preferably linear.

The carbon number of Rf ¹ is preferably 2-9, more preferably 4-9, particularly preferably 5-8, and particularly preferably 6-8.

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

The substitution rate of the fluorine atom of Rf ¹ is preferably 40 to 100%, more preferably 50 to 90%, and even more preferably 65 to 85%. The substitution rate of fluorine atoms refers to the ratio (%) of hydrogen atoms to fluorine atoms in alkyl groups having 1 to 9 carbon atoms.

Specific examples of Rf ¹ include CF ₃ CH _2- , CF ₃ CF ₂ CH _2- , CF ₃ (CF ₂ ) ₂ CH _2- , CF ₃ (CF ₂ ) ₃ CH ₂ CH _2- , and CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₄ CH _2- , CF ₃ (CF ₂ ) ₅ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ CH ₂ -, (CF ₃ ) ₂ CH-, (CF ₃ ) ₂ C (CH ₃ ) CH _2- , (CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH _2- , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH _2- , H (CF ₂ ) ₂ CH _2- , H (CF ₂ ) ₄ CH _2- , H (CF ₂ ) ₆ CH _2- , H (CF ₂ ) ₈ CH ₂ -and so on.

Among these, CF ₃ (CF ₂ ) ₂ CH _2- , CF ₃ (CF ₂ ) ₃ CH ₂ CH _2- , CF ₃ (CF ₂ ) ₄ CH _2- , CF ₃ (CF ₂ ) ₅ CH ₂ CH _2- , H (CF ₂ ) ₆ CH _2- , particularly preferably CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ -or CF ₃ (CF ₂ ) ₄ CH _2- .

In the general formula (I), R represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aryl group having 6 to 8 carbon atoms. Among these, an alkyl group having 1 to 8 carbon atoms is preferable.

The carbon number of the alkyl group having 1 to 8 carbons is preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 to 3, and particularly preferably 1. The carbon number of the alkenyl group having 2 to 8 carbon atoms is preferably 2 to 6, more preferably 2 to 4, particularly preferably 2 or 3, and particularly preferably 1. The number of carbon atoms of the aryl group having 6 to 8 carbon atoms is preferably 6 or 7, and more preferably 6.

Specific examples of R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, isopentyl, neo Amyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, allyl, phenyl, benzyl, phenethyl and the like. Among these, methyl, n-butyl, allyl, phenyl, and benzyl are preferred, methyl or n-butyl is more preferred, and methyl is particularly preferred.

In the general formula (I), l1 represents 0 to 10, more preferably 0 to 6, particularly preferably 0 to 4, and particularly preferably 0.

In the general formula (I), m is an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.

n1 represents 1 to 25, preferably 8 to 22, and more preferably 10 to 16.

Here, l1 and n1 represent the average addition number of an alkylene oxide. Here, the fluorine-containing compound used in the present invention is not a single compound, but a molecule The amount or the number of additions of the alkylene oxide has a distributed mixture. Therefore, l1 and n1 are values calculated from the number average molecular weight, and are not limited to integers.

In formula (I), the carbon number of particularly good Rf ¹ is 4 to 9, the fluorine substitution ratio of Rf ¹ is 50 to 90%, n1 is 8 to 22, and 11 is 0.

<< Compounds represented by general formula (II) >>

In the general formula (II), Rf ² and Rf ³ each independently represent a fluorine-containing alkyl group having 1 to 9 carbon atoms having 2 or more fluorine atoms; 12 and 13 each independently represent 0 to 10, and m represents 2 to An integer of 4 and n2 represents 1 to 25.

Rf ² and Rf ³ are synonymous with Rf ¹ in the general formula (I).

The carbon numbers of Rf ² and Rf ^{3 are} preferably 2 to 9, more preferably 4 to 9, and even more preferably 4 to 7.

The structure of the terminals of Rf ² and Rf ³ is synonymous with Rf ¹ in the general formula (I), and the preferred ranges are also the same.

The substitution rates of the fluorine atoms of Rf ² and Rf ^{3 are} synonymous with those of Rf ¹ in the general formula (I), and the preferred ranges are also the same.

Specific examples of Rf ² and Rf ^{3 are} synonymous with Rf ¹ in the general formula (I). In particular, as Rf ² and Rf ³ , CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ , H (CF ₂ ) ₆ CH ₂ , particularly preferably CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ .

In the general formula (II), l2 and l3 each independently represent 0 to 10, preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0.

In the general formula (II), m is each independently an integer of 2 to 4, preferably 2 or 3, and more preferably 2.

n2 represents 1 to 25, preferably 8 to 16, and more preferably 10 to 14.

Here, l2, l3, and n2 represent the average addition number of an alkylene oxide, and it is synonymous with l1 and n1 in General formula (I).

In formula (II), it is preferable that the carbon numbers of Rf ² and Rf ³ are each independently 4 to 9, the fluorine substitution ratios of Rf ² and Rf ³ are each independently 50 to 90%, n2 is 8 to 16, and l2 It is 0 ~ 4, and l3 is 0 ~ 4.

As preferable specific examples of the fluorine-containing compound (C), the following compounds may be mentioned, but the fluorine-containing compound (C) used in the present invention is not limited to these compounds. The fluorine-containing compound (C) is not a single compound, but a mixture having a distribution in molecular weight or the number of alkylene oxide additions. The number of repeating units in the following specific examples is calculated from the number average molecular weight. A representative structure is exemplified by the average bonus number.

The number average molecular weight of the fluorine-containing compound (C) is preferably 200 to 2000, more preferably 400 to 1800, and even more preferably 600 to 1600.

The number average molecular weight of the fluorine-containing compound can be calculated by adding the number average molecular weight of the polyethylene glycol of the synthetic raw material and the molecular weight of the modifying group. The number-average molecular weight of polyethylene glycol used as a synthetic raw material can be calculated by measuring the hydroxyl value.

The content of the fluorine-containing compound (C) in the curable composition of the present invention is preferably 2 to 10% by mass, more preferably 3 to 8% by mass, and even more preferably 4 to 6 with respect to the amount of all components except the solvent. quality%. When the content of the fluorine-containing compound (C) is 2% by mass or more, the releasability is further improved. also. When the content of the fluorine-containing compound (C) is 10% by mass or less, the pattern shape is further optimized. The fluorine-containing compound (C) may be used alone or in combination of two or more. When two or more kinds of fluorine-containing compounds (C) are used, the total amount thereof falls within the above range.

<Polymerization inhibitor>

The curable composition of the present invention preferably contains a polymerization inhibitor. The content of the polymerization inhibitor is preferably 0.001 to 0.1% by mass, more preferably 0.005 to 0.08% by mass, and even more preferably 0.01 to 0.05% by mass, relative to the total polymerizable monomers. By blending a polymerization inhibitor in an appropriate amount, it is possible to suppress a change in viscosity over time while maintaining a high hardening sensitivity. The polymerization inhibitor may be added during the production of the polymerizable monomer, or may be added to the hardened composition of the present invention at a later time. Specific examples of the polymerization inhibitor include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical. Moreover, as a specific example of another polymerization inhibitor, the thing described in the paragraph number 0121 of Unexamined-Japanese-Patent No. 2012-169462 is mentioned, The content is integrated in the specification of this case.

<Surfactant>

The curable composition of the present invention may contain a surfactant as needed. In general, a so-called surfactant is a substance that has a hydrophobic portion and a hydrophilic portion in the molecule, and changes the properties of the interface significantly with a small amount of addition. The surfactant in the present invention is a substance having a hydrophobic part and a hydrophilic part in the molecule, and a small amount of addition to significantly reduce the surface tension of the hardenable composition. For example, it is added at 1% by mass or less with respect to the hardenable composition. A substance that reduces the surface tension of the curable composition from 40 mN / m to 30 mN / m or less. When a surfactant is contained in the curable composition of the present invention, the effect of improving the uniformity of coating or the effect of improving the mold release property can be expected.

As the surfactant used in the present invention, a nonionic surfactant is preferred, and a fluorine-based surfactant, a Si-based surfactant, and fluorine are more preferred. At least one type of Si-based surfactant, particularly preferably a fluorine-based non-ionic surfactant Ionic surfactant. Here, the "fluoro-Si-based surfactant" refers to a person having both the requirements of a fluorine-based surfactant and a Si-based surfactant.

Examples of the fluorine-based nonionic surfactant that can be used in the present invention include trade names Fluorad (Sumitomo 3M), Megafac (DIC), Surflon (AGC Seimi Chemical), Unidyne (DAIKIN Industries), Ftergent (NEOS), Eftop (Mitsubishi Materials Electronics), Polyflow (Kyoeisha Chemical), KP (Shin-Etsu Chemical Industry), Troyzol (TROY Chemical), PolyFox (OMNOVA), Capstone (DuPont), etc.

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

In the present invention, by blending at least one of the fluorine-containing compound represented by the general formula (I) and the fluorine-containing compound represented by the general formula (II), even if it is in a state that it does not substantially contain a surfactant, A low demolding force can also be achieved. The term "substantially free" means, for example, that the total amount of the fluorine-containing compound represented by the general formula (I) and the total amount of the fluorine-containing compound represented by the general formula (II) is 1% by mass. the following.

<Non-polymerizable compound>

In the present invention, a non-polymerizable compound having at least one hydroxyl group at its terminal or having a polyalkylene glycol structure in which an hydroxyl group is etherified and which does not substantially contain a fluorine atom and a silicon atom may be included.

Here, a non-polymerizable compound means a compound which does not have a polymerizable group.

The polyalkylene structure of the non-polymerizable compound is preferably a polyalkylene glycol structure containing an alkylene group having 1 to 6 carbon atoms, more preferably a polyethylene glycol structure, a polypropylene glycol structure, and a polybutadiene structure. The alcohol structure or a mixed structure thereof is particularly preferably a polyethylene glycol structure, a polypropylene glycol structure or a mixed structure thereof, and particularly preferably a polypropylene glycol structure.

In addition to the terminal substituents, it may consist essentially of a polyalkylene glycol structure only. The term "substantially" herein means that the constituent elements other than the polyalkylene glycol structure are 5% by mass or less of the whole, and preferably 1% by mass or less. Especially as a non-polymerizable compound, it is particularly preferable to include a compound composed of only a polypropylene glycol structure.

The polyalkanediol structure preferably has 3 to 100 alkanediol constituent units, more preferably 4 to 50 units, even more preferably 5 to 30 units, and particularly preferably 6 to 20 units.

The weight average molecular weight (MW) of the non-polymerizable compound is preferably 150 to 6000, more preferably 200 to 3000, particularly preferably 250 to 2000, and even more preferably 300 to 1200.

The fact that the fluorine atom and the silicon atom are not substantially contained means, for example, that the total content of the fluorine atom and the silicon atom is 1% or less, and it is preferable that the fluorine atom and the silicon atom are not included at all. Because it does not have fluorine atoms and silicon atoms, The compatibility of the polymerizable compound is increased, and in a composition that does not contain a solvent, coating uniformity, pattern formation during imprinting, and line edge roughness after dry etching are improved.

The non-polymerizable compound preferably has at least one hydroxyl group at the terminal or is etherified. As long as it has at least one hydroxyl group at the terminal end or the hydroxyl group is etherified, the remaining hydrogen atom at the terminal end or a terminal hydroxyl group may be substituted. The group which may be substituted as the hydrogen atom of the terminal hydroxyl group is preferably an alkyl group (that is, a polyalkylene glycol alkyl ether) and a fluorenyl group (that is, a polyalkylene glycol ester). More preferred is a polyalkanediol having all of its terminals as hydroxyl groups. A compound having a plurality (preferably 2 or 3) of polyalkylene glycol chains via a linking group may also be suitably used, but a polyalkylene glycol chain having no branched linear structure is preferred. Particularly preferred is a diol-type polyalkanediol.

Preferred specific examples of the non-polymerizable compound are polyethylene glycol, polypropylene glycol, these mono- or dimethyl ethers, mono- or dibutyl ethers, mono- or dioctyl ethers, mono- or dicetyl ethers, Monostearate, monooleate, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, these trimethyl ethers.

The content of the non-polymerizable compound is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, particularly preferably 0.5 to 7% by mass, and particularly preferably 1 to 5% by mass in all compositions other than the solvent.

<Other ingredients>

The hardenable composition of the present invention includes, in addition to the above-mentioned components, a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, an adhesion promoter, and a thermal polymerization initiator as needed. , Photobase generator, colorant, inorganic particles, elastomer particles, basic compounds, photoacid generator, photoacid proliferator, chain transfer agent, antistatic agent, Flow regulator, defoamer, dispersant, etc. Specific examples of such components include those described in paragraph numbers 092 to 0093 and paragraph numbers 0113 to 0137 of Japanese Patent Application Laid-Open No. 2008-105414, which are incorporated into the specification of this case.

In the present invention, by blending at least one of the fluorine-containing compound represented by the general formula (I) and the fluorine-containing compound represented by the general formula (II), even if it is a silane coupler having substantially no perfluoro group, In the form of a mixture or a polymerizable compound having an alkyl group containing two or more fluorine atoms, a low release force can also be achieved. Further, in the present invention, by not substantially containing a silane coupling agent having a perfluoro group, deterioration in storage stability of the curable composition can be prevented, and defects in the imprint pattern can be suppressed. The term "substantially free" means, for example, that the total amount of the fluorine-containing compound represented by the general formula (I) and the total amount of the fluorine-containing compound represented by the general formula (II) is 1% by mass. the following.

<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% by mass or less, more preferably 3% by mass or less, and particularly preferably does not substantially contain a solvent. Here, the term "substantially free of a solvent" means, for example, that the total mass in the curable composition of the present invention is 1% by mass or less.

When the curable composition of the present invention is coated on a substrate by an inkjet method, if the blending amount of the solvent is small, it is preferable because the viscosity change of the composition due to volatilization of the solvent can be suppressed.

As described above, the curable composition of the present invention does not necessarily include a solvent, but may be added arbitrarily when the viscosity of the composition is finely adjusted and the like. As this The types of solvents that can be preferably used in the curable composition of the present invention may be any solvent that is generally used in the photocurable curable composition or photoresist, and can dissolve and uniformly disperse the compound used in the present invention. In addition, as long as it does not respond to these components, it is not specifically limited. Examples of the solvent that can be used in the present invention include those described in Paragraph No. 0088 of Japanese Patent Application Laid-Open No. 2008-105414, the contents of which are incorporated in the description of this case.

The curable composition system of this invention can be adjusted by mixing each said component. Mixing of the hardenable composition of the present invention. Dissolution is usually performed in a range of 0 ° C to 100 ° C. Moreover, after mixing each said component, it is preferable to filter with the filter which has a pore diameter of 0.003 micrometer-5.0 micrometer, for example. The filtration system can be carried out in multiple stages or repeated many times. In addition, the filtered liquid may be re-filtered. The material of the filter used for filtration can be polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc., but it is not particularly limited.

The viscosity of the hardenable composition of the present invention at 23 ° C is preferably 15 mPa. Below s, more preferably 12mPa. Below s, especially preferred is 11mPa. Below s, especially good is 10mPa. s or less. By setting it as such a range, it becomes possible to improve inkjet discharge precision and the filling property of a pattern. In order to reduce the viscosity of the curable composition of the present invention while reducing the blending amount of the solvent, the polymerizable compound (A) preferably contains a reactive diluent. Examples of the polymerizable compound that functions as a reactive diluent include a polymerizable compound having one (meth) acrylate group.

The surface tension of the hardenable composition of the present invention is preferably 25 to 35 mN / m, more preferably 27 to 34 mN / m, particularly preferably 28 to 32 mN / m, and particularly preferably 29 to 31 mN / m. By setting it as such a range, IJ ejection property or surface smoothness can be improved. In particular, the curable composition of the present invention preferably has a viscosity of 15 mPa at 23 ° C. Below s and the surface tension is 25 ~ 35mN / m, more preferably the viscosity is 11mPa. Below s, the surface tension is 28 ~ 32mN / m, especially the viscosity is 10mPa. s or less and surface tension of 29 to 31 mN / m.

<Pattern formation method>

Hereinafter, a pattern forming method (pattern transfer method) using the curable composition of the present invention will be specifically described. In the pattern forming method of the present invention, the curable composition of the present invention is first coated on a substrate or a mold having a pattern, and the curing composition of the present invention is sandwiched between the mold and the substrate. Light exposure.

As a method for applying the curable composition of the present invention to a substrate, generally known coating methods can be used, and for example, a dip coating method, an air knife coating method, a curtain coating method, a wire rod coating method, and a gravure coating can be used. Method, a squeeze coating method, a spin coating method, a slit scanning method, or an inkjet method, etc., a coating film or a droplet is arranged on a substrate. In particular, since the curable composition of the present invention contains at least one of the fluorine-containing compound represented by the general formula (I) and the fluorine-containing compound represented by the general formula (II), the hardening composition may be used even when the inkjet method is used. The inkjet discharge accuracy is improved.

When the curable composition of the present invention is sandwiched between a mold and a substrate, helium gas may be introduced between the mold and the substrate. By using this method, gas can be penetrated through the quartz mold, and the elimination of residual air bubbles can be promoted. Missed. In addition, by reducing the dissolved oxygen in the curable composition, it is possible to suppress the barrier of radical polymerization during exposure. Instead of helium, a condensable gas may be introduced between the mold and the substrate. By using such a method, the introduced condensable gas system is condensed to reduce the volume, and the elimination of residual air bubbles can be further promoted. The so-called condensable gas refers to a gas that condenses due to temperature or pressure. For example, trichlorofluoromethane, 1,1,1,3,3-pentafluoropropane and the like can be used. Regarding the condensable gas, for example, reference can be made to the description in paragraph 0023 of Japanese Patent Application Laid-Open No. 2004-103817 and paragraph 0003 of Japanese Patent Application Laid-Open No. 2013-254783, which are incorporated into the specification of this case.

During exposure, the exposure illuminance should be in the range of 1 mW / cm ² to 200 mW / cm ² . When it is 1 mW / cm ² or more, the productivity can be improved because the exposure time can be shortened. When it is 200 mW / cm ² or less, the deterioration of the characteristics of the cured film due to the occurrence of side reactions is preferably suppressed. Preferably in the range of exposure amount ^{5mJ / cm 2 ~ 1000mJ / cm} 2 of. If it is less than 5 mJ / cm ² , the exposure margin becomes narrow, the photo-hardening becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur. On the other hand, if it exceeds 1000 mJ / cm ² , the cured film may be deteriorated due to the decomposition of the composition.

In addition, in order to suppress the radical polymerization obstruction caused by oxygen during exposure, inert gases such as nitrogen, helium, argon, and carbon dioxide may be flowed, and the oxygen concentration in the atmosphere is preferably controlled to 10 kPa or less. The oxygen concentration in the atmosphere is more preferably 3 kPa or less, and even more preferably 1 kPa or less.

The pattern forming method of the present invention is that after the pattern forming layer (the layer formed of the curable composition of the present invention) is hardened by light irradiation, if necessary, the hardened pattern may be heated to further advance the pattern. Step by step hardening. The heat for curing the curable composition of the present invention after light irradiation is preferably 150 to 280 ° C, and more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes.

As a specific example of the pattern forming method, those described in paragraph numbers 0125 to 0136 of Japanese Patent Application Laid-Open No. 2012-169462 can be cited, and the contents thereof are incorporated into the specification of this case.

The pattern forming method of the present invention is applicable to a pattern inversion method. Specifically, a photoresist pattern is formed on a substrate to be processed having a carbon film (SOC) by the pattern forming method of the present invention. Next, after the photoresist pattern is covered with a Si-containing film (SOG), the upper portion of the Si-containing film is etched back to expose the photoresist pattern, and the exposed photoresist pattern is removed by an oxygen plasma or the like to form the photoresist pattern. Reverse pattern of Si film. Furthermore, the reverse pattern containing the Si film is used as an etching mask, and the carbon film on the lower layer is etched to transfer the reverse pattern to the carbon film. Finally, the carbon film to which the above-mentioned reverse pattern is transferred is used as an etching mask to etch the substrate. As examples of such a method, refer to paragraphs 0016 to 0030 of Japanese Patent Application Laid-Open No. 5-267253, Japanese Patent Application Laid-Open No. 2002-110510, and Japanese Patent Application Laid-Open No. 2006-521702, the contents of which are incorporated into the description of this case.

In addition, the pattern forming method of the present invention may include: a step of coating an underlayer film composition on a substrate to form an underlayer film; a step of coating the curable composition of the present invention on a surface of the underlayer film; using a substrate and having a pattern A step of curing the curable composition of the present invention by light irradiation in a state where the curable composition of the present invention and an underlayer film are sandwiched between molds; and a step of peeling the mold. Furthermore, it can also be coated on a substrate After the underlayer film composition is irradiated with heat or light, a part of the underlayer film composition is hardened, and then the curable composition of the present invention is applied.

The lower-layer film composition contains, for example, a curable main agent. The curable main agent system may be thermosetting or photocuring, and is preferably thermosetting. The molecular weight of the curable main agent is preferably 400 or more, and may be a low-molecular compound or a polymer, and is preferably a polymer. The molecular weight of the curable main agent is preferably 500 or more, more preferably 1,000 or more, and even more preferably 3,000 or more. The upper limit of the molecular weight is preferably 200,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. When the molecular weight is 400 or more, the volatilization of the components can be more effectively suppressed. For example, there may be mentioned those described in Japanese Patent Application Publication No. 2009-503139 in paragraph numbers 0040 to 0056, and the contents thereof are incorporated into the specification of this case.

The content of the curable main agent is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more in all components other than the solvent. The curable main agent may be two or more types. In this case, the total amount is preferably in the above range.

The underlayer film composition preferably contains a solvent. The preferred solvent is a solvent having a boiling point of 80 to 200 ° C under normal pressure. The type of the solvent may be any solvent that can dissolve the underlayer film composition, and a solvent having any one or more of an ester structure, a ketone structure, a hydroxyl group, and an ether structure is preferred. Specifically, the preferred solvent is a single or mixed solvent selected from propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, γ-butyrolactone, propylene glycol monomethyl ether, and ethyl lactate. A solvent containing propylene glycol monomethyl ether acetate is particularly preferable from the viewpoint of coating uniformity.

The content of the above-mentioned solvent in the underlayer film composition is optimally adjusted according to the viscosity, coatability, and intended film thickness of components other than the solvent, but from the viewpoint of improving coatability, 70% It is added in a range of at least mass%, preferably at least 90% by mass, more preferably at least 95% by mass, and even more preferably at least 99% by mass.

The lower film composition system may contain at least one of a surfactant, a thermal polymerization initiator, a polymerization inhibitor, and a catalyst as other components. These blending amounts are preferably 50% by mass or less with respect to all components other than the solvent.

The underlayer film composition can be adjusted by mixing the above components. Moreover, after mixing each said component, it is preferable to filter with the filter which has a pore diameter of 0.003 micrometer-5.0 micrometer, for example. The filtration system can be carried out in multiple stages or repeated many times. In addition, the filtered liquid may be re-filtered. The material of the filter used for filtration can be polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc., but it is not particularly limited.

The underlayer film composition is applied on a substrate to form an underlayer film. As a method for coating on a substrate, for example, a dip coating method, an air knife coating method, a curtain coating method, a wire rod coating method, a gravure coating method, a squeeze coating method, a spin coating method, and a slit scanning method can be used. Method, inkjet method, etc., a coating film or a droplet is arranged on a substrate. From the viewpoint of film thickness uniformity, a spin coating method is more preferred. Then, the solvent was dried. The preferred drying temperature is 70 ° C to 130 ° C. The hardening is more preferably performed by active energy (preferably heat and / or light). It is preferable to heat-harden at a temperature of 150 ° C to 250 ° C. The step of drying the solvent and the step of hardening may be performed simultaneously. As described above, it is preferable to apply a curable composition of the present invention after coating a part of the underlayer film composition by applying heat or light to harden a part of the underlayer film composition. If such a means is adopted, when the curable composition of the present invention is photocured, the lower layer film composition is also completely cured, and the adhesiveness tends to further increase.

The film thickness of the underlayer film formed from the curable composition of the present invention varies depending on the intended use, but is about 0.1 nm to 100 nm, preferably 1 to 20 nm, and more preferably 2 to 10 nm. The underlayer film composition can also be applied by multiple application. The resulting lower layer film is preferably as flat as possible.

The substrate (substrate or support) can be selected according to various applications, such as quartz, glass, optical film, ceramic material, vapor-deposited film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, etc. Polymer substrates such as paper, SOG (Spin On Glass), polyester film, polycarbonate film, polyimide film, TFT array substrate, electrode plate for PDP, glass or transparent plastic substrate, ITO or metal There are no particular restrictions on conductive substrates, insulating substrates, semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon. However, when used for etching, as described later, it is preferable to use a semiconductor as a substrate.

<Pattern>

As described above, the pattern formed by the pattern forming method of the present invention can be used as a permanent film (a photoresist for a structural member) or an etching resist used in a liquid crystal display (LCD) or the like.

Moreover, the solvent resistance of the pattern using the curable composition of this invention is also favorable. The curable composition in the present invention is preferably a solvent The resistance of the agent is high, and it is particularly preferable that the film thickness does not change when immersed in an N-methylpyrrolidone solvent at 25 ° C for 10 minutes in a solvent used in a general substrate manufacturing process.

The pattern formed by the pattern forming method of the present invention is also suitable as an etching photoresist. When the curable composition of the present invention is used as an etching photoresist, first, for example, a silicon wafer having a thin film of SiO ₂ or the like is used as a base material, and a nanometer-level Fine pattern. Then, in the case of wet etching, hydrogen fluoride or the like is used, and in the case of dry etching, etching is performed using an etching gas such as CF ₄ to form a desired pattern on the substrate. The hardenable composition of the present invention is also excellent in etching resistance against dry etching using carbon fluoride or the like.

<Method for Manufacturing Semiconductor Device>

The method for manufacturing a semiconductor device according to the present invention is characterized by using the above pattern as an etching mask. Using the above pattern as an etching mask, the substrate is treated. For example, a pattern is used as an etching mask, and dry etching is performed to selectively remove the upper layer portion of the substrate. By repeating such a process on the substrate, a semiconductor device can be obtained. The semiconductor device is, for example, an LSI (Large Scale Integrated Circuit).

[Example]

Examples are given below to explain the present invention more specifically. The materials, usage amounts, proportions, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited by the specific examples shown below. In addition, unless otherwise specified in advance, "%" is the quality benchmark.

<Synthesis of fluorine-containing compound (C)>

The fluorine-containing compounds (C-1) to (C-16) were synthesized by the methods described below.

Synthesis of fluorinated compound (C-1)

After mixing 11.8 g (0.105 mol) of potassium tertiary butoxide (manufactured by Wako Pure Chemical Industries) and 150 mL of tertiary butanol (manufactured by Wako Pure Chemical Industries), the inner temperature was kept below 25 ° C in a water bath 20.1 g (0.10 mol) of 2,2,3,3,4,4,4-heptafluorobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Furthermore, 19.5 g (0.10 mol) of tert-butyl bromoacetate (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped while the internal temperature of the mixed solution was kept below 25 ° C. After dropping, the mixture was reacted at 25 ° C for 2 hours, and then 200 mL of a 1N aqueous sodium hydroxide solution (manufactured by Wako Pure Chemical Industries) was added, and the mixture was reacted at 70 ° C for 3 hours. After the reaction was completed, after cooling, 15 mL of concentrated hydrochloric acid, 100 mL of ethyl acetate were added and stirred, and then liquid separation was performed. The obtained organic layer was washed with 100 mL of 0.1N hydrochloric acid water, and then washed with 100 mL of pure water, and then concentrated under reduced pressure to obtain 24.5 g of (yield 95%) 2-((2,2,3 , 3,4,4,4-heptafluorobutyl) oxy) acetic acid.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ = ppm,): δ = 4.11 (t, 2H), 4.30 (s, 2H), 6.61 (br, 1H).

Next, 12.9 g (0.050 mol) of 2-((2,2,3,3,4,4,4-heptafluorobutyl) oxy) acetic acid and 28.9 g (0.053 mol) of polyethylene were stirred and mixed. Diethylene glycol monomethyl ether (number average molecular weight 550, manufactured by Sigma-Aldrich), 0.48 g (2.5 mmol) of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries), 50 mL of toluene, using Diane A Dean-Stark apparatus was reacted under heating and reflux for 4 hours to perform dehydration condensation. After the reaction, 300 mL of chloroform and 150 mL of 2% sodium bicarbonate water were used for liquid separation extraction. The obtained organic layer was washed with 150 mL of 0.1N hydrochloric acid water, and then washed with 150 mL of pure water, and then concentrated under reduced pressure to obtain 37.5 g (yield 96%) of the target fluorine-containing compound (C-1 ) Is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.38 (s, 3H), 3.55 (t, 2H), 3.65 (s, 42H), 3.72 (t, 2H), 4.13 ( t, 2H), 4.28 (s, 2H), 4.33 (t, 2H).

Synthesis of fluorinated compound (C-2)

In addition to using 26.4g (0.10 mole) of 3,3,4,4,5,5,5,6,6,6-nonafluorohexanol (manufactured by Wako Pure Chemical Industries), 18.4g (0.053 mole) of polyethylene Except for diol monomethyl ether (number-average molecular weight 350, manufactured by Sigma-Aldrich), in the same manner as in the synthesis of the fluorine-containing compound (C-1), the target fluorine-containing compound (C-2) was obtained as a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 2.48 (m, 2H), 3.38 (s, 3H), 3.55 (t, 2H), 3.65 (s, 26H), 3.72 ( t, 2H), 3.86 (t, 2H), 4.15 (s, 2H), 4.32 (t, 2H).

Synthesis of fluorinated compound (C-3)

In addition to using 26.4g (0.10 mole) of 3,3,4,4,5,5,5,6,6,6-nonafluorohexanol (manufactured by Wako Pure Chemical Industries), it is compatible with the above-mentioned fluorine-containing compounds (C-1 Synthesis of) Similarly, the target fluorine-containing compound (C-3) was obtained as a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 2.48 (m, 2H), 3.38 (s, 3H), 3.55 (t, 2H), 3.65 (s, 42H), 3.72 ( t, 2H), 3.86 (t, 2H), 4.15 (s, 2H), 4.32 (t, 2H).

Synthesis of fluorinated compound (C-4)

In addition to using 30.0g (0.10 mol) of 2,2,3,3,4,4,5,5,5,6,6,6-undecfluorohexanol (manufactured by Wako Pure Chemical Industries), 18.4g (0.053 mol) Ear) except polyethylene glycol monomethyl ether (number average molecular weight 350, manufactured by Sigma-Aldrich), the same as the above-mentioned synthesis of the fluorine-containing compound (C-1), the target fluorine-containing compound (C-4) was obtained. , Is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.38 (s, 3H), 3.54 (t, 2H), 3.64 (s, 26H), 3.72 (t, 2H), 4.13 ( t, 2H), 4.28 (s, 2H), 4.33 (t, 2H).

Synthesis of fluorinated compound (C-5)

In addition to using 30.0g (0.10 mole) of 2,2,3,3,4,4,5,5,5,6,6,6-undecfluorohexanol (manufactured by Wako Pure Chemical Industries), it contains fluorine Synthesis of Compound (C-1) Similarly, the target fluorine-containing compound (C-5) was obtained as a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.38 (s, 3H), 3.54 (t, 2H), 3.64 (s, 42H), 3.72 (t, 2H), 4.13 ( t, 2H), 4.28 (s, 2H), 4.33 (t, 2H).

Synthesis of fluorinated compound (C-6)

In addition to using 30.0g (0.10 mol) of 2,2,3,3,4,4,5,5,5,6,6,6-undecfluorohexanol (made by Wako Pure Chemical Industries), 39.4g (0.053 mol Ear) except for polyethylene glycol monomethyl ether (number average molecular weight 750, manufactured by Sigma-Aldrich), the same fluorine-containing compound (C-1) was synthesized as in the above, to obtain the target fluorine-containing compound (C-6) , Is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.38 (s, 3H), 3.54 (t, 2H), 3.64 (s, 58H), 3.72 (t, 2H), 4.13 ( t, 2H), 4.28 (s, 2H), 4.33 (t, 2H).

Synthesis of fluorinated compound (C-7)

In addition to using 36.4g (0.10 mole) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctanol (manufactured by Wako Pure Chemical Industries), Similarly to the above-mentioned synthesis of the fluorine-containing compound (C-1), the target fluorine-containing compound (C-7) was obtained as a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 2.49 (m, 2H), 3.38 (s, 3H), 3.55 (t, 2H), 3.65 (s, 42H), 3.72 ( t, 2H), 3.86 (t, 2H), 4.15 (s, 2H), 4.32 (t, 2H).

Synthesis of fluorinated compound (C-8)

In addition to using 36.4g (0.10 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol (manufactured by Wako Pure Chemical Industries), 39.4 g (0.053 moles) of polyethylene glycol monomethyl ether (number-average molecular weight 750, manufactured by Sigma-Aldrich), in the same manner as in the synthesis of the above-mentioned fluorine-containing compound (C-1), the target fluorine-containing compound ( C-8) is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 2.49 (m, 2H), 3.38 (s, 3H), 3.55 (t, 2H), 3.65 (s, 58H), 3.72 ( t, 2H), 3.86 (t, 2H), 4.15 (s, 2H), 4.32 (t, 2H).

Synthesis of fluorinated compound (C-9)

In addition to using 36.4g (0.10 mole) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluorooctanol (made by Wako Pure Chemical Industries), 52.5 g (0.053 moles) of polyethylene glycol monomethyl ether (number average molecular weight 1000, Uniox M-1000, manufactured by Nippon Oil), in the same manner as in the synthesis of the fluorine-containing compound (C-1), the target content was obtained. Fluorine compound (C-9) is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 2.49 (m, 2H), 3.38 (s, 3H), 3.55 (t, 2H), 3.65 (s, 74H), 3.72 ( t, 2H), 3.86 (t, 2H), 4.15 (s, 2H), 4.32 (t, 2H).

Synthesis of fluorinated compound (C-10)

In addition to using 33.2 g (0.10 mol) of 2,2,3,3,4,4,5,5,5,6,6-dodecylfluoroheptanol (manufactured by Tokyo Chemical Industry Co., Ltd.), it is compatible with the above-mentioned fluorine-containing compound (C Synthesis of -1) Similarly, the target fluorine-containing compound (C-10) was obtained as a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.37 (s, 3H), 3.54 (t, 2H), 3.64 (s, 42H), 3.72 (t, 2H), 4.13 ( t, 2H), 4.27 (s, 2H), 4.33 (t, 2H), 6.08 (tt, 1H).

Synthesis of fluorinated compound (C-11)

The target fluorine-containing compound (C-11) was obtained as a colorless liquid in the same manner as in the synthesis of the fluorine-containing compound (C-1) except that 54.0 g of Megafac F-444 (manufactured by DIC) was used.

Synthesis of fluorinated compound (C-12)

A target fluorine-containing compound (C-) was obtained in the same manner as in the synthesis of the fluorine-containing compound (C-1) except that 10 g (0.025 mole) of polyethylene glycol (number average molecular weight 400, manufactured by Sigma-Aldrich) was used. 12) is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.65 (s, 28H), 3.72 (m, 4H), 4.12 (t, 4H), 4.28 (s, 4H), 4.33 ( m, 4H).

Synthesis of fluorinated compound (C-13)

The target fluorine-containing compound (C-) was obtained in the same manner as in the synthesis of the fluorine-containing compound (C-1) except that 15 g (0.025 mole) of polyethylene glycol (number average molecular weight 600, manufactured by Sigma-Aldrich) was used. 13) is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.65 (s, 44H), 3.72 (m, 4H), 4.12 (t, 4H), 4.28 (s, 4H), 4.33 ( m, 4H).

Synthesis of fluorinated compound (C-14)

In addition to using 26.4g (0.10 mole) of 3,3,4,4,5,5,5,6,6,6-nonafluorohexanol (manufactured by Wako Pure Chemical Industries), 15g (0.025 mole) of polyethylene The target fluorine-containing compound (C-14) was obtained as a colorless liquid in the same manner as in the synthesis of the fluorine-containing compound (C-1) except for the alcohol (number-average molecular weight 600, manufactured by Sigma-Aldrich).

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 2.48 (m, 4H), 3.65 (s, 44H), 3.72 (t, 4H), 3.86 (t, 4H), 4.15 ( s, 4H), 4.32 (t, 4H).

Synthesis of fluorinated compound (C-15)

In addition to using 30.0g (0.10 mol) of 2,2,3,3,4,4,5,5,5,6,6,6-Undecafluorohexanol (manufactured by Wako Pure Chemical Industries), 15g (0.025 mol) Except for polyethylene glycol (number average molecular weight 600, manufactured by Sigma-Aldrich), the target fluorine-containing compound (C-15) was obtained as a colorless liquid in the same manner as in the above-mentioned synthesis of the fluorine-containing compound (C-1).

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 3.65 (s, 44H), 3.72 (m, 4H), 4.13 (t, 4H), 4.27 (s, 4H), 4.33 ( m, 4H), 6.08 (tt, 2H).

Synthesis of fluorinated compound (C-16)

The target fluorine-containing compound (C-16) was obtained in the same manner as in the synthesis of the fluorine-containing compound (C-1) except that 17.5 g (0.025 mole) of polypropylene glycol (number-average molecular weight 700, manufactured by Sigma-Aldrich) was used. ) Is a colorless liquid.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ = ppm,): δ = 1.14 (d, 30H), 1.23 (d, 6H), 3.2-3.8 (m, 34H), 4.12 (t, 4H), 4.28 (s, 4H), 5.02 (m, 2H).

<Preparation of hardenable composition for photoimprint>

The polymerizable compound (A), the photopolymerization initiator (B), and the fluorine-containing compound (C) were mixed at a mass ratio shown in Tables 1 and 2, and the content was 200 ppm (0.02 mass) based on the curable composition. %), A 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a polymerization inhibitor. This was filtered through a 0.1 μm PTFE filter to prepare the hardenable compositions X-1 to X-16 for photoimprinting according to the present invention and the hardenable compositions R-1 to R-4 for comparison. Using an E-type viscometer RE85L (Toki Sangyo) and a surface tensiometer CBVP-A3 (Kyowa Interface Chemistry), the viscosity and surface tension of the prepared hardening composition at 23 ° C were measured.

The details of the polymerizable compound (A), the photopolymerization initiator (B), and the comparative compound (S) used in the examples and comparative examples are as follows.

<Polymerizable compound (A)>

A-1: 2-phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry, Viscoat # 192)

A-2: Synthesis from α, α'-dichloro-m-xylene and acrylic acid

A-3: 2- (perfluorohexyl) ethyl acrylate (manufactured by Daikin Industries, R-1620)

<Photopolymerization initiator (B)>

B-1: Irgacure 819 (manufactured by BASF)

B-2: Darocure 1173 (manufactured by BASF)

<Comparative Compound (S)>

S-1: ZONYL FSO-100 (made by Dupont)

ZONYL FSO-100 is a chemical structure of F (CF ₂ CF ₂ ) _x CH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H, x = 1 ~ 7, y = 0 ~ 15.

<Preparation of lower film composition>

3 g of NK oligo EA-7140 / PGMAc (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) was dissolved in 997 g of propylene glycol monomethyl ether acetate, and then filtered through a 0.1 μm tetrafluoroethylene filter to obtain a lower layer membrane composition. .

NK oligomer EA-7140 / PGMAc (solid content 70%)

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

(Evaluation)

The obtained curable compositions for photoimprint of each of the examples and comparative examples were evaluated as follows. The results are shown in Table 2 below.

<Inkjet discharge accuracy>

On a silicon wafer, an inkjet printer DMP-2831 (manufactured by FUJIFILM Dimatix) was used to dispense a hardening composition for photoimprint, the temperature of which was adjusted to 23 ° C. with a droplet volume of 1 pl per nozzle, The droplets were applied on a silicon wafer in a square arrangement with 100 μm intervals.

The 2500 points on a 5 mm square of the coated substrate were observed, and the deviation from the square arrangement was measured to calculate the standard deviation σ. The inkjet discharge accuracy is evaluated as A to D as follows.

A: σ <3μm

B: 3μm ≦ σ <5μm

C: 5μm ≦ σ <10μm

D: 10μm ≦ σ

<Evaluation of release force>

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

On the surface of the lower film on the silicon wafer, an inkjet printer DMP-2831 (manufactured by FUJIFILM Dimatix) was used, and a droplet amount of 1 pl per nozzle was used to spit out light embossing with the temperature adjusted to 23 ° C The sexual composition is applied on the lower layer film so that the droplets are arranged in a square array with an interval of about 100 μm.

For the hardenable composition that has been coated on the underlayer film, contact it with a quartz mold under a reduced pressure of 0.1 atmosphere (line / gap = 1/1, line width 30nm, groove depth 60nm, line edge roughness 3.0nm) Using a high-pressure mercury lamp from the side of the quartz mold, exposure was performed under the condition of 100 mJ / cm ² . After the exposure, the quartz mold was removed and the demolding force (F) at that time was measured. The mold release force (F) was measured according to the method described in Comparative Examples described in [0102] to [0107] of Japanese Patent Application Laid-Open No. 2011-206977. The mold release force (F) is evaluated as A to E as follows.

A: F <13N

B: 13N ≦ F <15N

C: 15N ≦ F <20N

D: 20N ≦ F <30N

E: 30N ≦ F

As is clear from the results in Table 3, the curable composition for photoimprint obtained in Examples 1 to 16 was excellent in mold release property and inkjet discharge accuracy.

On the other hand, Comparative Example 1 shows that although the amount of Zonyl FSO-100 added was as small as 1%, the surface tension of the composition was significantly reduced, and the inkjet ejection accuracy and mold releasability were poor.

It can be seen that the addition amount of Zonyl FSO-100 of Comparative Example 2 is 0.3%, which is less than that of Comparative Example 1. Although the surface tension of the composition becomes an appropriate value, the inkjet discharge accuracy is improved, but the mold release is worse. Furthermore, Zonyl FSO-100 series cannot uniformly dissolve 2% or more in the hardenable composition for photoimprint.

It is understood that Comparative Examples 3 and 4 do not contain a fluorine-containing compound represented by the general formula (I) or the general formula (II), and thus have poor mold release properties.

As described above, according to the present invention, it is understood that the curable composition for photoimprint contains a polymerizable compound, a photopolymerization initiator, a fluorine-containing compound represented by the general formula (I), and At least one of the fluorinated compounds shown can provide good mold release properties and inkjet discharge accuracy.

In addition, it can be seen that if the viscosity of the curable composition of the present invention differs by 1 mPa. s, has a great impact on the effect of the present invention. In addition, it can be seen that even if the curable composition of the present invention has the same viscosity, if the surface tension is different by 3 mN / m, for example, the effect of the present invention is greatly affected.

Claims (12)

A curable composition for photoimprint, comprising a polymerizable compound, a photopolymerization initiator, and a fluorine-containing compound. The content of the fluorine-containing compound is 2 to 10% by mass, and the fluorine-containing compound includes the following general formula ( At least one compound represented by I) and a compound represented by the following general formula (II); In the general formulae (I) and (II), Rf ¹ to Rf ³ each independently represent a fluorine-containing alkyl group having 1 to 9 carbon atoms having 2 or more fluorine atoms; R represents an alkyl group having 1 to 8 carbon atoms, Alkenyl group with 2 to 8 carbon atoms, aryl group with 6 to 8 carbon atoms; 11 to 13 each independently represent 0 to 10; m each independently represents an integer of 2 to 4; n1 and n2 each independently represent 1 to 25 . For example, the curable composition for photoimprint according to claim 1 contains 2 to 10% by mass of the fluorine-containing compound with respect to all components other than the solvent. The curable composition for photoimprint according to claim 1 or 2, wherein m is 2 in the general formula (I) or (II). The curable composition for photoimprint according to claim 1 or 2, wherein in the general formula (I), R is a methyl group. For example, the curable composition for photoimprint according to claim 1 or 2, wherein the terminal structure of Rf ¹ to Rf ³ in the general formula (I) or (II) is -CF ₃ or -C (HF ₂ ). The curable composition for photoimprint according to claim 1 or 2, wherein the polymerizable compound is a (meth) acrylate compound. The curable composition for photoimprint according to claim 1 or 2, wherein the polymerizable compound is a compound having an aromatic group. The curable composition for photoimprint according to claim 1 or 2, wherein the curable composition for photoimprint does not substantially contain a solvent. For example, the curable composition for photoimprint of item 1 or 2, wherein the viscosity of the curable composition for photoimprint at 23 ° C is 15 mPa. s or less and the surface tension is 25 ~ 35mN / m. A pattern forming method comprising applying a curable composition for photoimprint according to any one of claims 1 to 9 on a base material or a mold having a pattern, and sandwiching the light pressure between the mold and the base material. In the state of the curable composition for printing, light irradiation is performed. The pattern forming method according to claim 10, wherein the method of applying the curable composition for photoimprint on a substrate or a mold having a pattern is an inkjet method. A pattern obtained by a pattern forming method as claimed in claim 10 or 11.