Photocurable resin composition and method of forming patterns using the same

Abstract

The present invention relates to a photocurable resin composition usable in a nanoimprint process which is capable of overcoming low productivity of conventional semiconductor processes for optical devices and electronic devices, and a method of forming patterns using the same. Specifically, the present invention relates to a photocurable resin composition including a specific perfluorinated acrylic compound for improving release property between a nanoimprint mold and the photocurable resin composition, and a method of forming patterns using the same.

Claims

1. A method of forming patterns comprising: forming a fine pattern layer by applying a photocurable resin composition to one surface of a substrate and releasing the composition into a mold, the composition including 30 to 60 wt % of a fluorine-based acrylic compound (A) represented by Chemical Formula 1 below, 10 to 65 wt % of an acrylic compound (B) having one or two photopolymerizable functional group(s) in a molecule, and 0.001 to 5 wt % of a photoinitiator (D); and photocuring by irradiating light to the fine pattern layer, wherein the acrylic compound (B) includes an acrylic compound represented by Chemical Formula 3 below: ##STR00010## in Chemical Formula 1, R.sub.1 and R.sub.2 are each independently hydrogen or (C1-C10)alkyl; and L.sub.1 is CF.sub.2(OCF.sub.2CF.sub.2).sub.mOCF.sub.2, and m is an integer selected from 1 to 5, and ##STR00011## in Chemical Formula 3, R.sub.5 is hydrogen or (C1-C10)alkyl; R.sub.6 is (C1-C10)alkyl, (C3-C20)cycloalkyl, (C3-C20)heterocycloalkyl, (C6-C20)aryl(C1-C10)alkyl, (C6-C20)aryl, (C3-C20)heteroaryl, di(C1-C10)alkylsilyl, tri(C1-C10)alkylsilyl, di(C1-C10)alkoxysilyl, tri(C1-C10)alkoxysilyl, di(C1-C10)alkyl(C6-C20)arylsilyl, or tri(C6-C20)arylsilyl; and the alkyl, aryl-substituted alkyl, cycloalkyl, heterocycloalkyl, aryl, alkylaryl, heteroaryl, trialkylsilyl, dialkylarylsilyl, and triarylsilyl of R.sub.6 are each independently substituted with Si(OR.sub.21).sub.3, wherein R.sub.21 is (C1-C10)alkyl or (C3-C20)cycloalkyl.

2. The method of claim 1, wherein the applying is performed by a method selected from spin coating, bar coating, spray coating, and ink jet coating.

3. The method of claim 1, wherein a dry application thickness of the fine pattern layer is 1 to 150 nm.

4. The method of claim 1, wherein the composition further includes a compound (C) having three or more functional groups selected from the photopolymerizable functional group in a molecule, and a functional group capable of reacting with the photopolymerizable functional group.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows a method of forming patterns using a composition according to the present invention.

DETAILED DESCRIPTION OF MAIN ELEMENTS

(2) 10: Substrate 20: Resin composition 30: Stamp

BEST MODE

(3) Hereinafter, a photocurable resin composition and a method of forming patterns using the same according to the present invention will be described in more detail through Examples including the accompanying drawings. Meanwhile, the following exemplary embodiments and Examples are provided as a reference for explaining the present invention in detail, and therefore, the present invention is not limited thereto, but may be implemented in various ways.

(4) Unless defined otherwise, all technical and scientific terms used herein have the same meanings generally understood by those skilled in the art to which the present invention pertains, and terms used in the detailed description of the present invention effectively describe specific exemplary embodiments, and are not intended to limit the present invention.

(5) Terms alkyl, alkoxy, and other substituents including alkyl part described in the present invention include all linear or branched forms. In addition, aryl described in the present invention, which is an organic radical derived from aromatic hydrocarbon by removal of one hydrogen, includes a single ring system or a fused ring system suitably including 4 to 7 ring atoms, preferably, 5 or 6 ring atoms in each ring, and even includes a form in which a plurality of aryls are connected by a single bond. Specific examples of the aryl may include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, etc., but the present invention is not limited thereto. Further, term heteroaryl described in the present invention, which is an organic radical derived from aromatic hydrocarbon by removal of one hydrogen, may be a monocyclic or polycyclic aromatic hydrocarbon radical including 3 to 8 ring atoms that include one or more heteroatoms selected from B, N, O, S, P(O), Si and P, and includes a single ring system or a fused ring system suitably including 3 to 7 ring atoms, preferably, 5 or 6 ring atoms in each ring, and even includes a form in which a plurality of heteroaryls are connected to each other by a single bond.

(6) Term cycloalkyl described in the present invention means a completely saturated and a partially unsaturated hydrocarbon ring including 3 to 9 carbon atoms, and includes fused aryl or heteroaryl. Term heterocycloalkyl described in the present invention may be a monocyclic or polycyclic non-aromatic radical including 4 to 10 ring atoms that include one or more heteroatoms selected from B, N, O, S, P(O), Si and P.

(7) The photocurable resin composition for imprinting according to the present invention may have high transparency, and may form a cured film, a nanostructure, etc., having remarkably improved close-adhesion with a substrate, and may form fine patterns by using various forms of molds.

(8) In addition, the resin composition according to the present invention may include a fluorine-based acrylic compound (A) represented by Chemical Formula 1 below, an acrylic compound (B) having one or two photopolymerizable functional group(s) in a molecule, and a photoinitiator (D) to suppress swelling or peeling phenomenon, etc., at an interface with a substrate:

(9) ##STR00006##

(10) in Chemical Formula 1,

(11) R.sub.1 and R.sub.2 are each independently hydrogen or (C1-C10)alkyl; and

(12) L.sub.1 is (CF.sub.2).sub.n or CF.sub.2(OCF.sub.2CF.sub.2).sub.mOCF.sub.2, n is an integer selected from 2 to 10, and m is an integer selected from 1 to 5.

(13) Further, the resin composition according to the present invention may have the above-described composition to exhibit excellent release property even without performing additional release treatment on the mold, such that it is possible to perform continuous transfer, thereby manufacturing a cured film, a nanostructure, etc., using the same with high productivity.

(14) The resin composition according to an exemplary embodiment of the present invention may have the above-described combination to exhibit good miscibility and may implement excellent release property even without performing additional release treatment on the mold. Here, in view of providing more effective release property, R.sub.1 and R.sub.2 of the fluorine-based acrylic compound (A) represented by Chemical Formula 1 may be each independently hydrogen or (C1-C7)alkyl; and m may be an integer of 1 or 2, preferably, R.sub.1 and R.sub.2 of the fluorine-based acrylic compound (A) represented by Chemical Formula 1 may be each independently selected from hydrogen, methyl, ethyl, propyl, etc. Further, in view of excellent etching resistance as well as the above-described effects, more preferably, the fluorine-based acrylic compound (A) may be one or more selected from 1H,1H,4H,4H-perfluoro-1,4-butanediol diacrylate, 1H,1H,5H,5H-perfluoro-1,5-pentanediol diacrylate, 1H,1H,6H,6H-perfluoro-1,6-hexanediol diacrylate, 1H, 1H,8H, 8H-perfluoro-1,8-octanediol diacrylate, 1H,1H,9H,9H-perfluoro-1,9-nonanediol diacrylate, 1H,1H,10H,10H-perfluoro-1,10-decanediol diacrylate, 1H,1H,12H,12H-perfluoro-1,12-undecanediol diacrylate, 1H, 1H,8H,8H-perfluoro-3,6-dioxaoctane-1,8-diol diacrylate), 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol diacrylate (C.sub.14H.sub.10F.sub.12O.sub.7), 1H, 1H,14H,14H-perfluoro-3,6,9,12-tetraoxatetradecane-1,14-diol diacrylate (C.sub.16H.sub.10F.sub.16O.sub.8), fluorinated polyethylene glycol diacrylate, etc., but is not limited thereto.

(15) Further, the resin composition according to an exemplary embodiment of the present invention may have a combination including one or more selected from acrylic compounds (B) represented by Chemical Formulas 2 and 3 below to improve a gap fill property with the etched substrate:

(16) ##STR00007##

(17) in Chemical Formulas 2 and 3,

(18) R.sub.3, R.sub.4 and R.sub.5 are each independently hydrogen or (C1-C10)alkyl;

(19) R.sub.6 is hydrogen, (C1-C10)alkyl, (C3-C20)cycloalkyl, (C3-C20)heterocycloalkyl, (C6-C20)aryl(C1-C10)alkyl, (C6-C20)aryl, (C3-C20)heteroaryl, di(C1-C10)alkylsilyl, tri(C1-C10)alkylsilyl, di(C1-C10)alkoxysilyl, tri(C1-C10)alkoxysilyl, di(C1-C10)alkyl(C6-C20)arylsilyl, tri(C6-C20)arylsilyl or

(20) ##STR00008##
p is an integer of 1 to 5, and R.sub.11 is hydrogen, (C1-C10)alkyl or (C6-C20)aryl;

(21) L.sub.2 is a single bond, (C1-C10)alkylene, (C6-C20)arylene or

(22) ##STR00009##
and q is an integer of 1 to 5; and

(23) the alkyl, aryl-substituted alkyl, cycloalkyl, heterocycloalkyl, aryl, alkylaryl, heteroaryl, trialkylsilyl, dialkylarylsilyl, triarylsilyl of R.sub.6, and the alkylene and arylene of L.sub.2 may be each independently substituted with one or more substituents independently selected from the group consisting of fluorine, cyano, nitro, OR.sub.21, SR.sub.21, (C.sub.6-C.sub.10)aryl, O(C.sub.6-C.sub.10)aryl, hydroxy(C.sub.1-C.sub.5)alkyl, halo(C.sub.1-C.sub.7)alkyl, Si(OR.sub.21).sub.3, NR.sub.21R.sub.22C(O)R.sub.21, COOR.sub.21 and C(O)NR.sub.21R.sub.22, wherein R.sub.21 to R.sub.23 are each independently (C1-C10)alkyl, (C3-C20)cycloalkyl, (C3-C20)heterocycloalkyl, (C6-C20)aryl or (C3-C20)heteroaryl, and the heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P(O), Si and P.

(24) Here, it is preferred that the acrylic compound (B) simultaneously includes a photopolymerizable functional group and a functional group capable of reacting with the photopolymerizable functional group, wherein the photopolymerizable functional group may be an acrylic group, etc., and the functional group capable of reacting with the photopolymerizable functional group may be a hydroxyl group, a thiol group, an alkoxysilyl group, etc., but is not limited thereto.

(25) In order to have the above-described effects, a specific example of the acrylic compound (B) included in the resin composition according to the present invention may be one or more selected from diacrylate-based compounds such as 3,5,7,9-tetraoxa-4,6,8-trisilaundecane-1,11-diol dimethacrylate, 4,6,8-hexamethyl-3,5,7,9-tetraoxa-4,6,8-trisilaundecane-1,11-diol dimethacrylate, 4,6,8-trimethyl-4,6,8-triphenyl-3,5,7,9-tetraoxa-4,6,8-trisilaundecane-1,11-diol dimethacrylate, 1,4-cyclohexanedimethanol-1,4-diacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, triethyleneglycol diacrylate, polyethyleneglycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, etc., and monoacrylate-based compounds such as 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 3-phenoxybenzyl acrylate, 3-phenoxybenzyl methacrylate, phenoxy tetraethyleneglycol acrylate, phenoxy triethyleneglycol acrylate, phenoxy diethyleneglycol acrylate, phenoxy polyethyleneglycol acrylate, phenoxy tetraethyleneglycol methacrylate, phenoxy triethyleneglycol methacrylate, phenoxy diethyleneglycol methacrylate, methoxy polyethyleneglycol methacrylate, tetrahydrofuryl acrylate, cyclohexyl methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl acrylate, 3-(methacryloxypropyl)trimethoxysilane, 3-(acryloxypropyl)trimethoxysilane), etc. In view of improvement of mutual miscibility of the compositions and improvement close-adhesion with the substrate, it is preferred to include two or more selected from 2-phenoxyethyl acrylate, tetrahydrofuryl acrylate, 3-(methacryloxypropyl)trimethoxysilane, 3-phenoxybenzyl acrylate, phenoxytetraethylene glycol acrylate, isobornyl acrylate, phenoxy diethylene glycol acrylate, 3-(methacryloxypropyl)trimethoxysilane, polyethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,4-cyclohexanedimethanol-1,4-diacrylate, dimethylol tricyclodecane diacrylate, and dipropylene glycol diacrylate, etc.

(26) Further, when wet etching is performed, it is preferred that post-baking is additionally performed to prevent undercut due to penetration of an etching solution. Here, the post-baking may be performed at normal temperature, preferably, 90 to 150 C., but the temperature of the post-baking is not limited thereto.

(27) The resin composition according to the present invention may have excellent etching resistance and etching selectivity to form uniformly and evenly coated cured film, nanostructure, etc., and to form fine patterns by using various forms of molds, etc., or using the etching solution.

(28) The resin composition according to the present invention may have excellent release property with a mold and may form transparent patterns having good surface film quality by mixing 30 to 60 wt % of the fluorine-based acrylic compound (A), 10 to 65 wt % of the acrylic compound (B), and 0.001 to 5 wt % of the photoinitiator (D). Here, the resin composition may further include 1 to 25 wt % of a compound (C) to be capable of excellently improving, in particular, etching resistance to carbon tetrafluoride (CF.sub.4).

(29) A viscosity of the resin composition having the above composition ratio according to an exemplary embodiment of the present invention is preferably 5 to 1000 cps (centipoise, 25 C.), but is not limited thereto. In order to further improve permeability of the resin in a mold for imprinting, it is preferred that the viscosity is 5 to 100 cps (25 C.), and more preferably, 5 to 20 cps (25 C.).

(30) A shape, a size, etc., of concavo-convex patterns of the mold according to the present invention are not limited, and may be appropriately determined according to a shape, a size, etc., of patterns of a target cured film or a target nanostructure. A cross-sectional shape of each concave part in the concavo-convex patterns is not specifically limited, but may be varied, for example, in a square, a rectangle, a semicircle, a triangle, a shape similar to these shapes, an irregular shape, etc. Here, a depth of each concave part of the concavo-convex pattern is not specifically limited, but is preferably 1 nm to 100 m, and a width of an opening part of each concave part is not specifically limited, but is preferably 1 nm to 100 m.

(31) The resin composition according to an exemplary embodiment of the present invention may further include a compound (C) which is a multifunctional photocrosslinking compound in view of increasing adhesion force with the substrate. The compound (C) may be mixed with the fluorine-based acrylic compound (A) and the acrylic compound (B), etc., that are mixed in the resin composition according to the present invention to remarkably improve close-adhesion force between the substrate and the resin composition and may have high miscibility with the fluorine-based acrylic compound (A) to exhibit excellent and uniform close-adhesion force at a heterogeneous interface. Specific examples of the compound (C) which is the multifunctional photocrosslinking compound may be one or more selected from trimethylolpropane tris(3-mercaptopropionate), tris(2-hydroxyethyl isocyanurate)triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate, etc., but is not limited thereto.

(32) The present invention provides a method of forming patterns including: forming a fine pattern layer by applying a photocurable resin composition to one surface of a substrate and releasing the composition into a mold, the composition including a fluorine-based acrylic compound (A) represented by Chemical Formula 1, an acrylic compound (B) having one or two photopolymerizable functional group(s) in a molecule, and a photoinitiator (D); and photocuring by irradiating light to the fine pattern layer.

(33) The resin composition according to an exemplary embodiment of the present invention further includes: a compound (C) having three or more functional groups selected from the photopolymerizable functional group in a molecule, and a functional group capable of reacting with the photopolymerizable functional group, which is preferred since it is able to minimize swelling or peeling phenomenon, etc., at an interface with a substrate.

(34) Here, the acrylic compound (B) may be one or more selected from Chemical Formulas 2 and 3, and the compound (C) may be one or more selected from trimethylolpropane tris(3-mercaptopropionate), tris(2-hydroxyethyl isocyanurate)triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate, etc., but is not limited thereto.

(35) Further, the photoinitiator (D) according to an exemplary embodiment of the present invention acts to photocure the resin composition, and is not limited as long as it is a general photoinitiator. Specific examples thereof may include one or more selected from benzionalkylether, benzophenone, benzyl dimethylkatal, hydroxycyclohexyl phenylacetone, chloroacetophenone, 1,1-dichloro acetophenone, diethoxy acetophenone, hydroxyl acetophenone, 2-chorothioxanthone, 2-ethylanthraquinone (2-ETAQ), 1-hydroxycyclohexyl phenyl ketone (Irgacure 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, and methylbenzoylformate, etc., but is not limited thereto.

(36) In the method of forming patterns according to an exemplary embodiment of the present invention, the coating is preferably performed by a method selected from spin coating, bar coating, spray coating, and inkjet coating, etc., and may be performed by general application methods.

(37) The fine pattern layer formed by the method of forming patterns according to the present invention is not limited, but preferably has a dry applying thickness of 1 to 150 nm, preferably, 1 to 100 nm, and more preferably, 1 to 50 nm, which is preferred since it is able to minimize a residual layer after UV imprinting.

(38) Hereinafter, the present invention is described in detail on the basis of Examples and Comparative Examples. Meanwhile, the following Examples are provided by way of example for explaining the present invention in more detail, and therefore, the present invention is not limited thereto.

Example 1

(39) Preparation of Photocurable Resin Composition

(40) 1H,1H,4H,4H-perfluoro-1,4-butanediol diacrylate (47 g), phenoxyethyl acrylate (24 g), tetrahydrofuryl acrylate (23 g), 3-(methacryloxypropyl) trimethoxysilane (1 g), trimethylolpropane tris(3-mercaptopropionate) (1 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature (25 C.) for 24 hours, thereby preparing a photocurable resin composition.

(41) B. Method of Forming Patterns

(42) The photocurable resin composition was spin-coated on a silicon wafer substrate (10 cm10 cm) at a rotation speed of 3,000 rpm for 30 seconds. A urethane mold (mass 15 g, ground part 5 mm5 mm) having rectangular patterns shown in FIG. 1 was mounted on the spin-coated substrate, and then, an entire surface was exposed for 3 minutes at an exposure amount of 13 mW/cm.sup.2 (UV A standard) using a proximity exposure machine TME-150 PRC manufactured by Topcon Co., Ltd. The exposure amount was measured by using an integrating light-meter UIT-102 manufactured by Ushio Electric Co., Ltd., and a receiver UVD-365PD. After the exposure, the mold was removed, and post-baked in an oven at 120 C. for 5 minutes to form patterns (dry coating thickness=5 m).

(43) Physical properties of the patterns manufactured by the method as described above were measured as follows, and shown in Table 1 below.

(44) Evaluation of Coating Property

(45) States before and after the curing were confirmed using a scanning electron microscope (SEM, Hitachi S-4700). Here, when a material having poor miscibility was used, comb patterns were confirmed at the time of spin coating, but the present invention had a clear film quality without the comb patterns.

(46) 2) Measurement of Viscosity

(47) For measuring the viscosity of the photocurable resin composition, an initial viscosity (based on 25 C.) was measured using a DV-II+VISCOMETER (Brookfield) at 41 spindle/30 rpm. The measurement amount (3 mL) was the same, and an error was minimized by measuring the viscosity in a state in which there were no bubbles.

(48) 3) Measurement of Etching Resistance

(49) For confirming etching resistance, a thickness was confirmed by Alpha-step by etching through inductively coupled plasma (ICP) equipment. A gas for etching was CF.sub.4, and the etching was performed three times (i.e., primary, secondary, and tertiary etchings) in the same equipment under the same conditions. The thickness after etching was measured 3 times continuously and an average value was used. The etched thickness and etching time (min) were confirmed to calculate the etching resistance according to the following equation, and expressed as an average value of the primary, secondary, and tertiary etchings.
Etching resistance=(etched thickness (um)/etching time (min))

Example 2

(50) Preparation of Photocurable Resin Composition

(51) 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol diacrylate (38 g), 4,6,8-hexamethyl-3,5,7,9-tetraoxa-4,6,8-trisilaundecane-1,11-diol dimethacrylate (31 g), polyethyleneglycol diacrylate (13 g), triethyleneglycol dimethacrylate (13 g), 3-(methacryloxypropyl)trimethoxysilane (1 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature for 24 hours, thereby preparing a photocurable resin composition.

(52) B. Method of Forming Patterns

(53) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Example 2 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Example 3

(54) Preparation of Photocurable Resin Composition

(55) 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol diacrylate (45 g), 1,4-cyclohexanedimethanol-1,4-diacrylate (32 g), polyethyleneglycol diacrylate (5 g), triethyleneglycol dimethacrylate (13 parts by weight), 3-(methacryloxypropyl)trimethoxysilane (1 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature for 24 hours, thereby preparing a photocurable resin composition.

(56) B. Method of Forming Patterns

(57) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Example 3 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Example 4

(58) Preparation of Photocurable Resin Composition

(59) A photocurable resin composition was prepared under the same conditions as Example 3 except for using 3-phenoxybenzyl acrylate rather than using triethyleneglycol dimethacrylate in the photocurable resin composition of Example 3.

(60) B. Method of Forming Patterns

(61) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Example 4 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Example 5

(62) Preparation of Photocurable Resin Composition

(63) 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol diacrylate (45 g), 1,4-cyclohexanedimethanol-1,4-diacrylate (16 g), phenoxy tetraethyleneglycol acrylate (5 g), 3-phenoxybenzyl acrylate (29 g), 3-(methacryloxypropyl)trimethoxysilane (1 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature for 24 hours, thereby preparing a photocurable resin composition.

(64) B. Method of Forming Patterns

(65) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Example 5 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Example 6

(66) Preparation of Photocurable Resin Composition

(67) 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol diacrylate (40 g), dimethylol tricyclodecane diacrylate (10 g), isobornyl acrylate (26 g), phenoxy diethyleneglycol acrylate (20 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature for 24 hours, thereby preparing a photocurable resin composition.

(68) B. Method of Forming Patterns

(69) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Example 6 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Example 7

(70) Preparation of Photocurable Resin Composition

(71) 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol diacrylate (41 g), dimethylol tricyclodecane diacrylate (5 g), dipropyleneglycol diacrylate (35 g), dipentaerythritol hexaacrylate (DPHA) (1 g), phenoxy diethyleneglycol acrylate (14 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature for 24 hours, thereby preparing a photocurable resin composition.

(72) B. Method of Forming Patterns

(73) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Example 7 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Comparative Example 1

(74) Preparation of Photocurable Resin Composition

(75) 1H, 1H,4H,4H-perfluoro-1,4-butanediol diacrylate (10 g), phenoxyethyl acrylate (61 g), tetrahydrofuryl acrylate (23 g), methacryloxypropyl trimethoxysilane (1 g), trimethylolpropane tris(3-mercaptopropionate) (1 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature for 24 hours, thereby preparing a photocurable resin composition.

(76) B. Method of Forming Patterns

(77) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Comparative Example 1 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Comparative Example 2

(78) Preparation of Photocurable Resin Composition

(79) 1H,1H,4H,4H-perfluoro-1,4-butanediol diacrylate (70 g), phenoxyethyl acrylate (10 g), tetrahydrofuryl acrylate (14 g), methacryloxypropyl trimethoxysilane (1 g), trimethylolpropane tris(3-mercaptopropionate) (1 g), and Irgacure 184 (4 g) were put into a Nalgene 100 ml PE container, and stirred at room temperature for 24 hours, thereby preparing a photocurable resin composition.

(80) B. Method of Forming Patterns

(81) Patterns were formed under the same condition as step B of Example 1 except for using the photocurable resin composition prepared in Comparative Example 2 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

Comparative Example 3

(82) Preparation of Photocurable Resin Composition

(83) A photocurable resin composition was prepared by the same method as Example 1 except for using 1,4-butanediol diacrylate (CAS number:1070-70-8) rather than using 1H, 1H,4H,4H-perfluoro-1,4-butanediol diacrylate of Example 1.

(84) B. Method of Forming Patterns

(85) Patterns were formed under the same condition as in B of Example 1 except for using the photocurable resin composition prepared in Comparative Example 3 rather than using the photocurable resin composition prepared in Example 1, and physical properties thereof were measured and shown in Table 1 below.

(86) TABLE-US-00001 TABLE 1 CF.sub.4 etching Coating Viscosity resistance Release property (cps) (um/min) property Example 1 Clear 8.0 0.28 Example 2 Clear 12.5 0.27 Example 3 Clear 19.3 0.38 Example 4 Clear 20.6 0.40 Example 5 Clear 16.0 0.45 Example 6 Clear 13.5 0.50 Example 7 Clear 12.5 0.31 Comparative Comb patterns 9.5 0.52 X Example 1 were shown Comparative Comb patterns 8.2 0.58 X Example 2 were shown Comparative Comb patterns 9.2 0.60 X Example 3 were shown

(87) As shown in Table 1, it could be appreciated that when the compound represented by Chemical Formula 1 was not used like Comparative Example 3, or when the photocurable resin composition out of the composition ratio of the present invention was used like Comparative Examples 1 and 2, the release property with the imprint mold was poor, and the etching resistance with regard to the carbon tetrafluoride was remarkably reduced. In addition, it could be appreciated that it was not possible to implement the clear film quality even in the evaluation of the coating property.

(88) On the contrary, as shown in Examples 1 to 7, it could be appreciated that when the composition and the composition ratio of the present invention were satisfied, the release property with the imprint mold was excellent, and close-adhesion force with the substrate was also remarkably improved. In particular, as shown in the Examples, it could be confirmed that when the resin composition included 38 to 45 parts by weight of the fluorine-based acrylic compound (A), it was possible to form patterns having the film quality with high reliability.