TW201135362A - Resin compositions for light imprint, pattern forming method, and etching mask - Google Patents

Abstract

This invention provides resin compositions for light imprint, which has excellent etching-resistance and heat-resistance, and can be used in the etching mask in high-precision processing of substrate, and a pattern forming method. The resin compositions for light imprint contain curable monomer (A), photo-polymerization initiator (B), and viscosity regulator (C). The curable monomer (A) contains the cycloaliphatic vinyl ether compound as shown in formula (1) and cycloaliphatic vinyl ether compound as shown in formula (2), where the weight ratio of compound shown in the formula(1) to that shown in the formula (2) is in the range between 20/80 to 95/5. { in the formula (1) X represents hydrogen atom, -OH, -CH2-OH, -O-CH=CH2 or-CH2-O-CH=CH2. where A1~A4 represent respectively hydrogen atom, methyl, ethyl, phenyl, -OH, -CH2-OH, -O-CH=CH2 or -CH2-O-CH=C H2, with the proviso that at least one of X or A1~A4 is -O-CH=CH2 or -CH2-O-CH=C H2, where m, n, o is 0 or 1}, {in the formula, P and Q represents respectively hydrogen atom or-(CH2)a-OR15 (R15 represents vinyl or hydrogen atom, a represents 0 or 1, with the proviso that at least one of the P and Q is (CH2)a-OR15 (where R15 is vinyl) and Z is hydrogen atom, methyl or ethyl }.

Description

[Technical Field] The present invention relates to a resin composition for photoimprint which is excellent in etching resistance and heat resistance of a cured product, and a pattern of the resin composition for photoimprinting is used. The forming method and the etching mask. [Prior Art] A method of forming a fine pattern on a semiconductor substrate or a metal substrate. Conventionally, a photosensitive resin is applied onto a substrate, and a pattern is formed by exposure through a mask, and then etched through a mask using photolithography. This photosensitive resin. However, photolithography has complicated processes and high cost and high cost problems such as exposure devices. Further, when the substrate has deformation or minute projections, the resolution cannot be improved because of the problem of the depth of focus, so that the problem of pattern formation accuracy is likely to occur. Therefore, the imprint method is disclosed as a method of forming a fine pattern at a low cost by a contact process (for example, refer to Patent Document 1). Imprinting is a technique in which a mold having a desired pattern is pressed against a resin material coated on a substrate to form a desired pattern on the resin on the substrate. The embossing method is known as a hot embossing method in which a thermoplastic resin is used to form a pattern by heat, and a photo embossing method in which a pattern is formed by light irradiation using a photocurable resin. In particular, photoimprinting can form patterns at low temperatures and low pressures, so there is no need for heating and cooling procedures. 'Because of the high yield, it has become a technology that has attracted attention in recent years (refer to Non-Patent Document 1 and Non-patent). Literature 2).光-01 (Non-Patent Document 3) manufactured by Toyo Seiki Co., Ltd. -5-201135362, which uses an acrylic monomer, is known as a photocurable resin. In addition, a method of processing a fine pattern on a substrate is a dry etching method. When a substrate is processed by photoimprinting, etching resistance of a photocurable resin is necessary in order to be used as a resist mask during etching. . Patent Document 2 discloses an example 9 in which etching resistance is improved by blending an acrylic monomer having a ring structure [Prior Art Document] [Patent Document] [Patent Document 1] U.S. Patent Publication No. 5,7 7 2,9 0 5 [Patent Document 2] JP-A-2007-84625 (Patent Document 3) JP-A-2007-72374 (Non-Patent Document) [Non-Patent Document 1] T. Bailey, BJ Chooi, M. Colburn, M. Meissi , S. Shaya, JG Ekerdt, SV Screenivasan, CG Willson: J. Vac. Sci. Technol., B 1 8 (2000) p. 3 5 72 [Non-Patent Document 2] A. Kumar, GM Whitesides: Appl. Phys Lett, 63 (1 993) p. 2002 [Non-Patent Document 3] PAK-01 Catalogue of Toyo Seisakusho Co., Ltd. [Summary of the Invention] However, it is pointed out that a composition using an acrylic monomer is used as a resin for photoimprinting. It has strong skin irritation and large volume shrinkage at the time of hardening, and because of the high water absorption rate, it is not easy to form many problems such as a precise pattern. In addition, in the processing of the substrate by the dry etching method, the etching mask obtained from the cured product of the acrylic single--6-201135362 body is resistant to etching for processing of difficult-to-machine materials or high aspect ratio processing. Sex is not enough. Further, in Patent Document 3, a resin composition containing a polymer ruthenium compound having a photocuring function is disclosed as a resin composition for room temperature photoimprinting which is excellent in etching resistance, but in the case where the resin itself has a ruthenium structure' After the etching, a hard residue containing an inorganic component may be generated, which may cause damage to the substrate. Therefore, the resin structure is preferably composed of an organic material. In view of the above-described circumstances, it is an object of the present invention to provide a resin composition for photoimprint which is suitable for photoimprinting and which is excellent in etching resistance and heat resistance of a cured film of an etching mask for high-precision processing of a substrate. And a method of forming a pattern of the resin composition for photoimprinting. In order to achieve the above object, the inventors of the present invention have found that a resin composition for photoimprint containing a specific two or more kinds of vinyl ether compounds having a cyclic hydrocarbon structure having a crosslinked structure as a curable monomer is used. The cured product is excellent in etching resistance and heat resistance, and is suitable as an etching mask for processing a substrate with high precision. The present invention is based on the above findings and has the following points. A resin composition for photoimprinting comprising a curable monomer (A) and a photopolymerization initiator (B), wherein the curable monomer (A) contains a fat represented by the following formula (1) The weight ratio of the cyclic vinyl ether compound and the alicyclic vinyl ether compound represented by the formula (2), and the compound represented by the formula (1) and the formula (2) (the weight of the compound represented by the formula (1) / (the weight of the compound represented by the formula (2)) is 20/80 to 95/5. 201135362 [Chemical 1] Formula (1)

In the formula, X represents a hydrogen atom, -OH, -ch2-oh, -o-ch = ch2 or -CH2-0-CH = CH2. A1 to A4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a phenyl group, -OH, -ch2-oh, -o-ch = ch2 or -ch2-o-ch = ch2. However, at least one of X and ai ~ A4 is -0-ch = ch2 or -ch2-o-CH = CH2. m, η, 〇 means 0 or 1}. [Chemical 2]

In the formula (2), P and Q each independently represent a hydrogen atom or -(CH2)a-ORI5 (wherein R15 represents a vinyl group or a hydrogen atom, and a represents 0 or 1 respectively). However, at least one of P and Q is -((^^-(^^(feet^ is vinyl)) represents a hydrogen atom, a methyl group or an ethyl group.) 2. The resin composition for photoimprint described in the above 1, It contains 49 to 99% by weight of a curable monomer (Α), and contains 0.01 to 30 parts by weight of the photopolymerization initiator (B) with respect to 100 parts by weight of the curable monomer (A). The resin composition for photoimprint according to 1 or 2, wherein the total of the alicyclic-8-201135362 vinyl ether compound represented by the formula (1) and the formula (2) contained in the curable monomer (A) The amount of the resin composition for photoimprint according to any one of the above 1 to 3, further comprising 0.1 to 100 by weight based on 100 parts by weight of the curable monomer (Α). 5. The viscosity-adjusting agent (C). The resin composition for photoimprint according to the above 4, wherein the viscosity modifier (C) is one or more kinds of high molecular weight polymers having a molecular weight (Mw) of 1,000 or more. The resin composition for photoimprint according to any one of the above 1 to 5, wherein the glass transition temperature of the cured product after ultraviolet irradiation (utilization in a nitrogen stream) The film thickness of the resin composition for photoimprint according to any one of the above 1 to 6 is 1 〇. A cured product of nm to 40 μm. 8. A method of forming a pattern comprising coating a resin composition for photoimprint according to any one of the above 1 to 6 on a substrate to form a coating film. a step of bringing the pattern surface of the mold having the desired pattern into contact with the surface of the coating film of the resin composition, pressurizing the resin composition to fill the pattern, and hardening the filling resin composition by light irradiation. The step of forming the cured resin from the mold. The method for forming the pattern described in the above 8, further comprising the step of etching the substrate with a cured resin as a mask. 10. A microstructure By bringing the pattern shape of the mold having the desired pattern into contact with the resin surface of the resin composition for photoimprint described in any one of the above 1 to 6, and pressurizing the resin composition to fill the pattern, Irradiating the enamel resin composition through -9-201135362 light After the resin composition is cured, the surface of the grease is peeled off from the mold. 11. An etching mask comprising the cured product of the resin composition for photoimprint according to any one of the above 1 to 6. The resin composition for photoimprinting of the present invention is excellent in etch resistance and heat resistance, and is suitable as a high-precision processing reticle. [Embodiment] The resin composition for photoimprint of the present invention contains the above formula. (1) an alicyclic vinyl ether compound and an aliphatic alkenyl ether compound represented by the above formula (2) as a curable monomer (A). Formula (1) of the vinyl ether compound represented by the above formula (1) Preferably, it is a hydrogen atom, -OH, -CH2-OH, -〇-CH=CH2 or -CH=CH2, and further, A1 to A4 are preferably a hydrogen atom, a methyl group, an ethyl group, -OH, -CH2- OH, -0-CH = CH2 or -CH2-0-CH = CH η, 〇 is preferably 0 or 1. Preferred examples of the vinyl ether compound represented by the formula (1) are listed below. In the case of the hardened tree, the etch of the plate is shown in the ring group B, X C Η 2 * 0 - group, benzene 2 ' m ' is given by -10- 201135362 [Chemical 3]

-11 - 201135362

Production.

OH

OH

HO

HO

The above compound is particularly preferably a compound represented by the following formula. 【化5】

-12- 201135362 【化6】

In particular, the compounds represented by the following formulas are particularly preferred. 【化7】

Two or more of the above compounds may also be used as the vinyl ether compound of the above formula (1). On the other hand, in the formula (2) of the vinyl ether compound represented by the above formula (2), P is preferably a hydrogen atom, -OH, -CH2-OH, -0-CH = CH2 or -ch2-o-. Ch = ch2, Q is preferably a hydrogen atom, -OH, -ch2-oh, -13-201135362 o-ch = ch2^-ch2-o-ch = ch2 > further, z is preferably a hydrogen atom, Methyl or ethyl. Preferred examples of the vinyl ether compound represented by the formula (2) are as follows. 【化8】

-14- 201135362 Especially the compounds shown by the following formula are more preferred. 【化9】

Two or more of the above compounds may also be used as the weight ratio of the vinyl ether compound represented by the formula (2 vinyl ether compound. In the present invention, the vinyl ether compound half represented by the formula (1)) (1) The weight of the compound) / (weight of the compound represented by the formula (2)) ~ 95/5, preferably 20/80 to 9 0/10. The content of the compound represented by the formula (1) is small. In this case, the film forming property of the resin is not good, and when the coating is applied, the resin is easily shrunk and the coating property is not good. On the other hand, the glass transition temperature and the dry etching resistance of the photocured material are low, so that it is not good. Further, the amount of the vinyl ether compound represented by the above formula (1) and formula (2) used in the present invention is preferably 80% by weight or more, and more preferably 90%. The curable monomer other than the above formula (1) and formula (2) contained in the above-mentioned compound (1) and the above-mentioned vinyl ether compound may be, for example, butanediol divinyl ether. Octylene glycol diethylene glycol divinyl ether, diethylene glycol divinyl ether, trivinyl ether, etc. to impart softness, may contain For example, cyclohexanedienyl ether, hydrogenated bisphenol A divinyl ether, trimethylolpropane) 3 and formula (2) are 20/80 vinyl ether cloth in the substrate. The total content of the material contained in the above-mentioned hard), the compound alkenyl ether shown in the above hard), diol diethylethanol, diethylenetrivinyl-15-201135362 ether, etc., to increase the crosslinking density and increase the surface hardness. . The blending amount can be suitably used within a range that does not impair the etching resistance, heat resistance, and substrate adhesion of the cured resin. Further, in the resin composition for photoimprint of the present invention, the content of the curable monomer (A) is preferably 49 to 99% by weight, more preferably 60 to 95%, in addition to the solvent contained as necessary. %, more preferably 70 to 95% by weight. The photopolymerization initiator (B) used in the resin composition for photoimprint of the present invention is preferably a photoradical polymerization initiator or a photocationic polymerization initiator, but is not limited, and thus both may be used. use. In particular, a photocationic polymerization initiator is preferred, and a known one such as a salt of a salt, a phosphonium salt or a scale salt can be used as a photocationic polymerization initiator. The photocationic polymerization initiator is exemplified by, for example, bis(alkylphenyl)iodonium hexafluorophosphate, diphenyliodide hexafluorophosphate, diphenyliodide hexafluoroantimonate, di(dodecylphenyl). Iodine tetrakis(pentafluorophenyl)borate, bis[4-(diphenylindenyl)phenyl]thioether dihexafluorophosphate, bis[4-(diphenylfluorenyl)phenyl]sulfide Ether dihexafluoroantimonate, bis[4-(diphenylfluorenyl)phenyl] sulfide ditetrafluoroborate, bis[4-(diphenylfluorenyl)phenyl] sulfide tetrakis(pentafluoro) Phenyl)borate, diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylphosphonium hexafluoroantimonate, diphenyl-4 -(phenylthio)phenylhydrazine tetrafluoroborate, diphenyl-4-(phenylthio)phenylphosphonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenyl Hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis[4-(2-(2-hydroxy-16-[4-201135362] Ethoxy))phenylphenyl)phenyl]thioether dihexafluorophosphate, di(di(4-(2-hydroxyethoxy)) Phenylfluorenyl)phenyl]thioether fluorodecanoate, bis[4-(bis(4-(2-hydroxyethoxy))phenyl)phenyl]thioether ditetrafluoroborate, bis[4 -(bis(4-(2-hydroxy)oxyphenyl)phenyl]thioether tetrakis(pentafluorophenyl)boronic acid. In particular, di(alkylphenyl)iodonium hexafluorophosphate or diphenylhexafluorophosphate is preferred. These photopolymerization initiators may be used alone or in combination of two or more. Further, the above photopolymerizer may contain a solvent in consideration of dispersibility in the composition. In the resin composition for photoimprint of the present invention, the content of the photopolymerization initiator (B) is more preferably 0.01 to 30 parts by weight with respect to 1 part by weight of the curable monomer (A). 15 parts by weight, particularly preferably 0.5 parts by weight. Further, in order to increase the efficiency of the photopolymerization initiators to promote polymerization, the photopolymerization initiators may also contain known sensitizing agents. In particular, the sensitizer is effective for increasing the cationic polymerization initiator. The sensitizers are exemplified by hydrazine, thioxanthone, diphenylketone thioxanthone, phenothiazene, anthraquinone and the like. Further, the sensitizing dye is exemplified by a pyranyl salt-based dye, a merocyanine-based dye, a quinoline-based dye, an alkenylquinoline-based dye, a coumarin-based dye, a thioxanthene dye, an anthraquinone dye, or an oxalate. A cyanine dye, a cyanine dye, a rhodamine dye, a pyridinium dye, or the like. In particular, when the lanthanide sensitizer and the cationic polymerization initiator are used, the sensitivity is greatly improved. Dibutoxy oxime, dipropoxy fluorene-* «—1_. ——/\ iodine base and other iodine key to make the combined amount is preferably ~10 light, color is phenothiazine thiobenzene It is effective as a compound of ruthenium, such as ketone-type 倂-倂 (UVS-1331, UVS-1221 manufactured by Kawasaki Kasei Co., Ltd.). The resin composition for photoimprint of the present invention preferably contains a viscosity adjusting agent (C). The viscosity modifier (C) is used to adjust the viscosity of the composition when the film is formed from the composition, and to adjust the coatability of the composition and the thickness of the obtained film. As the viscosity modifier (C), a known thermoplastic resin, a thermosetting resin or a high molecular weight polymer of a liquid resin can be used. In particular, a high molecular weight polymer containing one or more kinds of molecular weights (Mw) 1, 〇〇〇 〜 1, 〇〇〇, 〇〇〇 is preferable, and may be used in combination with several kinds as appropriate. The viscosity adjusting agent (C) is preferably an aromatic ring-containing resin or a ring-containing resin which is excellent in compatibility with the photopolymerization initiator (B), and examples thereof include an ethylene/methylphenyl norbornene copolymer (for example). JP-A-2005-239975), ethylene/norbornene/methylphenyl norbornene copolymer (for example, as described in JP-A-2005-239975), polystyrene, tricyclodecane vinyl ether A polymer (for example, those described in JP-A-2005-113049), a methylphenylnorbornane vinyl ether polymer, and an ethylene/norbornene copolymer (for example, Topas manufactured by Ticona Co., Ltd., Apel manufactured by Mitsui Chemicals, Inc.) a hydrogenated product of a cyclic olefin ring-opening polymer (for example, ZEONEX · ZEONOR manufactured by Zeon Corporation, Japan), and a hydrogenated product of a cyclic olefin ring-opening polymer containing a polar group (for example, manufactured by JSR Corporation) ARTON) and so on. Further, a hydroxyl group-containing resin may be used, or the hydroxyl group-protected resin may be suitably used as the viscosity adjuster (C) for improving the adhesion of the substrate. For example, polyhydroxystyrene, styrene/hydroxystyrene-18-201135362 copolymer, acetal protective polymer of styrene/hydroxystyrene copolymer, hydroxystyrene/tricyclodecane vinyl ether copolymer, hydroxyl group An acetal protective material of a styrene/tricyclodecane vinyl ether copolymer, a block copolymer of a hydroxystyrene/ethyl vinyl ether, a random copolymer, and the like. Although the above viscosity adjusting agent (C) can be suitably used, it is especially an ethylene/methylphenyl norbornene copolymer, a methylphenylnorbornane vinyl ether polymer, polyhydroxystyrene, or styrene. The /hydroxystyrene copolymer and its acetal protector are preferred. These viscosity modifiers (C) may be used singly or in combination of two or more. In the resin composition, the content of the viscosity modifier (C) is preferably 0.1 to 1 part by weight, more preferably 0.5 to 50 parts by weight per 1 part by weight of the above curable monomer (A). It is particularly preferably 0.5 to 10 parts by weight. A resin containing a hydroxyl group can also be used in the viscosity modifier (C), but the resin composition can be cured without affecting the polymerization of the hardening monomer. A known method such as a spin coating method, a solution casting method (solution casting method), a dipping method, or a dropping method can be suitably used as the film forming method using the resin composition for photoimprint of the present invention. The thickness of the resin film for photoimprint formed by the resin composition for photoimprint of the present invention can be arbitrarily adjusted to adjust the viscosity of the resin composition by adjusting the viscosity by the viscosity adjusting agent (C) or by dilution with a solvent. . The film thickness before hardening suitable for film formation and in-plane uniformity of photoimprinting is preferably 10 nm to 40 μm, more preferably 30 nm to ΙΟμπι. It can be used at least on the surface of yttrium, aluminum, copper, sapphire, SiO 2 (yttria), SiC (yttrium carbide), GaN (gallium nitride), inGaN (-19-201135362 indium gallium nitride), GaAs (arsenic) Gallium), AlGaAs (aluminum gallium arsenide), AlGaP (aluminum phosphide), ITO (indium tin oxide), glass, a resin film, or the like is used as a support substrate to which a resin composition is applied when a film is formed. When a photo-imprintable resin film is formed, it is preferred that the film has a small amount of residual volatile components. When a large amount of residual volatile components are present, a foaming phenomenon or the like occurs on the resin film during photoimprinting, and the transfer precision of the pattern is lowered. As described above, when a resin film is formed from the resin composition for photoimprint of the present invention, a solvent is preferably used. The solvent can be used arbitrarily as long as it can dissolve the composition, and it is preferred to use an organic solvent. For example, the ketone solvent is exemplified by cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, etc., and the ester solvent is exemplified by ethylene glycol monomethyl ether acetate and diethylene glycol. Alcohol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol Monomethyl ether acetate, butanediol monomethyl ether acetate, polyethylene glycol monomethyl ether acetate, etc., aromatic hydrocarbon solvents are listed as toluene, xylene, mesitylene, chlorobenzene Ethylbenzene, diethylbenzene, etc., especially xylene 'cyclohexanone or polyethylene glycol monomethyl ether acetate is preferred. These solvents may be used singly or in combination of two or more solvents. When a solvent is added to the resin composition, it is also possible to dissolve by appropriately heating to dissolve the resin. The solvent can be optionally formulated in accordance with the thickness of the formed film. When the film is formed by the spin coating method, the evaporation rate of the solvent can be increased by the high-speed rotation of the gas stream, and the solvent is volatilized during the spin coating process to obtain a resin which can be used for photoimprinting with a small amount of residual volatile components in the -20-201135362 film. In order to ensure the in-plane uniformity of the spin coating film, the boiling point of the solvent used for spin coating is preferably from 70 ° C to 25 ° C, and a boiling point lower than that of the curable monomer (A ) used may be suitably used. The solvent of the boiling point. In addition, in order to further reduce the residual volatile component in the film, after spin coating, it may be heated and dried by a hot plate, a hot air dryer, a vacuum dryer or the like to obtain a resin film for photoimprint. Further, the heating and drying temperature in this case is preferably a temperature lower than the boiling point of the curable monomer (A) to be used. On the other hand, since the solvent casting method (solution casting method), the dipping method, the dropping method, and the like are used, it is difficult to volatilize the solvent during coating. Therefore, when a solvent is used, it is necessary to apply a wind drying or a heating drying process after coating. of. The film thickness which can reduce the residual volatile component in the film is preferably such that the film thickness of the formed film is 40 μm or less before curing. In the present invention, when a film is formed from a resin composition for photoimprint, a flat agent may be blended. A known material can be used as the flattening agent, but an anthrone compound, a fluorine compound, an acrylic compound, or an acrylic acid/anthrone compound is preferable. Examples of the fluorenone-based compound include DISPARLON 1761 and DISPARLON 1711EF manufactured by Nanben Chemical Co., Ltd., and fluorine-based compounds include, for example, MEGAFACE F-470 and F-470 manufactured by Dainippon Ink Chemical Co., Ltd., and acrylic compounds such as DISPARLON LF-1980, LF-. 1 9 82, an acrylic acid/fluorenone compound is exemplified by, for example, DISPARLON UVX-270, UVX-27 1 and the like. The amount of the flat agent to be added is selected and used within a range that does not impair the etching resistance and the substrate adhesion. Further, if necessary, an antifoaming agent, an antioxidant, a heat-resistant stabilizer, a weathering stabilizer, a light stabilizer or the like may be added to the resin composition for photoimprint of the present invention. Further, a compound having a hydroxyl group such as bisphenol A, hydrogenated bisphenol A, 1-adamantanol, 2·adamantanol, tricyclodecanol or calixarene may be added as an adhesion for improving adhesion to a substrate. Sexual imparting agent. The amount of the compound can be appropriately used within a range that does not impair the functions such as heat resistance and etching resistance of the resin composition. Although the resin composition can be used as it is in the case of photoimprinting, it is preferred to remove the particulate matter due to foreign matter from the viewpoint of improving the transfer precision by filtration using a known method. It is also possible to change an appropriate filter material depending on the type of the resin composition to be used. Further, a filter having no charge trapping ability can also be suitably used. The filter hole diameter is preferably 0.45 μηι or less. The resin composition for photoimprint of the present invention is cured by irradiation with ultraviolet rays or the like, and the irradiation conditions can be appropriately changed depending on the type and composition ratio of the resin composition, the film thickness, and the like. The ultraviolet ray wavelength to be irradiated can be appropriately selected and used as an irradiation source having high sensitivity in accordance with the type of the photopolymerization initiator and the sensitizer. Examples of the ultraviolet irradiation light source include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an LED lamp, sunlight, a carbon arc, and the like. In addition to ultraviolet rays, for example, visible light, infrared rays, X rays, alpha rays, ? rays, gamma rays, electron rays, or the like can be used as the activation energy ray. Further, if necessary, the resin may be heated during irradiation of an active energy ray such as ultraviolet rays during photoimprinting or after irradiation. The unreacted material in the hardened resin can be reduced by heating, and the hardenability of the resin or the adhesion to the supporting substrate can be improved by heating. The heating is usually 30 to 8 (TC is preferable, and the glass transition temperature of the resin is preferably lower than that of the resin after curing. Further, the post-UV curing by further irradiating ultraviolet rays to increase the curing rate of the resin can also be applied to the ultraviolet demolition after irradiation. The cured product obtained by the ultraviolet ray irradiation of the resin composition for photoimprint of the present invention has a cylindrical glass transition temperature. Further, when a cured product is used as an etching mask for substrate processing, conditions such as dry etching are used. The processing surface temperature is high, and therefore the etching mask is preferably a material having a high glass transition temperature. The glass transition temperature of the cured product composed of the resin composition for photoimprint of the present invention (under a nitrogen stream, using a differential scanning amount) The calorimetry method is preferably 80 ° C or more, more preferably 100 ° C or more, and still more preferably 120. (: The above photo-embossing resin composition of the present invention can be used by known photoimprint method. 'Forming a microstructure on the substrate. The resulting microstructure can be used as an etch mask when the substrate is micromachined. In terms of photoimprint, the pattern of the invention is preferably formed. The following steps are included: (1) a step of forming a coating film by applying the resin composition for photoimprint of the present invention to a substrate, and (2) forming a pattern surface of the mold having a desired pattern and formed The step of contacting the surface of the coating film, pressurizing the resin composition to fill the pattern, and (3) the step of hardening the resin composition filled in the pattern by irradiation of light, -23-201135362 (4) hardening The step of peeling off the cured product of the resin composition from the surface of the mold, and further comprising (5) etching the aforementioned substrate with the formed microstructure as a mask can select an appropriate device from among various products listed In order to realize a process excellent in pattern transfer precision and improved in productivity, it is preferable to use an imprinting condition with a small molding pressure and a short molding time. Further, the mold is made in the atmosphere. When it comes into contact with the surface of the resin, due to the size, shape or resin viscosity of the pattern, pattern defects of air bubbles may be generated. In addition, photopolymerization hindered by moisture or oxygen in the atmosphere may also cause hardening of the resin. Therefore, if necessary, it is also possible to apply a photo-imprint method in which the inside of the apparatus system is subjected to a reduced pressure treatment, the mold is brought into contact with the surface of the resin under reduced pressure, and the light is hardened under pressure to reduce the light. The embossing reticle of the present invention is used for photoimprinting by using an inert gas, dry air, or other gas displacement device system that does not hinder the hardening of the resin. The etch mask of the present invention is formed by photoimprinting using a resin composition for photoimprinting. Forming a microstructure of a predetermined pattern on the material, and etching the substrate with the etch mask to form a predetermined pattern on the substrate body. In order to quickly form a pattern on the substrate via etching, it is preferred to etch light The resin residual film (resin remaining on the bottom surface of the pattern concave portion) formed on the cover is thin. The etching can be performed by a general technique such as dry etching or wet etching such as physical etching or chemical etching. For example, reactive ion etching may be used. Further, the residual film of the residual resin after etching may be removed by treatment such as dissolving the resin in the solution - 24, 2011, 35362 or ashing. The use of the photoimprint product using the resin composition for photoimprint of the present invention is exemplified by an environmentally-friendly type such as an LED, an organic EL or a solar panel, an optical device such as an optical waveguide, a light guide plate, or a diffraction grating. The use of biological devices such as bio-components, fluid elements such as microfluidics and microreactors, data storage media, and circuit boards. [Examples] The present invention is illustrated by the following examples, but should not be construed as being limited to the examples. A: Modulation method of resin composition &lt;Examples 1 to 2 1. Comparative Examples 1 to 4> As shown in Table 1, a curable monomer (A), a photopolymerization initiator (B), a viscosity modifier (C), and an adhesion imparting agent were used ( D), a sensitizer (E), a flat agent (F), and a solvent (G) were used to prepare the resin compositions for photoimprint of Examples 1 to 21 and Comparative Examples 1 to 4. Further, in Table 1, the photopolymerization initiator 'B (B), the viscosity modifier (C), the adhesion imparting agent (D), the sensitizer (E), the flat agent (F), and the solvent (G) It is the content (parts by weight) relative to 100 parts by weight of the curable monomer. The composition of each composition was prepared in the yellow light chamber under a fluorescent lamp having a wavelength of 500 nm or less. 1. The curable monomer (A), the viscosity modifier -25-201135362 (c), the adhesion imparting agent (D), and the sensitizer (E) are weighed in a predetermined container, and stirred and mixed. 2. The photopolymerization initiator (B) and the flattening agent (ρ) were placed in the container of the above 1 and mixed and defoamed using ThinkyMixer (THINKY Co., Ltd.). 3. Reconciliation using a solvent (G) The solvent (G) and the resin composition obtained in the above 2 were weighed in a predetermined ratio, and stirred and dissolved. 4. A filter made of a 0.45 μηι nylon filter (Li fe AS SURE manufactured by Sumitomo 3M Co., Ltd.) was used to prepare a resin composition for photoimprint. The components described in Table 1 are shown below. • Hardenable monomer (A): as described in Table 2. • Photopolymerization initiator (B) B-1: 50% by weight of propylene carbonate solution of di(alkylphenyl) iodine hexafluorophosphate (WPI-1 13 manufactured by Wako Pure Chemical Industries, Ltd.) • Viscosity adjustment Agent (C) The weight average molecular weight (Mw) of the resin C-1 used in the viscosity modifier (C) is by gel permeation chromatography (GPC) using a GPC apparatus manufactured by Waters, in the column: Shodex The company's K-805L/K-806L, column temperature: 40 °C, solvent: chloroform, liquid volume: 0.8mL / min. The weight average molecular weight (Mw) of the resins C-2, C-3, and C-4 used in the viscosity modifier (C) is a GPC apparatus manufactured by Tosoh Corporation, and is used in the column: TSK G2000Hx2 manufactured by Tosoh Corporation. /TSK G3000H/TSK G4000H, column temperature: 40 ° C, dissolved U: THF, liquid volume: 1.0 m L / mi η. -26- 201135362 C-1: Ethylene/5-methyl-5-phenylbicyclo[2,2,1]hept-2-copolymer (Mw: 50,000, JP-A-2005-23997 5) Methylphenyl norbornene copolymer) C-2: tricyclodecane vinyl ether polymer (Mw: tributyl decane vinyl ether polymer described in 18,000 Å 2 00 5-113 049) C- 3: Polyhydroxystyrene (MARUKA LYNCUR M S-2 manufactured by Jiushan Petrochemical Co., Ltd., Mw4,000~6,0〇〇) C-4: Styrene/hydroxystyrene copolymer via tricyclodecane ethylene Hydroxy acetal protection protected by ether (Mw: 8,5〇〇) • Adhesion imparting agent (D) Dl : 1-Golden base basal acid D-2 : hydrogenated bisphenol A • sensitizer ( E) El: 9,10-dipropoxy fluorene (UVS-1221 manufactured by Kawasaki Kasei Co., Ltd.) • Flat agent (F) F-1: anthrone-based flat agent (DISP ARLON 1761 manufactured by Nanben Chemical Co., Ltd.) • Solvent (G) G-1 : xylene G-2 : cyclohexanone &lt;Comparative Example 5, Comparative Example 7 &gt; Comparative Examples 5 and 7 were used as the similar products of the acrylic photocurable resin PAK-01 (manufactured by Toyo Seisakusho Co., Ltd., -27 to 201135362). &lt;Comparative Example 6 and Comparative Example 8&gt; Epoxy photocurable resin SU-8_3010 (manufactured by Nippon Kayaku Co., Ltd.) was used as Comparative Examples 6 and 8. B: Preparation of Resin Film The resin compositions of Examples 1 to 16 and Examples 18 to 21 and Comparative Examples 1 to 8 were applied by the following spin coating method. The substrate was stored in a dry library having a humidity of 25% or less for 24 hours or more (manufactured by E&M Co., Ltd., surface orientation 1.0.0), and 2 sapphire substrate (Kyocera). Face orientation 0· 0. 0. 1 ). The resin composition for photoimprinting was applied onto a substrate by a spin coater (SC-308H manufactured by EHC Co., Ltd.) to prepare a resin film for photoimprint. The resin films of Comparative Examples 6 and 8 were pre-baked at 95 ° C for 2 min on a hot plate after spin coating in order to volatilize the solvent according to the resin solution specification. The resin composition of Example 17 was used as follows. Film formation by bar coating. The substrate was stored in a dry library having a humidity of 25% or less for 4 hours or more (manufactured by E&M Co., Ltd., surface orientation 1.0.0). The resin composition for photoimprint was dropped on a Si substrate and coated with an applicator. -28- 201135362 C: Hardening method of resin film In the resin film produced as described above, Examples 1 to 2, Comparative Examples 1 to 4, 6, and 8 were dried in the air, and Comparative Examples 5 and 7 were placed in a nitrogen atmosphere. UV irradiation was performed. In Examples 1 to 4 and 17, and Comparative Example 1 and Comparative Examples 5 to 8, high-pressure mercury lamps (described as Hg in Table 1) were used as UV light sources, and Examples 5 to 16 and 18 to 21' Comparative Examples 2 to 4 were used. An LED lamp (EXECURE-H-1VC manufactured by HOYA Co., Ltd.) having a wavelength of 365 nm was used as a UV light source and hardened by an irradiation dose of 50 mW/cm 2 and a UV irradiation amount shown in Table 1. The resin cured films of Comparative Examples 6 and 8 were post-baked at 95 ° C X 2 m i η in a hot air dryer (under a nitrogen stream) after UV curing in order to promote curing of the resin after UV irradiation according to the resin specification. Further, in the viscosity modifier (C) of Example 10, a C-4: styrene/hydroxystyrene copolymer acetal protection protected by tricyclodecane vinyl ether, heat at 40 ° C was used. The transparent film treated with the release agent on the plate was subjected to UV irradiation to be hardened. D = Evaluation of the resin film The resin film produced from the resin composition for photoimprint was measured for coating property, film thickness, substrate adhesion, and glass transition temperature of the cured film. Further, for the cured film formed on the Si substrate, the S i etching selection ratio was evaluated from the etching rate in accordance with the Si etching condition. For the cured film formed on the sapphire (hereinafter referred to as S ap ) substrate, the S ap etching selection ratio was evaluated from the etching rate in accordance with the S ap etching conditions. The results are shown in Table 1. -29- 201135362 Etching rate (coating property) Observe the surface state of the hardenable composition after it is applied onto a Si or Sap substrate by spin coating or a bar coater, and observe whether or not a uniform coating film is formed, according to the following. Benchmarks are evaluated. 〇: Get a uniform film. X: A case where the coating film was uneven and shrunk was observed. The sample having a coatability of X was not evaluated as follows. (Thickness) For the sample evaluated as the coating property, the film thickness of the hardened film was measured after UV curing. The film thicknesses of the hardened films of Examples 1 to 16, 18 to 21 and Comparative Examples 1 and 5 to 8 were measured by a reflection film thickness meter (FE-3 000 manufactured by Otsuka Electronics Co., Ltd.). The film thickness of the cured film of Example 17 was measured by a high-frequency film thickness meter (double film thickness meter LZ-3 00 manufactured by Kett Scientific Research Institute). (Substrate adhesion) For the sample whose evaluation property was evaluated as 〇, the number of cells remaining on the substrate was evaluated in 100 cells by the 1 mm checkerboard test of the old JI S K5 40 0 by the cell tape peeling method. . For example, when there are 50 cells remaining in 100 cells, it is 50/1 00. (glass transition temperature: Tg) For the cured film of 980 nm or more formed on the substrates of Si -30-201135362 of Examples 1, 3, 5, 6, 16 to 20, and Comparative Examples 1, 5, differential scanning calorimetry was used. The instrument (EXSTAR6000, DSC6200 manufactured by Seiko Instruments Inc.) obtained the glass transition temperature from the endothermic peak at the time of temperature rise. Since the differential scanning calorimeter could not detect the endothermic peak of the crosslinked cured film on the si substrate of Comparative Example 6, a thermomechanical analyzer with a stress-strain measurement function (EXSTAR 6000, TMA/ manufactured by Seiko Instruments Inc.) was used. SS6000), the quartz probe tip is pressed against the cured film with a fixed load, and the temperature is increased to soften the resin, and the action of embedding the front end of the quartz probe to obtain the glass transition temperature. (Si etching selection ratio) The cured films formed on the Si substrates of Examples 1, 3, 5 to 9, 1 1 to 14 and 20, and Comparative Examples 1, 5, and 6 were evaluated by the following methods. A part of the surface of the cured resin film produced was masked with a polyimide tape to prepare a sample. Next, the sample was etched under a general S i etching condition using a fluorine-based gas using a dry etching machine. The masking tape was peeled off, and the etching rate was measured by measuring the difference in height between the treated surface and the non-treated surface. Further, etching was performed under the same conditions, and the etching rate of the Si substrate was evaluated by the etching rate of the Si substrate. The etching ratio of the etching ratio of Si = the etching rate of the resin. (Sap etching selection ratio) The cured films formed on the S ap substrates of Examples 2 and 4 and Comparative Examples 7 and 8 were evaluated by the following methods. -31 - 201135362 A part of the surface of the resin cured film produced by the shielding member is shielded to form a sample. Next, the sample was etched under a S ap etching condition using a C12-based gas using a dry etching machine. The shielding member was peeled off, and the etching rate was measured by measuring the difference in height between the treated surface and the non-treated surface. Further, etching was performed under the same conditions, and the etching rate of the S ap etching selection ratio = S ap / the etching rate of the resin was evaluated from the etching rate of the S ap substrate. 201135362 ΐ [1] wn im 〇ο 卜1 30. 0 1 88.5 ο t-re ◦ C3 CO L/3 eJ o OO CQ s •_a st— (/) 眯m 担is s 鲣it m 〇S CM 100/100 1 Example 14| | 72. 0 | d&gt; οό 9 α&gt; 86.2 Ο s 9 e&gt;J c»i 〇1 657. 0 1 ca CiJ o LT3 〇岩 I loo/ioo I σ&gt; iB cn i 闺 lie 1 18. 0 I ο ο %£&gt; ΟΟ ο ο Ο Cvj oc*i 〇1 850· 0 I ss C— 〇1Λ 1 loo/ioo I LA CO Example 12| ! 80. 0 1 ο CM CO ΟΟ e ο e C^0 e-ϊ oo (β c— 2 a o Lf» 〇 1 loo/ioo | C·- II Example 11 ! 70. 0 | 1 30.0 1 88.5 ο ιτΐ oo μ k /» esa | 378. 0 1 S o iA LO 〇C*3 I loo/ioo | ! 1.87 Example 10 [ 70.0 ] 1 30. 〇Π 87.7 ο ΙΛ ou? s 〇Irt tJ〇〇s LO | loo/ Ioo | Example 9 | 70. 0 1 1 30.0 1 88.9 Ο LT» ο LA LA o | 376. 0 | s 1-3 9 lo 〇t*« I loo/ioo | 1-13⁄4 OO 00 Rev Q 〇1 *- 1 30.0 1 Ο LO o Ξ LA e | 212.0 | s «-J s 卜bO 〇芑| loo/ioo | 83 卜握佩〇C&gt; t— ο Η 90.9 Ο LT9 o un C&gt;0 | 369. 0 | ss 卜bO 〇CO «〇[95/100 1 丨1.84 VO 闺Κ Ο ο ο ύ 92.2 Ο LO o bO Oso |Λ 〇i 1078 I ! 70/100 1 U*d LA XT) mm in Γ 80^1 1 20. 0 1 91.3 Ο LT3 oc〇a LA Q ssr·— «Λ 〇| 1089 | [32/100 1 1.67 闺佩1 90. 0 1 ο ο 86.2 1_10JJ e css 〇C*3 Q | looo | & ra c/5 〇| 1052 | | loo/ioo | 1 0.35 1 Example 3 1 90. 0 1 丨—10.0—1 81.4 9 LT&gt; ΙΟ ec Cl old | looo | bO 〇1 '118 1 | 30/100 1 t/3 S CS 闺1K 1 90. 0 1 ο ο 90.7 ο LA 〇css o «) c» i 〇bo as I looo | A (0 «✓5 〇| iioo | 100/100 1 0.37 1 闺K ο ο ο CO Ο LA 〇CO I looo | 〇| 1057 1 | 60/100 I 1.58 τ CM &lt; Jc i V0 i S5g |S s gt-fi- two esi ώ CO oo ess Λ 1 1 ta. z es« 0 m lirwT Qing Teng cT B Helmet I substrate type! 1Coatability 1 nS it ffi m tear w fc a m Si etching selection ratio Sap etching selection ratio 1 hardening monomer 1 photopolymerization initiator 1 viscosity adjuster adhesion imparting agent|sensitizer| | flattening agent|solvent-33- 201135362 [T丨3«] Comparative Example 8 fffe results of ooa fO OJ 1 resin film 〇S 〇〇100/100 CO o Comparative Example 7 Μ) tZ3 oo 〇. to (/*3 〇ο s 0/100 &lt;0.21 Comparative Example 6 ω oo ς〇〇ο 芑0/100 SO 丨Comparative Example 5 I eo fcO 〇ο 〇〇σ&gt; 0/100 r- s c&gt; Comparative Example 4 〇CD Ln 〇〇e**3 Esi cr&gt; ο u1» Ο LO Ο I 253. 0 I so ΙΛ A (9 to X Comparative Example 3 I loo.o | Cvj esj Ο LA Ο ΙΛ ο 1 253. 0 1 ss Γ- SC/3 X 丨Compare Example 2丨〇〇ο s (Λ 窆Ο LA ο un Lrt esi i 441.0 ss P&quot;· CO X 丨 Comparative Example 1J I ιοο.οΙ Ο U9 cr&gt; Ο ei ο CO osoo 〇ΙΛ S 2/100 eo esi 丨Example 21| ο sos CM 〇&gt; ο Ln ο LT3 o | 253.0 ] ss 卜 cx (Q VO Ο CO 1 100/100 I embodiment 20 丨ο so CVJ C0 σ» ο Ln ο ΙΛ two oss t-t /3 〇〇〇c*·» 11/100 CO C*9 s 丨Example 19 ο ο os CJ c-4 σ&gt; Ο bT9 ο LA oss Γ—〇10/100 ΙΛ CN} Example 18 es ο s σ» CD ui &lt;=&gt; U9 Q sse— •J; 〇ITS 100/100 5 丨Example 17| ο ο ο g σι QO 〇〇CD iA ο ο ro UT9 o ec B3 ao 1/3 〇39000 2/100 t —丨Example 16| 〇〇ο s CM OS) σ&gt; 〇ΙΛ ο ΙΛ o | 108. 5 I a Uj o Γ — 〇t— 88/100 «SJ 1^9 &lt;c CM Jc T LT5 to i匡•fvllIP Λ C«J Λ CJ5 ο A Cn&gt; 丄z I z uv light source CN 1 _ % Helmet substrate coating (nra) substrate adhesion b Silver Si etching selection ratio m paste 00 hardening single boat § Fl fl · photopolymerization initiator viscosity modifier adhesion imparting agent 1 sensitizer 1 flat agent solvent -34- 201135362 [Table 3] Table 2 Sturdy single (A) abbreviated as 彳h compound name A-1 TCDVE = ketone vinyl ether A-2 MPNBVE s-Tianji-5-phenyl bicyclo [2,2,11hept-2-vinyl ether A- 3 1-AdVE 1-Resinyl vinyl ether A-4 2-AdVE 2·金刚院基乙储酸 A-5 TDO-DVE Dioxane Divinyl Ether A-6 BDDVE Butanediol II According to the results shown in Table 1, the cured product obtained from the resin composition for photoimprint of the present invention has a glass transition temperature, an S? etching selectivity ratio or a Sap etching selection ratio of the evaluation item. It is excellent in heat resistance and etching resistance. On the other hand, as shown in Table 1, the hardening monomer is one of the compounds containing only the formula (1) or the formula (2) and does not contain the other. The composition (Comparative Examples 1 and 3), and the composition of the formula (1) or the formula (2) in the composition other than the present invention (Comparative Example 2' 4) had poor coatability and could not be on the substrate. The film was formed well, or the glass transition temperature of the obtained cured film was low. Further, in Comparative Examples 5 to 8 using the conventional composition, the glass transition temperature was low or the Si etching selectivity ratio and the Sap etching selection ratio were low. : Production of Microstructures The following examples of the fabrication of the microstructures are shown in Examples 22 to 27. The quartz mold and the transparent resin mold treated with the fluorine-based release agent were fabricated by UV-embossing on -35-201135362. Microstructure. &lt;Example 22&gt;: Microstructure preparation using a quartz mold Using the resin composition for photoimprint described in Example 4, a microstructure was formed on a Si substrate by the following method. (1) The resin composition for photoimprint described in Example 4 was spin-coated on a 2-inch Si substrate to obtain a resin film having a film thickness of 1,052 nm. (2) A 10 mm-angle quartz mold having a hole pattern of a width of 10 μm and a depth of 350 nm was formed on the surface, and pressed against the surface of the resin film by a pressure of 0.2 MPa for 10 seconds to fill the resin in the pattern. (3) The resin is cured by irradiation with an ultraviolet light having an irradiation amount of 100 μm/cm 2 using an LED lamp having a wavelength of 3 65 nm. (4) After the pressure is released, the surface of the resin is released from the mold, and the microstructure is obtained on the Si substrate. &lt;Example 23&gt;: Microstructure preparation using a quartz mold Using the resin composition for photoimprint described in Example 5, a microstructure was formed on a Si substrate by the following method. (1) The resin composition for photoimprint described in Example 5 was spin-coated on a 2 Å Si substrate to obtain a resin film having a film thickness of 809 nm. (2) A 10 mm angle quartz mold having a hole pattern of a width of 10 μm and a depth of 305 nm was formed on the surface, and pressed against the surface of the resin film by a pressure of 0.2 MPa for 10 seconds to fill the resin in the pattern. . (3) The LED is irradiated with an ultraviolet light having a wavelength of 3 to 65 nm and irradiated with -36 to 201135362 of an irradiation amount of 750 mJ/cm2 to harden the resin. (4) After the pressure is released, the surface of the resin is released from the mold, and a microstructure is formed on the Si substrate. &lt;Example 24&gt;: Using the microstructure of the transparent resin mold, the resin composition for photoimprint described in Example 8 was used, and a microstructure was formed on the Sap substrate by the following method. (1) Example 8 The resin composition for photoimprint described above was spin-coated on a 2-inch Sap substrate to obtain a resin film having a film thickness of 340 nm. (2) The spin-coated substrate is placed in a system capable of decompression treatment, and subjected to a reduced pressure treatment to 10, OOOPa, and a diameter of a column pattern of 23 7 nm in diameter and 188 nm in height is formed on the surface under reduced pressure. 2 吋 Transparent resin mold, pressed against the surface of the resin film by the pressure of IMP a, maintained for 丨〇 second, so that the resin is filled in the pattern. (3) The resin is cured by irradiation with an ultraviolet light having an irradiation amount of i〇〇〇mJ/cm2 using an LED lamp having a wavelength of 365 nm. (4) The inside of the system under reduced pressure is returned to normal pressure, and after the pressure is released, the surface of the resin is released from the mold to form a microstructure on the Sap substrate. &lt;Example 2 2: Preparation of a microstructure using a transparent resin mold The resin composition for photoimprint described in Example 9 was used to form a microstructure on a Si substrate by the following method. (1) The resin composition for photoimprint of Example 9 was spin-coated on a 2 吋 Si substrate to obtain a resin film having a film thickness of 171 nm. -37- 201135362 (2) A 2-inch transparent resin mold having a column shape of 23 7 nm and a height of 188 nm was formed on the surface, and pressed against the surface of the resin film at a pressure of 10 MPa for 10 seconds to fill the resin. Within the pattern. (3) The resin was cured by irradiation with an ultraviolet light having an irradiation amount of 750 mJ/cm 2 using an LED lamp having a wavelength of 365 nm. (4) After the pressure is released, the surface of the resin is released from the mold, and a microstructure is formed on the Si substrate. &lt;Example 26&gt;: Microstructure preparation using a transparent resin mold The resin composition for photoimprint described in Example 1 was used to form a microstructure on a Si substrate by the following method. (1) The resin composition for photoimprint of Example 1 was spin-coated on a 2 吋Si substrate to obtain a resin film having a film thickness of 173 nm. (2) The spin-coated substrate was placed at 40 ° C. On the hot plate, a 2 inch diameter transparent resin mold having a column shape of 237 nm and a height of 188 nm was formed on the surface, and pressed against the surface of the resin film at a pressure of 10 MPa for 10 seconds to fill the resin in the pattern. . (3) The LED lamp having a wavelength of 3 to 65 nm was used to maintain the illuminance at 20 mW/cm 2 for 38 seconds, and irradiated with ultraviolet rays having an irradiation amount of 760 mJ/s m 2 to cure the resin. (4) After the pressure is released, the surface of the resin is released from the mold, and a microstructure is formed on the Si substrate. &lt;Example 2 7&gt;: Microstructure using a transparent resin mold -38-201135362 Using the resin composition for photoimprint described in Example 1 1, a microstructure was formed on a Si substrate by the following method. (1) The resin composition for photoimprint of Example 1 1 was spin-coated on a 2 吋 Si substrate to obtain a resin film having a film thickness of 173 nm. (2) A 2-inch transparent resin mold having a column shape of 237 nm in diameter and 188 nm in height was formed on the surface, and pressed against the surface of the resin film at a pressure of 1 MPa for 10 seconds to fill the resin in the pattern. (3) The illuminance was maintained at 20 mW/cm 2 for 38 seconds using an LED lamp having a wavelength of 3 65 nm, and irradiated with ultraviolet rays having an irradiation amount of 760 mJ/cm 2 to cure the resin. (4) After the pressure is released, the surface of the resin is released, and a microstructure is formed on the Si substrate. F: Transferability evaluation of microstructures The microstructures on the substrates obtained in Examples 22 to 27 were evaluated, and those who used the UV imprinting precision transfer mold pattern were evaluated as those who could not accurately transfer the mold pattern. The evaluation was X, and the results are shown in Table 3. [Table 4] Table 3_____ UV Imprint Example Resin Composition for Photoimprint Pattern Transfer Evaluation Example 22 Resin Composition of Example 4 Example 23 Resin Composition of Example 5 Example 24 Example啲 resin composition 〇 Example 25 Resin composition of Example 9 〇 Example 26 Resin composition of Example 10 〇 Example 27 Example 1 啲 resin composition 〇-39- 201135362 The microstructure obtained in Example 22 The laser microscope photograph of the surface is shown in Fig. 1. The column pattern of the microstructure is 10 μηι in width and 355 nm in height. As a result of measuring the film thickness of the pattern concave portion by a reflection film thickness meter, the residual film 20 nm (the thickness of the resin remaining on the bottom surface of the pattern concave portion) was measured. The microstructural cross section and the SEM photograph of the surface obtained in Example 25 are shown in Figs. The pore pattern of the microstructure is 240 nm in diameter, 184 nm in depth, and 9 nm in residual film (resin thickness remaining on the bottom surface of the concave portion of the pattern). The SEM photograph of the microstructured cross section obtained in Example 27 is shown in Fig. 4. The pore pattern of the micro structure is 240 nm in diameter, 184 nm in depth, and 25 nm in residual film (resin thickness remaining on the bottom surface of the recess of the pattern). The above results are obtained by a quartz mold and a microstructure of the same shape according to the method of forming the pattern of the present invention. Further, the residual film thickness of the microstructure (the thickness of the resin remaining on the bottom surface of the concave portion of the pattern) can be controlled by adjusting the initial coating film thickness in accordance with the pattern size. G: Evaluation of substrate processing <Example 2 8 &gt; The microstructure obtained in Example 25 was used as an etching mask, and the Si substrate was dry-etched. The substrate to which the etching mask is attached is etched under a general Si etching condition using a fluorine-based gas using a dry etching machine. -40-201135362 The SEM photograph of the cross section of the Si substrate processed product obtained is shown in Fig. 5. A fine pattern having a diameter of 243 nm and a depth of 1 77 nm was formed on the surface of Si via the above etching process. <Example 2 9> The microstructure obtained in Example 27 was used as an etching mask, and the Si substrate was dry-etched. The substrate to which the etching mask is attached is etched under a general Si etching condition using a fluorine-based gas using a dry etching machine. The SEM photograph of the obtained Si substrate processed product cross section is shown in Fig. 6. A fine pattern of 243 nm in diameter and 175 nm in depth was formed on the Si surface by the etching process. The results of Example 28 and Example 29 show that the microstructure of the present invention is excellent in etching resistance and can be used as an etching mask. The substrate is processed with precision. As described above, the present invention can provide a resin composition for photoimprint which is excellent in etching resistance and heat resistance, a method for forming the pattern thereof, and an etching mask using the resin composition. [Industrial Applicability] The resin composition for photoimprint of the present invention can be used for producing an etching mask for forming a fine pattern on a semiconductor substrate or a metal substrate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a laser microscope showing a microstructured surface obtained in Example 22 of the present invention. -41 - 201135362 Fig. 2 is a SEM photograph showing a microstructural section obtained in Example 25 of the present invention. Fig. 3 is a SEM photograph showing the microstructured surface obtained in Example 25 of the present invention. Fig. 4 is a SEM photograph showing a microstructure cross section obtained in Example 27 of the present invention. Fig. 5 is a SEM photograph showing a cross section of a processed article of a Si substrate obtained in Example 28 of the present invention. Fig. 6 is a SEM photograph showing a cross section of a processed article of a Si substrate obtained in Example 29 of the present invention. -42 -

Claims (1)

201135362 VII. Application for a patent garden: 1. A resin composition for photoimprint, characterized in that it contains a curable monomer (A) and a photopolymerization initiator (B), and the curable monomer (A) contains the following The alicyclic vinyl ether compound represented by the formula (1) and the alicyclic vinyl ether compound represented by the formula (2), and the weight ratio of the compound represented by the formula (1) and the formula (2) ((formula) (1) The weight of the compound shown) / (the weight of the compound represented by the formula (2))) is 20/8 0 to 95/5, [Chemical 1 0] Formula (1) (wherein, X represents a hydrogen atom, -OH, -CH2-OH, -〇-CH = CH2 or -CH2-0-CH = CH2, and A1 to A4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a phenyl group , -OH, -ch2-oh, -o-ch = ch2 or -ch2-o-CH = CH2; but at least one of X and A1 to A4 is - 0-CH = CH2 or - CH2-0-CH = CH2 ; m, η, 0 means 〇 or 1 ;) [Chemical I 1] Formula (2) D (wherein p and Q each independently represent a hydrogen atom or -(CH2)a-〇R15 (R15 represents a vinyl or hydrogen atom, a represents 0 or 1 respectively): but at least one of P and Q is -(CH2)a -OR15 (1115 is a vinyl group); Z represents a hydrogen atom, a -43-201135362 group or an ethyl group). (2) The resin composition for photoimprint according to the first aspect of the invention, which contains 49 to 99% by weight of the curable monomer (A), and contains 100 parts by weight of the curable monomer (A). 0.01 to 30 parts by weight of the photopolymerization initiator (B). 3. The resin composition for photoimprint according to claim 1 or 2, wherein the alicyclic vinyl ether compound represented by the formula (1) and the formula (2) contained in the curable monomer (A) The total amount is 80% by weight or more. The resin composition for photoimprint according to any one of claims 1 to 3, which further contains 0.1 to 100 parts by weight of viscosity adjustment with respect to 100 parts by weight of the curable monomer (A). Agent (C). 5. The resin composition for photoimprint according to item 4 of the patent application, wherein the viscosity modifier (C) is one or more high molecular weight polymers having a molecular weight (Mw) of 1,000 or more. The resin composition for photoimprint according to any one of claims 1 to 5, wherein the glass transition temperature of the cured product after ultraviolet irradiation (in a nitrogen stream, by differential scanning calorimetry) is 80 Above °C. 7. A resin film for photoimprinting, which is obtained by a resin composition for photoimprinting according to any one of claims 1 to 6 which has a film thickness of 10 nm to 40 μm. Composition. And a method of forming a pattern, comprising: coating a resin composition for photoimprinting according to any one of claims 1 to 6 on a substrate to form a coating film; a step of contacting the pattern surface of the mold of the pattern with the surface of the coating film of the resin composition, pressurizing the resin composition to fill the pattern of -44-201135362; and heating the resin composition by light irradiation a step of hardening; and a step of peeling the hardened resin from the mold. 9. The method of forming a pattern of claim 8 wherein the method further comprises the step of etching the substrate with a cured resin as a mask. 10. A micro-structure in which a pattern shape of a mold having a desired pattern is brought into contact with a resin surface of a resin composition for photoimprint according to any one of claims 1 to 6 to be pressurized. The resin composition is filled in the pattern, and the resin composition of the filled resin is cured by light irradiation, and the surface of the cured resin is peeled off from the mold. 1 1. An etching reticle comprising a cured product of a resin composition for photoimprinting according to any one of claims 1 to 6. -45 -