JPWO2016194644A1 - Photo-curable composition for nanoimprint - Google Patents

Abstract

Provided is a photocurable composition for nanoimprint, which can form a cured product excellent in heat resistance and etching resistance by irradiation with light. The photocurable composition for nanoimprints of the present invention is a photocurable composition for nanoimprints containing a cationic curable compound, wherein the cationic curable compound comprises a compound represented by the following formula (a), The weight average value of Onishi parameter of the cationic curable compound is 3.2 or less, the weight average value of the ring parameter is 0.4 or more, and the cured product of the photocurable composition for nanoimprint is maintained at 250 ° C. for 30 minutes. The weight reduction rate by simultaneous measurement of thermogravimetry and differential heat is 10% or less. [Chemical 1]

Description

  The present invention relates to a photocurable composition for nanoimprint and a method for producing a fine pattern substrate using the same. This application claims the priority of Japanese Patent Application No. 2015-110484 filed in Japan on May 29, 2015, and Japanese Patent Application No. 2015-207747 filed in Japan on October 22, 2015, and its contents Is hereby incorporated by reference.

  Light emitting diodes (LEDs) are excellent in energy conversion efficiency and have a long life, so that they are frequently used in electronic devices and the like. The LED element has a structure in which a light emitting layer made of a GaN-based semiconductor is laminated on an inorganic material substrate. However, there is a large refractive index difference between the inorganic material substrate, the GaN-based semiconductor, and the atmosphere, and most of the total amount of light generated in the light-emitting layer disappears due to repeated internal reflection, resulting in poor light extraction efficiency. . For this reason, a method of improving the light extraction efficiency by forming a fine pattern of about several μm on the surface of the inorganic material substrate and laminating a light emitting layer made of a GaN-based semiconductor thereon is adopted.

  As a method for forming a fine pattern, a lithography method and a nanoimprint method are known. The lithography method is expensive and the process is complicated. On the other hand, the nanoimprint method is advantageous because a fine pattern can be produced by a very simple device and process.

  In the nanoimprint method, a resist coating film is formed on a substrate, a mold having a fine pattern shape is pressed on the coating film to transfer a fine pattern, and then the coating film is cured and used as a mask. A fine pattern can be formed on the substrate by dry etching the substrate. However, masks formed using conventional resists may cause resist burning when dry etching is performed in a high-temperature environment, and the process temperature of dry etching is limited by the heat resistance temperature of the resist. Met.

  As methods for improving dry etching resistance under high temperature conditions, Patent Documents 1 and 2 describe a method of adding a large amount of a high molecular weight component to a resist or adding an inorganic filler.

  However, when a large amount of a high molecular weight component is added, there is a problem that transferability and coating property are lowered. In addition, when an inorganic filler is added, a hard residue may be generated after dry etching, thereby reducing the yield.

Japanese Patent No. 4022312 Japanese Patent No. 5000112

Therefore, the objective of this invention is providing the photocurable composition for nanoimprint which can form the hardened | cured material excellent in heat resistance and etching resistance by irradiating light.
Another object of the present invention is to provide a method for producing a substrate having a fine pattern using the photocurable composition for nanoimprint, and a method for producing a semiconductor device comprising the substrate having the fine pattern.

  As a result of intensive studies to solve the above problems, the inventors of the present invention include a compound represented by the following formula (a), the weight average value of Onishi parameter is 3.2 or less, and the weight average value of ring parameter is 0.8. It has been found that a photocurable composition for nanoimprinting containing a cationic curable compound that is 4 or more can form a cured product having excellent etching resistance when irradiated with light. In addition, when the weight loss rate by thermogravimetric / differential thermal simultaneous measurement when the cured product of the photocurable composition for nanoimprint is maintained at 250 ° C. for 30 minutes is 10% or less, dry etching is performed in a high temperature environment. It has been found that the resist shows high etching resistance and can prevent occurrence of resist burning. The present invention has been completed based on these findings.

（式中、Ｒ¹〜Ｒ¹⁸は同一又は異なって、水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基を示す。Ｘは、単結合又は連結基を示す）That is, the present invention is a photocurable composition for nanoimprinting containing a cationic curable compound, wherein the cationic curable compound includes a compound represented by the following formula (a), and Onishi of the cationic curable compound: The weight average value of the parameters is 3.2 or less, the weight average value of the ring parameters is 0.4 or more, and the cured product of the photocurable composition for nanoimprints is maintained at 250 ° C. for 30 minutes. Provided is a photocurable composition for nanoimprinting, which has a weight loss rate of 10% or less by simultaneous differential heat measurement.

(In the formula, R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, or a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent. X represents a single bond or a linking group)

（式中、Ａｒ¹〜Ａｒ³は同一又は異なって、水素原子、ハロゲン原子、又は置換基を有していてもよい芳香族炭化水素基若しくは複素環式基を示す）
で表されるカチオン部を有する光カチオン重合開始剤（１）を含有する前記のナノインプリント用光硬化性組成物を提供する。The present invention also provides the following formula (b-1)
[(Y) _k B (Phf) _4-k ] ^- (b-1)
[Wherein, Y represents an aromatic hydrocarbon group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms which may have a substituent (excluding a group containing a halogen atom). Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom. k is an integer of 1 to 3]
An anion moiety represented by the following formula (b-2)

(In the formula, Ar ^{1 to} Ar ³ are the same or different and each represents a hydrogen atom, a halogen atom, or an optionally substituted aromatic hydrocarbon group or heterocyclic group)
The said photocurable composition for nanoimprints containing the photocationic polymerization initiator (1) which has a cation part represented by these is provided.

  The present invention also provides the above-mentioned photocurable composition for nanoimprint, further comprising a silicone-based surface conditioner and / or a hydrocarbon-based surface conditioner.

  The present invention also provides the photocurable composition for nanoimprints, wherein the content of the compound represented by formula (a) is 20 to 70% by weight of the total amount (100% by weight) of the photocurable composition for nanoimprints. provide.

In the present invention, as the cationic photopolymerization initiator, together with the cationic photopolymerization initiator (1), BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbF ₅ OH ⁻ , and the following formula (b-3)
[(Rf) _t PF _6-t ] ^- (b-3)
(In the formula, Rf is an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and t is an integer of 0 to 5)
A photocationic polymerization initiator (2) having an anion part selected from anions represented by formula (b-2) and a cation part represented by the formula (b-2), 1 part by weight of the photocationic polymerization initiator (1) The said photocurable composition for nanoimprint containing 0.1-2 weight part with respect to is provided.

  The present invention also includes a step of applying the photocurable composition for nanoimprinting onto an inorganic material substrate to form a coating film, pressing a mold against the obtained coating film, and transferring a concavo-convex shape to the coating film. Provided is a method for manufacturing a fine pattern substrate in which a mask is formed through a step of irradiating light, and the substrate is etched using the obtained mask.

  The present invention also provides the method for producing the fine pattern substrate, wherein the heat treatment is further performed after the light irradiation.

  The present invention also provides the method for producing the fine pattern substrate, wherein the heat treatment is performed at 100 to 220 ° C.

  The present invention also provides the method for producing the fine pattern substrate, wherein the etching is dry etching using a gas containing chlorine atoms.

  The present invention also provides a method for manufacturing a semiconductor device including a step of obtaining a fine pattern substrate by the method for manufacturing a fine pattern substrate.

That is, the present invention relates to the following.
[1] A photocurable composition for nanoimprinting containing a cationic curable compound, wherein the cationic curable compound contains a compound represented by formula (a), and the weight average of Onishi parameters of the cationic curable compound Thermogravimetric / differential simultaneous measurement when the value is 3.2 or less, the weight average value of the ring parameter is 0.4 or more, and the cured product of the photocurable composition for nanoimprint is maintained at 250 ° C. for 30 minutes. The photocurable composition for nanoimprints in which the weight loss rate due to the is 10% or less.
[2] The compound represented by the formula (a) is 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis ( 3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1- The photocurable composition for nanoimprints according to [1], which is at least one compound selected from the group consisting of yl) propane and 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane. object.
[3] For nanoimprinting according to [1] or [2], wherein the content of the compound represented by formula (a) is 20 to 70% by weight of the total amount (100% by weight) of the photocurable composition for nanoimprinting Photocurable composition.
[4] The content of the compound represented by the formula (a) is 20 to 70% by weight of the total amount (100% by weight) of the cationic curable compound contained in the photocurable composition for nanoimprinting. [3] The photocurable composition for nanoimprints according to any one of [3].
[5] In addition to the compound represented by the formula (a), the cationic curable compound has two or more aromatic rings or alicyclic rings in one molecule (excluding the compound represented by the formula (a)). And a photocurable composition for nanoimprints according to any one of [1] to [4], which contains at least one selected from oxetane compounds having two or more aromatic rings or alicyclic rings in one molecule. object.
[6] Epoxy compound (excluding the compound represented by formula (a)) having two or more aromatic rings or alicyclic rings in one molecule, and oxetane compound having two or more aromatic rings or alicyclic rings in one molecule The photocurable composition for nanoimprints according to [5], wherein the content of is 30 to 80% by weight of the total amount (100% by weight) of the photocurable composition for nanoimprints.
[7] Epoxy compounds having two or more aromatic rings or alicyclic rings per molecule (excluding compounds represented by formula (a)), and oxetane compounds having two or more aromatic rings or alicyclic rings in one molecule The photocurable composition for nanoimprints according to [5] or [6], wherein the content of is 30 to 80% by weight of the total amount (100% by weight) of the cationic curable compound contained in the photocurable composition for nanoimprints object.
[8] An epoxy compound (excluding a compound represented by formula (a)) having two or more aromatic rings or alicyclic rings in one molecule and one aromatic ring or alicyclic ring. Any one of [5] to [7], wherein the sum of the contents of two or more oxetane compounds in the molecule is 80% by weight or more of the total amount of the cationic curable compounds contained in the photocurable composition for nanoimprinting. The photocurable composition for nanoimprints described in 1.
[9] The following formula (b-1)
[(Y) _k B (Phf) _4-k ] ^- (b-1)
[Wherein, Y represents an aromatic hydrocarbon group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms which may have a substituent (excluding a group containing a halogen atom). Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom. k is an integer of 1 to 3]
The nanoimprint according to any one of [1] to [8], comprising a photocationic polymerization initiator (1) having an anion moiety represented by formula (b-2) and a cation moiety represented by formula (b-2): Photocurable composition.
[10] As the photocationic polymerization initiator, together with the photocationic polymerization initiator (1), BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbF ₅ OH ⁻ , and the following formula (b-3)
[(Rf) _t PF _6-t ] ^- (b-3)
(In the formula, Rf is an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and t is an integer of 0 to 5)
A photocationic polymerization initiator (2) having an anion part selected from anions represented by formula (b-2) and a cation part represented by the formula (b-2), 1 part by weight of the photocationic polymerization initiator (1) The photocurable composition for nanoimprints according to [9], which is contained in an amount of 0.1 to 2 parts by weight based on the weight.
[11] The ratio of the total amount of the photocationic polymerization initiator (1) and the photocationic polymerization initiator (2) in the total polymerization initiator contained in the photocurable composition for nanoimprint is 90% by weight or more, [9 ] Or the photocurable composition for nanoimprints described in [10].
[12] The photocurable composition for nanoimprints according to any one of [1] to [11], further comprising a silicone-based surface conditioner and / or a hydrocarbon-based surface conditioner.
[13] The content of the silicone-based surface conditioner and the hydrocarbon-based surface conditioner is 0.005 to 10 parts by weight with respect to 100 parts by weight of the cationic curable compound contained in the photocurable composition for nanoimprints. [12] The photocurable composition for nanoimprints according to [12].
[14] The photocurable composition for nanoimprints according to any one of [1] to [13], wherein the etching selectivity (Es / Er) of the cured product is 0.6 or more.
[15] The photocurable composition for nanoimprints according to any one of [1] to [14] is applied on an inorganic material substrate to form a coating film, and a mold is pressed against the obtained coating film. A method for producing a fine pattern substrate, wherein a mask is formed through a step of transferring an uneven shape and a step of irradiating light to a coating film, and the substrate is etched using the obtained mask.
[16] The method for producing a fine pattern substrate according to [15], wherein the heat treatment is further performed after the light irradiation.
[17] The method for producing a fine pattern substrate according to [16], wherein the heat treatment is performed at 100 to 220 ° C.
[18] The method for producing a fine pattern substrate according to any one of [15] to [17], wherein dry etching is performed using a gas containing chlorine atoms as the etching.
[19] A method for manufacturing a semiconductor device, including a step of obtaining a fine pattern substrate by the method for manufacturing a fine pattern substrate according to any one of [15] to [18].

Since the photocurable composition for nanoimprinting of the present invention has the above-described configuration, it is excellent in rapid curing property and thin film curing property, and can be rapidly formed by irradiation with light.
Moreover, since the cured product of the photocurable composition for nanoimprinting of the present invention is excellent in heat resistance and etching resistance, when the cured product is used as a mask when etching an inorganic material substrate (for example, a sapphire substrate), The etching temperature can be arbitrarily set without being limited by the heat-resistant temperature of the mask, and the inorganic material substrate can be selectively etched without causing resist burning. A pattern can be formed.
Then, when a light emitting layer, a semiconductor layer, and the like are stacked on an inorganic material substrate (for example, PSS (Patterned Sapphire Substrate) etc.) on which the fine pattern is formed, a light emitting element having excellent light extraction efficiency can be formed. In addition, a semiconductor device including the light-emitting element has characteristics such as high luminance, long life, low power consumption, and low heat generation.

[Cation curable compound]
The photocurable composition for nanoimprinting of the present invention contains at least a compound represented by the formula (a) (hereinafter sometimes referred to as “compound (A)”) as a cationic curable compound. Since the compound (A) has excellent cationic curability, it can impart fast curability and thin film curability to the photocurable composition for nanoimprint.

In formula (a), R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent. Indicates. X represents a single bond or a linking group.

As a halogen atom in R < ¹ > -R < ¹⁸ >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be mentioned, for example.

The hydrocarbon group in R ^{1 to} R ¹⁸ includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

  Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3); vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2- 2-20 carbon atoms (preferably 2-10, particularly preferably 2) such as butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 5-hexenyl group, etc. -3) alkenyl groups; alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3) such as ethynyl groups and propynyl groups. That.

As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, or the like, such as a cyclohexane having about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members). An alkyl group; a cycloalkenyl group of about 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8 members) such as cyclopentenyl group and cyclohexenyl group; norbornyl group, norbornenyl group, perhydronaphthalene-1 -Yl group, adamantyl group, tetracyclo [4.4.0.1 ^2,5 . And a bridged cyclic hydrocarbon group such as 1 ^7,10 ] dodecan-3-yl group.

  Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as a phenyl group and a naphthyl group.

  The hydrocarbon group may be any of various substituents [eg, halogen atom, oxo group, hydroxyl group, substituted oxy group (eg, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group] Group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] It may be. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

Examples of the hydrocarbon group that may contain an oxygen atom or a halogen atom in R ^{1 to} R ¹⁸ include a group in which at least one hydrogen atom in the above-described hydrocarbon group is substituted with a group having an oxygen atom or a halogen atom, etc. Can be mentioned. Examples of the group having an oxygen atom include hydroxyl group; hydroperoxy group; C _1-10 alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, and isobutyloxy group; C _2-10 alkenyloxy group; C _1-10 alkyl group, C _2-10 alkenyl group, a halogen atom, and C _1-10 optionally C _6-14 optionally having a substituent selected from alkoxy groups Aryloxy groups (for example, tolyloxy group, naphthyloxy group, etc.); C _7-18 aralkyloxy groups such as benzyloxy group, phenethyloxy group; acetyloxy group, propionyloxy group, (meth) acryloyloxy group, benzoyloxy group C _1-10 acyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxy C _1-10 alkoxycarbonyl group such as carbonyl group; C _1-10 alkyl group, C _2-10 alkenyl group, halogen atom, and optionally substituted substituent selected from C _1-10 alkoxy group _6-14 aryloxycarbonyl group (for example, phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.); C _7-18 aralkyloxycarbonyl group such as benzyloxycarbonyl group; epoxy group-containing group such as glycidyloxy group An oxetanyl group-containing group such as an ethyl oxetanyloxy group; a C _1-10 acyl group such as an acetyl group, a propionyl group, or a benzoyl group; an isocyanate group; a sulfo group; a carbamoyl group; an oxo group; _Examples thereof _include a group bonded through a C _1-10 alkylene group.

Examples of the alkoxy group in R ^{1 to} R ¹⁸ include C _1-10 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group.

Examples of the substituent that the alkoxy group may have include, for example, a halogen atom, a hydroxyl group, a C _1-10 alkoxy group, a C _2-10 alkenyloxy group, a C _6-14 aryloxy group, a C _1-10 Acyloxy group, mercapto group, C _1-10 alkylthio group, C _2-10 alkenylthio group, C _6-14 arylthio group, C _7-18 aralkylthio group, carboxyl group, C _1-10 alkoxycarbonyl group, C _{6- 14} aryloxycarbonyl group, C _7-18 aralkyloxycarbonyl group, amino group, mono or di C _1-10 alkylamino group, C _1-10 acylamino group, epoxy group-containing group, oxetanyl group-containing group, C _1-10 And an acyl group, an oxo group, and a group in which two or more of these are bonded through a single bond or a C _1-10 alkylene group.

  In the above formula (a), X represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group (—CO—), an ether bond (—O—), Examples thereof include an ester bond (—COO—), a carbonate group (—O—CO—O—), an amide group (—CONH—), and a group in which a plurality of these are linked.

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. can be mentioned, for example. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, Examples include cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

  Examples of the compound represented by the above formula (a) include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1) -Yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane and the like. These can be used alone or in combination of two or more.

The compound represented by the above formula (a) is obtained by reacting, for example, a compound represented by the following formula (a ′) with a peracid (for example, peracetic acid) in the double bond portion in the formula (a ′). Can be produced by epoxidizing the. In the following formula (a ′), R ^{1 to} R ¹⁸ and X are the same as described above.

  The content of the compound (A) (when two or more types are contained, the total amount) is, for example, 20 to 70% by weight, preferably 30 to 65% by weight, particularly preferably 40 to 40% by weight of the total amount of the photocurable composition for nanoimprint. 60% by weight, most preferably 50-60% by weight.

  Further, the content of the compound (A) (the total amount when containing two or more) is, for example, 20 to 70% by weight, preferably 30 to 30% by weight of the total amount of the cationic curable compound contained in the photocurable composition for nanoimprint. It is 65% by weight, particularly preferably 40 to 60% by weight, and most preferably 50 to 60% by weight.

  In the photocurable composition for nanoimprinting of the present invention, in addition to the above compound (A), other cationic curable compounds have a weight average value of Onishi parameter of 3.2 or less and a weight average value of ring parameter of 0.4. In the range which becomes the above, you may contain 1 type (s) or 2 or more types.

  Other cationic curable compounds include compounds having at least one (preferably two or more) cationically polymerizable group in one molecule. Examples of the cationically polymerizable group include electron donating groups such as an epoxy group, an oxetanyl group, and a vinyl ether group.

  The molecular weight or weight average molecular weight (by polystyrene conversion by GPC) of other cationic curable compounds is, for example, 100 or more and less than 10,000, preferably 200 or more and less than 10,000, particularly preferably 400 or more and less than 10,000, and most preferably 400 to 5,000. .

  Examples of other cationic curable compounds having an epoxy group as a cationic polymerizable group (hereinafter sometimes referred to as “other epoxy compounds”) include alicyclic epoxy compounds other than the compound (A) (for example, cyclohexene). Compounds containing one or more oxide groups in one molecule); aromatic glycidyl ether type epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds; hydrogenating said aromatic glycidyl ether type epoxy compounds Alicyclic glycidyl ether-based epoxy compounds obtained by conversion to mono- or polyglycidyl ethers of aliphatic polyhydric alcohols (for example, 2,2 ′-(2,5,8-trioxanonane-1,9-diyl) bisoxirane) Chain aliphatic glycidyl ether type epoxy compounds such as glycidyl And the like glycidyl amine epoxy compounds; ester-based epoxy compound.

  Other epoxy compounds also include compounds in which an epoxy group is directly bonded to an alicyclic ring such as a compound represented by the following formula.

R ′ in the above formula represents a group obtained by removing p —OH groups from the structural formula of a p-valent alcohol. P and k each represent a natural number. p is preferably 1 to 6, and k is preferably 1 to 30. Examples of the p-valent alcohol [R ′-(OH) _p ] include C _1-15 polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol. When p is 2 or more, k in the group in parentheses may be the same or different. Examples of the compound represented by the above formula include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, trade name “EHPE3150”, ( Daicel Co., Ltd.] can be preferably used.

  Examples of other cationic curable compounds having an oxetanyl group as a cationic polymerizable group (hereinafter sometimes referred to as “oxetane compounds”) include 3,3-bis (vinyloxymethyl) oxetane and 3-ethyl-3. -Hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl- 3- (Hexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] Benzene, bis ([1-ethyl (3-oxetanyl)] methyl) ether, 4,4′-bis [ 3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 4,4′-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl, 1,4-bis [(3-ethyl-3-oxetanyl) Methoxymethyl] cyclohexane, 1,4-bis ([(3-ethyl-3-oxetanyl) methoxy] methyl) benzene, 3-ethyl-3 ([(3-ethyloxetane-3-yl) methoxy] methyl) oxetane, Examples include xylylene bisoxetane. In the present invention, for example, trade names “ARON OXETANE OXT-121”, “ARON OXETANE OXT-221” (above, manufactured by Toagosei Co., Ltd.), trade names “ETERNACOLL OXBP” (manufactured by Ube Industries), etc. It is also possible to use commercially available products.

  Examples of other cationic curable compounds having a vinyl ether group as the cationic polymerizable group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1, -Cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol mono Vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether Le, penta propylene glycol monovinyl ether oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, and these derivatives.

  Other cationic curable compounds include, for example, a main chain having a skeleton selected from a polycarbonate skeleton, a polyester skeleton, a polydiene skeleton, a novolac skeleton, and the like, and the cation at the terminal and / or side chain of the main chain. A compound having a polymerizable group is also included.

  In the present invention, it is preferable to contain another epoxy compound and / or oxetane compound as the other cationic curable compound, and in particular, it has an aromatic ring or an alicyclic ring (in particular, the aromatic ring or alicyclic ring in one molecule). Use of at least one selected from other epoxy compounds having two or more) and oxetane compounds having aromatic rings or alicyclic rings (in particular, having two or more aromatic rings or alicyclic rings in one molecule). It is preferable in that a cured product having excellent dry etching resistance can be obtained.

  The content of other cationic curable compounds (the total amount when containing two or more) is, for example, 30 to 80% by weight, preferably 35 to 70% by weight, particularly preferably the total amount of the photocurable composition for nanoimprints. It is 40 to 65% by weight, most preferably 40 to 55% by weight.

  The content of other cationic curable compounds (the total amount when containing two or more types) is, for example, 30 to 80 of the total amount of curable compounds (particularly cationic curable compounds) contained in the photocurable composition for nanoimprints. % By weight, preferably 35-70% by weight, particularly preferably 40-65% by weight, most preferably 40-55% by weight.

  The sum of the content of the compound (A) and the other cationic curable compound is, for example, 80% by weight or more, preferably 90% by weight or more, particularly 90% by weight or more of the total amount of the cationic curable compound contained in the photocurable composition for nanoimprinting. Preferably it is 95 weight% or more. The upper limit of the sum of the contents is 100% by weight.

[Photocationic polymerization initiator]
The cationic photopolymerization initiator is a compound that generates a cationic species by light irradiation and initiates a curing reaction of the cationically curable compound. The cationic photopolymerization initiator is composed of a cation moiety that absorbs light and an anion moiety that is a source of acid generation.

（式中、Ａｒ¹〜Ａｒ³は同一又は異なって、水素原子、ハロゲン原子、又は置換基を有していてもよい芳香族炭化水素基若しくは複素環式基を示す）
で表されるカチオン部を有する光カチオン重合開始剤（１）を含有することが好ましい。The photocurable composition for nanoimprinting of the present invention has the following formula (b-1)
[(Y) _k B (Phf) _4-k ] ^- (b-1)
[Wherein Y represents an aromatic hydrocarbon group or a heterocyclic group which may have a substituent (excluding a group containing a halogen atom). Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom. k is an integer of 1 to 3]
An anion moiety represented by the following formula (b-2)

(In the formula, Ar ^{1 to} Ar ³ are the same or different and each represents a hydrogen atom, a halogen atom, or an optionally substituted aromatic hydrocarbon group or heterocyclic group)
It is preferable to contain the photocationic polymerization initiator (1) which has a cation part represented by these.

  The aromatic hydrocarbon group in Y is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, for example, an aryl having 6 to 30 carbon atoms such as a phenyl group, a biphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, or the like. The group can be mentioned.

The heterocyclic ring constituting the heterocyclic group for Y includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. As such a heterocyclic ring, a heterocyclic ring having 4 to 30 carbon atoms is preferable. For example, a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, 5-membered rings such as isoxazole ring and γ-butyrolactone ring; 6-membered rings such as 4-oxo-4H-pyran ring, tetrahydropyran ring and morpholine ring; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring Condensed ring such as chroman ring and isochroman ring; 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^{4, 8]} nonane-2-one ring, the bridge ring), heterocyclic rings containing sulfur atom as a hetero atom (e.g., thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, 5-membered ring; 6-membered ring such as 4-oxo-4H-thiopyran ring; condensed ring such as benzothiophene ring, etc., heterocycle containing a nitrogen atom as a hetero atom (for example, pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole) 5-membered ring such as ring, triazole ring; 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring; indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring And a condensed ring such as a purine ring). Examples of the (monovalent) heterocyclic group include groups in which one hydrogen atom has been removed from the above structural formula of the heterocyclic ring.

Y may have one or more substituents. The substituent is a group other than a group containing a halogen atom. For example, a C _1-12 alkyl group, a C _3-6 cycloalkyl group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, a C _6-12 Examples thereof include an arylthio group, a C _2-7 alkylcarbonyl group, a C _2-7 alkoxycarbonyl group, a phenyl group, and a benzoyl group. When Y has two or more substituents, these substituents may be the same or different.

The perfluoroalkyl group is preferably a C _1-8 (preferably C _1-4 ) perfluoroalkyl group, such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, perfluoropentyl, perfluoro Linear C _1-8 (preferably C _1-4 ) perfluoroalkyl group such as fluorooctyl group; branched C _3-8 (preferably C _3-4 ) such as heptafluoroisopropyl and nonafluoroisobutyl groups Perfluoroalkyl groups; C _3-8 (preferably C _3-4 ) perfluorocycloalkyl groups such as perfluorocyclopropyl and perfluorocyclobutyl groups.

The perfluoroalkoxy group is preferably a C _1-8 (preferably C _1-4 ) perfluoroalkoxy group, such as trifluoromethoxy, pentafluoroethoxy, heptafluoropropoxy, nonafluorobutoxy, perfluoropentyloxy, Linear C _1-8 such as perfluorooctyloxy group (preferably C _1-4 ) perfluoroalkoxy group; branched C _3-8 such as heptafluoroisopropoxy, nonafluoroisobutoxy group (preferably C _3-4 ) and a perfluoroalkoxy group.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be mentioned, for example.

Y is particularly preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, particularly preferably a phenyl group (C ₆ H ₅ ) or a biphenylyl group (C ₆ H ₅ C ₆ H ₄ ).

Examples of Phf include a pentafluorophenyl group (C ₆ F ₅ ), a trifluorophenyl group (C ₆ H ₂ F ₃ ), a tetrafluorophenyl group (C ₆ HF ₄ ), and a trifluoromethylphenyl group (CF ₃ C ₆ H _4), bis (trifluoromethyl) phenyl group _{((CF 3) 2 C 6} H 3), pentafluoroethyl phenyl group _{(CF 3 CF 2 C 6 H} 4), bis (pentafluoroethyl) phenyl group ( (CF ₃ CF ₂ ) ₂ C ₆ H ₃ ), fluoro-trifluoromethylphenyl group (CF ₃ C ₆ H ₃ F), fluoro-bis (trifluoromethyl) phenyl group ((CF ₃ ) ₂ C ₆ H ₂ F), fluoro - pentafluoroethyl phenyl group - ani a _{(CF 3 CF 2 C 6 H} 3 F), fluoro-bis (pentafluoroethyl) phenyl group _{((CF 3 CF 2) 2} C 6 H 2 F) , etc. Rukoto can. In the present invention, pentafluorophenyl group (C ₆ F ₅ ), fluoro-bis (pentafluoroethyl) is particularly preferable in that it is excellent in thin film curability and the obtained cured product is particularly excellent in heat resistance and heat yellowing resistance. ) A phenyl group ((CF ₃ CF ₂ ) ₂ C ₆ H ₂ F) is preferred.

As the anion part of the photocationic polymerization initiator (1), [(C ₆ H ₅ ) B (C ₆ F ₅ ) ₃ ] ⁻ , [(C ₆ H ₅ ) B ((CF ₃ CF ₂ ) _2] C ₆ H ₂ F) ₃ ] ⁻ , [(C ₆ H ₅ C ₆ H ₄ ) B (C ₆ F ₅ ) ₃ ] ^{− and the} like are preferable.

Examples of the aromatic hydrocarbon group and the heterocyclic group in Ar ^{1 to} Ar ³ include the same examples as those described above for Y. In addition, examples of the substituent that the aromatic hydrocarbon group and the heterocyclic group may have include the same examples as the substituent that Y may have.

  Examples of the cation moiety of the photocationic polymerization initiator (1) include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2 -Naphthyldiphenylsulfonium, tris (4-fluorophenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p -Tolylthio) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfo , 4- (phenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4 -(2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide Bis {4- [bis (4-methoxyphenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2- Chlorophenylthio) phenyldiphenylsulfur 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10- Dihydroanthracen-2-yl-di-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl-diphenylsulfonium, 2-[(di-p-tolyl) Sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-t-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (4-t-butylbenzoyl) phenylthio ] Phenyldiphenylsulfonium, 4- [4- (ben Zoylphenylthio)] phenyl-di-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiantrenium, 5-phenylthiantrenium, 5- Tolylthanthrenium, 5- (4-ethoxyphenyl) thientrenium, 5- (2,4,6-trimethylphenyl) thiantrenium, [4- (4-biphenylylthio) phenyl] -4-biphenylyl And phenylsulfonium, [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium, and the like.

  Specific examples of the cationic photopolymerization initiator (1) in the present invention include 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, bis [4- (diphenylsulfonio) phenyl] sulfide phenyltris (penta Fluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (2-thioxanthonylthio) phenyl] phenyl-2- And thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate.

  The content of the cationic photopolymerization initiator (1) (when two or more are included, the total amount) is, for example, 0.1 with respect to 100 parts by weight of the cationic curable compound contained in the photocurable composition for nanoimprinting. -10.0 parts by weight, preferably 0.3-5.0 parts by weight, particularly preferably 0.5-4.0 parts by weight, and most preferably 1.0-3.0 parts by weight.

  In the present invention, as the photocationic polymerization initiator, one or two or more other photocationic polymerization initiators (2) may be used in combination with the photocationic polymerization initiator (1).

Examples of the cationic photopolymerization initiator (2) include BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbF ₅ OH ⁻ , and the following formula (b-3)
[(Rf) _t PF _6-t ] ^- (b-3)
(In the formula, Rf is an alkyl group in which 80% or more (preferably all hydrogen atoms) of hydrogen atoms are substituted with fluorine atoms, and t is an integer of 0 to 5)
And a photocationic polymerization initiator having an anion moiety selected from the anions represented by formula (b) and a cation moiety represented by the formula (b-2).

  As the anion part of the photocationic polymerization initiator (2) in the present invention, among others, the anion part represented by the above formula (b-3) can further improve the heat resistance of the resulting cured product. Is preferable. That is, as the photocationic polymerization initiator (2), a photocationic polymerization initiator having an anion moiety represented by the above formula (b-3) and a cation moiety represented by the above formula (b-2) is used. It is preferable to do.

  Examples of the photocationic polymerization initiator (2) include diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate and the like.

  When the photocationic polymerization initiator (2) is used in combination with the photocationic polymerization initiator (1), the photocationic polymerization initiator (1) in the total amount of the photocationic polymerization initiator contained in the photocurable composition for nanoimprinting of the present invention. ) Is, for example, 20.0% by weight or more, preferably 33.3% by weight or more, more preferably 50.0% by weight or more, particularly preferably 65% by weight or more, most preferably 75% by weight or more, Preferably it is 80 weight% or more.

  Moreover, when using a photocationic polymerization initiator (2) together with a photocationic polymerization initiator (1), the usage-amount of the photocationic polymerization initiator (2) with respect to 1 weight part of photocationic polymerization initiators (1) is as follows. For example, 0.1 to 2 parts by weight. The upper limit of the amount of the photocationic polymerization initiator (2) used is preferably 1.5 parts by weight, more preferably 1 part by weight, particularly preferably 0.75 part by weight, and most preferably 0.5 part by weight. . Moreover, the minimum of the usage-amount of a photocationic polymerization initiator (2) becomes like this. Preferably it is 0.15 weight part, Most preferably, it is 0.2 weight part.

  By using the photocationic polymerization initiator (1) and the photocationic polymerization initiator (2) in the above range, a cured product having particularly excellent heat resistance tends to be obtained.

  The photocurable composition for nanoimprinting of the present invention may contain other polymerization initiator in addition to the above-mentioned photocationic polymerization initiators (1) and (2) as a polymerization initiator, but for nanoimprinting of the present invention. The proportion of the total amount of the photocationic polymerization initiators (1) and (2) in the total polymerization initiator contained in the photocurable composition is, for example, 50% by weight or more, preferably 70% by weight or more, and particularly preferably 90%. % By weight or more. By containing the photocationic polymerization initiators (1) and (2) in the above range, a cured product having particularly excellent heat resistance tends to be obtained.

[Other ingredients]
The photocurable composition for nanoimprinting of the present invention may contain other components as necessary in addition to the above components. Examples of other components include curable compounds other than those described above, solvents, surface conditioners (= leveling agents), photosensitizers (for example, thioxanthone compounds), antifoaming agents, coupling agents (for example, silane cups) Conventional additives such as a ring agent and the like, surfactants, inorganic fillers, flame retardants, ultraviolet absorbers, ion adsorbers, phosphors, mold release agents, dispersants, and dispersion aids. These can be used alone or in combination of two or more.

(Surface conditioner)
The photocurable composition for nanoimprints of the present invention contains a surface conditioner, and when forming a coating film by a spin coating method or the like, it suppresses the generation of edge beads and forms a coating film having excellent surface smoothness. It is preferable in that it can be performed.

  Examples of the surface conditioner include silicone-based surface conditioners (for example, polyether-modified polysiloxane, polyester-modified polysiloxane, aralkyl-modified polysiloxane, etc.), hydrocarbon-based surface conditioners [for example, poly (meth) acrylate, polyether-modified Poly (meth) acrylate, fluorine-modified poly (meth) acrylate, etc. (both including homopolymers and copolymers)]. These can be used alone or in combination of two or more.

  The molecular weight of the surface conditioning agent is, for example, 3000 or more, preferably 4000 to 150,000, more preferably 5000 to 100,000, particularly preferably 7000 to 100,000, and most preferably 10,000 to 50,000.

  As the surface conditioner, for example, commercially available products such as trade names “BYK-UV3510”, “BYK-350”, “BYK-352”, “BYK-354” (above, manufactured by BYK Japan Japan Co., Ltd.) are suitable. Can be used for

  The content of the surface conditioning agent (the total amount when containing two or more types) is, for example, 0.005 to 10 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the cationic curable compound contained in the photocurable composition for nanoimprint. Is 0.01-7 parts by weight, particularly preferably 0.05-5 parts by weight.

(solvent)
The photocurable composition for nanoimprinting of the present invention may contain a solvent.

  Examples of the solvent include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3- Esters such as methoxybutyl acetate and 1-methoxy-2-propyl acetate; ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol Ethers such as monoethyl ether; 3-methoxy Examples include alcohols such as ethanol and 1-methoxy-2-propanol; ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and mesitylene. it can. These can be used alone or in combination of two or more.

  Among them, it is preferable from the viewpoint of applicability to use a solvent having a boiling point (at 760 mmHg) of, for example, 100 to 210 ° C, preferably 120 to 200 ° C, particularly preferably 135 to 180 ° C.

  The content of the solvent (the total amount in the case of containing two or more types) is a range in which the concentration of the non-volatile content contained in the photocurable composition for nanoimprint is 3 to 90% by weight (preferably 5 to 80% by weight). The viscosity [at 25 ° C., shear rate 20 (1 / s)] of the photocurable composition for nanoimprinting of the present invention by adding a solvent is, for example, 0.1 to 500 mPa · s. Adjustment to a degree (preferably 1 to 200 mPa · s) is preferable from the viewpoint of improving coating properties.

[Photocurable composition for nanoimprint]
The photocurable composition for nanoimprinting of the present invention can be prepared, for example, by stirring and mixing the above components at a predetermined ratio and defoaming under vacuum as necessary.

The weight average value of Onishi parameter of all cationic curable compounds contained in the photocurable composition for nanoimprinting of the present invention is 3.2 or less, preferably 3.15 or less, particularly preferably 3.1 or less, and most preferably. Is 3.05 or less. The lower limit of the weight average value of the Onishi parameter is, for example, 1.8, preferably 2.0. Therefore, a cured product having excellent etching resistance can be formed. The weight average value (OP _avg ) of the Onishi parameter when the nanoimprint photocurable composition contains only one cationic curable compound is the same as the Onishi parameter value (OP).

The Onishi parameter is a parameter that empirically indicates etching resistance, and is calculated by the following equation. The smaller the value of the Onishi parameter (OP or OP _avg ), the greater the etching resistance.
OP = N / (Nc-No)
(In the formula, N is the total number of atoms constituting the cation curable compound, Nc is the number of carbon atoms contained in the cation curable compound, and No is the number of oxygen atoms contained in the cation curable compound)

When the photocurable composition for nanoimprint contains two or more types of cationic curable compounds (for example, Z type), the Onishi parameter of all cationic curable compounds [including cationic curable compounds (1) to (Z)] The weight average value (OP _avg ) is the weight average value of the Onishi parameter calculated from the above formula, and is calculated by the following formula.
OP _avg = (G ¹ × OP ¹ + G ² × OP ² +... G ^Z × OP ^Z ) / 100
(In the formula, OP ^{1 to} OP ^Z are Onishi parameter values of each cationic curable compound contained in the photocurable composition for nanoimprint, and G ^{1 to} G ^Z are all cations contained in the photocurable composition for nanoimprint. The content ratio of each cationic curable compound in the amount of the curable compound (100% by weight) is indicated, and G ¹ +... + G ^Z = 100. Z represents an integer of 2 or more)

The weight average value of the ring parameters of all cationic curable compounds contained in the photocurable composition for nanoimprinting of the present invention is 0.4 or more, preferably 0.45 or more, particularly preferably 0.5 or more. is there. Note that the upper limit of the weight average value of the ring parameters is, for example, 0.8, preferably 0.75. Therefore, a cured product having excellent etching resistance can be formed. The weight average value (RP _avg ) of the ring parameter when the photocurable composition for nanoimprinting contains only one kind of cationic curable compound is the same as the value (RP) of the ring parameter.

The ring parameter is an empirical parameter indicating etching resistance, and is calculated by the following equation. The larger the value of the ring parameter (RP or RP _avg ), the greater the etching resistance.
RP = Mcr / Mtot
(In the formula, Mcr is the atomic weight of carbon atoms forming a ring structure in the cationic curable compound, and Mtot is the total atomic weight of the cationic curable compound)

When the photocurable composition for nanoimprint contains two or more types of cationic curable compounds (for example, Z type), the ring parameters of all cationic curable compounds [including cationic curable compounds (1) to (Z)] The weight average value (RP _avg ) is a weight average value of the ring parameter calculated from the above formula, and is calculated by the following formula.
RP _avg = (G ¹ × RP ¹ + G ² × RP ² +... G ^Z × RP ^Z ) / 100
(Wherein, RP ¹ to Rp ^Z is a ring parameter of the cationically curable compounds contained in the nanoimprint photocurable composition, G ¹ ~G ^Z is as above, in nanoimprint photocurable composition The content ratio of each cation curable compound in the total cation curable compound amount (100% by weight) contained is represented by G ¹ +... + G ^Z = 100. Z represents an integer of 2 or more)

  The photocurable composition for nanoimprinting of the present invention is excellent in thin film curability and can be cured quickly by light irradiation to form a cured product excellent in etching resistance.

  The light (active energy ray) used for the light irradiation may be any light that allows the polymerization reaction of the photocurable composition for nanoimprinting to proceed, and includes infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Of these, ultraviolet rays are preferable because they are easy to handle. For irradiation with ultraviolet rays, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a UV-LED, a laser, or the like can be used.

The light irradiation condition when forming a thin film having a film thickness of 1 μm by irradiating with ultraviolet rays is such that the integrated light quantity is about 50 to 4000 mJ / cm ² .

  The cured product obtained by the above method is excellent in etching resistance (particularly dry etching resistance), and the etching selectivity (Es / Er) is, for example, 0.6 or more, preferably 0.7 or more, particularly preferably 0.75 or more. It is. That is, since the etching rate of the inorganic material substrate (for example, sapphire substrate) is higher than that of the cured product serving as a mask, the rate at which the resist is etched when the inorganic material substrate is etched is suppressed to a low level. In addition, a desired fine pattern (for example, a pattern having a pattern width of 4 μm or less and an aspect ratio of 0.3 to 3.0) can be formed with high accuracy. Note that Es is an etching rate of an inorganic material substrate such as a sapphire substrate, and Er is an etching rate of a cured product of the photocurable composition for nanoimprinting of the present invention. Moreover, an etching rate and an etching selectivity can be measured by the method as described in an Example.

  Further, the cured product has excellent heat resistance, and the weight reduction rate when maintained at 250 ° C. for 30 minutes is 10% or less, preferably 9% or less, particularly preferably 8% or less, and most preferably 7% or less. It is. Therefore, if the photocurable composition for nanoimprinting of the present invention is used, it is possible to prevent resist burning from occurring when dry etching is performed in a high temperature environment. The weight reduction rate can be measured by the method described in the examples.

[Production method of fine pattern substrate]
The method for producing a fine pattern substrate according to the present invention comprises applying the photocurable composition for nanoimprinting onto an inorganic material substrate to form a coating film, and then applying a mold (for example, a mold made of polydimethylsiloxane) to the resulting coating film. Etc.), a mask is formed through a step of transferring the uneven shape and a step of irradiating the coating film with light, and the substrate is etched using the obtained mask.

  As the inorganic material substrate, for example, an inorganic material substrate such as a silicon substrate, a sapphire substrate, a ceramic substrate, an alumina substrate, a gallium phosphide substrate, a gallium arsenide substrate, an indium phosphide substrate, or a gallium nitride substrate may be used. it can.

  Examples of the method for applying the photocurable composition for nanoimprinting onto the inorganic material substrate include a spin coating method, a screen printing method, a curtain coating method, and a spray method.

  For example, the coating conditions for forming a coating film by spin coating are preferably in the following range. That is, the rotation speed of the inorganic material substrate is preferably about 300 to 5000 rpm, for example, the initial rotation speed is rotated at 300 to 1000 rpm for about 5 to 20 seconds, and then rotated at 3000 to 5000 rpm for 20 seconds or more to drive off the solvent. Is preferred. The temperature during spin coating is preferably about 20 to 28 ° C., for example.

  As thickness of a coating film, it is 0.1-20 micrometers, for example, Preferably it is 0.2-4 micrometers. In this invention, since the said photocurable composition for nanoimprints is used, it is excellent in thin film sclerosis | hardenability.

  The light irradiation conditions are the same as in the case of curing the photocurable composition for nanoimprint. The cured product obtained by light irradiation can be suitably used as a mask for etching an inorganic material substrate.

After light irradiation, post-cure may be performed before or after release. Etching accuracy can be improved by performing post cure. Post-cure can be performed by heating and / or light irradiation. When performing post-cure by heating, it is preferable to heat at 100-220 degreeC for about 30 second-3 hours, for example. Moreover, when performing post-cure by light irradiation, it is preferable to irradiate for about 3 to 100 seconds with the irradiation intensity of about 10-200 mW / cm < ² >, for example.

  Examples of the method for etching the inorganic material substrate include a dry etching method and a wet etching method. In the present invention, it is particularly preferable to employ a dry etching method, and in particular, it is preferable to employ a dry etching method using a gas containing chlorine atoms from the viewpoint of enabling highly accurate fine processing.

  In the manufacturing method of the fine pattern board | substrate of this invention, since the said photocurable composition for nanoimprints is used, the hardened | cured material excellent in heat resistance and etching tolerance can be formed. Therefore, resist burning does not occur even when the work of etching the inorganic material substrate using the obtained cured product as a mask is performed under high temperature conditions, and the temperature condition of the etching process is limited by the heat resistant temperature of the resist. There is nothing. And the inorganic material board | substrate with which the highly accurate fine pattern was formed in the surface, ie, a fine pattern board | substrate, can be manufactured by using the said hardened | cured material as a mask.

[Semiconductor device]
A semiconductor device according to the present invention includes a semiconductor element such as an LED element including the fine pattern substrate as a structural unit. For example, an LED display, LED illumination, a light source for optical communication, a traffic light, an electric bulletin board, and a large video device. Etc. are included.

  For example, the LED element includes a light emitter obtained by growing a light emitting layer (GaN layer) on the surface of a fine pattern substrate by metal organic vapor phase epitaxy (MOVPE), a lens, a wiring, and the like.

  The semiconductor device of the present invention is manufactured by laminating a light emitting layer, a semiconductor layer, and the like on the fine pattern substrate obtained through the above-described steps, for example, through the step of obtaining the fine pattern substrate by the method for producing a fine pattern substrate. can do.

  Therefore, the method for manufacturing a semiconductor device of the present invention includes at least a step of obtaining a fine pattern substrate by the method for manufacturing a fine pattern substrate. The method for manufacturing a semiconductor device of the present invention preferably further includes a step of laminating a light emitting layer, a semiconductor layer, and the like on the fine pattern substrate obtained through the above steps.

  Since the semiconductor device of the present invention includes a fine pattern substrate formed using the photocurable composition for nanoimprints of the present invention, it has excellent light extraction efficiency, high brightness, long life, low power consumption, low heat generation, etc. It has the following characteristics.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. Moreover, the following weight average molecular weight is the value of polystyrene conversion by GPC.

Preparation Example 1 [Preparation of (3,4,3 ′, 4′-diepoxy) bicyclohexyl]
A dehydration catalyst was prepared by stirring and mixing 70 g (0.68 mol) of 95 wt% sulfuric acid and 55 g (0.36 mol) of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).
In a 3 L flask equipped with a stirrer, a thermometer, and a distillation pipe filled with a dehydrating agent and kept warm, 1000 g (5.05 mol) of hydrogenated biphenol (= 4,4′-dihydroxybicyclohexyl), the above 125 g of the dehydration catalyst (0.68 mol as sulfuric acid) and 1500 g of pseudocumene prepared in Step 1 were added, and the flask was heated. The generation of water was confirmed when the internal temperature exceeded 115 ° C. The temperature was further raised to raise the temperature to the boiling point of pseudocumene (internal temperature 162 to 170 ° C.), and dehydration reaction was carried out at normal pressure. By-product water was distilled off and discharged out of the system through a dehydration tube. The dehydration catalyst was liquid under the reaction conditions and was finely dispersed in the reaction solution. After about 3 hours, almost theoretical amount of water (180 g) was distilled, and the reaction was terminated.
After completion of the reaction, the pseudocumene was distilled off from the liquid in the reactor using a 10-stage Oldershaw type distillation column, and then distilled at an internal pressure of 10 Torr (1.33 kPa) and an internal temperature of 137 to 140 ° C. , 731 g of bicyclohexyl-3,3′-diene was obtained.

The obtained bicyclohexyl-3,3′-diene (243 g) and ethyl acetate (730 g) were charged into a reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was controlled to 37.5 ° C. 274 g of peracetic acid in ethyl acetate (peracetic acid concentration: 29.1 wt%, moisture content: 0.41 wt%) was added dropwise over about 3 hours. After completion of the dropwise addition, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 270 g of a compound. The obtained compound had an oxirane oxygen concentration of 15.0% by weight. In ¹ H-NMR measurement, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed in the vicinity of δ3.1 ppm. From the above, it was confirmed that the obtained compound was (3,4,3 ′, 4′-diepoxy) bicyclohexyl.

Preparation Example 2 [Preparation of 2,2-bis (3,4-epoxycyclohexane-1-yl) propane]
36 g of water, 12.0 g of sodium hydrogen sulfate, 500 g of isopropylidene-4,4′-dicyclohexanol (manufactured by Aldrich) as a solvent in a 1 L jacketed flask equipped with a stirrer, a condenser, a thermometer and a nitrogen introduction tube 500 g of Solvesso 150 (manufactured by ExxonMobil) was added and dehydrated at 100 ° C. The reaction was terminated when no more water distilled.
When the reaction solution was analyzed by gas chromatography, 2,2-bis (3,4-cyclohexenyl) propane was produced in a yield of 96%. The obtained reaction solution was washed with 500 mL of ion exchanged water using a separatory funnel, and then the organic layer was distilled under reduced pressure to obtain 387.0 g of colorless and transparent liquid 2,2-bis (3,4-cyclohexenyl) propane. Got. The purity was 96.1%.

100 g of the obtained 2,2-bis (3,4-cyclohexenyl) propane and 30 g of ethyl acetate were charged into a 1 L jacketed flask similar to the above, and the temperature in the reaction system was adjusted while blowing nitrogen into the gas phase. Over about 2 hours, 307.2 g of peracetic acid in ethyl acetate (peracetic acid concentration: 29.1% by weight, moisture content: 0.47% by weight) was added dropwise over about 2 hours to reach 30 ° C. After completion of the dropwise addition, the reaction was terminated by aging at 30 ° C. for 3 hours.
Thereafter, the reaction-terminated liquid was washed with water at 30 ° C., and deboiling was performed at 70 ° C./20 mmHg to obtain 99.4 g of a compound.
The obtained compound had an oxirane oxygen concentration of 11.3% and a viscosity of 3550 cP (25 ° C.). Further, from ¹ H-NMR, a peak derived from an internal double bond in the vicinity of δ4.5 to 5 ppm disappeared, and generation of a proton peak derived from an epoxy group was confirmed in the vicinity of δ2.9 to 3.1 ppm. From the above, it was confirmed that the obtained compound was 2,2-bis (3,4-epoxycyclohexane-1-yl) propane.

Preparation Example 3 [Preparation of bis (3,4-epoxycyclohexylmethyl) ether]
To a 5 L reactor, 499 g (12.48 mol) of granular sodium hydroxide and 727 mL of toluene were added, and after purging with nitrogen, a solution of 484 mL of tetrahydrobenzyl alcohol 420 g (3.74 mol) in toluene was added at 70 ° C. Aged for 1.5 hours. Next, 419 g (2.20 mol) of methanesulfonic acid tetrahydrobenzyl was added, and the mixture was aged for 3 hours under reflux, and then cooled to room temperature. The reaction was stopped by adding 1248 g of water, followed by liquid separation.
The separated organic layer was concentrated and then distilled under reduced pressure to obtain ditetrahydrobenzyl ether as a colorless transparent liquid (yield 85%). The ¹ H-NMR spectrum of the obtained ditetrahydrobenzyl ether was measured.
¹ H-NMR (CDCl ₃ ): δ 1.23-1.33 (m, 2H), 1.68-1.94 (m, 6H), 2.02-2.15 (m, 6H), 3.26-3.34 (m, 4H), 5.63-7.70 (m, 4H)

  200 g (0.97 mol) of the obtained ditetrahydrobenzyl ether, 0.39 g of 20% SP-D (acetic acid solution) and 669 mL of ethyl acetate were added to the reactor, and the temperature was raised to 40 ° C. Next, 608 g of 29.1% peracetic acid was added dropwise over 5 hours and aged for 3 hours. Thereafter, the organic layer was washed 3 times with an alkaline aqueous solution and twice with ion-exchanged water, and then distilled under reduced pressure to obtain bis (3,4-epoxycyclohexylmethyl) ether (molecular weight 238) as a colorless transparent liquid. (Yield 77%).

Preparation Example 4 [Preparation of 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane]
[1,3-Bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro- (3-phenyl-1H-inden-1-ylidene) (tricyclohexylphosphine) ruthenium (II) (trade name) under nitrogen atmosphere "Umicore M2", manufactured by Umicore) 0.08 g (equivalent to 0.0001 mol per mol of 4-vinyl-1-cyclohexene) 90.0 g of toluene (super-dehydrated, manufactured by Wako Pure Chemical Industries, Ltd.) In a 300 mL three-necked flask.
While blowing nitrogen into the gas phase portion, 89.5 g of 4-vinyl-1-cyclohexene was charged with a syringe and stirred at 40 ° C. for 24 hours. The concentrated residue obtained by concentrating the reaction solution was purified by simple distillation under reduced pressure (0.9 kPa) to obtain Compound (1) as a fraction at 125 to 126 ° C. The yield based on 4-vinyl-1-cyclohexene was 47.4%.
¹ H-NMR confirmed the disappearance of the proton peak at δ5.1-4.9 corresponding to the terminal olefin of 4-vinyl-1-cyclohexene, and therefore compound (1) was 1,2-bis It was confirmed to be (3-cyclohexenyl) ethylene.

15 g (0.08 mol) of the obtained compound (1) was dissolved in 150 g of ethyl acetate. Thereto, 65.5 g (0.26 mol) of metachloroperbenzoic acid was added at 30 ° C. over 1 hour, and the mixture was stirred at 30 ° C. for 2 hours. Thereafter, 379 g of a 10% by weight sodium thiosulfate aqueous solution was added to the obtained reaction solution and stirred for 30 minutes, 150 g of toluene was added to separate the solution, and the aqueous layer was extracted again with 150 g of toluene.
The obtained organic layers were mixed, washed twice with 384 g of a 7 wt% aqueous sodium hydrogen carbonate solution and twice with 300 g of water, and the organic layer was concentrated.
The resulting concentrated residue was purified by silica gel column chromatography to obtain 12.1 g of colorless and transparent viscous compound (2) (yield 64%).
The oxirane oxygen concentration of the compound (2) is 19.98% by weight. In ¹ H-NMR, the peak disappearance of δ5.8 to 5.2 ppm derived from the double bond of the compound (2) and the epoxy group are derived. Proton peak formation at δ 3.3 to 3.1 ppm and 2.7 to 2.4 ppm was confirmed. From the above, it was confirmed that the obtained compound (2) was 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane.

Examples 1-6, Comparative Examples 1-4
According to the composition shown in the table (unit: parts by weight), each component was charged into a flask, and stirred and mixed at room temperature to obtain a uniform photocurable composition for nanoimprinting.
The resulting photocurable composition for nanoimprint was evaluated by the following method. The evaluation results are summarized in the following table.

(1) Onishi parameter value The Onishi parameter (OP _avg ) value was calculated from the following equation.
OP _avg = (G ¹ × OP ¹ + G ² × OP ² +... G ^Z × OP ^Z ) / 100
Wherein, OP ¹ ~OP ^Z is of the formula OP = N / (Nc-No )
(In the formula, N is the total number of atoms constituting the cation curable compound, Nc is the number of carbon atoms contained in the cation curable compound, and No is the number of oxygen atoms contained in the cation curable compound)
Is the Onishi parameter value of each cation curable compound contained in the photocurable composition for nanoimprints, and G ^{1 to} G ^Z are the total cation curable compound amount contained in the photocurable composition for nanoimprints. The content ratio of each cationic curable compound in (100% by weight) is shown, and G ¹ +... + G ^Z = 100. Z represents an integer of 2 or more]

(2) Ring parameter value The ring parameter (RP _avg ) value was calculated from the following equation.
RP _avg = (G ¹ × RP ¹ + G ² × RP ² +... G ^Z × RP ^Z ) / 100
[Wherein, RP ^{1 to} RP ^Z are the following formulas: RP = Mcr / Mtot
(In the formula, Mcr is the atomic weight of carbon atoms forming a ring structure in the cationic curable compound, and Mtot is the total atomic weight of the cationic curable compound)
It is the ring parameter value of each cationic curable compound contained in the photocurable composition for nanoimprint, calculated in G ^{1 to} G ^Z and Z are the same as above]

(3) Heat resistance evaluation The photocurable composition for nanoimprint obtained in Examples and Comparative Examples was applied on a silicon wafer with a thickness of 2 μm using a spin coater, and irradiated with ultraviolet rays (1000 mJ / cm ² ). Thus, a thin film cured product was obtained on the silicon wafer. The cured product is peeled off from the silicon wafer, weighed in an aluminum sample pan, and using a thermogravimetric / differential thermal simultaneous measurement device (trade name “EXSTAR6300”, manufactured by SII Nano Technology Co., Ltd.) The temperature was raised from 30 ° C. to 150 ° C. at 20 ° C./minute, held at 150 ° C. for 10 minutes, and then heated from 150 ° C. to 250 ° C. at 20 ° C./minute and held at 250 ° C. for 30 minutes. The heat resistance was evaluated by measuring the weight loss rate.

(4) Evaluation of dry etching resistance The photocurable composition for nanoimprint obtained in Examples and Comparative Examples was applied on a sapphire substrate with a thickness of 2 μm using a spin coater, and ultraviolet rays (1000 mJ / cm ² ). Was irradiated to form a thin cured product. After heating this sapphire substrate with cured product at 150 ° C. for 10 minutes, a portion of the cured product is masked with polyimide tape, and using an ICP type RIE apparatus, the flow rate is ₂ SCCM Cl ₂ gas, 9 SCCM BCl ₃ gas. Etching was performed for 6 minutes under the conditions of a degree of vacuum of 0.1 Pa, an ICP power of 150 W, a bias power of 75 W, and a substrate stage set temperature of 40 ° C. After removing the polyimide tape used for masking, the difference in thickness between the masking surface (unetched surface) and the non-masking surface (etched surface) is measured by a step gauge (trade name “T-4000”, Kosaka Co., Ltd.) And the etching rate per minute of the cured product layer was determined.
The sapphire substrate on which the cured product was not laminated was also masked with a polyimide tape in the same manner as described above and etched to obtain the etching rate per minute.
The etching selectivity was calculated from the following formula to evaluate dry etching resistance.
Etching selectivity = Es ′ / Er
(In the formula, Es ′ is the etching rate of the sapphire substrate, and Er is the etching rate of the cured product of the photocurable composition for nanoimprint obtained in Examples and Comparative Examples)

The compounds used in the examples and comparative examples are as follows.
<Cation curable compound>
(Compound represented by Formula (a))
(A-1): (3,4,3 ′, 4′-diepoxy) bicyclohexyl (using the compound obtained in Preparation Example 1 above), molecular weight: 194
(A-2): 2,2-bis (3,4-epoxycyclohexane-1-yl) propane (using the compound obtained in Preparation Example 2 above), molecular weight: 236
(A-3): bis (3,4-epoxycyclohexylmethyl) ether (using the compound obtained in Preparation Example 3 above), molecular weight: 238
(A-4): 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane (using the compound obtained in Preparation Example 4 above), molecular weight: 236
(Cation curable compound having two or more aromatic rings in one molecule)
OXBP: 4,4′-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl, weight average molecular weight: 411, trade name “ETERNACOLL OXBP”, manufactured by Ube Industries, Ltd. N-890: modified novolak epoxy Resin, weight average molecular weight: 3000 or more, trade name “EPICLON N-890”, manufactured by DIC Corporation EPPN-503: epoxy resin containing glycidyloxyphenyl skeleton, weight average molecular weight: 2000 or more, trade name “EPPN-503 ”Manufactured by Nippon Kayaku Co., Ltd. (cationic curable compound having no two or more aromatic rings or alicyclic rings in one molecule)
OXT-121: 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, average molecular weight: 334, trade name “ARON OXETANE OXT-121”, manufactured by Toagosei Co., Ltd. EX-850: 2 , 2 ′-(2,5,8-trioxanonane-1,9-diyl) bisoxirane, molecular weight: 218, trade name “Denacol EX-850”, manufactured by Nagase ChemteX Corporation <Photocationic polymerization initiator>
(B-1): 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate (B-2): [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium tris (penta Fluoroethyl) trifluorophosphate <Surface conditioner>
BYK-350: acrylic copolymer, molecular weight: about 20,000, trade name “BYK-350”, manufactured by BYK Japan Japan, BYK-UV3510: mixture of polyether-modified polydimethylsiloxane and polyether, molecular weight: about 9000 , Trade name "BYK-UV3510", manufactured by Big Chemie Japan Co., Ltd.

The photocurable composition for nanoimprinting of the present invention is excellent in rapid curability and thin film curability, and can form a cured product quickly by irradiation with light.
In addition, since the cured product of the photocurable composition for nanoimprinting of the present invention is excellent in heat resistance and etching resistance, when the cured product is used as a mask when etching an inorganic material substrate, it is limited by the heat resistant temperature of the mask. The etching temperature can be arbitrarily set without causing the resist to burn, and the inorganic material substrate can be selectively etched, and a highly accurate fine pattern can be formed on the surface of the inorganic material substrate. .
Then, when a light emitting layer, a semiconductor layer, and the like are stacked on the inorganic material substrate having the fine pattern formed on the surface, a light emitting element having excellent light extraction efficiency can be formed. A semiconductor device including the light emitting element It has characteristics such as high brightness, long life, low power consumption, and low heat generation.

Claims (10)

A photocurable composition for nanoimprinting containing a cationic curable compound, wherein the cationic curable compound contains a compound represented by the following formula (a), and the weight average value of the Onishi parameter of the cationic curable compound is 3.2 or less, the weight average value of the ring parameter is 0.4 or more, and the weight by simultaneous measurement of thermogravimetric / differential heat when maintaining the cured product of the photocurable composition for nanoimprint at 250 ° C. for 30 minutes A photocurable composition for nanoimprints having a reduction rate of 10% or less.

(In the formula, R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, or a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent. X represents a single bond or a linking group) Following formula (b-1)
[(Y) _k B (Phf) _4-k ] ^- (b-1)
[Wherein, Y represents an aromatic hydrocarbon group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms which may have a substituent (excluding a group containing a halogen atom). Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom. k is an integer of 1 to 3]
An anion moiety represented by the following formula (b-2)

(In the formula, Ar ^{1 to} Ar ³ are the same or different and each represents a hydrogen atom, a halogen atom, or an optionally substituted aromatic hydrocarbon group or heterocyclic group)
The photocurable composition for nanoimprints of Claim 1 containing the photocationic polymerization initiator (1) which has a cation part represented by these.   Furthermore, the photocurable composition for nanoimprints of Claim 1 or 2 containing a silicone type surface conditioning agent and / or a hydrocarbon type surface conditioning agent.   4. The light for nanoimprinting according to claim 1, wherein the content of the compound represented by formula (a) is 20 to 70% by weight of the total amount (100% by weight) of the photocurable composition for nanoimprinting. Curable composition. As the photocationic polymerization initiator, together with the photocationic polymerization initiator (1), BF ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , SbF ₅ OH ⁻ , and the following formula (b-3)
[(Rf) _t PF _6-t ] ^- (b-3)
(In the formula, Rf is an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and t is an integer of 0 to 5)
A photocationic polymerization initiator (2) having an anion part selected from anions represented by formula (b-2) and a cation part represented by the formula (b-2), 1 part by weight of the photocationic polymerization initiator (1) The photocurable composition for nanoimprints according to any one of claims 2 to 4, which is contained in an amount of 0.1 to 2 parts by weight based on the weight.   The photocurable composition for nanoimprints according to any one of claims 1 to 5 is applied onto an inorganic material substrate to form a coating film, and a mold is pressed against the obtained coating film to transfer the uneven shape. The manufacturing method of the fine pattern board | substrate which forms a mask through the process and the process of irradiating light to a coating film, and etches a board | substrate using the obtained mask.   The manufacturing method of the fine pattern board | substrate of Claim 6 which heat-processes after light irradiation.   The manufacturing method of the fine pattern board | substrate of Claim 7 which heat-processes at 100-220 degreeC.   The manufacturing method of the fine pattern board | substrate of any one of Claims 6-8 which performs dry etching by the gas containing a chlorine atom as etching.   The manufacturing method of a semiconductor device including the process of obtaining a fine pattern board | substrate by the manufacturing method of the fine pattern board | substrate of any one of Claims 6-9.