Curable composition for imprinting, cured product, method for producing imprint pattern, and method for producing device

Abstract

The present invention provides: a curable composition for imprinting, the curable composition containing a polymerizable compound, a polymerization initiator, and one or more organic phosphorus compounds selected from the group consisting of organic phosphoric acid derivatives, organic phosphonic acid derivatives, and organic phosphine oxide derivatives in which a carbonyl group is not directly bonded to a phosphorus atom; a cured product of the curable composition for imprinting; a method for producing an imprint pattern using the curable composition for imprinting; and a method for producing a device, said method the method for producing an imprint pattern.

Description

S硬化性組成物、硬化物、インプリントパターンの製造方法及びデバイスの製造方法

[0001] The present invention relates to a curable composition for imprinting, a cured product, a method for manufacturing an imprint pattern, and a method for manufacturing a device.

[0002] The imprint method is a technique for transferring a fine pattern onto a material by pressing a mold (commonly called a mold or stamper) having a pattern formed thereon. Since it is possible to easily produce a precise fine pattern by using the imprint method, it has been expected to be applied in various fields in recent years. In particular, nanoimprint technology for forming a fine pattern at the nano-order level has attracted attention.

[0003] Patent Document 1 describes a liquid material for nanoimprinting, characterized in that the number concentration of particles having a particle size of 0.07 μm or more is less than 310 particles / mL.

[0004] Japanese Patent Application Laid-Open No. 2016-164977

[0005] Two methods have been proposed for imprinting: thermal imprinting and curing imprinting, based on their transfer methods. In thermal imprinting, a mold is pressed onto a thermoplastic resin heated above its glass transition temperature (Tg), and a fine pattern is formed by releasing the mold after cooling. While this method allows for the selection of various materials, it has drawbacks, such as the need for high pressure during pressing and the difficulty in forming fine patterns due to reduced dimensional accuracy caused by thermal shrinkage. On the other hand, in curing imprinting, for example, a mold is pressed against a film formed from an imprint-curable composition, and then photocured or thermally cured before the mold is released. Because the imprinting is done on an uncured material, some or all of the high-pressure application and high-temperature heating can be omitted, making it possible to easily create fine patterns. Furthermore, because the dimensional change before and after curing is small, it has the advantage of being able to form fine patterns with high accuracy. Recently, new developments such as nanocasting, which combines the advantages of both thermal and curing imprinting, and reversal imprinting, which creates three-dimensional layered structures, have also been reported.

[0006] In the curing-type imprint method, an imprint-curable composition is applied to a support (with adhesion treatment applied to the surface if necessary) to form a film, and then a mold made of a light-transmitting material such as quartz is pressed onto it. With the mold pressed in place, the imprint-curable composition is cured by light irradiation or heating, and then the mold is released to produce a cured product with the desired pattern transferred onto it. Methods for applying the imprint-curable composition to the support include spin coating and inkjet methods. Spin coating is an application method with excellent productivity due to its high throughput. Furthermore, the method of performing microfabrication using the transferred imprint pattern as a mask is called nanoimprint lithography (NIL), and is being developed as a next-generation lithography technology to replace the current ArF immersion process. Therefore, the imprint-curable composition used in NIL, like EUV resists, must be able to resolve ultrafine patterns of 20 nm or less, and must have high etching resistance as a mask when microfabrication of the workpiece. Specific examples of imprintable curable compositions intended for use as masks include those described in Japanese Patent No. 5426814, Japanese Patent Publication No. 2015-009171, Japanese Patent Publication No. 2015-185798, Japanese Patent Publication No. 2015-070145, Japanese Patent Publication No. 2015-128134, and the like.

[0007] In the imprint method, a small release force is required to separate the mold from the cured product of the imprint curable composition, in order to suppress deformation, fracture, and damage to the mold. In this specification, a small release force is also referred to as having excellent release properties.

[0008] The present invention aims to provide an imprint curable composition that exhibits excellent release properties in releasing the resulting cured product from a mold, a cured product of the imprint curable composition, a method for manufacturing an imprint pattern using the imprint curable composition, and a method for manufacturing a device including the method for manufacturing the imprint pattern.

[0009] Representative embodiments of the present invention are shown below. <1> A curable composition for imprinting, comprising a polymerizable compound, a polymerization initiator, and one or more organophosphorus compounds selected from the group consisting of organophosphorus derivatives, organophosphonic acid derivatives, and organophosphine oxide derivatives in which a carbonyl group is not directly bonded to a phosphorus atom. <2> The curable composition for imprinting according to <1>, wherein the content of the organophosphorus compound is 0.001 to 0.1% by mass with respect to the total solid content of the composition. <3> The curable composition for imprinting according to <1>, wherein the content of the organophosphorus compound is 0.005 to 0.02% by mass with respect to the total solid content of the composition. <4> The curable composition for imprinting according to any one of <1> to <3>, wherein the organophosphorus compound comprises an organophosphorus compound having an aromatic ring. <5> The curable composition for imprinting according to any one of <1> to <4>, wherein the organophosphorus derivative comprises a phosphate ester. <6> The imprint curable composition according to any one of <1> to <5>, wherein the organic phosphonic acid derivative comprises a phosphonic acid ester. <7> The imprint curable composition according to any one of <1> to <6>, wherein the organic phosphine oxide derivative comprises a compound in which an aromatic hydrocarbon group is directly bonded to a phosphorus atom. <8> The imprint curable composition according to any one of <1> to <7>, wherein the organic phosphine oxide derivative comprises at least one of triphenylphosphine oxide and its derivatives. <9> The imprint curable composition according to any one of <1> to <8>, wherein the organic phosphorus compound is an organic phosphine oxide derivative in which a carbonyl group is not directly bonded to a phosphorus atom. <10> The imprint curable composition according to any one of <1> to <9>, wherein the polymerizable compound comprises a polymerizable compound having an aromatic hydrocarbon group and a polymerizable compound not having an aromatic hydrocarbon group. <11> A cured product obtained by curing the imprint curable composition according to any one of <1> to <10>.<12> A method for forming a pattern using a support and a mold, comprising: an application step of applying an imprint curable composition described in any one of <1> to <10> to an application member selected from the group consisting of a support and a mold; a contact step of bringing a member not selected as the application member from the group consisting of the support and the mold into contact with the imprint curable composition as a contact member; a curing step of curing the imprint curable composition into a cured product; and a peeling step of peeling the mold from the cured product. <13> A method for manufacturing a device, comprising a step of etching using the pattern obtained by the method for manufacturing an imprint pattern described in <12> as a mask.

[0010] The present invention provides an imprint curable composition that exhibits excellent release properties in releasing the resulting cured product from a mold, a cured product of the imprint curable composition, a method for manufacturing an imprint pattern using the imprint curable composition, and a method for manufacturing a device including the method for manufacturing the imprint pattern.

[0011] The contents of the present invention will be described in detail below. In this specification, "~" is used to mean that the numerical values ​​written before and after it are included as the lower limit and upper limit. In this specification, "(meth)acrylate" represents acrylate and methacrylate, "(meth)acrylic" represents acrylic and methacrylic, and "(meth)acryloyl" represents acryloyl and methacryloyl. "(meth)acryloyloxy" represents acryloyloxy and methacryloyloxy. In this specification, "imprint" preferably refers to pattern transfer with a size of 1 nm to 10 mm, and more preferably refers to pattern transfer with a size of approximately 10 nm to 100 μm (nanoimprint). In the notation of groups (atomic groups) in this specification, notations that do not specify substituted and unsubstituted include both those with and without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "light" includes not only light with wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, as well as electromagnetic waves and radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. Laser light such as 248 nm excimer lasers, 193 nm excimer lasers, and 172 nm excimer lasers can also be used. This light may be monochromatic light (single-wavelength light) passed through an optical filter, or light with multiple different wavelengths (composite light). In this specification, unless otherwise specified, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values ​​according to gel permeation chromatography (GPC measurement). In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by Tosoh Corporation) as the column.Unless otherwise specified, the eluent shall be measured using THF (tetrahydrofuran). Unless otherwise specified, detection shall be performed using a UV (ultraviolet) wavelength 254 nm detector. Unless otherwise specified in this specification, the temperature shall be 23°C, the atmospheric pressure shall be 101325 Pa (1 atm), and the relative humidity shall be 50% RH. In this specification, the term "process" shall include not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended function of the process is achieved. In this specification, total solids shall be the total mass of the components of the composition excluding the solvent. In this specification, solids concentration shall be the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, preferred embodiment combination shall be more preferred embodiment.

[0012] The curable composition for imprinting according to the present invention comprises a polymerizable compound, a polymerization initiator, and one or more organophosphorus compounds selected from the group consisting of organophosphate derivatives, organophosphonic acid derivatives, and organophosphine oxide derivatives in which a carbonyl group is not directly bonded to a phosphorus atom. Hereinafter, one or more organophosphorus compounds selected from the group consisting of organophosphate derivatives, organophosphonic acid derivatives, and organophosphine oxide derivatives in which a carbonyl group is not directly bonded to a phosphorus atom will also be referred to as "specific compounds."

[0013] The imprint curable composition of the present invention exhibits excellent release properties between the resulting cured product and the mold. Although the mechanism by which the above effect is obtained is unknown, it is presumed to be as follows. In nanoimprinting, excellent release properties of the cured product of the imprint curable composition from the mold are required. Excellent release properties can suppress deformation and breakage of the pattern. The imprint curable composition of the present invention contains an organophosphorus compound. This organophosphorus compound is thought to segregate on the surface of the composition when in contact with the mold. Therefore, when peeling from the mold, the organophosphorus compound adheres to the mold, reducing the interfacial energy between the mold and the cured product, resulting in excellent release properties. Furthermore, since the organophosphorus compound is unevenly distributed on the surface of the cured product, and a layer-like state of the organophosphorus compound is formed on the surface of the cured product, it is thought that the resistance to dry etching is improved. In addition, since the organophosphorus compound adheres to the mold, it is thought that the adhesion of polymerizable compounds in the imprint curable composition to the mold is suppressed, and mold contamination is also suppressed. The present invention will be described in detail below.

[0014] <Specific Compounds> The imprint curable composition of the present invention contains one or more organophosphorus compounds (specific compounds) selected from the group consisting of organophosphorus derivatives, organophosphonic acid derivatives, and organophosphine oxide derivatives in which a carbonyl group is not directly bonded to a phosphorus atom. The organophosphorus compound is preferably a compound that does not have a radical polymerizable group.

[0015] The organophosphorus compound preferably includes an organophosphorus compound having an aromatic ring, more preferably an organophosphorus compound having an aromatic hydrocarbon ring, and even more preferably an organophosphorus compound having a benzene ring.

[0016] [Organic Phosphate Derivatives] As organic phosphate derivatives, phosphate esters are preferred, and phosphate triesters are more preferred. Examples of phosphate esters include triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, and tris(isopropylphenyl) phosphate; monoalkyldiaryl phosphates having 1 to 20 carbon atoms in the alkyl group, such as octyldiphenyl phosphate and isodecyldiphenyl phosphate; dialkylmonoaryl phosphates having 1 to 20 carbon atoms in the alkyl group, such as dimethylphenylmonophenyl phosphate; trialkyl phosphates having 1 to 20 carbon atoms in the alkyl group, such as triethyl phosphate, tributyl phosphate, and trioctyl phosphate; and trialkoxyalkyl phosphates having 1 to 20 carbon atoms in the alkoxy group, such as tributoxyethyl phosphate.

[0017] [Organic Phosphonic Acid Derivatives] Phosphonic acid esters are preferred as organic phosphonic acid derivatives, and phosphonic acid diesters are more preferred. Examples of phosphonic acid esters include diaryl phosphonates such as di-o-tolylmethylphosphonate, diphenyl α-chlorobenzylphosphonate, and diphenylphenylphosphonate; and dialkyl phosphonates with 1 to 20 carbon atoms in the alkyl group, such as dimethylphosphonate, diethylphosphonate, diethylbenzylphosphonate, and diethylcyanomethylphosphonate. Furthermore, organic phosphonic acid derivatives may also be compounds having a phosphonic acid structure, which is a tautomutant of phosphonic acid. Examples of such compounds include triphenyl phosphite and tris(nonylphenyl)phosphite.

[0018] [Organophosphine Oxide Derivatives] The organophosphine oxide derivatives included as specific compounds are those in which the carbonyl group is not directly bonded to the phosphorus atom. In this specification, "direct bond between structures" means that structures are bonded to each other without the intermediary of a linking group, and "not directly bonded to the phosphorus atom with a carbonyl group" means that the structure does not have a single bond between the phosphorus atom and the carbonyl group without the intermediary of a linking group.

[0019] The organic phosphine oxide derivatives preferably include compounds in which an aromatic hydrocarbon group is directly bonded to a phosphorus atom, and more preferably include at least one of triphenylphosphine oxide and its derivatives. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms. Examples of triphenylphosphine oxide derivatives include those having substituents such as an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) or a halogen atom (preferably Br) on the phenyl group. Examples of organic phosphine oxide derivatives include triphenylphosphine oxide, tris(3-bromophenyl)phosphine oxide, tris(4-methylphenyl)phosphine oxide, diphenyl[9,9'-spirobio[9H-fluorene]-2-yl]phosphine oxide, bis[2-[(oxo)diphenylphosphine]phenyl]ether, 1,8-bis(diphenylphosphine)naphthalene, diphenylphosphine oxide, methyl(diphenyl)phosphine oxide, cyclohexyldiphenylphosphine oxide, tributylphosphine oxide, and tricyclohexylphosphine oxide. Among these, the composition of the present invention is particularly preferably composed of triphenylphosphine oxide as a specific compound.

[0020] [Content] The content of organophosphorus compounds relative to the total solid content of the imprint curable composition is preferably 0.001 to 0.1% by mass, more preferably 0.003 to 0.05% by mass, and even more preferably 0.005 to 0.02% by mass. Furthermore, the content of organophosphorus compounds relative to the total mass of polymerizable compounds contained in the imprint curable composition is preferably 0.001 to 0.1% by mass, more preferably 0.003 to 0.05% by mass, and even more preferably 0.005 to 0.02% by mass. In particular, the content of organophosphorus compounds relative to the total mass of polymerizable compounds having aromatic groups contained in the imprint curable composition is preferably 0.001 to 0.2% by mass, more preferably 0.003 to 0.10% by mass, and even more preferably 0.01 to 0.04% by mass. The imprint curable composition may contain two or more organophosphorus compounds. In that case, it is preferable that the total content of all organophosphorus compounds contained in the imprint curable composition is within the above range.

[0021] <Polymerizable Compounds> The imprint curable composition of the present invention contains polymerizable compounds. In the imprint curable composition of the present invention, it is preferable that the polymerizable compound is the component with the highest content among the components other than the solvent contained in the imprint curable composition. The polymerizable compound may have one polymerizable group or two or more polymerizable groups in one molecule. At least one of the polymerizable compounds contained in the imprint curable composition preferably contains 2 to 5 polymerizable groups in one molecule, more preferably 2 to 4, and even more preferably 2 or 3. There is no particular type of polymerizable group that the polymerizable compound has, but examples include groups having ethylenically unsaturated groups, cyclic ether groups (epoxy groups, glycidyl groups, oxetanyl groups), etc., and groups having ethylenically unsaturated groups are preferred. Examples of groups having an ethylenically unsaturated group include (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamino group, vinyl group, vinyloxy group, allyl group, vinylphenyl group, etc., with (meth)acryloyl group or (meth)acryloyloxy group being more preferred, and acryloyl group or acryloyloxy group being even more preferred.

[0022] It is preferable that at least one polymerizable compound included in the imprint curable composition has a cyclic structure. Examples of such cyclic structures include aliphatic hydrocarbon rings Cf and aromatic hydrocarbon rings Cr. In particular, it is preferable that the polymerizable compound has an aromatic hydrocarbon ring Cr, and more preferably a benzene ring. Furthermore, it is also a preferred embodiment of the present invention to include both polymerizable compounds having an aromatic hydrocarbon group and polymerizable compounds not having an aromatic hydrocarbon group. The molecular weight of the polymerizable compound is preferably 100 to 900.

[0023] At least one of the polymerizable compounds is preferably represented by the following formula (I-1).

[0024] L ２０ This is a 1+q2 valent linking group, and examples include linking groups in cyclic structures. Examples of cyclic structures include the ring Cf, ring Cr, ring Cn, ring Co, and ring Cs described later.２１ and R ２２ each independently represents a hydrogen atom or a methyl group. L ２１ and L ２２ each independently represents a single bond or a linking group L described below. L ２０ and L ２１ or L ２２ may be bonded with or without the linking group L to form a ring. L ２０ , L ２１ and L ２２ may have a substituent T. A plurality of substituents T may combine to form a ring. When there are a plurality of substituents T, they may be the same or different from each other. q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1.

[0025] (Substituents T) The following groups can be considered as substituents T as described above: halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl groups having 6 to 30 carbon atoms), heterocyclic groups (preferably heterocyclic groups having 1 to 30 carbon atoms), amino groups (preferably amino groups having 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups having 1 to 30 carbon atoms), aryloxy groups (preferably aryloxy groups having 6 to 30 carbon atoms) Aryloxy group), heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 30 carbon atoms), acyl group (preferably an acyl group having 2 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), heterocyclic oxycarbonyl group (preferably a heterocyclic oxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably an acyl group having 2 to 30 carbon atoms) Amino group), aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), sulfamoylamino group (preferably a sulfamoylamino group having 0 to 30 carbon atoms), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), alkyl Thio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), heterocyclic thio group (preferably a heterocyclic thio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms), arylsulfonylamino group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms),Heterocyclic sulfonyl groups (preferably heterocyclic sulfonyl groups having 1 to 30 carbon atoms), heterocyclic sulfonylamino groups (preferably heterocyclic sulfonylamino groups having 1 to 30 carbon atoms), alkylsulfinyl groups (preferably alkylsulfinyl groups having 1 to 30 carbon atoms), arylsulfinyl groups (preferably arylsulfinyl groups having 6 to 30 carbon atoms), heterocyclic sulfinyl groups (preferably heterocyclic sulfinyl groups having 1 to 30 carbon atoms), ureido groups (preferably ureido groups having 1 to 30 carbon atoms), hydroxyl groups, nitro groups, carboxyl groups, sulfo groups, phosphoric acid groups, carboxylic acid amide groups, sulfonic acid amide groups, imide groups, phosphino groups, mercapto groups, cyano groups, alkylsulfino groups, arylsulfino groups, arylazo groups, heterocyclic azo groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, hydrazino groups, imino groups. These groups may have further substituents if they are further substituted groups.

[0026] [High Molecular Weight Polymerizable Compounds] The imprint curable composition may also contain polymerizable compounds having a weight-average molecular weight of 800 or more (hereinafter also referred to as "high molecular weight polymerizable compounds"). Examples of high molecular weight polymerizable compounds include compounds containing silicon atoms (Si) (silicon-containing compounds), compounds containing a cyclic structure (ring-containing compounds), and dendrimer-type compounds. Silicon-containing compounds or ring-containing compounds are preferred, and silicon-containing compounds are more preferred.

[0027] The weight-average molecular weight of the high molecular weight polymerizable compound is 800 or more, preferably 1,000 or more, more preferably 1,500 or more, and even more preferably over 2,000. There is no particular upper limit for the weight-average molecular weight, but for example, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, even more preferably 5,000 or less, even more preferably 3,500 or less, and especially even more preferably 3,000 or less. By setting the molecular weight above the above lower limit, the volatilization of the compound is suppressed, and the properties of the composition and coating film are stabilized. In addition, good viscosity for maintaining the shape of the coating film can be ensured. Furthermore, good release properties of the film can be achieved by compensating for the effect of keeping the amount of release agent small. Setting the molecular weight below the above upper limit is preferable because it makes it easier to ensure the low viscosity (fluidity) necessary for pattern filling.

[0028] -Silicon-containing compounds- Examples of silicon-containing compounds include compounds having a silicone skeleton. Specifically, examples include compounds having at least one of the following: a D-unit siloxane structure represented by formula (S1) and a T-unit siloxane structure represented by formula (S2). In formula (S1) or formula (S2), R Ｓ１ ~R Ｓ３ Each of the symbols independently represents a hydrogen atom or a monovalent substituent, and each of the symbols independently represents a bonding site with another structure. Ｓ１ ~R Ｓ３ Each of these substituents is preferably a monovalent substituent. Preferred monovalent substituents are aromatic hydrocarbon groups (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and even more preferably with 6 to 10 carbon atoms) or aliphatic hydrocarbon groups (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12 carbon atoms, and even more preferably with 1 to 6 carbon atoms), and among these, cyclic or linear (linear or branched) alkyl groups (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and even more preferably with 1 to 3 carbon atoms) or groups containing polymerizable groups are more preferred.

[0029] Examples of specific silicon-containing compound structures include the following examples (s-1) to (s-9), shown as partial structures. In these formulas, Q is a group containing the polymerizable group mentioned above. Multiple of these structures may exist in a compound, or they may exist in combination.

[0030]

[0031] The silicon-containing compound is preferably a reaction product of a silicone resin and a compound having a polymerizable group. A reactive silicone resin is preferred as the silicone resin. Examples of reactive silicone resins include modified silicone resins having the silicone skeleton described above, such as monoamine-modified silicone resins, diamine-modified silicone resins, special amino-modified silicone resins, epoxy-modified silicone resins, alicyclic epoxy-modified silicone resins, carbinol-modified silicone resins, mercapto-modified silicone resins, carboxy-modified silicone resins, hydrogen-modified silicone resins, amino-polyether-modified silicone resins, epoxy-polyether-modified silicone resins, and epoxy-aralkyl-modified silicone resins. The polymerizable group compound is preferably a compound having a polymerizable group and a group that can react with an alkoxysilyl group or a silanol group, and more preferably a compound having a polymerizable group and a hydroxyl group. Furthermore, when using the above-mentioned modified silicone resin as the silicone resin, the polymerizable group compound may be a compound having a polymerizable group and a group that reacts with amino groups, epoxy groups, mercapto groups, carboxyl groups, etc., contained in the modified silicone resin. The preferred embodiment of the polymerizable group in the above-mentioned polymerizable compound is the same as the preferred embodiment of the polymerizable group in the polymerizable compound described above. Among these, hydroxyalkyl (meth)acrylate is preferred as the above-mentioned polymerizable compound, and 2-hydroxyethyl (meth)acrylate is more preferred. More specifically, it is preferable that the compound is a reaction product of a compound having a polymerizable group and a group that can react with an alkoxysilyl group or a silanol group (for example, a hydroxyl group) and a silicone resin having an alkoxysilyl group or a silanol group.

[0032] -Ring-containing compounds- Examples of cyclic structures of ring-containing compounds include aromatic rings and alicyclic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocyclic rings. Aromatic hydrocarbon rings are preferably those with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Specific examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, phenalene rings, fluorene rings, benzocyclooctene rings, acenaphthylene rings, biphenylene rings, indene rings, indan rings, triphenylene rings, pyrene rings, chrysene rings, perylene rings, and tetrahydronaphthalene rings. Among these, benzene rings or naphthalene rings are preferred, and benzene rings are more preferred. Aromatic rings may also have a structure in which multiple rings are linked together, for example, biphenyl structures and diphenylalkane structures (for example, 2,2-diphenylpropane). (The aromatic hydrocarbon ring defined here is referred to as aCy.) The aromatic heterocycle preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples include thiophene rings, furan rings, dibenzofuran rings, pyrrole rings, imidazole rings, benzimidazole rings, pyrazole rings, triazole rings, tetraazole rings, thiazole rings, thiadiazole rings, oxadiazole rings, oxazole rings, pyridine rings, pyrazine rings, pyrimidine rings, pyridazine rings, isoindole rings, indole rings, indazole rings, purine rings, quinoridine rings, isoquinoline rings, quinoline rings, phthalazine rings, naphthyridine rings, quinoxaline rings, quinazoline rings, sinnoline rings, carbazole rings, acridine rings, phenazine rings, phenothiazine rings, phenoxatiyne rings, and phenoxazine rings. (The aromatic heterocycle defined here is referred to as hCy.) The alicyclic ring preferably has 3 to 22 carbon atoms, more preferably 4 to 18, and even more preferably 6 to 10.Specifically, examples of aliphatic hydrocarbon rings include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, dicyclopentadiene, spirodecane, spirononane, tetrahydrodicyclopentadiene, octahydronaphthalene, decahydronaphthalene, hexahydroindan, bornane, norbornane, norbornene, isobornane, tricyclodecane, tetracyclododecane, and adamantane rings. Examples of aliphatic heterocycles include pyrrolidine, imidazolidine, piperidine, piperazine, morpholine, oxirane, oxetane, oxolane, oxane, and dioxane rings. (The alicyclic rings defined here are referred to as fCy).

[0033] In the present invention, when the high molecular weight polymerizable compound is a ring-containing compound, it is preferably a compound containing an aromatic hydrocarbon ring, and more preferably a compound having a benzene ring. For example, a compound having a structure represented by the following formula (C-1) can be mentioned.

[0034] In the formula, Ar represents the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle. L １ and L ２Each of these is independently a single bond or a linking group. Examples of linking groups include oxygen atoms (oxy groups), carbonyl groups, amino groups, alkylene groups (preferably with 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms), or combinations thereof. Among these, (poly)alkylene oxy groups are preferred. A (poly)alkylene oxy group may consist of a single alkylene oxy group or multiple repeating alkylene oxy groups. Furthermore, the order of the alkylene group and the oxy group is not limited. The number of repeating alkylene oxy groups is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. Also, an alkylene group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6 carbon atoms) may be interposed in the (poly)alkylene oxy group in relation to the parent ring Ar or polymerizable group Q. Therefore, (poly)alkylene oxy = alkylene group may also be present. ３ is any substituent, including alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms), alkenyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3 carbon atoms), aryl groups (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11 carbon atoms), hydroxyl groups, carboxyl groups, alkoxy groups (preferably 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6 carbon atoms), acyl groups (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3 carbon atoms; alkylcarbonyl groups are also preferred), and aryloyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11 carbon atoms). ３ is a single bond or a linking group. As a linking group, the above L １ , L ２ An example is given. n3 is an integer greater than or equal to 0, preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0. Q １ and Q ２Each of these is an independently polymerizable group, and the above examples of polymerizable groups are preferred. In ring-containing compounds, increasing the number of side chains having polymerizable groups makes it possible to form a strong crosslinked structure during curing, which tends to improve resolution. From this viewpoint, nq is 1 or more, and preferably 2 or more. As an upper limit, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Similarly, from the viewpoint of easily forming a uniform crosslinked structure, when a group or substituent containing a polymerizable group is introduced into a cyclic structure, it is preferable that the substituents are arranged in series.

[0035] -Dendrimer-type compounds- High molecular weight polymerizable compounds may also be dendrimer-type compounds. A dendrimer refers to a dendritic polymer having a structure that branches regularly from a center. A dendrimer consists of a central molecule called a core (stem) and side chain portions called dendrons (branches). While the compound as a whole is generally fan-shaped, it may also be a dendrimer in which the dendrons spread out in a semicircular or circular shape. A polymerizable compound can be made by introducing a group having a polymerizable group into the dendron portion of this dendrimer (for example, the terminal portion that is away from the core). If a (meth)acryloyl group is used as the polymerizable group to be introduced, a dendrimer-type polyfunctional (meth)acrylate can be made. For dendrimer-type compounds, for example, one can refer to the matters disclosed in Japanese Patent No. 5512970, and the description in the above publication is incorporated herein by reference.

[0036] - Polymerizable Group Equivalents - High molecular weight polymerizable compounds preferably have a polymerizable group equivalent of 130 or more, more preferably 150 or more, even more preferably 160 or more, even more preferably 190 or more, and even more preferably 240 or more. The upper limit of the polymerizable group equivalent is preferably 2,500 or less, more preferably 1,800 or less, even more preferably 1,000 or less, even more preferably 500 or less, even more preferably 350 or less, and may also be 300 or less.

[0037] The polymerizable group equivalent is calculated using the following formula: (Polymerizable group equivalent) = (Number-average molecular weight of the polymerizable compound) / (Number of polymerizable groups in the polymerizable compound)

[0038] If the polymerizable group equivalent of the high molecular weight polymerizable compound is above the lower limit, the elastic modulus during curing will be within an appropriate range, resulting in excellent mold release properties. On the other hand, if the polymerizable group equivalent is below the upper limit, the crosslinking density of the cured product pattern will be within an appropriate range, resulting in excellent resolution of the transfer pattern.

[0039] In high molecular weight polymerizable compounds, the number of polymerizable groups is preferably two or more per molecule in the case of silicon-containing compounds, more preferably three or more, and even more preferably four or more. The upper limit is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, and even more preferably 20 or less. In the case of ring-containing compounds, it is preferable to have two or more per molecule. The upper limit is preferably four or less, and more preferably three or less. Alternatively, in the case of dendrimer-type compounds, it is preferable to have five or more per molecule, more preferably 10 or more, and even more preferably 20 or more. The upper limit is preferably 1,000 or less, more preferably 500 or less, and even more preferably 200 or less.

[0040] - Viscosity - The viscosity of the high molecular weight polymerizable compound at 23°C is preferably 100 mPa·s or more, more preferably 120 mPa·s or more, and even more preferably 150 mPa·s or more. The upper limit of the viscosity is preferably 2,000 mPa·s or less, more preferably 1,500 mPa·s or less, and even more preferably 1,200 mPa·s or less.

[0041] In this specification, unless otherwise specified, viscosity is defined as the value measured using a RE85L E-type rotational viscometer manufactured by Toki Sangyo Co., Ltd., with a standard cone rotor (1°34' × R24), and the sample cup temperature controlled to 23°C. Other details regarding measurement are in accordance with JIS Z 8803:2011. Two samples are prepared for each level, and each is measured three times. The arithmetic mean of the total of six measurements is adopted as the evaluation value.

[0042] Examples of polymerizable compounds include the compounds used in the following examples, the compounds described in paragraphs 0017 to 0024 and the examples of Japanese Patent Publication No. 2014-090133, the compounds described in paragraphs 0024 to 0089 of Japanese Patent Publication No. 2015-009171, the compounds described in paragraphs 0023 to 0037 of Japanese Patent Publication No. 2015-070145, and the compounds described in paragraphs 0012 to 0039 of International Publication No. 2016 / 152597; however, the present invention is not to be construed as being limited thereto.

[0043] The polymerizable compound content relative to the total solid content of the imprint curable composition is preferably 30% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, even more preferably 55% by mass or more, and may be 60% by mass or more, and even more preferably 70% by mass or more. The upper limit is preferably less than 99% by mass, even more preferably 98% by mass or less, and may also be 97% by mass or less.

[0044] The boiling point of the polymerizable compound is preferably set and formulated in relation to the curing main agent contained in the adhesion layer forming composition described later. The boiling point of the polymerizable compound is preferably 500°C or lower, more preferably 450°C or lower, and even more preferably 400°C or lower. The lower limit is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 240°C or higher.

[0045] <Polymerization Initiator> The curable composition for imprinting according to the present invention contains a polymerization initiator.

[0046] The polymerization initiator contained in the imprint curable composition of the present invention may be a photopolymerization initiator or a thermal polymerization initiator, but a photopolymerization initiator is preferred. The photopolymerization initiator contained in the imprint curable composition of the present invention can be used without particular limitation as long as it is a compound that generates an active species that polymerizes the above-mentioned polymerizable compound upon light irradiation. The thermal polymerization initiator contained in the imprint curable composition of the present invention can be used without particular limitation as long as it is a compound that generates an active species that polymerizes the above-mentioned polymerizable compound upon heating. In particular, the polymerization initiator contained in the imprint curable composition of the present invention is preferably a photoradical polymerization initiator or a thermal radical polymerization initiator, and more preferably a photoradical polymerization initiator.

[0047] Examples of photoradical polymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, the contents of which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein. Any known thermal radical polymerization initiator can be used without particular limitation as the thermal radical polymerization initiator. Specifically, examples include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference. In addition, among the above-mentioned photopolymerization initiators, those that have the function of initiating polymerization by heat can also be added as thermal polymerization initiators.

[0048] In the present invention, the polymerization initiator is preferably an acylphosphine oxide-based polymerization initiator or an alkylphenone-based polymerization initiator.

[0049] Acylphosphine polymerization initiators are not particularly limited, but examples include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, benzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 3,4-dimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,6-dimethylbenzoyl)-ethylphosphine oxide. In addition, commercially available products such as Omnirad 819, Omnirad TPO H, and Omnirad TPO L (all manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (product names: both manufactured by BASF) can be used.

[0050] Examples of alkylphenone polymerization initiators include α-aminoketone compounds such as aminoacetophenone and α-hydroxyketone compounds such as hydroxyacetophenone. Examples of α-hydroxyketone compounds are not particularly limited, but include 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one, and the like. In addition, commercially available products such as Omnirad 184, Omnirad 1173, Omnirad 500, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (all manufactured by BASF) can be used. The α-aminoketone compound is not particularly limited, but examples include 2-benzyl-2-(dimethylamino)-4′-morpholinobylophenone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. Commercial products such as IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF) can also be used.

[0051] The content of the polymerization initiator in the curable composition for imprinting is, for example, 0.01 to 15% by mass, preferably 0.1 to 10% by mass, and more preferably 0.2 to 7% by mass, based on the total solid content of the composition. When two or more types of polymerization initiators are used, it is preferable that their total amount is within the above range. A polymerization initiator content of 0.01% by mass or more tends to improve sensitivity (rapid curing), resolution, line edge roughness, and coating film strength, which is preferable. On the other hand, a polymerization initiator content of 15% by mass or less tends to improve light transmittance, colorability, and storage stability, which is also preferable.

[0052] <Release Agent> The imprint curable composition of the present invention may further contain a release agent. The release agent content is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.6% by mass or more, relative to the total solid content of the composition. The upper limit is less than 2.0% by mass, preferably 1.5% by mass or less, and more preferably 1.0% by mass or less. By setting the release agent content to above the lower limit, good release properties are achieved, preventing peeling of the cured film and mold damage during demolding. Furthermore, by setting it to below the upper limit, excessive reduction in pattern strength during curing due to the effect of the release agent is avoided, and good resolution can be achieved. One type of release agent may be used or multiple types may be used. If multiple types are used, their total amount will be within the above range. The type of release agent is not particularly limited, but preferably it has the function of segregating at the interface with the mold and effectively promoting demolding from the mold. In the present invention, it is preferable that the release agent is substantially free of fluorine atoms and silicon atoms. "Substantially free" means that the total amount of fluorine atoms and silicon atoms is 1% by mass or less of the release agent, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less. Using a release agent that is substantially free of fluorine atoms and silicon atoms is preferable from the viewpoint of achieving high release properties for the film while providing excellent processing resistance to etching and the like in the imprint curable composition. Specifically, the release agent used in the present invention is preferably a surfactant. Alternatively, it is preferably an alcohol compound having at least one hydroxyl group at its terminus, or a compound having a (poly)alkylene glycol structure in which the hydroxyl group is etherified ((poly)alkylene glycol compound). The surfactant and (poly)alkylene glycol compound are preferably non-polymerizable compounds that do not have a polymerizable group Qp. Note that (poly)alkylene glycol means that the alkylene glycol structure may be a single structure or a structure in which multiple alkylene glycol structures are repeated and linked together.

[0053] <<Surfactants>> Nonionic surfactants are preferred as surfactants that can be used as release agents in the present invention. A nonionic surfactant is a compound having at least one hydrophobic part and at least one nonionic hydrophilic part. The hydrophobic part and the hydrophilic part may be located at the ends of the molecule or inside it. The hydrophobic part is composed of, for example, a hydrocarbon group, and the number of carbon atoms in the hydrophobic part is preferably 1 to 25, more preferably 2 to 15, even more preferably 4 to 10, and even more preferably 5 to 8. The nonionic hydrophilic part preferably has at least one group selected from the group consisting of an alcoholic hydroxyl group, a phenolic hydroxyl group, an ether group (preferably a (poly)alkylene oxy group, a cyclic ether group), an amide group, an imide group, a ureido group, a urethane group, a cyano group, a sulfonamide group, a lactone group, a lactam group, and a cyclocarbonate group. Among these, it is more preferable that the compound has an alcoholic hydroxyl group or an ether group (preferably a (poly)alkylene oxy group, a cyclic ether group).

[0054] <<Alcohol compounds, (poly)alkylene glycol compounds>> Preferred release agents used in the imprint curable composition of the present invention include, as described above, alcohol compounds having at least one hydroxyl group at the terminal end, or (poly)alkylene glycol compounds in which the hydroxyl group has been etherified.

[0055] The (poly)alkylene glycol compound preferably has an alkylene oxy group or a polyalkylene oxy group, and more preferably has a (poly)alkylene oxy group containing an alkylene group having 1 to 6 carbon atoms. Specifically, it preferably has a (poly)ethylene oxy group, a (poly)propylene oxy group, a (poly)butylene oxy group, or a mixed structure thereof, more preferably has a (poly)ethylene oxy group, a (poly)propylene oxy group, or a mixed structure thereof, and even more preferably has a (poly)propylene oxy group. The (poly)alkylene glycol compound may consist substantially of (poly)alkylene oxy groups, excluding terminal substituents. Here, "substantially" means that the components other than (poly)alkylene oxy groups account for 5% by mass or less of the total, and preferably 1% by mass or less. In particular, it is especially preferable that the (poly)alkylene glycol compound includes a compound consisting substantially of only (poly)propylene oxy groups.

[0056] In the (poly)alkylene glycol compound, the number of repeating alkylene oxy groups is preferably 3 to 100, more preferably 4 to 50, even more preferably 5 to 30, and even more preferably 6 to 20.

[0057] (Poly)alkylene glycol compounds may have hydroxyl groups at the remaining terminals, or the hydrogen atoms of the terminal hydroxyl groups may be substituted, as long as the terminal hydroxyl group is etherified. Preferred groups to which the hydrogen atoms of the terminal hydroxyl group may be substituted are alkyl groups (i.e., (poly)alkylene glycol alkyl ethers) and acyl groups (i.e., (poly)alkylene glycol esters). Compounds having multiple (preferably two or three) (poly)alkylene glycol chains via linking groups can also be preferably used.

[0058] Preferred specific examples of (poly)alkylene glycol compounds include polyethylene glycol, polypropylene glycol (e.g., manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), their mono or dimethyl ethers, mono or dibutyl ethers, mono or dioctyl ethers, mono or dicetyl ethers, monostearate esters, monooleate esters, polyoxyethylene glyceryl ethers, polyoxypropylene glyceryl ethers, polyoxyethylene lauryl ethers, and their trimethyl ethers.

[0059] The (poly)alkylene glycol compound is preferably a compound represented by the following formula (P1) or (P2). R in the formula Ｐ１ R is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms) which may be linear or cyclic, and linear or branched. Ｐ２ , R Ｐ３ R is a hydrogen atom or an alkyl group (preferably with 1 to 36 carbon atoms, more preferably 2 to 24, and even more preferably 3 to 12 carbon atoms) which may be linear or cyclic, and linear or branched. p is an integer of 1 or more, preferably an integer of 1 to 24, and more preferably an integer of 2 to 12. Ｐ４ q is a q-valent linking group, preferably an organic group, and more preferably a hydrocarbon group. Specifically, examples of hydrocarbon linking groups include alkane structures (preferably 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6 carbon atoms), alkene structures (preferably 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6 carbon atoms), and aryl structures (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms). q is an integer of 2 or more, preferably an integer from 2 to 8, more preferably an integer from 2 to 6, and even more preferably an integer from 2 to 4.

[0060] The weight-average molecular weight of the alcohol compound or (poly)alkylene glycol compound used as a mold release agent is preferably 150 to 6000, more preferably 200 to 3000, even more preferably 250 to 2000, and most preferably 300 to 1200. Examples of commercially available (poly)alkylene glycol compounds that can be used in the present invention include Olfin E1010 (manufactured by Nisshin Chemical Industry Co., Ltd.) and Brij35 (manufactured by Kishida Chemical Co., Ltd.).

[0061] <Polymerization Inhibitors> The curable composition for imprinting of the present invention preferably contains a polymerization inhibitor. Polymerization inhibitors have the function of quenching (inactivating) reactive substances such as radicals generated from the photopolymerization initiator, and play a role in suppressing the reaction of the curable composition for imprinting at low exposure levels. In particular, when other polymerizable compounds are included, it becomes possible to sufficiently dissolve the polymerization inhibitor, and the above effect is more likely to be exhibited. Examples of polymerization inhibitors include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, and N-phenylnaphthylamine. Suitable candidates include ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamineammonium salt, and bis(4-hydroxy-3,5-tert-butyl)phenylmethane. Polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Publication No. 2015 / 125469 can also be used. Specific examples of commercially available polymerization inhibitors include Q-1300, Q-1301, TBHQ (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the Kinopower series (manufactured by Kawasaki Chemical Industries, Ltd.). Additionally, the following compounds can be used (Me represents a methyl group). The polymerization inhibitor content is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass, relative to the total solid content of the composition. Setting this content above the lower limit allows the photopolymerization initiator to exhibit effective reactivity. Setting it below the upper limit prevents the transfer pattern from becoming distorted, enabling effective patterning. One polymerization inhibitor or multiple inhibitors may be used. If multiple inhibitors are used, their total amount is preferably within the above range.

[0062] <Solvent> The above-mentioned curable composition for imprinting may contain a solvent. A solvent is a compound that is liquid at 23°C and has a boiling point of 250°C or lower. When a solvent is included, its content is preferably, for example, 1% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more. It is also preferably, for example, 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less. Furthermore, it is also a preferred embodiment of the present invention that the solvent content relative to the total mass of the composition is 1% by mass or less. In the above embodiment, it is also preferable that the solvent content is 0.1% by mass or less, and also preferably 0.01% by mass or less. The lower limit of the above content is not particularly limited and may be 0% by mass. Only one type of solvent may be included, or two or more types may be included. When two or more types are included, it is preferable that the total amount is within the above range. In the present invention, it is preferable that the boiling point of the component with the highest content among the solvents is 200°C or lower, and more preferably 160°C or lower. By setting the boiling point of the solvent to a temperature below the above temperature, it becomes possible to remove the solvent from the imprint curable composition by baking. The lower limit of the boiling point of the solvent is not particularly limited, but 60°C or higher is practical, and it may be 80°C or higher, or even 100°C or higher. Organic solvents are preferred as the solvent. Preferably, the solvent is a solvent having one or more of the following groups: ester group, carbonyl group, alkoxy group, hydroxyl group, and ether group. Specific examples of solvents include alkoxy alcohols, propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, lactic acid esters, acetate esters, alkoxypropionic acid esters, linear ketones, cyclic ketones, lactones, and alkylene carbonates.Examples of alkoxy alcohols include methoxyethanol, ethoxyethanol, methoxypropanol (e.g., 1-methoxy-2-propanol), ethoxypropanol (e.g., 1-ethoxy-2-propanol), propoxypropanol (e.g., 1-propoxy-2-propanol), methoxybutanol (e.g., 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (e.g., 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), and methylpentanol (e.g., 4-methyl-2-pentanol). The propylene glycol monoalkyl ether carboxylate is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, with propylene glycol monomethyl ether acetate being particularly preferred. Furthermore, propylene glycol monoalkyl ether is preferred as propylene glycol monomethyl ether or propylene glycol monoethyl ether. Lactic acid ester is preferred as ethyl lactate, butyl lactate, or propyl lactate. Acetate ester or formic acid ester is preferred as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate. Alkoxypropionate ester is preferred as methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). Preferred linear ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone. Preferred cyclic ketones include methylcyclohexanone, isophorone, or cyclohexanone.As the lactone, γ-butyrolactone (γ-BL) is preferred. As the alkylene carbonate, propylene carbonate is preferred. In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or fewer heteroatoms. Preferred examples of ester solvents having 7 or more carbon atoms and 2 or fewer heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butanoate, with isoamyl acetate being particularly preferred. It is also preferable to use one with a flash point (hereinafter also referred to as fp) of 30°C or higher. Preferred components (M2) include propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methyl amyl ketone (fp: 42°C), cyclohexanone (fp: 30°C), pentyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp: 101°C), or propylene carbonate (fp: 132°C). Of these, propylene glycol monoethyl ether, ethyl lactate (EL), pentyl acetate, or cyclohexanone are more preferred, and propylene glycol monoethyl ether or ethyl lactate are particularly preferred. Here, "flash point" refers to the value listed in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich. A more preferred solvent is at least one selected from the group consisting of water, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, γ-butyrolactone, butyl acetate, propylene glycol monomethyl ether (PGME), ethyl lactate, and 4-methyl-2-pentanol, with at least one selected from the group consisting of PGMEA and PGME being even more preferred.

[0063] <UV Absorber> The imprint curable composition of the present invention may contain a UV absorber. The UV absorber absorbs stray light (flare light) generated during exposure, thereby suppressing the reach of reaction light to the photopolymerization initiator and playing a role in suppressing the reaction of the imprint curable composition at low exposure levels. Examples of UV absorbers include benzotriazole-based, triazine-based, cyanacrylate-based, benzophenone-based, and benzoate-based UV absorbers. The UV absorber content is preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass. One type of UV absorber or multiple types may be used. If multiple types are used, it is preferable that their total amount be within the above range.

[0064] <Other Components> Other components may be used in the imprint curable composition of the present invention. For example, it may contain sensitizers, antioxidants, etc. The content is not particularly limited, but it may be appropriately blended in an amount of about 0.01 to 20% by mass of the total solid content of the composition. Specific examples of other components included in the imprint curable composition of the present invention include the additives contained in the compositions described in Japanese Patent Publication No. 2013-036027, Japanese Patent Publication No. 2014-090133, and Japanese Patent Publication No. 2013-189537, and the details of these are incorporated herein by reference. Furthermore, the preparation of the composition and the method for producing the imprint pattern can also be referenced from the above publications, and the details of these are incorporated herein by reference.

[0065] <Physical Properties> In this invention, the curable composition for imprinting is made into a film, and the exposure dose is 300 mJ / cm ２ The elastic modulus of a 300 nm thick cured film obtained by irradiation is preferably 1.5 GPa or higher, more preferably 1.8 GPa or higher, and even more preferably 2.0 GPa or higher, calculated by the Oliver-Pharr method. A practical upper limit of 4.0 GPa or less is desirable. Having an elastic modulus of the cured film of the imprint curable composition above the lower limit allows for sufficient strength to be imparted to the imprint pattern, improving resolution. On the other hand, setting it below the upper limit improves mold release and reduces defects.

[0066] The curable composition for imprinting according to the present invention preferably has a difference of 1.5 mN / m or less between the surface tension of its total solids and the surface tension of the components obtained by excluding the release agent from the total solids of the curable composition for imprinting, more preferably 1.0 mN / m or less, and even more preferably 0.8 mN / m or less. As a lower limit, for example, a practical value of 0.01 mN / m or more, and even more preferably 0.1 mN / m or more, is desirable. The smaller this difference, the better the compatibility of the release agent in the curable composition for imprinting, and the more likely it is to form a homogeneous cured film.

[0067] <Storage Container> Conventional storage containers can be used as the container for the imprint curable composition used in the present invention. Furthermore, in order to suppress the incorporation of impurities into the raw materials and composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of six types of resin in six layers, or a bottle with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0068] (Method for manufacturing cured product and imprint pattern) The cured product of the present invention is a cured product obtained by curing the imprint curable composition of the present invention. Preferably, the cured product of the present invention is a patterned cured product (imprint pattern). The method for manufacturing the imprint pattern will be described below.

[0069] <Method for Manufacturing an Imprint Pattern> The present invention relates to a method for manufacturing an imprint pattern, comprising: an application step of applying the imprint curable composition of the present invention to a member to be applied to, selected from the group consisting of a support and a mold; a contact step of bringing a member not selected as the member to be applied from the group consisting of the support and the mold into contact with the imprint curable composition as a contact member; a curing step of curing the imprint curable composition into a cured product; and a peeling step of peeling the mold from the cured product.

[0070] [Application Step] The method for manufacturing an imprint pattern of the present invention includes an application step of applying the curable composition for imprinting of the present invention to a member to be applied to, selected from the group consisting of a support and a mold. In the application step, one member selected from the group consisting of a support and a mold is selected as the member to be applied to, and the curable composition for imprinting of the present invention is applied to the selected member to be applied to. Of the support and the mold, the selected one is the member to be applied to, and the other is the contact member. That is, in the application step, the curable composition for imprinting of the present invention may be applied to the support and then brought into contact with the mold, or it may be applied to the mold and then brought into contact with the support (which may have an adhesion layer, etc., as described later).

[0071] -Support- As a support, reference can be made to paragraph 0103 of Japanese Patent Application Publication No. 2010-109092 (corresponding US application is US Patent Application Publication No. 2011 / 0199592), and the contents of these provisions are incorporated herein. Specifically, examples of supports include silicon substrates, glass substrates, sapphire substrates, silicon carbide substrates, gallium nitride substrates, metallic aluminum substrates, amorphous aluminum oxide substrates, polycrystalline aluminum oxide substrates, GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGaInP, or ZnO. Specific examples of glass substrate materials include aluminosilicate glass, aluminoborosilicate glass, and bariumborosilicate glass. In the present invention, a silicon substrate is preferred as the substrate.

[0072] The above-mentioned support is preferably a member having an adhesion layer on the side to which the imprint curable composition is applied. The adhesion layer is preferably an adhesion layer formed by applying an adhesion layer forming composition, described later, to the support. Furthermore, the above-mentioned support may further have a liquid film, described later, on the side opposite to the side in contact with the support of the adhesion layer. The liquid film is preferably a liquid film formed by applying a liquid film forming composition, described later, onto the adhesion layer.

[0073] As the above-mentioned adhesion layer, for example, those described in paragraphs 0017 to 0068 of Japanese Patent Publication No. 2014-024322, paragraphs 0016 to 0044 of Japanese Patent Publication No. 2013-093552, the adhesion layer described in Japanese Patent Publication No. 2014-093385, the adhesion layer described in Japanese Patent Publication No. 2013-202982, etc., can be used, and the contents of these will be incorporated into this specification.

[0074] -Mold- In the present invention, the mold is not particularly limited. With regard to the mold, refer to paragraphs 0105 to 0109 of Japanese Patent Application Publication No. 2010-109092 (corresponding US application is US Patent Application Publication No. 2011 / 0199592), and the contents of these paragraphs are incorporated herein by reference. As the mold used in the present invention, a quartz mold is preferred. The pattern (line width) of the mold used in the present invention is preferably 50 nm or less in size. The pattern of the above mold can be formed according to the desired processing accuracy, for example, by photolithography or electron beam lithography, but in the present invention, the mold pattern manufacturing method is not particularly limited. Furthermore, a mold is preferred in which an imprint pattern including the shape of lines, holes, or pillars is formed as the imprint pattern. In particular, a mold is preferred in which an imprint pattern including the shape of lines, holes, or pillars with a size of 100 nm or less is formed.

[0075] -Application Method- There is no particular method for applying the imprint curable composition of the present invention to the member to be applied, and generally well-known application methods can be used. For example, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and inkjet methods are examples. Among these, the inkjet method and spin coating method are preferred. The imprint curable composition may also be applied by multiple coatings. In the method of arranging droplets by inkjet, the volume of the droplets is preferably about 1 to 20 pL, and it is preferable to arrange them on the support surface with intervals between them. The droplet interval can be set appropriately according to the volume of the droplets, but an interval of 10 to 1000 μm is preferred. In the case of the inkjet method, the droplet interval is the spacing between the inkjet nozzles. The inkjet method has the advantage of less loss of the imprint curable composition. Specific examples of methods for applying a curable composition for imprinting using an inkjet method include the methods described in Japanese Patent Publication No. 2015-179807 and International Publication No. 2016 / 152597, and these methods can be suitably used in the present invention. On the other hand, the spin-coating method has the advantage of high stability of the coating process and a wider range of usable materials. Specific examples of methods for applying a curable composition for imprinting using a spin-coating method include the methods described in Japanese Patent Publication No. 2013-095833 and Japanese Patent Publication No. 2015-071741, and these methods can be suitably used in the present invention.

[0076] -Drying Step- The method for manufacturing an imprint pattern of the present invention may further include a drying step for drying the imprint curable composition of the present invention applied in the application step. In particular, when a composition containing a solvent is used as the imprint curable composition of the present invention, it is preferable that the method for manufacturing an imprint pattern of the present invention includes a drying step. In the drying step, at least a portion of the solvent contained in the applied imprint curable composition of the present invention is removed. The drying method is not particularly limited, and drying by heating, drying by blowing air, etc., can be used without particular limitation, but drying by heating is preferred. The heating means is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. In the present invention, the layer formed from the imprint curable composition after the application step and the drying step, if necessary, and the layer before the contact step, is also called the "curable film".

[0077] [Contact Step] The method for manufacturing an imprint pattern of the present invention includes a contact step in which a member not selected as the member to be applied from the group consisting of the support and the mold is brought into contact with the imprint curable composition (curable film) as a contact member. If the support is selected as the member to be applied in the application step, in the contact step, the mold, which is the contact member, is brought into contact with the surface of the support to which the imprint curable composition of the present invention is applied (the surface on which the curable film is formed). If the mold is selected as the member to be applied in the application step, in the contact step, the support, which is the contact member, is brought into contact with the surface of the mold to which the imprint curable composition of the present invention is applied (the surface on which the curable film is formed). In other words, in the contact step, the imprint curable composition of the present invention is present between the member to be applied and the contact member. Details of the support and the mold are as described above.

[0078] When bringing the imprintable curable composition (curable film) of the present invention, applied to the member to be applied, into contact with the contact member, it is preferable that the pressing pressure be 1 MPa or less. By setting the pressing pressure to 1 MPa or less, the support and mold are less likely to deform, and pattern accuracy tends to improve. It is also preferable because the low pressure tends to allow for miniaturization of the equipment. Furthermore, it is also preferable to perform the contact between the curable film and the contact member in an atmosphere containing helium gas, a condensable gas, or both helium gas and a condensable gas.

[0079] [Curing Step] The method for manufacturing an imprint pattern of the present invention includes a curing step in which the above-mentioned curable composition for imprinting is cured. The curing step is performed after the contact step and before the peeling step. The method for manufacturing a cured product of the present invention includes a step of curing the curable composition for imprinting obtained by the method for manufacturing the curable composition for imprinting of the present invention. The curing step can be performed by the same method as the curing step in the method for manufacturing an imprint pattern of the present invention. Furthermore, it is preferable that the cured product is a cured product in which the mold has been peeled off by the peeling step described later. Examples of curing methods include curing by heating and curing by exposure, and the method can be determined according to the type of polymerization initiator contained in the curable composition for imprinting, but curing by exposure is preferred. For example, if the polymerization initiator is a photopolymerization initiator, the curable composition for imprinting can be cured by exposure in the curing step.

[0080] The exposure wavelength is not particularly limited and can be determined according to the polymerization initiator, but for example, ultraviolet light can be used. The exposure light source can be determined according to the exposure wavelength, but examples include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broadband light (light containing at least two wavelengths selected from the group consisting of the three wavelengths of g, h, and i-lines, and light with a wavelength shorter than i-line; for example, a high-pressure mercury lamp without an optical filter), semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, etc.), metal halide lamp, excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２ Examples include excimer lasers (wavelength 157 nm), extreme ultraviolet (EUV) light (wavelength 13.6 nm), and electron beams. Among these, exposure using i-line or broadband light is preferred.

[0081] The irradiation dose (exposure dose) during exposure should be sufficiently greater than the minimum irradiation dose required for curing the imprint-curable composition. The irradiation dose required for curing the imprint-curable composition can be appropriately determined by examining the consumption of unsaturated bonds in the imprint-curable composition, etc. The exposure dose is, for example, 5 to 1,000 mJ / cm². ２ It is preferable to keep it within the range of 10 to 500 mJ / cm². ２ It is more preferable to keep it within this range. The exposure illuminance is not particularly limited and should be selected in relation to the light source, but is generally between 1 and 500 mW / cm². ２ It is preferable to set the range to 10 to 400 mW / cm². ２It is more preferable to keep it within this range. The exposure time is not particularly limited and can be determined by considering the exposure intensity according to the amount of exposure, but it is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second. The temperature of the support during exposure is usually room temperature, but it may be exposed while heating to increase reactivity. Preparing the support in a vacuum state before exposure is effective in preventing air bubbles from being incorporated, suppressing the decrease in reactivity due to oxygen incorporation, and improving the adhesion between the mold and the curable composition for imprinting, so it may be irradiated with light in a vacuum state. The preferred vacuum level during exposure is 10 -１ It ranges from Pa to atmospheric pressure.

[0082] After exposure, the imprint-curable composition may be heated as needed. The heating temperature is preferably 150 to 280°C, more preferably 200 to 250°C. The heating time is preferably 5 to 60 minutes, and even more preferably 15 to 45 minutes. Alternatively, the heating step may be performed without exposure during the curing process. For example, if the polymerization initiator is a thermal polymerization initiator, the imprint-curable composition can be cured by heating during the curing process. In this case, the preferred heating temperature and heating time are the same as those used when heating is performed after exposure. The heating means are not particularly limited, and include the same heating means as those used in the drying step described above.

[0083] [Peeling Step] The method for manufacturing an imprint pattern of the present invention includes a peeling step for peeling the mold and the cured product. In the peeling step, the cured product obtained in the curing step is peeled from the mold, and a patterned cured product (also called a "cured product pattern") on which the pattern of the mold has been transferred is obtained. The obtained cured product pattern can be used for various purposes as described later. The present invention is particularly advantageous in that it can form nano-order fine cured product patterns, and furthermore, it can form cured product patterns with a size of 50 nm or less, and especially 30 nm or less. There is no particular lower limit to the size of the cured product pattern, but for example it can be 1 nm or more. The peeling method is not particularly limited and can be performed using, for example, a mechanical peeling device known in imprint pattern manufacturing methods.

[0084] (Device, Device Manufacturing Method, Cured Material Pattern Application) The device of the present invention includes the cured material of the present invention. Furthermore, the device of the present invention can be obtained, for example, by the device manufacturing method of the present invention described below. The device manufacturing method of the present invention includes the method for manufacturing the imprint pattern of the present invention. Specifically, examples include a device manufacturing method in which a pattern (cured material pattern) formed by the imprint pattern manufacturing method of the present invention is used as a permanent film used in liquid crystal display devices (LCDs) and the like, or as an etching resist (lithography mask) for semiconductor device manufacturing. In particular, the present invention discloses a method for manufacturing a circuit board, and a device manufacturing method including the above circuit board, which includes a step of obtaining a pattern (cured material pattern) by the imprint pattern manufacturing method of the present invention. Furthermore, in a preferred embodiment of the present invention, the method for manufacturing a circuit board may include a step of etching or ion implanting a substrate using the pattern (cured material pattern) obtained by the pattern formation method as a mask, and a step of forming an electronic component. The above circuit board is preferably a semiconductor device. That is, the present invention discloses a method for manufacturing a semiconductor device including the imprint pattern manufacturing method of the present invention. Furthermore, the present invention discloses a method for manufacturing a device comprising the steps of obtaining a circuit board by the above-described method for manufacturing a circuit board, and connecting the circuit board and a control mechanism for controlling the circuit board. In addition, by forming a grid pattern on a glass substrate of a liquid crystal display device using the imprint pattern manufacturing method of the present invention, polarizing plates with low reflection and absorption and large screen sizes (e.g., 55 inches, over 60 inches) can be manufactured inexpensively. That is, the present invention discloses a method for manufacturing a polarizing plate including the imprint pattern manufacturing method of the present invention, and a method for manufacturing a device including the polarizing plate. For example, polarizing plates described in Japanese Patent Application Publication No. 2015-132825 and International Publication No. 2011 / 132649 can be manufactured. Note that 1 inch is 25.4 mm.

[0085] The pattern (cured pattern) produced by the method for manufacturing imprint patterns of the present invention is also useful as an etching resist (lithography mask). That is, the present invention discloses a method for manufacturing a device that includes the method for manufacturing imprint patterns of the present invention and utilizes the obtained cured pattern as an etching resist. When using the cured pattern as an etching resist, one method is to first apply the method for manufacturing imprint patterns of the present invention to a support to form a pattern (cured pattern), and then use the obtained cured pattern as an etching mask to etch the support. In the case of wet etching, hydrogen fluoride, etc., and in the case of dry etching, CF ４ By etching with etching gases such as those described above, a pattern conforming to the desired shape of the cured material can be formed on the support.

[0086] Furthermore, patterns (cured patterns) produced by the method for manufacturing imprint patterns of the present invention can be suitably used to produce recording media such as magnetic disks, photodetectors such as solid-state image sensors, light-emitting elements such as LEDs (light-emitting diodes) and organic electroluminescent devices (OLEDs), optical devices such as liquid crystal displays (LCDs), optical components such as diffraction gratings, relief holograms, optical waveguides, optical filters, and microlens arrays, components for flat panel displays such as thin-film transistors, organic transistors, color filters, anti-reflective coatings, polarizing plates, polarizing elements, optical films, and columnar materials, as well as nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and guide patterns for fine pattern formation (directed self-assembly, DSA) using self-assembly of block copolymers. In other words, the present invention discloses methods for manufacturing these devices, including the method for manufacturing imprint patterns of the present invention.

[0087] <Composition for Forming an Adhesion Layer> As described above, by providing an adhesion layer between the support and the imprint curable composition, effects such as improved adhesion between the support and the imprint curable composition layer can be obtained. In the present invention, the adhesion layer is obtained by applying the adhesion layer forming composition onto the support using the same method as for the imprint curable composition, and then curing the composition. The components of the adhesion layer forming composition will be described below.

[0088] The adhesion layer-forming composition contains a curable component. The curable component is a component that constitutes the adhesion layer and may be either a high-molecular-weight component (e.g., molecular weight greater than 1000) or a low-molecular-weight component (e.g., molecular weight less than 1000). Specifically, resins and crosslinking agents are examples. These may be used individually or in combination of two or more types.

[0089] The total content of curable components in the adhesion layer forming composition is not particularly limited, but is preferably 50% by mass or more of the total solids, more preferably 70% by mass or more of the total solids, and even more preferably 80% by mass or more of the total solids. There is no particular upper limit, but is preferably 99.9% by mass or less.

[0090] The concentration of the curable component in the adhesion layer-forming composition (including the solvent) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably less than 1% by mass.

[0091] [Resin] The resin in the adhesion layer forming composition can be any known resin. The resin used in the present invention preferably has at least one of a radical polymerizable group and a polar group, and more preferably has both a radical polymerizable group and a polar group.

[0092] The presence of radical polymerizable groups results in an adhesive layer with excellent strength. Furthermore, the presence of polar groups improves adhesion to the support. Additionally, when a crosslinking agent is incorporated, the crosslinked structure formed after curing becomes stronger, further improving the strength of the resulting adhesive layer.

[0093] The radical polymerizable group preferably contains an ethylenically unsaturated bond-containing group. Examples of ethylenically unsaturated bond-containing groups include (meth)acryloyl group (preferably (meth)acryloyloxy group, (meth)acryloylamino group), vinyl group, vinyloxy group, allyl group, methylallyl group, propenyl group, butenyl group, vinylphenyl group, and cyclohexenyl group, with (meth)acryloyl group and vinyl group being preferred, (meth)acryloyl group being more preferred, and (meth)acryloyloxy group being even more preferred. The ethylenically unsaturated bond-containing group defined herein will be referred to as Et.

[0094] Furthermore, the polar group is preferably at least one of the following: acyloxy group, carbamoyloxy group, sulfonyloxy group, acyl group, alkoxycarbonyl group, acylamino group, carbamoyl group, alkoxycarbonylamino group, sulfonamide group, phosphoric acid group, carboxyl group, and hydroxyl group; more preferably at least one of the following: alcoholic hydroxyl group, phenolic hydroxyl group, and carboxyl group; and even more preferably an alcoholic hydroxyl group or a carboxyl group. The polar group defined herein is referred to as polar group Po. The polar group is preferably a nonionic group.

[0095] The resin in the adhesion layer-forming composition may further contain a cyclic ether group. Examples of cyclic ether groups include epoxy groups and oxetanyl groups, with epoxy groups being preferred. The cyclic ether group defined herein is referred to as the cyclic ether group Cyt.

[0096] Examples of the above resins include (meth)acrylic resins, vinyl resins, novolac resins, phenolic resins, melamine resins, urea resins, epoxy resins, and polyimide resins, and it is preferable that the resin is at least one of (meth)acrylic resins, vinyl resins, and novolac resins.

[0097] The weight-average molecular weight of the above resin is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more. The upper limit is preferably 1,000,000 or less, and may be 500,000 or less.

[0098] The above resin preferably has at least one constituent unit of the following formulas (1) to (3).

[0099]

[0100] In the formula, R １ and R ２ Each of these is independently either a hydrogen atom or a methyl group. ２１ and R ３ L is an independent substituent. １ , L ２ and L ３ Each of these is independently either a single bond or a linking group. n2 is an integer from 0 to 4. n3 is an integer from 0 to 3. Q １ This is an ethylenically unsaturated bond-containing group or a cyclic ether group. Q ２ This group is an ethylenically unsaturated bond-containing group, a cyclic ether group, or a polar group.

[0101] R １ and R ２ A methyl group is preferred.

[0102] R ２１ and R ３ Each of these is independently preferably a methyl group.

[0103] R ２１When there are multiple such rings, they may be linked together to form a cyclic structure. In this specification, linking includes not only the form of bonding and continuity, but also the form of condensation (ring fusion) by losing some atoms. Unless otherwise specified, the linked cyclic structure may contain oxygen atoms, sulfur atoms, and nitrogen atoms (amino groups). Examples of the formed cyclic structures include aliphatic hydrocarbon rings (hereinafter exemplified as ring Cf) (e.g., cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc.), aromatic hydrocarbon rings (hereinafter exemplified as ring Cr) (benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), and nitrogen-containing heterocycles (hereinafter exemplified as ring Cn) (e.g., pyrrole ring, imidazole ring, pyrrole Examples include razole rings, pyridine rings, pyrroline rings, pyrrolidine rings, imidazolidine rings, pyrazolidine rings, piperidine rings, piperazine rings, morpholine rings, etc.), oxygen-containing heterocycles (the following examples will be referred to as ring Co) (furan rings, pyran rings, oxirane rings, oxetane rings, tetrahydrofuran rings, tetrahydropyran rings, dioxane rings, etc.), and sulfur-containing heterocycles (the following examples will be referred to as ring Cs) (thiophene rings, thiirane rings, thietan rings, tetrahydrothiophene rings, tetrahydrothiopyran rings, etc.).

[0104] R ３ When there are multiple such elements, they may be linked together to form a ring structure. Examples of the ring structures that can be formed include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.

[0105] L １ , L ２ , L ３Each of these is preferably a single bond or a linking group L described later. Among these, a single bond or an alkylene group or (oligo)alkyleneoxy group defined by the linking group L is preferred, and an alkylene group is more preferred. The linking group L preferably has a polar group Po as a substituent. It is also preferred that the alkylene group has a hydroxyl group as a substituent. In this specification, "(oligo)alkyleneoxy group" means a divalent linking group having one or more "alkyleneoxy" units. The number of carbon atoms in the alkylene chain in the constituent unit may be the same or different for each constituent unit.

[0106] n2 is preferably 0 or 1, and more preferably 0. n3 is preferably 0 or 1, and more preferably 0.

[0107] Q １ The ethylenically unsaturated bond-containing group Et is preferred.

[0108] Q ２ A polar group is preferred, and an alkyl group having an alcoholic hydroxyl group is more preferred.

[0109] The above resin may further include at least one of the following constituent units (11), (21), and (31). In particular, in the resin included in the present invention, it is preferable that constituent unit (11) is combined with constituent unit (1), constituent unit (21) is combined with constituent unit (2), and constituent unit (31) is combined with constituent unit (3).

[0110]

[0111] In the formula, R １１ and R ２２ Each of these is independently either a hydrogen atom or a methyl group. １７ R is a substituent. ２７ Each of these is an independent substituent. n21 is an integer from 0 to 5. ３１ Each of these is an independent substituent, and n31 is an integer between 0 and 3.

[0112] R １１ and R ２２ A methyl group is preferred.

[0113] R １７ It is preferable that the group contains a polar group or a cyclic ether group. １７ If the group contains a polar group, it is preferable that it contains the polar group Po described above, and more preferably that it is the polar group Po described above, or a substituent substituted with the polar group Po described above. １７ If the group contains a cyclic ether group, it is preferably a group containing the cyclic ether group Cyt, and more preferably a substituent substituted with the cyclic ether group Cyt.

[0114] R ２７ is a known substituent, R ２７ At least one of them is preferably a polar group. n21 is preferably 0 or 1, and more preferably 0. ２７ When there are multiple such elements, they may be linked together to form a ring structure. Examples of the formed ring structures include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.

[0115] R ３１ Known substituents are preferred. n31 is an integer from 0 to 3, preferably 0 or 1, and more preferably 0. ３１ When there are multiple such elements, they may be linked together to form a ring structure. Examples of the ring structures that can be formed include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.

[0116] The linking group L may be an alkylene group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6 carbon atoms), an alkenylene group (preferably with 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3 carbon atoms), an (oligo)alkylene oxy group (preferably with 1 to 12 carbon atoms in one constituent unit, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms; the number of repeating groups may be 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30), an arylene group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, or -NR Ｎ- and linking groups relating to combinations thereof. The alkylene group, alkenylene group, and alkyleneoxy group may have substituents. For example, the alkylene group may have a hydroxyl group.

[0117] The linking chain length of the linking group L is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The linking chain length refers to the number of atoms in the atomic group involved in linking that are located along the shortest path. For example, -CH ２ If -(C=O)-O- then the answer is 3.

[0118] The alkylene group, alkenylene group, and (oligo)alkyleneoxy group defined by the linking group L may be linear or cyclic, and may be linear or branched.

[0119] The atoms constituting the linking group L preferably include carbon atoms, hydrogen atoms, and, if necessary, heteroatoms (at least one selected from oxygen atoms, nitrogen atoms, and sulfur atoms). The number of carbon atoms in the linking group is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. The number of hydrogen atoms may be determined according to the number of carbon atoms, etc. The number of heteroatoms is preferably 0 to 12, more preferably 0 to 6, and even more preferably 0 to 3, for each of the oxygen, nitrogen, and sulfur atoms.

[0120] The above resins may be synthesized by conventional methods. For example, a resin having the constituent units of formula (1) can be appropriately synthesized by known methods relating to the addition polymerization of olefins. A resin having the constituent units of formula (2) can be appropriately synthesized by known methods relating to the addition polymerization of styrene. A resin having the constituent units of formula (3) can be appropriately synthesized by known methods relating to the synthesis of phenolic resins.

[0121] The above resins may be used individually or in combination with others.

[0122] In addition to those described above, resins used as curing components may be those described in paragraphs 0016-0079 of International Publication No. 2016 / 152600, paragraphs 0025-0078 of International Publication No. 2016 / 148095, paragraphs 0015-0077 of International Publication No. 2016 / 031879, and paragraphs 0015-0057 of International Publication No. 2016 / 027843, the contents of which are incorporated herein by reference.

[0123] [Crosslinking agent] The crosslinking agent in the adhesion layer forming composition is not particularly limited as long as it promotes curing through a crosslinking reaction. In the present invention, it is preferable that the crosslinking agent forms a crosslinked structure by reacting with the polar groups of the resin. By using such a crosslinking agent, the resin is bonded more strongly, and a stronger film can be obtained.

[0124] Examples of crosslinking agents include epoxy compounds (compounds having epoxy groups), oxetanyl compounds (compounds having oxetanyl groups), alkoxymethyl compounds (compounds having alkoxymethyl groups), methylol compounds (compounds having methylol groups), and blocked isocyanate compounds (compounds having blocked isocyanate groups). Alkoxymethyl compounds (compounds having alkoxymethyl groups) are preferred because they can form strong bonds at low temperatures.

[0125] [Other components] In addition to the above components, the adhesion layer-forming composition may also contain other components.

[0126] Specifically, the mixture may contain one or more of the following: solvents, thermoacid generators, alkylene glycol compounds, polymerization initiators, polymerization inhibitors, antioxidants, leveling agents, thickeners, surfactants, etc. For the above components, those described in Japanese Patent Publication No. 2013-036027, Japanese Patent Publication No. 2014-090133, and Japanese Patent Publication No. 2013-189537 can be used. The content and other details may also be considered in reference to the descriptions in these publications.

[0127] -Solvent- In the present invention, the adhesion layer forming composition preferably contains a solvent (hereinafter also referred to as "adhesion layer solvent"). The solvent is preferably a compound that is liquid at 23°C and has a boiling point of 250°C or lower. The adhesion layer forming composition preferably contains 99.0% by mass or more of the adhesion layer solvent, more preferably 99.2% by mass or more, and may contain 99.4% by mass or more. That is, the total solid content concentration of the adhesion layer forming composition preferably is 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.6% by mass or less. The lower limit is preferably greater than 0% by mass, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more. By setting the proportion of the solvent within the above range, the film thickness during film formation tends to be kept thin, and the pattern formation performance during etching tends to improve.

[0128] The solvent may be present in the adhesion layer-forming composition as one type or as two or more types. If two or more types are present, it is preferable that their total amount falls within the above range.

[0129] The boiling point of the solvent for the adhesion layer is preferably 230°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 160°C or lower, and even more preferably 130°C or lower. The lower limit is preferably 23°C, and more preferably 60°C or higher. Setting the boiling point within the above range is preferable because it allows for easy removal of the solvent from the adhesion layer.

[0130] The solvent for the adhesion layer is preferably an organic solvent. The solvent is preferably one or more of the following: an ester group, a carbonyl group, a hydroxyl group, and an ether group. Among these, it is preferable to use an aprotic polar solvent.

[0131] Among the solvents used for the adhesion layer, preferred solvents include alkoxy alcohols, propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, lactic acid esters, acetate esters, alkoxypropionic acid esters, linear ketones, cyclic ketones, lactones, and alkylene carbonates, with propylene glycol monoalkyl ethers and lactones being particularly preferred.

[0132] <Liquid Film Forming Composition> In addition, in the present invention, it is also preferable to form a liquid film on the adhesion layer using a liquid film forming composition containing a radical polymerizable compound that is liquid at 23°C and 1 atm. In the present invention, the liquid film is obtained by applying the liquid film forming composition onto a support in the same manner as the imprint curable composition, and then drying the composition. By forming such a liquid film, the adhesion between the support and the imprint curable composition is further improved, and the wettability of the imprint curable composition on the support is also improved. The liquid film forming composition will be described below.

[0133] The viscosity of the liquid film-forming composition is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less, even more preferably 500 mPa·s or less, and most preferably 100 mPa·s or less. The lower limit of the viscosity is not particularly limited, but for example, it can be 1 mPa·s or more. The viscosity is measured according to the following method.

[0134] Viscosity is measured using a RE85L E-type rotational viscometer manufactured by Toki Sangyo Co., Ltd., with a standard cone rotor (1°34' × R24), and the sample cup is temperature-controlled to 23°C. The unit is expressed in mPa·s. Other details regarding the measurement conform to JIS Z 8803:2011. Two samples are prepared for each level, and each is measured three times. The arithmetic mean of the total of six measurements is adopted as the evaluation value.

[0135] [Radical Polymerizable Compound A] The liquid film-forming composition contains a radical polymerizable compound (radical polymerizable compound A) that is liquid at 23°C and 1 atm.

[0136] The viscosity of radical polymerizable compound A at 23°C is preferably 1 to 100,000 mPa·s. The lower limit is preferably 5 mPa·s or more, and more preferably 11 mPa·s or more. The upper limit is preferably 1,000 mPa·s or less, and more preferably 600 mPa·s or less.

[0137] Radical polymerizable compound A may be a monofunctional radical polymerizable compound having only one radical polymerizable group in one molecule, or a polyfunctional radical polymerizable compound having two or more radical polymerizable groups in one molecule. Monofunctional radical polymerizable compounds and polyfunctional radical polymerizable compounds may be used in combination. In particular, for the reason of suppressing pattern collapse, it is preferable that radical polymerizable compound A contained in the liquid film-forming composition contains a polyfunctional radical polymerizable compound, more preferably a radical polymerizable compound containing 2 to 5 radical polymerizable groups in one molecule, even more preferably a radical polymerizable compound containing 2 to 4 radical polymerizable groups in one molecule, and especially preferably a radical polymerizable compound containing 2 radical polymerizable groups in one molecule.

[0138] Furthermore, radical polymerizable compound A preferably contains at least one of an aromatic ring (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms) and an alicyclic ring (preferably with 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 6 carbon atoms), and more preferably contains an aromatic ring. The aromatic ring is preferably a benzene ring. Also, the molecular weight of radical polymerizable compound A is preferably 100 to 900.

[0139] The radical polymerizable groups of radical polymerizable compound A include ethylenically unsaturated bond-containing groups such as vinyl groups, allyl groups, and (meth)acryloyl groups, with (meth)acryloyl groups being preferred.

[0140] The radical polymerizable compound A is also preferably a compound represented by the following formula (I-1).

[0141]

[0142] L ２０The linking group is a 1+q2 valent group, and examples include a 1+q2 valent alkane group (preferably with 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms), an alkene group (preferably with 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), a heteroaryl group (preferably with 1 to 22 carbon atoms, more preferably 1 to 18, and even more preferably 1 to 10 carbon atoms; heteroatoms include nitrogen, sulfur, and oxygen atoms; 5-membered rings, 6-membered rings, and 7-membered rings are preferred), or a linking group containing a combination of these. Examples of groups formed by combining two aryl groups include groups having structures such as biphenyl, diphenylalkane, biphenylene, and indene. Examples of groups formed by combining a heteroaryl group and an aryl group include groups having structures such as indole, benzimidazole, quinoxaline, and carbazole.

[0143] L ２０ The linking group is preferably a linking group containing at least one selected from an aryl structure group and a heteroaryl structure group, and more preferably a linking group containing an aryl structure group.

[0144] R ２１ and R ２２ Each of these independently represents either a hydrogen atom or a methyl group.

[0145] L ２１ and L ２２ Each of these independently represents a single bond or the linking group L, and is preferably a single bond or an alkylene group.

[0146] L ２０ and L ２１ or L ２２ L may be bonded, with or without the linking group L, to form a ring. ２０ , L ２１ and L ２２ It may have substituents. Multiple substituents may be bonded together to form a ring. If there are multiple substituents, they may be the same or different from one another.

[0147] q2 is an integer between 0 and 5, preferably between 0 and 3, more preferably between 0 and 2, even more preferably 0 or 1, and particularly preferably 1.

[0148] As the radical polymerizable compound A, you can also use the compounds described in paragraphs 0017 to 0024 and the examples of Japanese Patent Publication No. 2014-090133, the compounds described in paragraphs 0024 to 0089 of Japanese Patent Publication No. 2015-009171, the compounds described in paragraphs 0023 to 0037 of Japanese Patent Publication No. 2015-070145, or the compounds described in paragraphs 0012 to 0039 of International Publication No. 2016 / 152597.

[0149] The content of radical polymerizable compound A in the liquid film-forming composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0150] The content of radical polymerizable compound A in the solid content of the liquid film-forming composition is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more. The upper limit may be 100% by mass. Radical polymerizable compound A may be used alone or two or more types. When two or more types are used, it is preferable that their total amount is within the above range.

[0151] Furthermore, it is preferable that the solid content of the liquid film-forming composition consists substantially of radical polymerizable compound A. When the solid content of the liquid film-forming composition consists substantially of radical polymerizable compound A, it means that the content of radical polymerizable compound A in the solid content of the liquid film-forming composition is 99.9% by mass or more, more preferably 99.99% by mass or more, and even more preferably consisting solely of polymerizable compound A.

[0152] [Solvent] The liquid film-forming composition preferably contains a solvent (hereinafter sometimes referred to as "liquid film solvent"). Examples of liquid film solvents include those described in the section on solvents for the adhesion layer above, and these can be used. The liquid film-forming composition preferably contains 90% by mass or more of the liquid film solvent, more preferably 99% by mass or more, and may contain 99.99% by mass or more.

[0153] The boiling point of the solvent for the liquid film is preferably 230°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 160°C or lower, and even more preferably 130°C or lower. The lower limit is preferably 23°C or higher, and more preferably 60°C or higher. Setting the boiling point within the above range is preferable because it allows for easy removal of the solvent from the liquid film.

[0154] [Radical Polymerization Initiators] The liquid film-forming composition may contain a radical polymerization initiator. Examples of radical polymerization initiators include thermal radical polymerization initiators and photoradical polymerization initiators, with photoradical polymerization initiators being preferred. Any known compounds can be used as photoradical polymerization initiators. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. For further details, refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference. Among these, acetophenone compounds, acylphosphine compounds, and oxime compounds are preferred. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-127, IRGACURE-819, IRGACURE-379, IRGACURE-369, IRGACURE-754, IRGACURE-1800, IRGACURE-651, IRGACURE-907, IRGACURE-TPO, IRGACURE-1173, etc. (all manufactured by BASF), and Omnirad 184, Omnirad TPO H, Omnirad 819, Omnirad 1173 (all manufactured by IGM Resins B.V.).

[0155] If a radical polymerization initiator is included, it is preferably present in an amount of 0.1 to 10% by mass, more preferably 1 to 8% by mass, and even more preferably 2 to 5% by mass, of the solid content of the liquid film-forming composition. When two or more radical polymerization initiators are used, it is preferable that their total amount be within the above range.

[0156] [Other ingredients] In addition to the above, the liquid film-forming composition may contain one or more polymerization inhibitors, antioxidants, leveling agents, thickeners, surfactants, etc.

[0157] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0158] <Preparation of Curable Composition for Imprinting> The various compounds listed in the table were mixed to obtain a mixture. In the table below, E-1 to E-11 correspond to specific compounds. Components in the columns marked with "-" in the table were not used. The above mixture was filtered through a 0.02 μm Nylon filter and a 3 nm UPE filter to prepare a curable composition for imprinting or a comparative composition.

[0159] <Evaluation of Mold Release Properties> As the quartz mold, a quartz mold having a line width of 20 nm and a depth of 55 nm with a line / space ratio [Line:Space = 1:1] was used, and a quartz mold spin-coated with the adhesion layer forming composition shown in Example 6 of Japanese Patent Application Publication No. 2014-024322 was used. In each example or comparative example, a FUJIFILM Dimatix inkjet printer DMP-2831 was used as the inkjet device to apply the above-mentioned imprint curable composition or each comparative composition onto a silicon wafer (silicon substrate) by inkjet method, and then sandwiched between the above-mentioned quartz molds under a helium atmosphere. The inkjet ejection pattern was arranged in a rhombic grid, with a diagonal spacing of 140 μm / 80 μm, and an ejection volume of 1 pL. A high-pressure mercury lamp was used from the quartz mold side to apply 100 mJ / cm². ２ After exposure under these conditions, the pattern was obtained by demolding the quartz mold.

[0160] In the patterns obtained above, the force required to demold the quartz mold (release force F, unit: N) was measured. For details, the measurement was performed in accordance with the method described in paragraphs 0102 to 0107 of Japanese Patent Application Publication No. 2011-206977 in the comparative example. The obtained release force F was evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "Release Properties" column of the table. -Evaluation Criteria- A: F ≤ 15N B: 15N < F ≤ 18N C: 18N < F ≤ 20N D: F > 20N

[0161] <Evaluation of Dry Etching Resistance> Using the samples prepared for the mold release evaluation, reactive ion etching was performed using an etching apparatus. The etching gas was CHF. ３ / CF ４ A / Ar mixed gas was selected, and the sample was cooled to 20°C during etching. Dry etching was performed under conditions of 60 seconds etching time, and the film thickness before and after treatment was measured. The film thickness reduction ER (Å / sec, 1 Å = 0.1 nm) as a percentage of time due to dry etching was calculated. The evaluation was performed according to the following criteria, and the evaluation results are recorded in the "Dry Etching Resistance" column of the table. -Evaluation Criteria- A: ER ≤ 10 Å / sec B: 10 Å / sec < ER < 15 Å / sec C: 15 Å / sec ≤ ER < 20 Å / sec D: 20 Å / sec ≤ ER

[0162] <Evaluation of Mold Contamination Suppression> A smooth quartz mold without a pattern was used as the quartz mold. As the inkjet device, a FUJIFILM Dimatix DMP-2831 inkjet printer was used to apply the above-mentioned imprint curable composition or comparative composition to a silicon wafer (silicon substrate) by inkjet method, and then sandwiched it between the above-mentioned quartz molds under a helium atmosphere. The inkjet ejection pattern was arranged in a rhombic grid, with a diagonal spacing of 140 μm / 80 μm, and an ejection volume of 1 pL. A high-pressure mercury lamp was used from the quartz mold side to apply 100 mJ / cm². ２ After exposure under the specified conditions, the quartz mold was demolded. The contact angle of the quartz mold that was in contact with the resist after demolding was measured, and mold contamination was evaluated using the following evaluation criteria based on the change in contact angle Δ, which is expressed by the following formula. The evaluation results are described in the "Mold Contamination Suppression" section. The above water contact angle was measured using a contact angle meter (DMs-501, Kyowa Interface Science Co., Ltd.), and the value of the contact angle 500 milliseconds after the water droplet contacted the surface of the object to be measured was measured three times and is the average value. Δ = (Water contact angle after 10 demoldings) - (Water contact angle after 5 demoldings) - Evaluation Criteria - A: Δ ≤ 5° B: 5° < Δ ≤ 7° C: 7° < Δ < 10° D: 10° ≤ Δ

[0163]

[0164]

[0165]

[0166] Details of each component in the table are as follows:

[0167] [Polymerizable Compounds] ・A-1: Phenylethylene glycol diacrylate ・A-2: Benzyl acrylate ・A-3: m-Xylenediacrylate ・A-4: Neopentyl glycol diacrylate ・A-5: Isobornyl acrylate ・A-6: 1,4-cis-butenediol diacrylate ・A-7: Stearyl acrylate ・A-8: 1,6-Hexanediol diacrylate ・A-9: Dimethylol tricyclodecane diacrylate ・A-10: Silicone-containing acrylate resin synthesized from silicone resin X-40-9225 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 2-hydroxyethyl acrylate

[0168] [Polymerization initiator] ・B-1: Omnirad 819 (manufactured by IGM REsins B.V.) ・B-2: Omnirad TPO (manufactured by IGM REsins B.V.) ・B-3: Omnirad TPO-L (manufactured by IGM REsins B.V.) B.V.) ・B-4: Omnirad 1173 (IGM REsins B.V.) ・B-5: Omnirad 369 (IGM REsins B.V.)

[0169] [Release Agents] ・C-1: SR-705 (manufactured by Aoki Oil & Fat Industry Co., Ltd.) ・C-2: SR-730 (manufactured by Aoki Oil & Fat Industry Co., Ltd.) ・C-3: Emulgen 320P (manufactured by Kao Chemical Corporation) ・C-4: Compound with the following structure ・C-5: Compound with the following structure ・C-6: Compound with the following structure ・C-7: Futergent 212M (manufactured by Neos Co., Ltd.)

[0170] [Polymerization inhibitor] ・D-1:4-OH-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical)

[0171] [Organic phosphorus compounds] ・E-1: Triphenylphosphine oxide ・E-2: Tris (3-bromophenyl) phosphine oxide ・E-3: Tris (4-methylphenyl) phosphine Oxide ・E-4: Diphenyl [9,9'-spirobi[9H-fluoren]-2-yl]phosphine Oxide ・E-5: Bis[2-[(oxo)diphenylphosphino]phenyl] Ether ・E-6: 1,8-Bis(diphenylphosphinyl)naphthalene ・E-7: Diphenylphosphine Oxide ・E-8: Methyl(diphenyl)phosphine Oxide・E-9: Cyclohexyldiphenylphosphine Oxide ・E-10: Tributylphosphine Oxide ・E-11: Tricyclohexylphosphine Oxide・E-12: JP-502 (manufactured by Johoku Kagaku Kogyo) ・E-13: Dietyl Ethylphosphonate

[0172] In the above structural formula, the subscripts in parentheses represent the number of repetitions.

[0173] As can be seen from the results above, the curable composition for imprinting of the present invention yielded a cured product with low release force and excellent release properties. In comparison, the compositions of Comparative Examples 1 to 3, which did not contain the specific compound, had high release force.

[0174] Furthermore, using the same method as described above for evaluating release properties, line-and-space structures, contact hole structures, dual damascene structures, and step structures were formed on silicon wafers using the imprint-curable compositions according to each embodiment. These patterns were then used as etching masks to dry etch the silicon wafers, and semiconductor devices were fabricated using these silicon wafers. No performance issues were found for any of the semiconductor devices. In addition, semiconductor devices were fabricated on substrates having an SOC (spin-on-carbon) layer using the imprint-curable compositions according to each embodiment, following the same procedure as described above. No performance issues were found for these semiconductor devices either.

Claims

polymerizable compound, Polymerization initiator and This invention comprises one or more organophosphorus compounds selected from the group consisting of organophosphorus derivatives, organophosphonic acid derivatives, and organophosphine oxide derivatives in which a carbonyl group is not directly bonded to the phosphorus atom. Curable composition for imprinting. 　 The curable composition for imprinting according to claim 1, wherein the content of the organophosphorus compound is 0.001 to 0.1% by mass relative to the total solid content of the composition. 　 The curable composition for imprinting according to claim 1, wherein the content of the organophosphorus compound is 0.005 to 0.02% by mass relative to the total solid content of the composition. 　 The curable composition for imprinting according to any one of claims 1 to 3, wherein the organophosphorus compound includes an organophosphorus compound having an aromatic ring. 　 The imprint curable composition according to any one of claims 1 to 3, comprising a phosphate ester as the organic phosphate derivative. 　 The curable composition for imprinting according to any one of claims 1 to 3, comprising a phosphonic acid ester as the organic phosphonic acid derivative. 　 The imprint curable composition according to any one of claims 1 to 3, comprising a compound in which an aromatic hydrocarbon group is directly bonded to a phosphorus atom as the organic phosphine oxide derivative. 　 The curable composition for imprinting according to any one of claims 1 to 3, wherein the organic phosphine oxide derivative comprises at least one of the same and its derivatives. 　 The curable composition for imprinting according to any one of claims 1 to 3, wherein the organic phosphorus compound is an organic phosphine oxide derivative in which a carbonyl group is not directly bonded to the phosphorus atom. 　 The curable composition for imprinting according to any one of claims 1 to 3, wherein the polymerizable compound includes a polymerizable compound having an aromatic hydrocarbon group and a polymerizable compound not having an aromatic hydrocarbon group. 　 A cured product obtained by curing the imprint curable composition according to any one of claims 1 to 3. 　 A method for forming a pattern using a support and a mold, An application step of applying the imprint curable composition according to any one of claims 1 to 3 to a member to be applied, selected from the group consisting of a support and a mold. A contact step in which a member not selected as the member to be applied from the group consisting of the support and the mold is brought into contact with the imprint curable composition as a contact member, A curing step in which the aforementioned curable composition for imprinting is used as a cured product, and The process includes a peeling step for separating the mold from the cured product. A method for manufacturing imprint patterns. 　 A method for manufacturing a device, comprising the step of etching using a pattern obtained by the method for manufacturing an imprint pattern described in claim 12 as a mask.

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