Composition for forming imprint pattern, cured product, method for producing imprint pattern, device, and method for producing device

Abstract

A composition for imprint pattern formation which comprises a polymerizable compound, a polymerization initiator, and a derivative of the polymerization initiator; a cured object obtained from the composition for imprint pattern formation; a device including the cured object; a method for producing an imprint pattern using the composition for imprint pattern formation; and a method for producing a device, the method including said method for producing an imprint pattern.

Description

[Technical Field]

[0001] The present invention relates to a composition for forming an imprint pattern, a cured product, a method for producing an imprint pattern, a device, and a method for producing a device. [Background technology]

[0002] Imprinting is a technique for transferring a fine pattern onto a material by pressing a patterned metal mold (commonly called a mold or stamper) onto the material. Because the imprinting method makes it possible to easily create precise fine patterns, it is expected to be applied in a variety of fields in recent years, including precision processing for semiconductor integrated circuits. In particular, nanoimprinting technology, which can form fine patterns on the nano-order level, has attracted attention. Patent Document 1 describes a photocurable composition containing a polymerizable compound (A) having an alkoxysilyl group in the molecule and a polymerization inhibitor (B), wherein the polymerization inhibitor (B) is at least one selected from the group consisting of a compound (B1) whose radical scavenging group is a benzoquinone group, a compound (B2) whose radical scavenging group is a sterically hindered phenolic hydroxyl group, and a compound (B3) whose radical scavenging group is a sterically hindered nitrogen-containing group. Patent Document 2 describes a curable composition for imprints, the curable composition for imprints comprising a polymerizable compound, a photopolymerization initiator, and a release agent, wherein the polymerizable compound is a light-transmitting polymerizable compound having a maximum value of the following absorption coefficient A of 1.8 L / (g cm) or less and a weight-average molecular weight of 800 or more, the polymerizable compound accounts for 50 mass% or more of the total solid content of the composition, the photopolymerization initiator has a maximum value of the following absorption coefficient B of 5,000 L / (mol cm) or more and the photopolymerization initiator accounts for 0.5 to 8.0 mass% of the total solid content of the composition, and the release agent is contained in an amount of 0.1 mass% or more and less than 1.0 mass% of the total solid content of the composition; absorption coefficient A: absorption coefficient per unit mass in a wavelength range of 250 to 400 nm in an acetonitrile solution, and B: molar absorption coefficient in a wavelength range of 250 to 400 nm in an acetonitrile solution. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-002231 [Patent Document 2] International Publication No. 2006 / 121162 Summary of the Invention [Problem to be solved by the invention]

[0004] As imprinting methods, methods called thermal imprinting and curing imprinting have been proposed based on the transfer method. In thermal imprinting, a mold is pressed into a thermoplastic resin heated to above its glass transition temperature (hereinafter sometimes referred to as "Tg"), and then the mold is released after cooling to form a fine pattern. This method can be used with a variety of materials, but it also has problems such as the difficulty of forming fine patterns due to the high pressure required during pressing and reduced dimensional accuracy caused by thermal shrinkage, etc. On the other hand, in the curing imprinting method, for example, a curable film formed from the imprint pattern-forming composition is photocured or thermally cured while a mold is pressed against the curable film, and then the mold is released. Since imprinting is performed on an uncured material, the application of high pressure and high temperature heating can be partially or entirely omitted, making it possible to easily produce fine patterns. Another advantage is that dimensional variation before and after curing is small, allowing fine patterns to be formed with high precision. Recently, new developments have been reported, such as the nanocasting method, which combines the advantages of both thermal imprinting and curing imprinting, and the reversal imprinting method, which produces three-dimensional layered structures. In the curable imprinting method, a composition for forming an imprint pattern is applied to a support (which may be subjected to adhesion treatment as necessary) and dried as necessary to form a curable film, after which a mold made of a light-transmitting material such as quartz is pressed against the support. With the mold pressed against the support, the curable composition for imprints is cured by light irradiation or heating, and the mold is then released to produce a cured product to which the desired pattern has been transferred. Methods for applying the curable composition for imprints onto a support include spin coating and inkjet printing. In particular, spin coating has the advantage of being an application method with excellent productivity from the viewpoint of high throughput. Furthermore, a method of performing microfabrication using a transferred imprint pattern as a mask is called nanoimprint lithography (NIL), and it is being developed as a next-generation lithography technology to replace the current ArF immersion process. Therefore, the imprint pattern-forming composition used in NIL must be capable of resolving ultrafine patterns of 20 nm or less, similar to EUV resists, and must also have high etching resistance as a mask for microfabrication of the target object. Specific examples of curable imprint compositions intended for use as masks include those described in Japanese Patent Publication No. 5426814, Japanese Patent Application Laid-Open No. 2015-009171, Japanese Patent Application Laid-Open No. 2015-185798, Japanese Patent Application Laid-Open No. 2015-070145, and Japanese Patent Application Laid-Open No. 2015-128134.

[0005] In such imprinting methods, after a curable film is formed from the composition for imprint pattern formation, defects may occur in the curable film, such as the generation of foreign matter in the curable film, as time passes.

[0006] The present invention aims to provide a composition for imprint pattern formation that suppresses the occurrence of defects even after the lapse of time after the formation of a curable film, a cured product of the composition for imprint pattern formation, a device including the cured product, a method for producing an imprint pattern using the composition for imprint pattern formation, and a method for producing a device including the method for producing an imprint pattern. [Means for solving the problem]

[0007] Representative embodiments of the present invention are described below. <1> polymerizable compound, a polymerization initiator, and Derivatives of the above polymerization initiators are included. A composition for forming an imprint pattern. <2> the content of the derivative is 1 to 10,000 parts by mass when the content of the polymerization initiator is 100 parts by mass; <1> The composition for imprint pattern formation according to claim 1. <3> the total content of the polymerization initiator and the derivative is 0.1 to 10.0 parts by mass, relative to 100 parts by mass of the total solid content of the composition for imprint pattern formation; <1> or <2> The composition for imprint pattern formation according to claim 1. <4> The polymerization initiator is a photopolymerization initiator. <1> ~ <3> 10. The composition for imprint pattern formation according to claim 9, wherein the imprint pattern forming layer is a polyimide film. <5> the polymerization initiator and the derivative are both acylphosphine oxide-based polymerization initiators or both alkylphenone-based polymerization initiators; <1> ~ <4> 10. The composition for imprint pattern formation according to claim 9, wherein the imprint pattern forming layer is a polyimide film. <6> One of the polymerization initiator and the derivative is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and the other is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. <1> ~ <5> 10. The composition for imprint pattern formation according to claim 9, wherein the imprint pattern forming layer is a polyimide film. <7> One of the polymerization initiator and the derivative is 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and the other is 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one. <1> ~ <5> 10. The composition for imprint pattern formation according to claim 9, wherein the imprint pattern forming layer is a polyimide film. <8> One of the polymerization initiator and the derivative is 2-hydroxy-2-methylpropiophenone, and the other is 1-hydroxycyclohexyl phenyl ketone. <1> ~ <5> 10. The composition for imprint pattern formation according to claim 9, wherein the imprint pattern forming layer is a polyimide film. <9> a polymerizable compound, and Contains a polymerization initiator, the polymerization initiator contains two or more oxime compounds, two or more acylphosphine compounds, or two or more alkylphenone compounds; A composition for forming an imprint pattern. <10> Further comprising a mold release agent, <1> ~ <9> 10. The composition for imprint pattern formation according to claim 9, wherein the imprint pattern forming layer is a polyimide film. <11> the composition further contains a solvent, and the content of the solvent is 90.0 to 99.0 mass% relative to the total mass of the composition for imprint pattern formation; <1> ~ <10> 10. The composition for imprint pattern formation according to claim 9, wherein the imprint pattern forming layer is a polyimide film. <12> <1> ~ <11> 2. A cured product obtained by curing the composition for imprint pattern formation according to any one of the above items. <13> A member to be applied selected from the group consisting of a support and a mold <1> ~ <11> an application step of applying the composition for imprint pattern formation according to any one of the above items; a contacting step of bringing a member, which is not selected as the application member from the group consisting of the support and the mold, into contact with the composition for imprint pattern formation as a contact member; a curing step of converting the imprint pattern-forming composition into a cured product; and A peeling step of peeling the mold from the cured product. A method for producing an imprint pattern. <14> the support is a member having an adhesive layer on the surface to which the imprint pattern forming composition is applied; <13> 1. A method for producing an imprint pattern according to claim 1. <15> <13> or <14> A device manufacturing method comprising the method for manufacturing an imprint pattern according to any one of claims 1 to 4. <16> <12> A device comprising the cured product described in 1. [Effects of the Invention]

[0008] According to the present invention, there are provided a composition for imprint pattern formation that suppresses the occurrence of defects even after the lapse of time after the formation of a curable film, a cured product of the composition for imprint pattern formation, a device including the cured product, a method for producing an imprint pattern using the composition for imprint pattern formation, and a method for producing a device that includes the method for producing an imprint pattern. DETAILED DESCRIPTION OF THE INVENTION

[0009] A typical embodiment of the present invention will be described below. For convenience, each component will be described based on this typical embodiment, but the present invention is not limited to such an embodiment.

[0010] In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved. In this specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it means that it includes both a group (atomic group) that has no substituent and a group (atomic group) that has a substituent. For example, when the term "alkyl group" is simply described, it means that it includes both an alkyl group that has no substituent (unsubstituted alkyl group) and an alkyl group that has a substituent (substituted alkyl group). In this specification, unless otherwise specified, the term "exposure" includes not only drawing using light but also drawing using particle beams such as electron beams and ion beams. Examples of energy beams used for drawing include the bright line spectrum of a mercury lamp, actinic rays such as far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light) and X-rays, and particle beams such as electron beams and ion beams. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", "(meth)acrylic" means either or both of "acrylic" and "methacrylic", and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl". In this specification, the solid content in a composition means other components excluding the solvent, and the content (concentration) of the solid content in a composition is expressed as the mass percentage of other components excluding the solvent relative to the total mass of the composition, unless otherwise specified. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, unless otherwise specified, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are expressed as polystyrene equivalent values ​​measured by gel permeation chromatography (GPC). These weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, measurements are performed using THF (tetrahydrofuran) as the eluent. Unless otherwise specified, GPC measurements are performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that there is another layer above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Furthermore, unless otherwise specified, the direction in which layers are stacked on the support is referred to as "above," or, if a photosensitive layer is present, the direction from the support to the photosensitive layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertical upward direction. 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).

[0011] (Composition for forming imprint patterns) In a first embodiment, the composition for imprint pattern formation of the present invention contains a polymerizable compound, a polymerization initiator, and a derivative of the polymerization initiator. In a second aspect, the composition for imprint pattern formation of the present invention comprises a polymerizable compound and a polymerization initiator, and the polymerization initiator comprises two or more oxime compounds, two or more acylphosphine compounds, or two or more alkylphenone compounds. Hereinafter, the composition for imprint pattern formation of the present invention related to the first aspect will also be referred to as the first composition for imprint pattern formation, and the composition for imprint pattern formation of the present invention related to the second aspect will also be referred to as the second composition for imprint pattern formation. Furthermore, hereinafter, when the term "the composition for imprint pattern formation of the present invention" is simply mentioned, it is intended to include both the first composition for imprint pattern formation and the second composition for imprint pattern formation.

[0012] According to the composition for imprint pattern formation of the present invention, the occurrence of defects is suppressed even after the lapse of time after the formation of a curable film. The mechanism by which the above effects are obtained is unknown, but is speculated as follows.

[0013] Conventionally, various studies have been conducted on compositions for imprint pattern formation containing a polymerizable compound and a polymerization initiator. As a result of extensive investigations, the present inventors have found that in a composition for imprint pattern formation containing a polymerizable compound and a polymerization initiator, defects such as the generation of foreign matter in the curable film may occur if time (e.g., 24 hours) passes after the formation of the curable film. This is presumably due to the precipitation of the polymerization initiator in the curable film. Therefore, the present inventors conducted extensive research and found that the occurrence of the above defects can be suppressed by including a polymerization initiator and a derivative of the polymerization initiator, or by configuring the polymerization initiator to include two or more oxime compounds, two or more acylphosphine compounds, or two or more alkylphenone compounds. This is presumably because, in the above embodiment, the crystallinity of the polymerization initiator is reduced, and precipitation in the curable film is suppressed. The composition for imprint pattern formation of the present invention will be described in detail below.

[0014] <Polymerizable compound> The composition for imprint pattern formation of the present invention contains a polymerizable compound. The first composition for imprint pattern formation and the second composition for imprint pattern formation have the same preferred embodiments of the polymerizable compound. In addition, unless otherwise specified below, the preferred aspects of the components contained in the first composition for imprint pattern formation and the second composition for imprint pattern formation are the same. In the composition for imprint pattern formation of the present invention, among the components other than the solvent contained in the composition for imprint pattern formation, the component contained in the greatest amount is preferably a polymerizable compound. The polymerizable compound may have one polymerizable group per molecule, or two or more polymerizable groups. At least one of the polymerizable compounds contained in the composition for imprint pattern formation preferably contains two to five polymerizable groups per molecule, more preferably two to four, even more preferably two or three, and even more preferably three. The type of polymerizable group possessed by the polymerizable compound is not particularly limited, but examples thereof include a group having an ethylenically unsaturated group, a cyclic ether group (epoxy group, glycidyl group, oxetanyl group), etc., with the group having an ethylenically unsaturated group being preferred. Examples of the group having an ethylenically unsaturated group include a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, a vinyloxy group, an allyl group, a vinylphenyl group, etc., with a (meth)acryloyl group or a (meth)acryloyloxy group being more preferred, and an acryloyl group or an acryloyloxy group being even more preferred.

[0015] At least one of the polymerizable compounds contained in the composition for imprint pattern formation preferably has a cyclic structure. Examples of such a cyclic structure include an aliphatic hydrocarbon ring (Cf) and an aromatic hydrocarbon ring (Cr). In particular, the polymerizable compound preferably has an aromatic hydrocarbon ring (Cr), and more preferably has a benzene ring. The molecular weight of the polymerizable compound is preferably 100 to 900.

[0016] At least one of the polymerizable compounds is preferably represented by the following formula (I-1). [ka]

[0017] L 20is a 1+q2-valent linking group, for example, a linking group having a cyclic structure. Examples of the cyclic structure include the above-mentioned ring Cf, ring Cr, ring Cn, ring Co, and ring Cs. R 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 the above-mentioned linking group L. 20 and L 21 or L 22 may be bonded to form a ring with or without a linking group L. 20 , L 21 and L 22 may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different. q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and further preferably 0 or 1.

[0018] [High molecular weight polymerizable compound] The composition for imprint pattern formation may also contain, as the polymerizable compound, a polymerizable compound having a weight average molecular weight of 800 or more (hereinafter also referred to as a "high molecular weight polymerizable compound"). 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, of which silicon-containing compounds or ring-containing compounds are preferred, and silicon-containing compounds are more preferred.

[0019] 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 to 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 even more preferably 3,000 or less. By setting the molecular weight at or above the lower limit, volatilization of the compound is suppressed, stabilizing the properties of the composition and the coating film. It also ensures good viscosity for maintaining the shape of the coating film. Furthermore, it complements the effect of limiting the amount of release agent to a small amount, thereby achieving good releasability of the film. Setting the molecular weight at or below the upper limit makes it easier to ensure the low viscosity (fluidity) required for pattern filling, which is preferable.

[0020] -Silicon-containing compounds- Examples of silicon-containing compounds include compounds having a silicone skeleton, specifically compounds having at least one of a siloxane structure of D units represented by the following formula (S1) and a siloxane structure of T units represented by the following formula (S2). [ka] In formula (S1) or formula (S2), R S1 ~R S3 each independently represents a hydrogen atom or a monovalent substituent, and each * independently represents a bonding site to another structure. R S1 ~R S3 are each preferably independently a monovalent substituent. The monovalent substituent is preferably an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms) or an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 6 carbon atoms), and among these, a cyclic or chain (straight-chain or branched) alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms) or a group containing a polymerizable group is preferred.

[0021] Specific examples of the silicon-containing compound structure, when expressed as a partial structure, include the following formulas (s-1) to (s-9). In the formulas, Q is a group containing the above-mentioned polymerizable group. A compound may have a plurality of these structures, or may have a combination of these structures.

[0022] [ka]

[0023] The silicon-containing compound is preferably a reaction product of a silicone resin and a compound having a polymerizable group. The silicone resin is preferably a reactive 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 compound having a polymerizable group is preferably a compound having a polymerizable group and a group capable of reacting with an alkoxysilyl group or a silanol group, and more preferably a compound having a polymerizable group and a hydroxy group. Furthermore, when the modified silicone resin described above is used as the silicone resin, a compound having a group that reacts with the polymerizable group and an amino group, epoxy group, mercapto group, carboxy group, or the like contained in the modified silicone resin may be used as the compound having the polymerizable group. The preferred embodiments of the polymerizable group in the compound having the polymerizable group are the same as the preferred embodiments of the polymerizable group in the polymerizable compound described above. Among these, the compound having a polymerizable group is preferably a hydroxyalkyl(meth)acrylate, and more preferably 2-hydroxyethyl(meth)acrylate. More specifically, it is preferably a reaction product of a compound having a polymerizable group and a group (for example, a hydroxy group) capable of reacting with an alkoxysilyl group or a silanol group, and a silicone resin having an alkoxysilyl group or a silanol group.

[0024] -Ring-containing compounds- Examples of the cyclic structure of the compound containing a ring (ring-containing compound) include an aromatic ring and an alicyclic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic hydrocarbon ring preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a fluorene ring, a benzocyclooctene ring, an acenaphthylene ring, a biphenylene ring, an indene ring, an indane ring, a triphenylene ring, a pyrene ring, a chrysene ring, a perylene ring, and a tetrahydronaphthalene ring. Of these, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The aromatic ring may have a structure in which multiple rings are linked together, such as a biphenyl structure or a diphenylalkane structure (e.g., 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 thereof include a thiophene ring, a furan ring, a dibenzofuran ring, a pyrrole ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, an oxadiazole ring, an oxazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an isoindole ring, an indole ring, an indazole ring, a purine ring, a quinolizine ring, an isoquinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a carbazole ring, an acridine ring, a phenazine ring, a phenothiazine ring, a phenoxathiin ring, and a phenoxazine ring. (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 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples of the aliphatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, a dicyclopentadiene ring, a spirodecane ring, a spirononane ring, a tetrahydrodicyclopentadiene ring, an octahydronaphthalene ring, a decahydronaphthalene ring, a hexahydroindane ring, a bornane ring, a norbornane ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring. Examples of the aliphatic heterocyclic ring include a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, an oxirane ring, an oxetane ring, an oxolane ring, an oxane ring, and a dioxane ring. (The alicyclic ring defined here is referred to as fCy)

[0025] 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, more preferably a compound having a benzene ring, such as a compound having a structure represented by the following formula (C-1):

[0026] [ka] In the formula, Ar represents the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle. L 1 and L 2 are each independently a single bond or a linking group. Examples of the linking group include an oxygen atom (oxy group), a carbonyl group, an amino group, an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), or a combination thereof. Among these, a (poly)alkyleneoxy group is preferred. The (poly)alkyleneoxy group may be one in which one alkyleneoxy group is connected, or a plurality of repeating alkyleneoxy groups may be connected. The order of the alkylene groups and oxy groups is not limited. The number of repeating alkyleneoxy groups is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. Furthermore, the (poly)alkyleneoxy group may be interposed by an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 6 carbon atoms) in relation to the linkage with the parent ring Ar or polymerizable group Q. Therefore, (poly)alkyleneoxy may be an alkylene group. R 3 is an optional substituent, and examples thereof include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and more preferably having 6 to 10 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 11 carbon atoms), a hydroxy group, a carboxy group, an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and more preferably having 1 to 6 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and more preferably having 2 to 3 carbon atoms; an alkylcarbonyl group is preferable), and an aryloyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and more preferably having 7 to 11 carbon atoms). L 3 is a single bond or a linking group. 1 ,L 2 Examples include: n3 is preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0. Q 1 and Q 2 are each independently a polymerizable group, and the above examples of polymerizable groups are preferred. In the ring-containing compound, 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 perspective, nq is 1 or more, preferably 2 or more. The upper limit is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. Similarly, from the viewpoint of facilitating the formation of a uniform crosslinked structure, when a group or a substituent containing a polymerizable group is introduced into a cyclic structure, the substituents are preferably arranged in series.

[0027] -Dendrimer-type compounds- The high molecular weight polymerizable compound may be a dendrimer-type compound. Dendrimer refers to a dendritic polymer with a structure that branches regularly from the center. Dendrimers are composed of a central molecule (trunk) called the core and side chain portions (branches) called dendrons. Although fan-shaped compounds are generally used overall, dendrimers with dendrons spreading out in semicircular or circular shapes are also possible. A polymerizable compound can be obtained by introducing a group having a polymerizable group into the dendron portion of this dendrimer (for example, the terminal portion away from the core). If a (meth)acryloyl group is used as the polymerizable group to be introduced, a dendrimer-type multifunctional (meth)acrylate can be obtained. For dendrimer-type compounds, reference can be made to the disclosures in, for example, Japanese Patent No. 5512970, the disclosure of which is incorporated herein by reference.

[0028] -Polymerizable group equivalent- The high molecular weight polymerizable compound preferably has a polymerizable group equivalent of 130 or more, more preferably 150 or more, even more preferably 160 or more, still 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, still more preferably 1,000 or less, still more preferably 500 or less, still more preferably 350 or less, and may be 300 or less.

[0029] The polymerizable group equivalent is calculated by the following formula. (Polymerizable group equivalent)=(number average molecular weight of polymerizable compound) / (number of polymerizable groups in polymerizable compound)

[0030] When the polymerizable group equivalent of the high molecular weight polymerizable compound is equal to or greater than the lower limit, the elastic modulus upon curing falls within an appropriate range, and it is believed that the release properties are excellent. On the other hand, when the polymerizable group equivalent is equal to or less than the upper limit, the crosslink density of the cured product pattern falls within an appropriate range, and it is believed that the resolution of the transfer pattern is excellent.

[0031] In the case of a silicon-containing compound, the number of polymerizable groups in a high molecular weight polymerizable compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more per molecule, and 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 a ring-containing compound, the number of rings in one molecule is preferably 2 or more, and the upper limit is preferably 4 or less, and more preferably 3 or less. Alternatively, in the case of a dendrimer-type compound, the number of such groups in one molecule is preferably 5 or more, 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.

[0032] -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.

[0033] Unless otherwise specified, viscosity in this specification is the value measured using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd., with a standard cone rotor (1°34' x R24) and the sample cup temperature adjusted to 23°C. Other measurement details comply with JIS Z8803:2011. Two samples are prepared for each level, and each is measured three times. The arithmetic mean of a total of six measurements is used as the evaluation value.

[0034] Examples of polymerizable compounds include the compounds used in the following examples, the compounds described in paragraphs 0017 to 0024 and examples of JP-A-2014-090133, the compounds described in paragraphs 0024 to 0089 of JP-A-2015-009171, the compounds described in paragraphs 0023 to 0037 of JP-A-2015-070145, and the compounds described in paragraphs 0012 to 0039 of WO 2016 / 152597, but the present invention should not be construed as being limited thereto.

[0035] The content of the polymerizable compound relative to the total solid content of the composition for imprint pattern formation is preferably 30% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, still more preferably 55% by mass or more, and may be 60% by mass or more, or even 70% by mass or more. The upper limit is preferably less than 99% by mass, more preferably 98% by mass or less, and may be 97% by mass or less.

[0036] The boiling point of the polymerizable compound is preferably set and formulated in relation to the curable main agent contained in the adhesive layer-forming composition described below. 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.

[0037] <Polymerization initiator> The composition for imprint pattern formation of the present invention contains a polymerization initiator. The first composition for imprint pattern formation contains a polymerization initiator and a derivative of the polymerization initiator. In the second composition for imprint pattern formation, the polymerization initiator contains two or more oxime compounds, two or more acylphosphine compounds, or two or more alkylphenone compounds.

[0038] The polymerizable compound contained in the composition for imprint pattern formation of the present invention may be a photopolymerization initiator or a thermal polymerization initiator, but is preferably a photopolymerization initiator. The photopolymerization initiator contained in the composition for imprint pattern formation of the present invention is not particularly limited as long as it is a compound that generates active species that polymerize the above-mentioned polymerizable compound upon irradiation with light. The thermal polymerization initiator contained in the composition for imprint pattern formation of the present invention is not particularly limited as long as it is a compound that generates active species that polymerize the above-mentioned polymerizable compound upon heating. The polymerization initiator is preferably a radical polymerization initiator or a cationic polymerization initiator, and more preferably a radical polymerization initiator. In the present invention, a plurality of polymerization initiators may be used in combination. First, the polymerization initiator contained in the first composition for imprint pattern formation and the derivatives of the polymerization initiator will be described below.

[0039] Examples of photoradical polymerization initiators included in the first imprint pattern-forming composition 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, hexaarylbiimidazoles, oxime compounds such as 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 details, see paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol.19, No.3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A are mentioned, the contents of which are also incorporated herein. The thermal radical polymerization initiator is not particularly limited and any known thermal radical polymerization initiator can be used. Specific examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference. Furthermore, among the above-mentioned photopolymerization initiators, those having the function of initiating polymerization by heat can also be added as thermal polymerization initiators.

[0040] In the present invention, it is preferable that the polymerization initiator and derivative contained in the first composition for imprint pattern formation are both acylphosphine oxide-based polymerization initiators, or both are alkylphenone photopolymerization initiators.

[0041] The acylphosphine polymerization initiator is not particularly limited, and examples thereof 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, bis(2,6-dimethylbenzoyl)-ethylphosphine oxide, etc. Commercially available products that can be used include Omnirad 819, Omnirad TPO H, Omnirad TPO L (all manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF), etc.

[0042] Examples of the alkylphenone polymerization initiator include α-aminoketone compounds such as aminoacetophenone, and α-hydroxyketone compounds such as hydroxyacetophenone. The α-hydroxyketone compound is not particularly limited, and examples thereof include 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl 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, etc. Commercially available products that can be used include Omnirad 184, Omnirad 1173, Omnirad 500, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (all manufactured by BASF), etc. The α-aminoketone compound is not particularly limited, but examples thereof include 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc. Commercially available products that can be used include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF).

[0043] Furthermore, one of the embodiments represented by the following (1A) to (1C) is also one of the preferred embodiments of the present invention. (1A) One of the polymerization initiator and the derivative is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and the other is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. (1B) Of the above polymerization initiator and the above derivative, one is 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and the other is 2(dimethylamino)2(4-methylbenzyl)1(4-morpholinophenyl)butan-1-one. (1C) One of the above polymerization initiator and the above derivative is 2-hydroxy-2-methylpropiophenone, and the other is 1-hydroxycyclohexyl phenyl ketone.

[0044] [Derivative] In the present invention, the derivative of the polymerization initiator is preferably a compound having the same partial structure as the polymerization initiator, and the formula weight of the partial structure is 40% by mass or more relative to the molecular weight of the polymerization initiator. The formula weight of the partial structure is preferably 60% by mass or more, more preferably 70% by mass or more, relative to the molecular weight of the polymerization initiator. Furthermore, the partial structure is a continuous structure linked by a covalent bond. In other words, when the polymerization initiator and the derivative have two or more identical partial structures in their molecules, only the one with the larger formula weight is used in the above calculation. In this way, by using a compound in which the same partial structure accounts for a large proportion as a polymerization initiator and its derivative, it is possible to reduce the crystallinity of the polymerization initiator, and it is thought that the occurrence of defects can be suppressed even if time passes in the form of a curable film. In the present invention, the derivative of the polymerization initiator may be a polymerization initiator or a compound that does not have polymerization initiation ability. When the derivative is a polymerization initiator (has polymerization initiation ability), either one may be the polymerization initiator and either one may be the derivative, but one may be determined as the polymerization initiator and the other as the derivative so that the ratio of the formula weight of the partial structure to the molecular weight of the above-mentioned derivative becomes large. Furthermore, when the derivative is a polymerization initiator, if one of the derivatives is one selected from the group consisting of the above-mentioned halogenated hydrocarbon derivatives, acylphosphine compounds, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds, α-hydroxyketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes, it is preferable that the other be the same type of compound. The term "same type of compound" means, for example, that if one of the derivatives is a halogenated hydrocarbon derivative, the other is a halogenated hydrocarbon derivative with a different structure. An example is an embodiment in which the polymerization initiator is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate and the derivative is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. In this case, the formula weight (271.28) of the partial structure in the derivative that is the same as that of the polymerization initiator is 271.28 / 316.34×100=86.1% by mass relative to the molecular weight (316.34) of the polymerization initiator. An example of a case where the derivative does not have polymerization initiation ability is an embodiment in which the polymerization initiator is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and the derivative is the following compound Z-1. Another example of a case where the derivative does not have polymerization initiation ability is an embodiment where the polymerization initiator is 2-hydroxy-2-methylpropiophenone and the derivative is the following compound Z-2. [ka]

[0045] The content of the polymerization initiator in the first composition for imprint pattern formation is, for example, 0.01 to 15 mass %, preferably 0.1 to 10 mass %, and more preferably 0.2 to 7 mass %, based on the total solid content of the composition. When two or more types of polymerization initiators are used, the total amount thereof is preferably within the above range. A polymerization initiator content of 0.01% by mass or more is preferred because it tends to improve sensitivity (fast curing), resolution, line edge roughness, and coating strength, while a polymerization initiator content of 15% by mass or less is preferred because it tends to improve light transmittance, colorability, storage stability, and the like. When the total solid content of the composition for imprint pattern formation is taken as 100 parts by mass, the total content of the polymerization initiator and the derivative is, for example, 0.01 to 15 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 7 parts by mass. When two or more types of polymerization initiators or two or more types of derivatives are used, the total amount of all of them is preferably within the above range.

[0046] When the content of the polymerization initiator in the first imprint pattern-forming composition is taken as 100 parts by mass, the content of the above-mentioned derivative is preferably 1 to 10,000 parts by mass, more preferably 5 to 2,000 parts by mass, and even more preferably 10 to 1,000 parts by mass. The polymerization initiator contained in the second composition for imprint pattern formation and the derivatives of the polymerization initiator will be described below.

[0047] The polymerization initiator in the second composition for imprint pattern formation contains two or more oxime compounds, two or more acylphosphine compounds, or two or more alkylphenone compounds. Details of the acylphosphine compound and the alkylphenone compound are the same as those of the acylphosphine polymerization initiator and the alkylphenone polymerization initiator described above. The oxime compound is not particularly limited, but examples include compounds having the following structure, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. [ka] Commercially available products such as IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A) are also suitable. TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito ChemiX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used.

[0048] Furthermore, one of the embodiments represented by the following (2A) to (2C) is also one of the preferred embodiments of the present invention. (2A) The polymerization initiator includes diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. (2B) The polymerization initiator includes 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone and 2(dimethylamino)2(4-methylbenzyl)1(4-morpholinophenyl)butan-1-one. (2C) The polymerization initiator includes 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone.

[0049] The total content of the polymerization initiator in the second composition for imprint pattern formation is, for example, 0.01 to 15 mass %, preferably 0.1 to 10 mass %, and more preferably 0.2 to 7 mass %, relative to the total solid content of the composition. A polymerization initiator content of 0.01% by mass or more is preferred because it tends to improve sensitivity (fast curing), resolution, line edge roughness, and coating strength, while a polymerization initiator content of 15% by mass or less is preferred because it tends to improve light transmittance, colorability, storage stability, and the like.

[0050] [Release agent] The composition for imprint pattern formation of the present invention preferably contains a release agent. The content of the release agent is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 0.6% by mass or more, based on the total solid content of the composition. The upper limit is preferably less than 1.0% by mass, more preferably 0.9% by mass or less, and even more preferably 0.85% by mass or less. By setting the content of the release agent to the above lower limit or more, the mold releasability is improved, and peeling of the cured film and damage to the mold during mold release can be prevented. On the other hand, by setting the content to the above upper limit or less, an excessive decrease in pattern strength during curing due to the influence of the release agent is not caused, and good resolution can be achieved. The release agent may be used alone or in combination with a plurality of types. When a plurality of types are used, the total amount thereof falls within the above range. The type of release agent is not particularly limited, but it is preferable that the release agent has the function of segregating at the interface with the mold and effectively promoting release 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 imparting excellent resistance to processing such as etching while realizing high releasability of the film of the curable composition for imprints. Specifically, the release agent used in the present invention is preferably a surfactant. Alternatively, it is preferably an alcohol compound having at least one hydroxy group at its terminal, or a compound having a (poly)alkylene glycol structure in which the hydroxy group has been etherified (a (poly)alkylene glycol compound). The surfactant and (poly)alkylene glycol compound are preferably non-polymerizable compounds having no polymerizable groups. Note that the term "(poly)alkylene glycol" may refer to a compound having one alkylene glycol structure or a compound having multiple repeating alkylene glycol structures linked together.

[0051] -Surfactants- The surfactant that can be used as the release agent in the present invention is preferably a nonionic surfactant. A nonionic surfactant is a compound having at least one hydrophobic moiety and at least one nonionic hydrophilic moiety. The hydrophobic moiety and the hydrophilic moiety may be located at the terminal or inside of the molecule. The hydrophobic moiety is composed of, for example, a hydrocarbon group, and the number of carbon atoms in the hydrophobic moiety 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 moiety 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)alkyleneoxy group or 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, a compound having an alcoholic hydroxyl group or an ether group (preferably a (poly)alkyleneoxy group or a cyclic ether group) is more preferred.

[0052] -Alcohol compounds, (poly)alkylene glycol compounds- As described above, preferred release agents for use in the curable composition for imprints of the present invention include alcohol compounds having at least one hydroxy group at the terminal, or (poly)alkylene glycol compounds in which the hydroxy group has been etherified.

[0053] Specifically, the (poly)alkylene glycol compound preferably has an alkyleneoxy group or a polyalkyleneoxy group, and more preferably has a (poly)alkyleneoxy group containing an alkylene group having 1 to 6 carbon atoms. Specifically, it preferably has a (poly)ethyleneoxy group, a (poly)propyleneoxy group, a (poly)butyleneoxy group, or a mixed structure thereof, more preferably a (poly)ethyleneoxy group, a (poly)propyleneoxy group, or a mixed structure thereof, and even more preferably has a (poly)propyleneoxy group. The (poly)alkylene glycol compound may be substantially composed of only (poly)alkyleneoxy groups, excluding terminal substituents. Here, "substantially" means that components other than (poly)alkyleneoxy groups account for 5% by mass or less of the total, preferably 1% by mass or less. In particular, it is particularly preferable for the (poly)alkylene glycol compound to include a compound substantially composed of only (poly)propyleneoxy groups.

[0054] The number of repeating alkyleneoxy groups in the (poly)alkylene glycol compound is preferably 3-100, more preferably 4-50, even more preferably 5-30, and even more preferably 6-20.

[0055] As long as the terminal hydroxyl groups of the (poly)alkylene glycol compound are etherified, the remaining terminals may be hydroxyl groups, or the hydrogen atoms of the terminal hydroxyl groups may be substituted. The groups that may replace the hydrogen atoms of the terminal hydroxyl groups are preferably alkyl groups (i.e., (poly)alkylene glycol alkyl ethers) or acyl groups (i.e., (poly)alkylene glycol esters). Compounds having multiple (preferably 2 or 3) (poly)alkylene glycol chains via linking groups can also be preferably used.

[0056] Preferred specific examples of the (poly)alkylene glycol compound include polyethylene glycol, polypropylene glycol (e.g., manufactured by 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 trimethyl ethers thereof.

[0057] The (poly)alkylene glycol compound is preferably a compound represented by the following formula (P1) or (P2). [ka] R in the formula P1 R is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms) which may be chain or cyclic, and may be straight or branched. P2 , R P3 is a hydrogen atom or an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, and even more preferably 3 to 12 carbon atoms), which may be chain-like or cyclic, and may be straight-chain or branched. p is preferably an integer of 1 to 24, and more preferably an integer of 2 to 12. R P4 is a q-valent linking group, preferably a linking group made of an organic group, and more preferably a linking group made of a hydrocarbon. Specific examples of linking groups made of a hydrocarbon include linking groups having an alkane structure (preferably having 1 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and even more preferably having 2 to 6 carbon atoms), linking groups having an alkene structure (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and even more preferably having 2 to 6 carbon atoms), and linking groups having an aryl structure (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms). q is preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and even more preferably an integer of 2 to 4.

[0058] The weight average molecular weight of the alcohol compound or (poly)alkylene glycol compound used as a release agent is preferably 150 to 6,000, more preferably 200 to 3,000, even more preferably 250 to 2,000, and still more preferably 300 to 1,200. Furthermore, examples of commercially available (poly)alkylene glycol compounds that can be used in the present invention include Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) and Brij35 (manufactured by Kishida Chemical Co., Ltd.).

[0059] <Solvent> The composition for imprint pattern formation of the present invention preferably contains a solvent. When a solvent-containing composition for imprint pattern formation is used, a curable film can be obtained by removing the solvent, for example, by drying. However, defects in the curable film after solvent removal are likely to occur, and it is believed that the present invention can effectively suppress such defects. In the present invention, the content of the solvent in the composition for imprint pattern formation is preferably 90.0 to 99.0 mass %, more preferably 92.0 to 99.0 mass %, and even more preferably 95.0 to 99.0 mass %, relative to the total mass of the composition for imprint pattern formation.

[0060] Examples of the solvent contained in the pattern-forming composition include alkoxy alcohols, propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, lactate esters, acetate esters, alkoxypropionate esters, chain ketones, cyclic ketones, lactones, and alkylene carbonates, with propylene glycol monoalkyl ethers and lactones being particularly preferred.

[0061] <Other additives> The composition for imprint pattern formation of the present invention may contain additives other than the above-mentioned polymerizable compound, polymerization initiator, release agent, and solvent, such as surfactants, sensitizers, antioxidants, and polymerization inhibitors. Specific examples of other additives contained in the pattern-forming composition that can be used in the present invention include the additives contained in the compositions described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537, the contents of which are incorporated herein by reference. Furthermore, the descriptions in the above publications can also be taken into consideration for the preparation of the pattern-forming composition and the method for producing a pattern, and the contents of these publications are incorporated herein by reference.

[0062] <Physical properties, etc.> The viscosity of a composition obtained by removing the solvent from the composition for imprint pattern formation (i.e., a composition prepared by mixing components (solids) other than the solvent in the composition for imprint pattern formation) is preferably 20.0 mPa·s or less, more preferably 15.0 mPa·s or less, even more preferably 11.0 mPa·s or less, and even more preferably 9.0 mPa·s or less. The lower limit of the viscosity is not particularly limited, but can be, for example, 5.0 mPa·s or more. The viscosity can be measured by known methods, for example, according to the method described below.

[0063] Viscosity is measured using a Toki Sangyo Co., Ltd. E-type rotational viscometer RE85L with a standard cone rotor (1°34' x R24) and the sample cup is temperature-controlled at 23°C. The unit is mPa·s. Other measurement details comply with JIS Z 8803:2011. Two samples are prepared for each level, and each is measured three times. The arithmetic mean of a total of six measurements is used as the evaluation value.

[0064] The surface tension (γResist) of the imprint pattern-forming composition excluding the solvent is preferably 28.0 mN / m or more, more preferably 30.0 mN / m or more, and may be 32.0 mN / m or more. Using a composition with high surface tension increases capillary force, enabling rapid filling of the composition into the mold pattern. The upper limit of the surface tension is not particularly limited, but from the viewpoint of the relationship with the adhesive layer and imparting inkjet suitability, it is preferably 40.0 mN / m or less, more preferably 38.0 mN / m or less, and may be 36.0 mN / m or less. The surface tension of the pattern-forming composition from which the solvent has been removed is measured at 23° C. using a surface tensiometer SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd., and a glass plate.

[0065] The Onishi parameter of the composition for imprint pattern formation excluding the solvent is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.7 or less. The lower limit of the Onishi parameter of the composition for pattern formation is not particularly limited, but may be, for example, 1.0 or more, or even 2.0 or more. The Ohnishi parameter can be determined for the solid content of the composition for imprint pattern formation by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all constituent components into the following formula: Onishi parameter = sum of the number of carbon atoms, hydrogen atoms, and oxygen atoms / (number of carbon atoms - number of oxygen atoms)

[0066] <Storage container> A conventionally known container can be used as a container for storing the composition for imprint pattern formation of the present invention. Furthermore, in order to prevent impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0067] (Method of producing cured product and imprint pattern) The cured product of the present invention is a cured product obtained by curing the composition for imprint pattern formation of the present invention. The cured product of the present invention is preferably a patterned cured product (imprint pattern). The method for producing the imprint pattern will be described below.

[0068] <Method of manufacturing imprint pattern> The method for producing an imprint pattern of the present invention includes an applying step of applying the composition for forming an imprint pattern of the present invention to a member to which the composition is to be applied, the member being selected from the group consisting of a support and a mold; a contacting step of bringing a member, which is not selected as the application member from the group consisting of the support and the mold, into contact with the composition for imprint pattern formation as a contact member; a curing step of converting the imprint pattern-forming composition into a cured product; and The method includes a peeling step of peeling the mold from the cured product.

[0069] [Applicable process] The method for producing an imprint pattern of the present invention includes an applying step of applying the composition for forming an imprint pattern of the present invention to a member to which the composition is to be applied, the member being selected from the group consisting of a support and a mold. In the applying step, one member selected from the group consisting of a support and a mold is selected as the member to which the composition for imprint pattern formation of the present invention is applied, and the composition for imprint pattern formation of the present invention is applied onto the selected member to which the composition is applied. One of the support and the mold is selected as the member to be applied, and the other is the contact member. That is, in the application step, the composition for imprint pattern formation of the present invention may be applied to a support and then brought into contact with a mold, or may be applied to a mold and then brought into contact with a support (which may have an adhesion layer, etc., as described below).

[0070] -Support- Regarding the support, the description in paragraph 0103 of Japanese Patent Laid-Open No. 2010-109092 (the corresponding U.S. application is U.S. Patent Application Publication No. 2011 / 0199592) can be referred to, the contents of which are incorporated herein by reference. Specific examples include silicon substrates, glass substrates, sapphire substrates, silicon carbide substrates, gallium nitride substrates, metal aluminum substrates, amorphous aluminum oxide substrates, polycrystalline aluminum oxide substrates, and substrates made of GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGaInP, or ZnO. Specific examples of glass substrate materials include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate is preferred as the substrate.

[0071] The support is preferably a member having an adhesive layer on the surface on which the imprint pattern forming composition is applied. The adhesive layer is preferably an adhesive layer formed by applying a composition for forming an adhesive layer, which will be described later, to a support. The support may further include a liquid film, which will be described later, on the surface of the adhesive layer opposite to the surface that contacts the support. The liquid film is preferably a liquid film formed by applying a liquid film-forming composition, which will be described later, onto the adhesive layer.

[0072] Examples of the adhesion layer that can be used include those described in paragraphs 0017 to 0068 of JP 2014-024322 A and paragraphs 0016 to 0044 of JP 2013-093552 A, adhesion layers described in JP 2014-093385 A, and adhesion layers described in JP 2013-202982 A, the contents of which are incorporated herein by reference.

[0073] -Mold- The mold used in the present invention is not particularly limited. Regarding the mold, the description in paragraphs 0105 to 0109 of JP 2010-109092 A (corresponding U.S. application is U.S. Patent Application Publication No. 2011 / 0199592) can be referred to, and the contents thereof are incorporated herein. A quartz mold is preferred as the mold used in the present invention. The pattern (line width) of the mold used in the present invention is preferably 50 nm or less. The mold pattern can be formed according to the desired processing accuracy by, for example, photolithography or electron beam lithography, but the mold pattern manufacturing method is not particularly limited in the present invention. Furthermore, a mold on which an imprint pattern including any one of a line, hole, and pillar shape is formed is preferred. Among these, a mold that forms an imprint pattern including any of lines, holes, and pillars with a size of 100 nm or less is preferred.

[0074] -How to apply- The method for applying the composition for imprint pattern formation of the present invention to a substrate is not particularly limited, and any commonly known application method can be used, such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and inkjet coating. Among these, the ink jet method and the spin coating method are preferable. The imprint pattern forming composition may also be applied by multiple coatings. In the method of disposing droplets by the inkjet method, the volume of the droplets is preferably about 1 to 20 pL, and the droplets are preferably disposed on the support surface with intervals between them. The droplet interval may be set appropriately depending on 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 interval between the inkjet nozzles. The inkjet method has the advantage that there is little loss of the imprint pattern-forming composition. Specific examples of methods for applying the composition for imprint pattern formation by the inkjet method include those described in JP 2015-179807 A and WO 2016 / 152597 A, and the methods described in these documents can also be suitably used in the present invention. On the other hand, the spin coating method has the advantage of being a highly stable coating process and widening the range of materials that can be used. Specific examples of methods for applying the composition for imprint pattern formation by spin coating include those described in JP-A-2013-095833 and JP-A-2015-071741, and the methods described in these documents can also be suitably used in the present invention.

[0075] -Drying process- The method for producing an imprint pattern of the present invention may further include a drying step of drying the composition for imprint pattern formation of the present invention applied in the applying step. In particular, when a solvent-containing composition is used as the composition for forming an imprint pattern of the present invention, the method for producing an imprint pattern of the present invention preferably includes a drying step. In the drying step, at least a portion of the solvent contained in the applied composition for imprint pattern formation of the present invention is removed. The drying method is not particularly limited, and drying by heating, drying by air blowing, etc. can be used without any 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 composition for imprint pattern formation after the applying step and the drying step, which is performed as needed, but before the contacting step, is also referred to as a "curable film." By using the composition for imprint pattern formation of the present invention, the occurrence of defects in the curable film over time is suppressed.

[0076] [Contact process] The method for producing an imprint pattern of the present invention includes a contacting step of contacting a member from the group consisting of the support and the mold that has not been selected as the application member with the composition for imprint pattern formation (curable film) as a contact member. When a support is selected as the member to be applied in the above-mentioned applying step, in the contacting step, a mold, which is a contacting member, is brought into contact with the surface of the support to which the composition for imprint pattern formation of the present invention has been applied (the surface on which the curable film has been formed). When a mold is selected as the member to be applied in the applying step, a support, which is a contact member, is brought into contact with the surface of the mold to which the composition for imprint pattern formation of the present invention has been applied (the surface on which the curable film has been formed) in the contacting step. That is, in the contacting step, the composition for imprint pattern formation of the present invention is present between the member to be applied and the contacting member. The details of the support and the mold are as described above.

[0077] When the composition for imprint pattern formation (curable film) of the present invention applied to a substrate is brought into contact with a contact member, the pressing pressure is preferably 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. This is also preferred because the low pressing pressure tends to enable the device to be made smaller. It is also preferable that the contact between the curable film and the contact member is carried out in an atmosphere containing helium gas or a condensable gas, or both helium gas and a condensable gas.

[0078] [Curing process] The method for producing an imprint pattern of the present invention includes a curing step of curing the above-described composition for imprint pattern formation into a cured product. The curing step is performed after the contacting step and before the peeling step. The method for producing a cured product of the present invention includes a step of curing the composition for imprint pattern formation obtained by the method for producing a composition for imprint pattern formation of the present invention. The curing step can be carried out by the same method as the curing step in the method for producing an imprint pattern of the present invention. Furthermore, the cured product is preferably in a state in which the mold has been released in the release step described below. The curing method may be curing by heating, curing by exposure to light, or the like, and may be determined depending on the type of polymerization initiator contained in the composition for imprint pattern formation, but curing by exposure to light is preferred. For example, when the polymerization initiator is a photopolymerization initiator, the composition for imprint pattern formation can be cured by exposure to light in the curing step.

[0079] The wavelength of the exposure light is not particularly limited and may be determined depending on the polymerization initiator, but for example, ultraviolet light or the like can be used. The exposure light source may be determined depending on the exposure wavelength, and examples thereof include g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broadband light (light containing light of at least two wavelengths selected from the group consisting of the three wavelengths of g, h, and i-line and light of a wavelength shorter than i-line; for example, a high-pressure mercury lamp when no optical filter is used), semiconductor laser (wavelengths of 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), F2 excimer laser (wavelength 157 nm), extreme ultraviolet (EUV) (wavelength 13.6 nm), and electron beam. Of these, exposure using i-rays or broadband light is preferred.

[0080] The irradiation dose (exposure dose) during exposure may be sufficiently greater than the minimum irradiation dose required for curing the composition for imprint pattern formation. The irradiation dose required for curing the composition for imprint pattern formation can be appropriately determined by examining the consumption of unsaturated bonds in the composition for imprint pattern formation, etc. The exposure dose is, for example, 5 to 1,000 mJ / cm 2 It is preferable to set the range to 10 to 500 mJ / cm 2 It is more preferable to set it in the range of The exposure illuminance is not particularly limited and may be selected depending on the relationship with the light source, but is preferably 1 to 500 mW / cm 2 It is preferable to set the range to 10 to 400 mW / cm 2 It is more preferable to set it in the range of The exposure time is not particularly limited and may be determined in consideration of the exposure illuminance depending on the amount of exposure, but is preferably 0.01 to 10 seconds, more preferably 0.5 to 1 second. The temperature of the support during exposure is usually room temperature, but exposure may be performed while heating to enhance reactivity. Preparing the support for exposure under a vacuum state is effective in preventing the inclusion of air bubbles, suppressing a decrease in reactivity due to the inclusion of oxygen, and improving the adhesion between the mold and the imprint pattern-forming composition, so light irradiation may be performed under a vacuum state. The preferred degree of vacuum during exposure is 10 -1 The pressure ranges from Pa to atmospheric pressure.

[0081] After exposure, the composition for imprint pattern formation may be heated, if necessary. The heating temperature is preferably 150 to 280° C., more preferably 200 to 250° C. The heating time is preferably 5 to 60 minutes, more preferably 15 to 45 minutes. In addition, in the curing step, only the heating step may be performed without performing exposure. For example, when the polymerization initiator is a thermal polymerization initiator, the composition for imprint pattern formation can be cured by performing heating in the curing step. In this case, preferred aspects of the heating temperature and heating time are the same as those in the case where heating is performed after exposure. The heating means is not particularly limited, and may be the same as the heating means used in the drying step described above.

[0082] [Peeling process] The method for producing an imprint pattern of the present invention includes a peeling step of peeling the mold and the cured product. In the peeling step, the cured product obtained in the curing step is peeled from the mold, yielding a patterned cured product (also referred to as a "cured product pattern") to which the mold pattern has been transferred. The resulting cured product pattern can be used for various applications, as described below. The present invention is particularly advantageous in that it can form fine cured product patterns on the nano-order, and can also form cured product patterns with a size of 50 nm or less, particularly 30 nm or less. There is no particular lower limit for the size of the cured product pattern, but it can be, for example, 1 nm or more. The peeling method is not particularly limited, and can be carried out using, for example, a mechanical peeling device known in the imprint pattern manufacturing method.

[0083] (Devices, device manufacturing methods, and applications of cured product patterns) The device of the present invention includes the cured product of the present invention. The device of the present invention can be obtained, for example, by the following method for producing the device of the present invention. The device manufacturing method of the present invention includes the imprint pattern manufacturing method of the present invention. Specifically, examples of the method include a device manufacturing method in which a pattern (cured product pattern) formed by the imprint pattern manufacturing method of the present invention is used as a permanent film for use in liquid crystal display devices (LCDs) and the like, or as an etching resist (lithography mask) for manufacturing semiconductor elements. In particular, the present invention discloses a method for manufacturing a circuit board, and a method for manufacturing a device including the circuit board, which include a step of obtaining a pattern (cured product pattern) by the imprint pattern manufacturing method of the present invention. Furthermore, a method for manufacturing a circuit board according to a preferred embodiment of the present invention may include a step of performing etching or ion implantation on a substrate using the pattern (cured product pattern) obtained by the pattern formation method as a mask, and a step of forming an electronic component. The circuit board is preferably a semiconductor element. That is, the present invention discloses a method for manufacturing a semiconductor device, which includes the imprint pattern manufacturing method of the present invention. Furthermore, the present invention discloses a method for manufacturing a device, which includes a step of obtaining a circuit board by the circuit board manufacturing method and a step of connecting the circuit board to a control mechanism that controls the circuit board. Furthermore, 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, it is possible to inexpensively manufacture polarizing plates with low reflection and absorption and large screen sizes (e.g., over 55 inches or 60 inches). That is, the present invention discloses a method for manufacturing a polarizing plate that includes the imprint pattern manufacturing method of the present invention, and a method for manufacturing a device that includes the polarizing plate. For example, the polarizing plates described in JP 2015-132825 A and WO 2011 / 132649 A can be manufactured. Note that 1 inch is 25.4 mm.

[0084] The pattern (cured product pattern) produced by the imprint pattern production method of the present invention is also useful as an etching resist (lithography mask). That is, the present invention discloses a device production method that includes the imprint pattern production method of the present invention and uses the obtained cured product pattern as an etching resist. When the cured product pattern is used as an etching resist, an embodiment is that a pattern (cured product pattern) is first formed on a support by applying the imprint pattern production method of the present invention, and then the support is etched using the obtained cured product pattern as an etching mask. By etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF4 in the case of dry etching, a pattern conforming to the shape of the desired cured product pattern can be formed on the support.

[0085] Furthermore, a pattern (cured product pattern) produced by the method for producing an imprint pattern of the present invention can also be preferably used for producing recording media such as magnetic disks, light-receiving elements such as solid-state imaging elements, light-emitting elements such as LEDs (light emitting diodes) and organic EL (organic electroluminescence), optical devices such as liquid crystal displays (LCDs), optical components such as diffraction gratings, relief holograms, optical waveguides, optical filters, and microlens arrays, members for flat panel displays such as thin-film transistors, organic transistors, color filters, anti-reflection films, polarizing plates, polarizing elements, optical films, and pillars, nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and guide patterns for fine pattern formation using the self-assembly of block copolymers (directed self-assembly, DSA), and the like. That is, the present invention discloses a method for manufacturing these devices, which includes a method for manufacturing an imprint pattern of the present invention.

[0086] <Adhesion layer-forming composition> As described above, by providing an adhesion layer between the support and the imprint pattern-forming composition, effects such as improved adhesion between the support and the imprint pattern-forming composition layer can be obtained. In the present invention, the adhesion layer is obtained by applying the adhesion layer-forming composition to the support using the same method as for the imprint pattern-forming composition, and then curing the composition. Each component of the adhesion layer-forming composition will be described below.

[0087] The composition for forming the adhesion layer contains a curable component. The curable component is a component that constitutes the adhesion layer, and may be either a high molecular weight component (for example, a molecular weight of more than 1000) or a low molecular weight component (for example, a molecular weight of less than 1000). Specific examples include resins and crosslinking agents. These may each be used alone or in combination of two or more.

[0088] The total content of the curable components in the adhesive layer-forming composition is not particularly limited, but is preferably 50% by mass or more of the total solid content, more preferably 70% by mass or more of the total solid content, and even more preferably 80% by mass or more of the total solid content. The upper limit is not particularly limited, but is preferably 99.9% by mass or less.

[0089] The concentration of the curable component in the composition for forming an adhesion layer (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.

[0090] 〔resin〕 The resin in the adhesive layer-forming composition can be a wide variety of known resins. 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.

[0091] The presence of a radical polymerizable group allows for an adhesive layer with excellent strength to be obtained. Furthermore, the presence of a polar group improves adhesion to the support. Furthermore, when a crosslinking agent is added, the crosslinked structure formed after curing becomes stronger, thereby improving the strength of the adhesive layer obtained.

[0092] The radical polymerizable group preferably contains an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a (meth)acryloyl group (preferably a (meth)acryloyloxy group or a (meth)acryloylamino group), a vinyl group, a vinyloxy group, an allyl group, a methylallyl group, a propenyl group, a butenyl group, a vinylphenyl group, and a cyclohexenyl group. Of these, a (meth)acryloyl group or a vinyl group is preferred, a (meth)acryloyl group is more preferred, and a (meth)acryloyloxy group is even more preferred. The ethylenically unsaturated bond-containing group defined here is referred to as Et.

[0093] Furthermore, the polar group is preferably at least one of an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an acyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an alkoxycarbonylamino group, a sulfonamide group, a phosphate group, a carboxy group, and a hydroxy group, more preferably at least one of an alcoholic hydroxy group, a phenolic hydroxy group, and a carboxy group, and even more preferably an alcoholic hydroxy group or a carboxy group. The polar group defined here is referred to as a polar group Po. The polar group is preferably a nonionic group.

[0094] The resin in the adhesive layer-forming composition may further contain a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group, and the epoxy group is preferred. The cyclic ether group defined here is referred to as a cyclic ether group Cyt.

[0095] Examples of the resin include (meth)acrylic resin, vinyl resin, novolac resin, phenol resin, melamine resin, urea resin, epoxy resin, and polyimide resin, and it is preferably at least one of (meth)acrylic resin, vinyl resin, and novolac resin.

[0096] The weight average molecular weight of the resin is preferably at least 4000, more preferably at least 6000, and even more preferably at least 8000. The upper limit is preferably at most 1,000,000, and may be at most 500,000.

[0097] The resin preferably has at least one structural unit represented by the following formulas (1) to (3).

[0098] [ka]

[0099] In the formula, R 1 and R 2 are each independently a hydrogen atom or a methyl group. 21 and R 3 are each independently a substituent. 1 , L 2 and L 3 are each independently a single bond or a linking group. n2 is an integer of 0 to 4. n3 is an integer of 0 to 3. Q 1 is an ethylenically unsaturated bond-containing group or a cyclic ether group. 2 is an ethylenically unsaturated bond-containing group, a cyclic ether group or a polar group.

[0100] R 1 and R 2 is preferably a methyl group.

[0101] R 21 and R 3 are each independently preferably the above-mentioned substituent T.

[0102] R 21When there are a plurality of groups, they may be linked together to form a cyclic structure. In this specification, the term "linked" means not only a mode in which they are bonded together and are continuous, but also a mode in which they are condensed (fused ring) by losing some atoms. Unless otherwise specified, the linked cyclic structure may contain an oxygen atom, a sulfur atom, or a nitrogen atom (amino group). Examples of the cyclic structure that can be formed include an aliphatic hydrocarbon ring (examples of which are hereinafter referred to as ring Cf) (e.g., cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc.), an aromatic hydrocarbon ring (examples of which are hereinafter referred to as ring Cr) (e.g., benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), a nitrogen-containing heterocycle (examples of which are hereinafter referred to as ring Cn) (e.g., pyrrole ring, imidazole ring, pyrrole ring, etc.), and the like. Examples of heterocyclic rings include a pyrazole ring, a pyridine ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring), oxygen-containing heterocyclic rings (examples of which are hereinafter referred to as Ring Co) (e.g., a furan ring, a pyran ring, an oxirane ring, an oxetane ring, a tetrahydrofuran ring, a tetrahydropyran ring, and a dioxane ring), and sulfur-containing heterocyclic rings (examples of which are hereinafter referred to as Ring Cs) (e.g., a thiophene ring, a thiirane ring, a thietane ring, a tetrahydrothiophene ring, and a tetrahydrothiopyran ring).

[0103] R 3 When there are a plurality of rings, they may be linked together to form a cyclic structure, such as a Cf ring, a Cr ring, a Cn ring, a Co ring, or a Cs ring.

[0104] L 1 , L 2 , L 3are each preferably independently a single bond or a linking group L described below. Among these, a single bond, or an alkylene group or (oligo)alkyleneoxy group defined by the linking group L is preferred, with an alkylene group being more preferred. The linking group L preferably has a polar group Po as a substituent. Also preferred is an embodiment in which the alkylene group has a hydroxy group as a substituent. In this specification, "(oligo)alkyleneoxy group" refers to a divalent linking group having one or more "alkyleneoxy" structural units. The number of carbon atoms in the alkylene chain in each structural unit may be the same or different for each structural unit.

[0105] n2 is preferably 0 or 1, and more preferably 0. n3 is preferably 0 or 1, and more preferably 0.

[0106] Q 1 is preferably an ethylenically unsaturated bond-containing group Et.

[0107] Q 2 is preferably a polar group, and more preferably an alkyl group having an alcoholic hydroxy group.

[0108] The above resin may further contain at least one of the following structural units (11), (21), and (31). In particular, in the resin included in the present invention, the structural unit (11) is preferably combined with the structural unit (1), the structural unit (21) is preferably combined with the structural unit (2), and the structural unit (31) is preferably combined with the structural unit (3).

[0109] [ka]

[0110] In the formula, R 11 and R 22 are each independently a hydrogen atom or a methyl group. 17 is a substituent. 27 is a substituent. n21 is an integer of 0 to 5. R 31is a substituent, and n31 is an integer of 0 to 3.

[0111] R 11 and R 22 is preferably a methyl group.

[0112] R 17 R is preferably a group containing a polar group or a group containing a cyclic ether group. 17 When R is a group containing a polar group, it is preferably a group containing the polar group Po described above, and more preferably the polar group Po described above or a substituent T substituted with the polar group Po described above. 17 When is a group containing a cyclic ether group, it is preferably a group containing the above-mentioned cyclic ether group Cyt, and more preferably a substituent T substituted with the above-mentioned cyclic ether group Cyt.

[0113] R 27 is a substituent, and R 27 At least one of the substituents is preferably a polar group. The substituent is preferably the substituent T. n21 is preferably 0 or 1, more preferably 0. R 27 When there are a plurality of rings, they may be linked together to form a cyclic structure. Examples of the cyclic structure that may be formed include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.

[0114] R 31 is preferably a substituent T. n31 is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. R 31 When there are a plurality of rings, they may be linked together to form a cyclic structure. Examples of the cyclic structure that may be formed include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.

[0115] Examples of the linking group L include an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), an (oligo)alkyleneoxy group (the number of carbon atoms in the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30 carbon atoms), an arylene group (preferably having 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, -NR N -, and linking groups resulting from combinations thereof. The alkylene group, alkenylene group, and alkyleneoxy group may have the above-mentioned substituent T. For example, the alkylene group may have a hydroxy group.

[0116] 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 located along the shortest path among the atomic groups involved in the linking. For example, in the case of -CH2-(C=O)-O-, the linking chain length is 3.

[0117] The alkylene group, alkenylene group, and (oligo)alkyleneoxy group defined by the linking group L may be chain or cyclic, and may be straight-chain or branched.

[0118] The atoms constituting the linking group L preferably contain carbon atoms and hydrogen atoms, and optionally heteroatoms (at least one selected from oxygen atoms, nitrogen atoms, sulfur atoms, etc.). 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 depending on 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 atoms, nitrogen atoms, and sulfur atoms, independently.

[0119] The resins may be synthesized by conventional methods. For example, a resin having a structural unit of formula (1) can be appropriately synthesized by a known method related to the addition polymerization of olefins. A resin having a structural unit of formula (2) can be appropriately synthesized by a known method related to the addition polymerization of styrene. A resin having a structural unit of formula (3) can be appropriately synthesized by a known method related to the synthesis of phenolic resins.

[0120] The above resins may be used alone or in combination.

[0121] In addition to the above, the resin used as the curable component may be any of those described in paragraphs 0016 to 0079 of WO 2016 / 152600, paragraphs 0025 to 0078 of WO 2016 / 148095, paragraphs 0015 to 0077 of WO 2016 / 031879, and paragraphs 0015 to 0057 of WO 2016 / 027843, the contents of which are incorporated herein by reference.

[0122] [Crosslinking agent] The crosslinking agent in the adhesive layer-forming composition is not particularly limited as long as it promotes curing by a crosslinking reaction. In the present invention, the crosslinking agent is preferably one that forms a crosslinked structure by reacting with a polar group of the resin. By using such a crosslinking agent, the resin is more strongly bonded, and a stronger film is obtained.

[0123] Examples of crosslinking agents include epoxy compounds (compounds having an epoxy group), oxetanyl compounds (compounds having an oxetanyl group), alkoxymethyl compounds (compounds having an alkoxymethyl group), methylol compounds (compounds having a methylol group), and blocked isocyanate compounds (compounds having a blocked isocyanate group), and alkoxymethyl compounds (compounds having an alkoxymethyl group) are preferred because they are capable of forming strong bonds at low temperatures.

[0124] [Other ingredients] The composition for forming an adhesion layer may contain other components in addition to the above components.

[0125] Specifically, the composition may contain one or more of a solvent, a thermal acid generator, an alkylene glycol compound, a polymerization initiator, a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, etc. The components described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537 can be used as the above components. The descriptions in the above publications can also be used for the content and other details.

[0126] -solvent- In the present invention, the composition for forming an adhesion layer preferably contains, in particular, a solvent (hereinafter also referred to as "adhesion layer solvent"). The solvent is, for example, preferably a compound that is liquid at 23°C and has a boiling point of 250°C or less. The composition for forming an adhesion layer preferably contains 99.0 mass% or more of the adhesion layer solvent, more preferably 99.2 mass% or more, and may contain 99.4 mass% or more. That is, the composition for forming an adhesion layer preferably has a total solids concentration of 1 mass% or less, more preferably 0.8 mass% or less, and even more preferably 0.6 mass% or less. The lower limit is preferably more than 0 mass%, more preferably 0.001 mass% or more, even more preferably 0.01 mass% or more, and even more preferably 0.1 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 pattern formability during etching tends to be improved.

[0127] The adhesive layer-forming composition may contain only one solvent, or may contain two or more solvents. When two or more solvents are contained, the total amount thereof is preferably in the above range.

[0128] 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. By setting the boiling point within the above range, the solvent can be easily removed from the adhesion layer, which is preferable.

[0129] The solvent for the adhesive layer is preferably an organic solvent. The solvent preferably has one or more of an ester group, a carbonyl group, a hydroxy group, and an ether group. Among them, it is preferable to use an aprotic polar solvent.

[0130] Among these, preferred solvents for the adhesion layer include alkoxy alcohols, propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, lactate esters, acetate esters, alkoxypropionate esters, chain ketones, cyclic ketones, lactones, and alkylene carbonates, with propylene glycol monoalkyl ethers and lactones being particularly preferred.

[0131] <Liquid film forming composition> 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 radically polymerizable compound that is liquid at 23°C and 1 atmosphere. In the present invention, the liquid film is obtained by applying the liquid film-forming composition to a support using the same method as for the imprint pattern-forming composition, and then drying the composition. Forming such a liquid film has the effect of further improving the adhesion between the support and the imprint pattern-forming composition, and also improving the wettability of the imprint pattern-forming composition on the support. The liquid film-forming composition will be described below.

[0132] 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 even more preferably 100 mPa·s or less. The lower limit of the viscosity is not particularly limited, but can be, for example, 1 mPa·s or more. The viscosity is measured according to the following method.

[0133] Viscosity is measured using a Toki Sangyo Co., Ltd. E-type rotational viscometer RE85L with a standard cone rotor (1°34' x R24) and the sample cup is temperature-controlled at 23°C. The unit is mPa·s. Other measurement details comply with JIS Z 8803:2011. Two samples are prepared for each level, and each is measured three times. The arithmetic mean of a total of six measurements is used as the evaluation value.

[0134] [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 atmosphere.

[0135] The viscosity of the 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, more preferably 11 mPa·s or more. The upper limit is preferably 1,000 mPa·s or less, more preferably 600 mPa·s or less.

[0136] The radical polymerizable compound A may be a monofunctional radical polymerizable compound having only one radical polymerizable group per molecule, or a polyfunctional radical polymerizable compound having two or more radical polymerizable groups per molecule. A monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound may be used in combination. In particular, for the purpose of suppressing pattern collapse, the radical polymerizable compound A contained in the liquid film forming composition preferably contains a polyfunctional radical polymerizable compound, more preferably contains a radical polymerizable compound having 2 to 5 radical polymerizable groups per molecule, even more preferably contains a radical polymerizable compound having 2 to 4 radical polymerizable groups per molecule, and particularly preferably contains a radical polymerizable compound having two radical polymerizable groups per molecule.

[0137] The radical polymerizable compound A preferably contains at least one of an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms) and an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 6 carbon atoms), and more preferably contains an aromatic ring. The aromatic ring is preferably a benzene ring. The molecular weight of the radical polymerizable compound A is preferably 100 to 900.

[0138] The radically polymerizable group contained in the radically polymerizable compound A includes ethylenically unsaturated bond-containing groups such as a vinyl group, an allyl group, and a (meth)acryloyl group, and is preferably a (meth)acryloyl group.

[0139] The radical polymerizable compound A is also preferably a compound represented by the following formula (I-1).

[0140] [ka]

[0141] L 20 is a (1+q2)-valent linking group, and examples thereof include a (1+q2)-valent group having an alkane structure (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), a group having an alkene structure (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), a group having an aryl structure (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), a group having a heteroaryl structure (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and even more preferably 1 to 10 carbon atoms; heteroatoms include nitrogen atoms, sulfur atoms, and oxygen atoms; 5-, 6-, and 7-membered rings are preferred), or a linking group containing a group combining these. Examples of groups combining two aryl groups include groups having a structure such as biphenyl, diphenylalkane, biphenylene, and indene. Examples of a combination of a group having a heteroaryl structure and a group having an aryl structure include groups having structures such as indole, benzimidazole, quinoxaline, and carbazole.

[0142] L 20 is preferably a linking group containing at least one selected from a group having an aryl structure and a group having a heteroaryl structure, and more preferably a linking group containing a group having an aryl structure.

[0143] R 21 and R 22 each independently represents a hydrogen atom or a methyl group.

[0144] L 21 and L 22 each independently represents a single bond or the above linking group L, and is preferably a single bond or an alkylene group.

[0145] L 20 and L 21 or L 22 may be bonded to form a ring with or without a linking group L. 20 , L 21 and L 22 may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different.

[0146] q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 1.

[0147] As the radical polymerizable compound A, the compounds described in paragraphs

[0017] to

[0024] and examples of JP-A No. 2014-090133, the compounds described in paragraphs

[0024] to

[0089] of JP-A No. 2015-009171, the compounds described in paragraphs

[0023] to

[0037] of JP-A No. 2015-070145, and the compounds described in paragraphs

[0012] to

[0039] of WO 2016 / 152597 can also be used.

[0148] The content of the 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, and 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.

[0149] The content of the 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. Only one type of radical polymerizable compound A may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0150] It is also preferable that the solid content of the liquid film-forming composition consists essentially of the radical polymerizable compound A. When the solid content of the liquid film-forming composition consists essentially of the radical polymerizable compound A, it means that the content of the radical polymerizable compound A in the solid content of the liquid film-forming composition is 99.9 mass % or more, more preferably 99.99 mass % or more, and even more preferably consists of the polymerizable compound A alone.

[0151] 〔solvent〕 The liquid film-forming composition preferably contains a solvent (hereinafter, sometimes referred to as "liquid film solvent"). Examples of the liquid film solvent include those described above in the section on the adhesive layer solvent, 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.

[0152] The boiling point of the solvent for the liquid membrane 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. By setting the boiling point within the above range, the solvent can be easily removed from the liquid membrane, which is preferable.

[0153] [Radical Polymerization Initiator] 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 photoradical polymerization initiator can be used. 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, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For details, see paragraphs

[0165] to

[0182] of JP 2016-027357 A, the contents of 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, and the like (all manufactured by BASF), and Omnirad 184, Omnirad TPO H, Omnirad 819, Omnirad 1173 (all manufactured by IGM Resins BV).

[0154] When the radical polymerization initiator is contained, it is preferably 0.1 to 10 mass %, more preferably 1 to 8 mass %, and even more preferably 2 to 5 mass % of the solid content of the liquid film forming composition. When two or more radical polymerization initiators are used, the total amount thereof is preferably within the above range.

[0155] [Other ingredients] In addition to the above, the liquid film forming composition may contain one or more of polymerization inhibitors, antioxidants, leveling agents, thickeners, surfactants, and the like. [Example]

[0156] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the examples, unless otherwise specified, "parts" and "%" are by mass, and the ambient temperature (room temperature) in each step is 23°C.

[0157] <Preparation of Composition for Imprint Pattern Formation> In each example and comparative example, various compounds listed in the table below were mixed, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a polymerization inhibitor to a concentration of 200 ppm by mass (0.02% by mass) relative to the total amount of polymerizable compounds. The content of each component other than the solvent was the content (parts by mass) listed in the table, and the solvent content was adjusted so that the solids concentration of each composition was the value listed in the "Solids concentration (% by mass)" column in the table. A "100" in the "Solvent" column indicates that the solvent was used alone. Furthermore, in each composition, components marked with "-" were not added. This mixture was filtered through a 0.02 μm nylon filter and a 0.001 μm UPE filter to prepare a composition for forming an imprint pattern or a comparative composition.

[0158] [Table 1]

[0159] [Table 2]

[0160] Details of each component listed in the table are as follows: [Polymerizable compound] A-1 to A-11: Compounds listed in Table 3 below. [Polymerization initiator (photopolymerization initiator)] ·B-1: Omnirad TPO H (manufactured by IGM Resins BV) ·B-2: Omnirad TPO L (manufactured by IGM Resins BV) ·B-3: Omnirad 369E (manufactured by IGM Resins BV) ·B-4: Omnirad 379EG (manufactured by IGM Resins BV) ·B-5: Omnirad 1173 (manufactured by IGM Resins BV) ·B-6: Omnirad 184 (manufactured by IGM Resins BV) B-7: Irgacure OXE 02 (BASF) B-8: Irgacure OXE 01 (BASF) The structure of each photopolymerization initiator is as shown in Table 4 below. Here, B-1, B-2 and Z-1, B-3 and B-4, B-5, B-6 and Z-2, and B-7 and B-8 are in a relationship of derivatives with each other. [Release agent] C-1: Compound with the following structure C-2: Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) C-3: Brij35 (Kishida Chemical Co., Ltd.) [ka] 〔solvent〕 ·D-1:propyleneglycol monomethyl ether acetate(PGMEA) [Others (other additives)] Z-1 to Z-2: Compounds listed in Table 5 below

[0161] [Table 3]

[0162] [Synthesis of A-1 (Silicone-Acrylate-Containing Resin 1)] Silicone resin X-40-9225 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) (10 parts), 2-hydroxyethyl acrylate (58.1 parts), and paratoluenesulfonic acid monohydrate (0.034 parts) were mixed, and the mixture was heated to 120°C. The mixture was stirred for 3 hours while distilling off the methanol produced by the condensation reaction, to allow the reaction to proceed, yielding 48 parts of A-1. A-2 to A-6 were synthesized in the same manner as A-1, except that the raw materials were changed as appropriate.

[0163] [Table 4]

[0164] [Table 5]

[0165] [Formation of underlayer film (adhesion layer)] In each of the examples and comparative examples, the composition for forming an adhesion layer described in Example 6 of JP 2014-024322 A was spin-coated onto a silicon wafer and heated for 1 minute using a hot plate at 250°C to form a 5 nm thick underlayer film (adhesion layer).

[0166] [Evaluation of coating film aging defects] The composition for imprint pattern formation was spin-coated onto a silicon wafer (silicon substrate) and heated using a hot plate at 80°C to form a coating film of the composition for imprint pattern formation on the silicon wafer. The thickness of the coating film was the thickness (µm) shown in the "Film Thickness" column in Table 1 or Table 2. The silicon wafer on which the coating film had been formed was left to stand in air for 24 hours in a clean room of Class 100, 23°C, and 50% humidity, and then observed with an optical microscope to count the number of defects with a maximum diameter of 100 µm or more. 2 The number of defects per film was calculated and evaluated according to the following criteria: The evaluation results are shown in the "Film Stability" column in the table. -Evaluation criteria- A: No defects were found in the coating. B: Density of defects in the coating is 1 / cm 2 It was as follows. C: Density of defects in the coating is 1 / cm 2 More than 5 pieces / cm 2 It was less than. D: Density of defects in the coating is 5 / cm 2 That was all.

[0167] From the above results, it can be seen that when a coating film is formed using the composition for imprint pattern formation of the present invention, the resulting coating film is less likely to develop defects even after 24 hours have passed. The composition according to Comparative Example 1 contains only one type of polymerization initiator and does not contain any derivatives thereof. In this embodiment, it is clear that defects occur in the coating film after 24 hours. The composition of Comparative Example 2 contains two polymerization initiators, but one of them is not a derivative of the other. Furthermore, the composition of Comparative Example 2 does not fall into any of the following categories: a composition containing two or more oxime compounds, a composition containing two or more acylphosphine compounds, or a composition containing two or more alkylphenone compounds. In these cases, defects were observed in the coating film after 24 hours.

[0168] In addition, an adhesion layer was formed on a silicon wafer using an adhesion layer-forming composition by the same method as the adhesion layer formation method described in the evaluation of coating film aging defects. A line and space structure, a contact hole structure, a dual damascene structure, and a staircase structure were formed on the adhesion layer of this silicon wafer with this adhesion layer using the imprint pattern-forming composition of each Example. Then, using this pattern as an etching mask, the silicon wafer was dry-etched, and semiconductor devices were fabricated using the silicon wafers. There were no performance issues with any of the semiconductor devices. Furthermore, using the above-mentioned adhesion layer-forming composition and the imprint pattern-forming composition of each Example, semiconductor devices were fabricated on substrates having an SOC (spin-on carbon) layer using the same procedure as above. There were also no performance issues with these semiconductor devices.

Claims

1. polymerizable compound, a polymerization initiator, and A derivative of the polymerization initiator is included, the total content of the polymerization initiator and the derivative is 0.1 to 10.0 parts by mass, relative to 100 parts by mass of the total solid content of the composition for imprint pattern formation; It is one of the embodiments represented by (1A) to (1C) below. A composition for forming an imprint pattern. (1A) One of the polymerization initiator and the derivative is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and the other is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. (1B) Of the above polymerization initiator and the above derivative, one is 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and the other is 2(dimethylamino)2(4-methylbenzyl)1(4-morpholinophenyl)butan-1-one. (1C) One of the polymerization initiator and the derivative is 2-hydroxy-2-methylpropiophenone, and the other is 1-hydroxycyclohexyl phenyl ketone.

2. 2. The composition for imprint pattern formation according to claim 1, wherein the content of the derivative is 1 to 10,000 parts by mass, relative to 100 parts by mass of the polymerization initiator.

3. The composition for imprint pattern formation according to claim 1 , wherein the polymerization initiator is a photopolymerization initiator.

4. The composition for imprint pattern formation according to any one of claims 1 to 3, wherein the polymerization initiator and the derivative are both acylphosphine oxide-based polymerization initiators, or both are alkylphenone-based polymerization initiators.

5. The composition for imprint pattern formation according to any one of claims 1 to 4, wherein one of the polymerization initiator and the derivative is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and the other is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate.

6. The composition for imprint pattern formation according to any one of claims 1 to 4, wherein one of the polymerization initiator and the derivative is 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and the other is 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one.

7. 5. The composition for imprint pattern formation according to claim 1, wherein one of the polymerization initiator and the derivative is 2-hydroxy-2-methylpropiophenone, and the other is 1-hydroxycyclohexyl phenyl ketone.

8. a polymerizable compound, and Contains a polymerization initiator, the polymerization initiator contains two or more oxime compounds, two or more acylphosphine compounds, or two or more alkylphenone compounds; the total content of the polymerization initiators is 0.1 to 10% by mass based on the total solid content of the composition; It is one of the embodiments represented by the following (2A) to (2C). A composition for forming an imprint pattern. (2A) The polymerization initiator includes diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate. (2B) The polymerization initiator includes 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone and 2(dimethylamino)2(4-methylbenzyl)1(4-morpholinophenyl)butan-1-one. (2C) The polymerization initiator contains 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone.

9. The composition for imprint pattern formation according to any one of claims 1 to 8, further comprising a release agent.

10. 10. The composition for imprint pattern formation according to claim 1, further comprising a solvent, the content of the solvent being 90.0 to 99.0 mass % relative to the total mass of the composition for imprint pattern formation.

11. A cured product obtained by curing the composition for imprint pattern formation according to any one of claims 1 to 10.

12. an applying step of applying the composition for imprint pattern formation according to any one of claims 1 to 10 to a member to which the composition is to be applied, the member being selected from the group consisting of a support and a mold; a contacting step of bringing a member, which is not selected as the application member from the group consisting of the support and the mold, into contact with the composition for imprint pattern formation as a contact member; a curing step of converting the imprint pattern-forming composition into a cured product; and a peeling step of peeling the mold from the cured product, A method for producing an imprint pattern.

13. The method for producing an imprint pattern according to claim 12 , wherein the support is a member having an adhesive layer on the surface on which the imprint pattern forming composition is applied.

14. A method for manufacturing a device, comprising the method for manufacturing an imprint pattern according to claim 12 or 13.

15. A device comprising the cured product of claim 11.

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