Material kit, curable composition, film forming method, and article manufacturing method

Abstract

To provide a novel technique regarding a material kit.SOLUTION: A material kit contains a curable composition and a layer forming composition for forming an adhesion layer which adheres the substrate and the curable composition, where the curable composition contains a polymerizable compound (a1), photoinitiator (b1) and solvent (d1), the viscosity of the curable composition at 23°C and 1 atmosphere is 1.3 mPa s or more and 60 mPa s or less, the content of the solvent (d1) for the total volume of the polymerizable compound (a1), the photoinitiator (b1) and the solvent (d1) is 5 vol.% or more and 95 vol.% or less, the boiling point of the solvent (d1) is less than 250°C at 1 atmosphere, the contact angle of the curable composition to the adhesion layer is 1.8[°] or less, and the contact angle of a composition in the state where the solvent (d1) is removed from the curable composition to the adhesion layer is 11[°] or more and 19[°] or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a material kit, a curable composition, a film-forming method, and a method for producing an article. [Background technology]

[0002] In semiconductor devices, MEMS, and the like, there is an increasing demand for miniaturization, and imprinting technology (photoimprinting technology) is attracting attention as a microfabrication technology. In imprinting technology, a mold having a fine concave-convex pattern formed on its surface is brought into contact with a curable composition supplied (applied) onto a substrate, and the curable composition is cured in this state. In this way, the mold pattern is transferred to a cured film of the curable composition, and a pattern is formed on the substrate. With imprinting technology, it is possible to form fine patterns (structures) on the order of several nanometers on a substrate.

[0003] An example of a pattern formation method using imprint technology will be described. First, a liquid curable material is discretely dropped (placed) in a pattern formation region on a substrate. The droplets of the curable composition placed in the pattern formation region spread across the substrate. This phenomenon is called press spreading. Next, a mold is brought into contact with (pressed against) the curable composition on the substrate. As a result, the droplets of the curable composition spread throughout the gap between the substrate and the mold due to capillary action. This phenomenon is called spreading. Furthermore, the curable composition fills the recesses that form the pattern of the mold due to capillary action. This phenomenon is called filling. The time required for spreading and filling to be completed is called filling time. Once filling of the curable composition is complete, the curable composition is irradiated with light to cure the curable composition. Then, the mold is separated from the cured curable composition on the substrate. By performing these steps, the pattern of the mold is transferred to the curable composition on the substrate, forming a pattern of the curable composition. Here, the pattern of the curable composition formed on the substrate includes a residual film. The residual film is a cured film remaining between the recessed portions (protruding portions of the mold pattern) of the cured film of the curable composition and the substrate.

[0004] Furthermore, in the photolithography process for manufacturing semiconductor devices, it is also necessary to planarize the substrate. For example, in extreme ultraviolet (EUV) exposure, a photolithography technology that has attracted attention in recent years, the depth of focus at which a projected image is formed becomes shallower as features become finer. Therefore, the unevenness of the surface of the substrate onto which the curable composition is applied must be kept to a few tens of nanometers or less. In imprinting technology, a level of flatness similar to that of EUV is also required to improve the filling ability and line width accuracy of the curable composition. A known planarization technique involves discretely dispensing droplets of a curable composition onto a substrate with unevenness in an amount corresponding to the unevenness, and then curing the curable composition while the substrate is in contact with a mold having a flat surface, thereby obtaining a flat surface.

[0005] In pattern formation methods and planarization techniques that utilize imprint technology, droplets of the curable composition dispensed onto a substrate are brought into contact with a mold without mutual contact, which inevitably results in air bubbles being trapped between the mold and the curable composition on the substrate. Such air bubbles take a long time to diffuse and disappear, which is one of the factors that reduces productivity (throughput). Therefore, a technique has been proposed in which droplets of the curable composition are bonded together before the curable composition on the substrate is brought into contact with the mold (see Patent Document 1).

[0006] However, with the technology disclosed in Patent Document 1, droplets of the curable composition dispensed onto the substrate spread so rapidly that they merge with each other, which can result in the curable composition spilling out of the desired region (designed liquid film region). The length of the curable composition spilling out of the desired region is referred to as the "spill amount." The spilled curable composition can erode adjacent imprint regions or adhere to the sidewalls of the mold, resulting in undesirable conditions.

[0007] In order to prevent overflow, Patent Document 2 discloses a technique for suppressing excessive spreading of the liquid film by utilizing the pinning effect. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-188736 [Patent Document 2] Special Publication No. 2010-530641 Summary of the Invention [Problem to be solved by the invention]

[0009] The inventors of the present invention have discovered a problem in that even if droplets combine to form a liquid film, the film may subsequently shrink. When the liquid film shrinks, it can cause edge unfilling defects, where the curable composition does not reach the edge of the mold. Patent Document 2 discloses a technology that utilizes the pinning effect to prevent overflow, but does not mention the shrinkage of the liquid film.

[0010] The present invention has been made in view of the above problems in the prior art, and has as its exemplary object to provide a new technique relating to, for example, a material kit. [Means for solving the problem]

[0011] In order to achieve the above object, one aspect of the present invention provides a material kit comprising a curable composition and a layer-forming composition for forming an adhesion layer that adheres a substrate and the curable composition, wherein the curable composition comprises a polymerizable compound (a1), a photopolymerization initiator (b1), and a solvent (d1), and the viscosity of the curable composition at 23°C and 1 atmosphere is 1.3 mPa·s or more and 60 mPa·s or less, the content of the solvent (d1) relative to the total volume of the polymerizable compound (a1), the photopolymerization initiator (b1), and the solvent (d1) is 5 vol% or more and 95 vol% or less, the boiling point of the solvent (d1) is less than 250°C at 1 atmosphere, the contact angle of the curable composition with the adhesion layer is 1.8° or less, and the contact angle of a composition in a state in which the solvent (d1) has been removed from the curable composition with the adhesion layer is 11° or more and 19° or less.

[0012] Further objects and other aspects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings. [Effects of the Invention]

[0013] According to the present invention, for example, a new technique relating to a material kit and a curable composition can be provided. [Brief explanation of the drawings]

[0014] [Figure 1] 1A to 1C are diagrams for explaining a pattern forming method (film forming method). [Figure 2] 1A to 1C are diagrams for explaining a pattern formation method (film formation method) by reverse imprinting. [Figure 3] FIG. 10 is a diagram illustrating the flow behavior of droplets of the curable composition during a waiting step. [Figure 4] FIG. 10 is a diagram showing a comparison between the prior art and the embodiment in terms of gas entrapment occurring during the contacting process. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments do not limit the invention according to the claims. Although multiple features are described in the embodiments, not all of these multiple features are necessarily essential to the invention, and multiple features may be combined arbitrarily. Furthermore, in the accompanying drawings, the same reference numerals are used to designate the same or similar components, and redundant explanations will be omitted.

[0016] In providing a new technology related to a film formation method, the present inventors have discovered physical property conditions under which droplets of a curable composition discretely dropped (disposed) on a substrate combine to form a continuous liquid film, and the liquid film does not spread too much or shrink. Hereinafter, a material kit according to an embodiment will be described, which includes a curable composition and a layer-forming composition for forming an adhesion layer that adheres the substrate and the curable composition.

[0017] [Curable composition] The curable composition (A) in the present disclosure is a curable composition for inkjet printing, and is a composition containing at least component (a1) which is a polymerizable compound, component (b1) which is a photopolymerization initiator, and component (d1) which is a solvent.

[0018] In this specification, the term "cured film" refers to a film obtained by polymerizing and curing a curable composition on a substrate. The shape of the cured film is not particularly limited, and the surface may have a patterned shape. The cured film remaining between the recessed portions (protruding portions of the mold pattern) of the cured film of the curable composition and the substrate is referred to as the "residual film."

[0019] <Component (a1): Polymerizable compound> Component (a1) is a polymerizable compound. In this specification, the polymerizable compound is a compound that reacts with a polymerization factor (such as a radical) generated from a photopolymerization initiator (component (b1)) to form a film made of a polymer compound through a chain reaction (polymerization reaction).

[0020] Examples of such polymerizable compounds include radically polymerizable compounds. The polymerizable compound of component (a1) may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0021] Examples of the radically polymerizable compound include (meth)acrylic compounds, styrene compounds, vinyl compounds, allyl compounds, fumaric compounds, and maleyl compounds.

[0022] The (meth)acrylic compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or one methacryloyl group include, but are not limited to, the following: Phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO-modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-Tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy (meth)acrylate, PO-modified phenoxy (meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate t)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pliers (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, 1- or 2-naphthyl(meth)acrylate, 1- or 2-naphthylmethyl(meth)acrylate, 3- or 4-phenoxybenzyl(meth)acrylate, chinoabenzyl(meth)acrylate, naphthalenemethyl(meth)acrylate,

[0023] Examples of commercially available monofunctional (meth)acrylic compounds include, but are not limited to, the following: Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (all manufactured by Toagosei), MEDOL10, M IBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat #150, #155, #158, #19 0, #192, #193, #220, #2000, #2100, #2150 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A, POB-A, OPP-EA (all manufactured by Kyoeisha Chemical Industry Co., Ltd.), KAYARAD (registered trademark) TC110S, R-564, R-128H (all manufactured by Nippon Kayaku), NK Ester AMP-10G, AMP-20G, A-LEN-10 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (all manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Daiichi Kogyo Seiyaku), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kohjin), HRD-01 (all manufactured by Nippon Shokubai)

[0024] Furthermore, examples of polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 9-Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, o-, m-, or p-benzenedi(meth)acrylate, o-, m-, or p-xylylenedi(meth)acrylate

[0025] Examples of commercially available polyfunctional (meth)acrylic compounds include, but are not limited to, the following: Iupimer (registered trademark) UV SA1002, SA2007 (all manufactured by Mitsubishi Chemical), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (all manufactured by Osaka Organic Chemical Industry), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical), KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku), Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei), Lipoxy (registered trademark) VR-77, VR-60, VR-90 (all manufactured by Showa Polymer), Oxol EA-0200, Oxol EA-0300 (all manufactured by Osaka Gas Chemicals), SR295, SR355 (all manufactured by Sartomer)

[0026] In the above-mentioned compound group, (meth)acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto. (Meth)acryloyl group means acryloyl group or methacryloyl group having an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are bonded via an ethylene oxide group block structure. PO represents propylene oxide, and PO-modified compound B represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are bonded via a propylene oxide group block structure.

[0027] Specific examples of styrene-based compounds include, but are not limited to, the following: Alkylstyrenes such as styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and iodine Halogenated styrenes such as styrene; nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, divinylbiphenyl, and other compounds having a styryl group as a polymerizable functional group.

[0028] Specific examples of vinyl compounds include, but are not limited to, the following: Vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate, and acrylonitrile; conjugated diene monomers such as butadiene, isoprene, and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; vinyl esters of organic carboxylic acids and their derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, etc.), (meth)acrylonitrile, and other compounds having a vinyl group as a polymerizable functional group.

[0029] In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0030] Examples of acrylic compounds include, but are not limited to, the following: Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate

[0031] Examples of fumaric compounds include, but are not limited to: Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate

[0032] Examples of maleyl compounds include, but are not limited to, the following: Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate

[0033] Examples of other radical polymerizable compounds include, but are not limited to, the following: Dialkyl esters of itaconic acid and their derivatives (dimethyl itaconate, diethyl itaconate, diisopropyl itaconate, di-sec-butyl itaconate, diisobutyl itaconate, di-n-butyl itaconate, di-2-ethylhexyl itaconate, dibenzyl itaconate, etc.), N-vinylamide derivatives of organic carboxylic acids (N-methyl-N-vinylacetamide, etc.), maleimide and its derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.)

[0034] When component (a1) is composed of multiple types of compounds having one or more polymerizable functional groups, it preferably contains both a monofunctional polymerizable compound and a polyfunctional polymerizable compound. The proportion of the polyfunctional polymerizable compound in component (a1) is preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably 40% by weight or more. This is because the combination of a monofunctional polymerizable compound and a polyfunctional polymerizable compound can provide a cured film with an excellent balance of properties, such as high mechanical strength, high dry etching resistance, and high heat resistance.

[0035] In the film-forming method of the present disclosure, it takes several milliseconds to several hundred seconds for droplets of the curable composition (A) discretely arranged on the substrate to combine and form a substantially continuous liquid film, necessitating a waiting step, as described below. During the waiting step, the solvent (d1) must be evaporated while the polymerizable compound (a1) must not evaporate. Therefore, the boiling point of each of the one or more polymerizable compounds contained in the polymerizable compound (a1) under normal pressure is preferably 250°C or higher, more preferably 300°C or higher, and even more preferably 350°C or higher. Furthermore, in order to achieve high dry etching resistance and high heat resistance in a cured film of the curable composition (A), it is preferable that the curable composition (A) contains at least a compound having a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Note that normal pressure refers to 1 atmosphere (atmospheric pressure).

[0036] The boiling point of the polymerizable compound (a1) generally correlates with the molecular weight. Therefore, the molecular weight of each of the one or more polymerizable compounds contained in the polymerizable compound (a1) is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more. However, even if the molecular weight is 200 or less, as long as the boiling point is 250°C or higher, it can be preferably used as the polymerizable compound (a1) in the present disclosure. Thus, it is preferable that the boiling point under normal pressure of each of the one or more polymerizable compounds contained in the polymerizable compound (a1) is 250°C or higher.

[0037] The vapor pressure of the polymerizable compound (component (a1)) at 80°C is preferably 0.001 mmHg or less. When the polymerizable compound (a1) contains one or more polymerizable compounds, it is preferable that each of the one or more polymerizable compounds has a vapor pressure of 0.001 mmHg or less at 80°C. This is because, although it is preferable to heat the curable composition to accelerate the volatilization of the solvent (component (d1)) described below, the volatilization of the polymerizable compound (a1) is suppressed during such heating.

[0038] The boiling points and vapor pressures of various organic compounds under normal pressure can be calculated using Hansen Solubility Parameters in Practice (HSPiP) 5th Edition 5.3.04 or the like.

[0039] <Oonishi parameters for component (a1)> Dry etching rate of organic compound V, total number of atoms in the organic compound N, total number of carbon atoms in the composition N C , and the total number of oxygen atoms in the composition N O is known to be related by the following formula (1). V∝N / (Nc-No) Equation (1) Here, N / (Nc-N0) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, U.S. Patent Application Publication No. 2020 / 0286740 discloses a technology for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP.

[0040] According to formula (1), it is suggested that the more oxygen atoms there are in the molecule of an organic compound, or the fewer aromatic ring structures or alicyclic structures there are in an organic compound, the larger the OP and the faster the dry etching rate.

[0041] In the curable composition (A) of the present disclosure, the OP of the component (a1) is 1.80 or more and 4.00 or less. The OP of the component (a1) is more preferably 2.00 or more and 3.50 or less, and particularly preferably 2.40 or more and 3.00 or less. By making the OP of the component (a1) 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. Furthermore, by making the OP of the component (a1) 1.80 or more, it becomes easy to remove the cured film of the curable composition (A) after processing the underlayer using the cured film of the curable composition (A). When the component (a1) is composed of multiple types of polymerizable compounds a1, a2, ..., a n When the component (a1) is composed of the polymerizable compounds, OP is calculated as a weighted average based on the molar fraction (molar fraction weighted average) as shown in the following formula (2). In this way, when the component (a1) contains one or more polymerizable compounds, the OP of the component (a1) is calculated as N / (N C -N O ) values ​​are calculated as the mole fraction weighted average.

number

[0042] In order to make the OP of component (a1) 1.80 or more and 4.00 or less, it is preferable to include, as at least component (a1), a compound (a1-1) having two or more cyclic structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0043] <Compound (a1-1): Polymerizable compound having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure> The polymerizable compound (a1) in the present disclosure may include a polymerizable compound (a1-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0044] The cyclic structure may be an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0045] The aromatic structure preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Specific examples of the aromatic ring include the following. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring

[0046] Among the aromatic rings described above, 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 ring or a bisphenyl ring.

[0047] The aromatic heterocyclic structure preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples of the aromatic heterocyclic ring include the following. Thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, quinolizine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring

[0048] The number of carbon atoms in the alicyclic structure is preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. The number of carbon atoms in the alicyclic structure is preferably 22 or less, more preferably 18 or less, even more preferably 6 or less, and even more preferably 5 or less. Specific examples thereof include the following. Cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, spirodecane ring, spirononane ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindane ring, bornane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring

[0049] Specific examples of the polymerizable compound (a1-1) having a boiling point of 250° C. or higher include, but are not limited to, the following: 3-phenoxybenzyl acrylate (mPhOBzA, OP 2.54, boiling point 367.4°C, vapor pressure at 80°C 0.0004mmHg, molecular weight 254.3), [ka] 1-naphthyl acrylate (NaA, OP 2.27, boiling point 317°C, vapor pressure at 80°C 0.0422mmHg, molecular weight 198), [ka] 2-phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2°C, vapor pressure at 80°C 0.0006mmHg, molecular weight 268.3), [ka] 1-Naphthylmethyl acrylate (Na1MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2), [ka] 2-Naphthylmethyl acrylate (Na2MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2), [ka] DPhPA (OP 2.38, boiling point 354.5°C, vapor pressure 0.0022mmHg at 80°C, molecular weight 266.3) shown in the formula below, [ka] PhBzA (OP 2.29, boiling point 350.4°C, vapor pressure 0.0022mmHg at 80°C, molecular weight 238.3) shown in the formula below, [ka] FLMA (OP2.20, boiling point 349.3℃, vapor pressure 0.0018mmHg at 80℃, molecular weight 250.3) shown in the following formula: [ka] ATMA (OP2.13, boiling point 414.9℃, vapor pressure 0.0001mmHg at 80℃, molecular weight 262.3) shown in the formula below, [ka] DNaMA (OP 2.00, boiling point 489.4°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 338.4) shown in the formula below, [ka] BPh44DA (OP 2.63, boiling point 444°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below, [ka] BPh43DA (OP 2.63, boiling point 439.5°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below, [ka] DPhEDA (OP2.63, boiling point 410℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.3) shown in the formula below, [ka] BPMDA (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4) shown in the following formula: [ka] Na13MDA (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3) shown in the formula below, [ka] The following formula (a1-1-1) (OP 2.40, boiling point 333.4℃, vapor pressure 0.0181mmHg at 80℃, molecular weight 199.2), [ka] The following formula (a1-1-2) (OP 2.40, boiling point 333.4℃, vapor pressure 0.0181mmHg at 80℃, molecular weight 199.2), [ka] The following formula (a1-1-3) (OP 1.86, boiling point 369.5℃, vapor pressure 0.0053mmHg at 80℃, molecular weight 193.3), [ka] The following formula (a1-1-4) (OP 2.85, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3), [ka] The following formula (a1-1-5) (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3), [ka] The following formula (a1-1-6) (OP 2.87, boiling point 421.0℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4), [ka] The following formula (a1-1-7) (OP 2.87, boiling point 465.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4), [ka] The following formula (a1-1-8) (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4), [ka] The following formula (a1-1-9) (OP 2.50, boiling point 433.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 320.3), [ka] The following formula (a1-1-10) (OP 2.64, boiling point 468.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 326.4), [ka] The following formula (a1-1-11) (OP 3.25, boiling point 553.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 358.4), [ka] The following formula (a1-1-12) (OP 2.63, boiling point 443.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.4), [ka] The following formula (a1-1-13) (OP 2.89, boiling point 509.3℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 406.4), [ka] The following formula (a1-1-14) (OP 2.63, boiling point 450.0℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.4), [ka] The following formula (a1-1-15) (OP 3.00, boiling point 476.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 366.4) [ka] The following formula (a1-1-16) (OP 2.68, boiling point 447.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4) [ka] The following formula (a1-1-17) (OP 2.36, boiling point 543.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 398.5), [ka] The following formula (a1-1-18) (OP 3.27, boiling point 526.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 396.4), [ka] The following formula (a1-1-19) (OP 2.71, boiling point 333.7℃, vapor pressure 0.0302mmHg at 80℃, molecular weight 244.3), [ka] The following formula (a1-1-20) (OP 2.73, boiling point 333.7℃, vapor pressure 0.0134mmHg at 80℃, molecular weight 258.3), [ka] The following formula (a-1-21) (OP 2.71, boiling point 319.2℃, vapor pressure 0.0566mmHg at 80℃, molecular weight 262.3), [ka] The following formula (a1-1-22) (OP 2.71, boiling point 336.9°C, vapor pressure 0.0055mmHg at 80°C, molecular weight 244.3): [ka] The following formula (a1-1-23) (OP 3.00, boiling point 370.9℃, vapor pressure 0.0021mmHg at 80℃, molecular weight 274.4), [ka] The following formula (a1-1-24) (OP 3.00, boiling point 376.4℃, vapor pressure 0.0005mmHg at 80℃, molecular weight 274.4), [ka] The following formula (a1-1-25) (OP 3.00, boiling point 379.4℃, vapor pressure 0.0002mmHg at 80℃, molecular weight 288.4), [ka] The following formula (a1-1-26) (OP 2.33, boiling point 360.8°C, vapor pressure at 80°C 0.0006mmHg, molecular weight 252.3), [ka] The following formula (a1-1-27) (OP 2.54, boiling point 371.5℃, vapor pressure 0.0003mmHg at 80℃, molecular weight 254.3), [ka] The following formula (a-1-28) (OP 2.57, boiling point 381.2℃, vapor pressure 0.0001mmHg at 80℃, molecular weight 268.3), [ka] The following formula (a1-1-29) (OP 2.57, boiling point 381.8℃, vapor pressure 0.0004mmHg at 80℃, molecular weight 268.3), [ka] The following formula (a1-1-30) (OP 2.50, boiling point 487.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 374.4), [ka] The following formula (a1-1-31) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3), [ka] The following formula (a1-1-32) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3), [ka] The following formula (a1-1-33) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3), [ka] The following formula (a1-1-34) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3), [ka] The following formula (a1-1-35) (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3), [ka]

[0050] <Compound (a1-2): Polymerizable compound containing at least Si atom> The polymerizable compound (a1) in the present disclosure may contain a polymerizable compound (a1-2) containing at least a Si atom. Furthermore, when the polymerizable compound (a1) contains the polymerizable compound (a1-2), the curable composition (A') from which the solvent (d1) has been removed preferably contains 10 wt % or more of Si atoms based on the total weight of the curable composition (A).

[0051] An example of the polymerizable compound (a1-2) containing at least a Si atom may be linear or branched. For example, cyclic siloxane compounds have the structures shown below. The polymerizable functional group in the group Q having a polymerizable functional group may be, for example, a radically polymerizable functional group. Specific examples of the radically polymerizable functional group include a (meth)acrylic group, a (meth)acrylamide group, a vinylbenzene group, an allyl ether group, a vinyl ether group, and a maleimide group. The group Q having a polymerizable functional group may be any of the groups having the polymerizable functional group described above. [ka]

[0052] Other examples of the polymerizable compound (a1-2) include a silsesquioxane skeleton as shown in the following chemical formula (I) and a silicone skeleton as shown in the following chemical formula (II): In chemical formula (I), m+n=8 (8≧m≧1), and R1 is a divalent organic group. In chemical formula (II), A, B, R2, and R3 are independently an alkyl group, cycloalkyl group, alkoxy group, phenyl group, or hydroxyl group having 1 to 6 carbon atoms, t is an integer of 1 to 3, and at least one of A and B is a polymerizable functional group. [ka] [ka]

[0053] Examples of the polymerizable functional group in the groups Q, A, and B having a polymerizable functional group include a radically polymerizable functional group. Specific examples of the radically polymerizable functional group include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0054] The silicon-containing (meth)acrylate compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylate compounds having one silicon-containing acryloyl group or methacryloyl group include, but are not limited to, the following: (2-acryloylethoxy)trimethylsilane, N-(3-acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, acryloxymethyltrimethoxysilane, (acryloxymethyl)phenethyltrimethoxysilane, acryloxymethyltrimethylsilane, (3-acryloxypropyl)dimethylmethoxysilane, (3-acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-acryloxypropyl)methyldichlorosilane, (3-acryloxypropyl)methyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)trichlorosilane, (3-acryloxypropyl)trimethoxysilane, (3-acryloxypropyl)tris(trimethylsiloxy)silane, acryloxytriisopropylsilane, acryloxytrimethylsilane, methacryloxymethyltrimethoxysilane, 0-(methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloylpropyltriisopropoxysilane, O-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyldimethylethoxysilane, (methacryloxymethyl)dimethylethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl silatrane, methacryloxypentamethyldisiloxane, (methacryloxymethyl)phenyldimethylsilane, methacryloxytrimethylsilane, methacryloxymethyltrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropyl pentamethyldisiloxane, 0-(methacryloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propylcarbamate, methacryloxymethyltris(trimethylsiloxy)silane, methacryloxyethoxytrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropyltris(vinyldimethylsiloxy)silane, methacryloxypropyltris(trimethylsiloxy)silane, 3-methacryloxypropyltriacetoxysilane, methacryloxypropylmethyldichlorosilane, methacryloxypropyltrichlorosilane, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, 3-methacryloxypropyldimethylchlorosilane, 0-methacryloxy(polyethyleneoxy)trimethylsilane, Poly(methacryloxypropylsilsesquioxane), Methacryloxypropylheptaisobutyl-T8-silsesquioxane, Methacryloxypropyltris(trimethylsiloxy)silane

[0055] Examples of commercially available silicon-containing monofunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200.A1, SIA0210.0, SIA0315.0, SIA0320.0 , SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481 .43, SIM6482.0, SIM6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM648 6.4, SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.48, SIM6481.5, SIM6 491.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, S IM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, SIM6486.65 (all manufactured by GELEST), TM-0701T, FM-0711, FM-0721, FM-0725 (all manufactured by JNC)

[0056] The silicon-containing (meth)acrylamide compound is a compound having one or more acrylamide groups or methacrylamide groups. Examples of monofunctional (meth)acrylamide compounds having one silicon-containing acrylamide group or methacrylamide group include, but are not limited to, the following: 3-Acrylamidepropyltrimethoxysilane, 3-Acrylamidepropyltris(trimethylsiloxy)silane

[0057] Examples of commercially available silicon-containing monofunctional (meth)acrylamide compounds include, but are not limited to, the following: SIA0146.0, SIA0150.0 (all manufactured by GELEST)

[0058] Furthermore, examples of polyfunctional (meth)acrylate compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: A linear polydimethylsiloxane modified at both ends with acryloxypropyl groups, a linear polydimethylsiloxane modified at both ends with methacryloxypropyl groups; a cyclic siloxane modified with a plurality of acryloxypropyl groups; a cyclic siloxane modified with multiple methacryloxypropyl groups; silsesquioxane modified with multiple acryloxypropyl groups; Silsesquioxane modified with multiple methacryloxypropyl groups

[0059] Examples of commercially available silicon-containing polyfunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (all manufactured by GELEST), FM-7711, FM-7721, FM-7725 (all manufactured by JNC), X-22-2445 (Shin-Etsu Chemical), AC-SQ TA-100, MAC-SQ TM-100, AC-SQSI-20, MAC-SQ SI-20 (all manufactured by Toagosei)

[0060] Also, for example, the following can be synthesized and / or obtained from "Ultraviolet curable branched siloxanes as low-k dielectric for imprint lithography" by Ogawa et al. Linear modified polydimethylsiloxane (MA-Si-12) with both ends modified with methacryloxypropyl groups, 8-membered ring siloxane (8-ring) modified with four methacryloxypropyl groups, 10-membered ring siloxane (10-ring) modified with five methacryloxypropyl groups

[0061] The blending ratio of component (a1) in the curable composition (A) is preferably 40% by weight to 99% by weight based on the total weight of component (a1), component (b1) (described below), and component (c1) (described below), i.e., the total weight of all components excluding solvent (d1). Furthermore, a blending ratio of 50% by weight to 95% by weight is more preferable, and a blending ratio of 60% by weight to 90% by weight is even more preferable. By making the blending ratio of component (a1) 40% by weight or more, the mechanical strength of the cured film of the curable composition is increased. Furthermore, by making the blending ratio of component (a1) 99% by weight or less, the blending ratios of components (b1) and (c1) can be increased, thereby achieving properties such as a fast photopolymerization rate. At least a portion of component (a1), which contains one or more polymerizable compounds, may be a polymer having a polymerizable functional group. Such a polymer preferably contains at least a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. For example, it is preferable to include at least one of the constitutional units represented by any of the following structures (1) to (6). [ka]

[0062] In the structures (1) to (6), the substituents R are each independently a substituent containing a partial structure containing an aromatic ring, and R 1is a hydrogen atom or a methyl group. In this specification, in the structural units represented by Structures (1) to (6), the portion other than R is the main chain of a specific polymer. The formula weight of the substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and even more preferably 150 or more. The upper limit of the formula weight of the substituent R is practically 500 or less.

[0063] The polymer having a polymerizable functional group is typically a compound with a weight-average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight-average molecular weight is not particularly limited, but is preferably 50,000 or less. By setting the weight-average molecular weight at or above the above-mentioned lower limit, the boiling point can be set to 250°C or higher, thereby further improving the mechanical properties after curing. Furthermore, by setting the weight-average molecular weight at or below the above-mentioned upper limit, the solubility in solvents is high, the viscosity is not too high, and the fluidity of discretely arranged droplets is maintained, thereby further improving the flatness of the liquid film surface. Note that, unless otherwise specified, the weight-average molecular weight (Mw) in this disclosure refers to that measured by gel permeation chromatography (GPC).

[0064] Specific examples of the polymerizable functional group possessed by the polymer include a (meth)acryloyl group, an epoxy group, an oxetane group, a methylol group, a methylol ether group, a vinyl ether group, etc. From the viewpoint of ease of polymerization, a (meth)acryloyl group is particularly preferred.

[0065] When a polymer having a polymerizable functional group is added as at least a part of component (a1), its content can be freely set as long as it falls within the viscosity specification described below. For example, it is preferably 0.1% by weight or more and 60% by weight or less, more preferably 1% by weight or more and 50% by weight or less, and even more preferably 10% by weight or more and 40% by weight or less, based on the total mass of all components excluding solvent (d1). By setting the content of the polymer having a polymerizable functional group to 0.1% by weight or more, it is possible to improve heat resistance, dry etching resistance, mechanical strength, and low volatility. Furthermore, by setting the content of the polymer having a polymerizable functional group to 60% by weight or less, it is possible to fall within the upper limit of the viscosity specification described below.

[0066] <Component (b1): Photopolymerization initiator> Component (b1) is a photopolymerization initiator. In this specification, a photopolymerization initiator is a compound that senses light of a specific wavelength and generates the above-mentioned polymerization factors (radicals). Specifically, a photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals when exposed to light (infrared rays, visible light, ultraviolet rays, far ultraviolet rays, charged particle rays such as X-rays and electron beams, or radiation). Component (b1) may be composed of only one type of photopolymerization initiator, or may be composed of multiple types of photopolymerization initiators.

[0067] Examples of the radical generator include, but are not limited to, the following: 2,4,5-Triarylimidazole dimers which may have a substituent, such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone Benzophenone derivatives such as 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, and 1,2-benz Quinones such as anthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl benzyl derivatives such as dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone;Acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one;

[0068] Examples of commercially available radical generators include, but are not limited to, the following: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark) TPO, LR8893, LR8970 (all manufactured by BASF), Ubecryl P36 (manufactured by UCB)

[0069] Of the above-mentioned radical generators, the component (b1) is preferably an acylphosphine oxide-based polymerization initiator. Among the above-mentioned radical generators, the acylphosphine oxide-based polymerization initiator is as follows: Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide

[0070] The blending ratio of component (b1) in the curable composition (A) is preferably 0.1% by weight to 50% by weight, based on the total weight of components (a1), (b1), and (c1) described below, i.e., the total weight of all components excluding solvent (d1). Furthermore, the blending ratio of component (b1) in the curable composition (A) is more preferably 0.1% by weight to 20% by weight, and even more preferably 1% by weight to 20% by weight, based on the total weight of all components excluding solvent (d1). By incorporating component (b1) in a ratio of 0.1% by weight or more, the curing rate of the composition can be increased, improving reaction efficiency. Furthermore, by incorporating component (b1) in a ratio of 50% by weight or less, a cured film with a certain level of mechanical strength can be obtained.

[0071] <Component (c1): Non-polymerizable compound> In addition to the above-described components (a1) and (b1), the curable composition (A) of the present disclosure may further contain a non-polymerizable compound as component (c1) depending on various purposes, as long as the effects of the present disclosure are not impaired. Examples of such component (c1) include compounds that do not have a polymerizable functional group such as a (meth)acryloyl group and that do not have the ability to sense light of a specific wavelength and generate the above-described polymerization factor (radical). Examples of non-polymerizable compounds include sensitizers, hydrogen donors, surfactants (c1), antioxidants, polymer components, and other additives. Component (c1) may contain multiple types of the above-described compounds.

[0072] The sensitizer is a compound that is added as needed for the purpose of accelerating the polymerization reaction and improving the reaction conversion rate. One type of sensitizer may be used alone, or two or more types may be used in combination.

[0073] Examples of sensitizers include sensitizing dyes. Sensitizing dyes are compounds that are excited by absorbing light of a specific wavelength and interact with the photopolymerization initiator, component (b1). Here, the interaction refers to energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator, component (b1). Specific examples of sensitizing dyes include, but are not limited to, the following: Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes

[0074] The hydrogen donor is a compound that reacts with the initiating radical generated from the photopolymerization initiator (component (b1)) or the radical at the polymer growth terminal to generate a radical with higher reactivity. When the photopolymerization initiator (component (b1)) is a photoradical generator, it is preferable to add a hydrogen donor.

[0075] Specific examples of such hydrogen donors include, but are not limited to, the following: Amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanolamine, and N-phenylglycine; mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionic acid esters.

[0076] The hydrogen donor may be used alone or in combination of two or more kinds. The hydrogen donor may also function as a sensitizer.

[0077] In the present disclosure, the contact angle of the curable composition (A) with the adhesive layer can be controlled to a desired value by adding the surfactant (c1). In particular, the fluorine-containing surfactant described below exerts a pinning effect at the three-phase interface between the substrate, the curable composition, and air, thereby increasing the contact angle.

[0078] The surfactant (c1) also functions as an internal mold release agent, reducing the interfacial bonding strength between the mold and the curable composition, i.e., reducing the mold release force in the mold release step described below. In this specification, "internal mold release" means that the surfactant is added to the curable composition before the curable composition placement step. Surfactants such as silicon-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants can be used as the surfactant (c1). However, in the present disclosure, there is a limit to the amount of surfactant (c1) added, as described below. The surfactant (c1) in the present disclosure is not polymerizable. One type of surfactant (c1) may be used alone, or two or more types may be mixed together.

[0079] Fluorine-based surfactants include the following: Polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols with perfluoroalkyl groups, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers

[0080] The fluorosurfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, etc. in part of its molecular structure (for example, a terminal group). For example, pentadecaethylene glycol mono 1H,1H,2H,2H-perfluorooctyl ether can be mentioned.

[0081] As the fluorine-based surfactant, commercially available products may be used. Examples of commercially available fluorine-based surfactants include the following: Megafac (registered trademark) F-444, TF-2066, TF-2067, TF-2068, abbreviated as DEO-15 (all manufactured by DIC), Fluorad FC-430, FC-431 (all manufactured by Sumitomo 3M), Surflon (registered trademark) S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all manufactured by Tochem Products), PF-636, PF-6320, PF-656, PF-6520 (all manufactured by OMNOVA Solutions), Unidyne (registered trademark) DS-401, DS-403, DS-451 (all manufactured by Daikin Industries), Ftergent (registered trademark) 250, 251, 222F, 208G (all manufactured by Neos)

[0082] The surfactant (c1) may also be a hydrocarbon surfactant. Examples of the hydrocarbon surfactant include alkyl alcohol polyalkylene oxide adducts and polyalkylene oxides in which alkylene oxides having 2 to 4 carbon atoms are added to alkyl alcohols having 1 to 50 carbon atoms.

[0083] Examples of alkyl alcohol polyalkylene oxide adducts include the following. Methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide / propylene oxide adduct

[0084] The terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group that can be produced simply by adding a polyalkylene oxide to an alkyl alcohol, and the hydroxyl group may be substituted with other substituents, such as polar functional groups such as a carboxyl group, an amino group, a pyridyl group, a thiol group, or a silanol group, or hydrophobic functional groups such as an alkyl group or an alkoxy group.

[0085] Examples of polyalkylene oxides include the following: Polyethylene glycol, polypropylene glycol, their mono- or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, mono- or didecyl ethers, monoadipate esters, monooleate esters, monostearate esters, monosuccinate esters

[0086] The alkyl alcohol polyalkylene oxide adduct may be a commercially available product. Examples of commercially available alkyl alcohol polyalkylene oxide adducts include the following: Polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), randomly polymerized polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R) manufactured by Aoki Oil & Fat Industries, polyoxyethylene methyl ether (Pluriol® A760E) manufactured by BASF, and polyoxyethylene alkyl ether (Emulgen series) manufactured by Kao.

[0087] Alternatively, commercially available polyalkylene oxides may be used, such as BASF's ethylene oxide-propylene oxide copolymer (Pluronic PE6400).

[0088] The surfactant (c1) may also be a silicone surfactant, such as those commercially available under the trade names SI-10 series (Takemoto Yushi Co., Ltd.), Megafac Paintad 31 (Dainippon Ink and Chemicals, Inc.), and KP-341 (Shin-Etsu Chemical Co., Ltd.).

[0089] The surfactant (c1) may also be a surfactant containing at least both a fluorine atom and a silicon atom. Examples of surfactants containing both a fluorine atom and a silicon atom include the following: Product names: X-70-090, X-70-091, X-70-092, X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), product names: Megafac R-08, XRB-4 (all manufactured by Dainippon Ink and Chemicals, Inc.)

[0090] The blending ratio of component (c1) excluding surfactant in the curable composition (A) is preferably 0.01% by weight or more and 50% by weight or less, based on the total weight of components (a1), (b1), and (c1), i.e., the total weight of all components excluding solvent (d1). Furthermore, the blending ratio of component (c1) excluding surfactant in the curable composition (A) is more preferably 0.01% by weight or more and 50% by weight or less, and even more preferably 0.01% by weight or more and 20% by weight or less, based on the total weight of all components excluding solvent (d1). By setting the blending ratio of component (c1) excluding surfactant to 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0091] <Component (d1): Solvent> The curable composition according to the present disclosure includes, as solvent (d1), a solvent having a boiling point of 100°C or higher but lower than 250°C under normal pressure. Examples of component (d1) include solvents in which component (a1) and component (b1) dissolve, such as alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. Component (d1) may be used singly or in combination of two or more. The boiling point of component (d1) under normal pressure is 100°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of component (d1) under normal pressure is lower than 250°C, preferably lower than 200°C. If the boiling point of component (d1) under normal pressure is lower than 100°C, the evaporation rate in the waiting step described below will be too fast, which may result in component (d1) volatilizing before the droplets of the curable composition (A) combine together, preventing the droplets of the curable composition (A) from combining together. Furthermore, if the boiling point of component (d1) under normal pressure is 250°C or higher, the solvent (d1) may not volatilize sufficiently in the waiting step described below, and component (d1) may remain in the cured product of the curable composition (A). Here, when component (d1) contains one or more solvents, the boiling point of each of the one or more solvents under normal pressure is preferably 100°C or higher and lower than 250°C (e.g., 100°C or higher and lower than 200°C).

[0092] Examples of alcohol-based solvents include the following: Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl Monoalcohol solvents such as alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyalcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin.

[0093] Examples of ketone solvents include the following: Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchone

[0094] Examples of ether solvents include the following: Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran

[0095] Examples of the ester solvent include the following: Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate Ether, Diethylene Glycol Mono-n-Butyl Ether Acetate, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl Ether Acetate, Dipropylene Glycol Monomethyl Ether Acetate, Dipropylene Glycol Monoethyl Ether Acetate, Glycol Diacetate, Methoxytriglycol Acetate, Ethyl Propionate, n-Butyl Propionate, Isoamyl Propionate, Diethyl Oxalate, Di-n-Butyl Oxalate, Methyl Lactate, Ethyl Lactate, n-Butyl Lactate, n-Amyl Lactate, Diethyl Malonate, Dimethyl Phthalate, Diethyl Phthalate

[0096] Examples of nitrogen-containing solvents include the following: N-Methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone

[0097] Among the above-mentioned solvents, ether-based solvents and ester-based solvents are preferred, and from the viewpoint of excellent film-forming properties, ether-based solvents and ester-based solvents having a glycol structure are more preferred.

[0098] Furthermore, the following are more preferred: Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate

[0099] Furthermore, particularly preferred is propylene glycol monomethyl ether acetate. Other examples include ethyl isocyanurate di(meth)acrylate.

[0100] In the present disclosure, a preferred solvent is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure, specifically, a solvent selected from propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate, either singly or in combination.

[0101] In the present disclosure, a polymerizable compound having a boiling point of 80° C. or higher and lower than 250° C. under normal pressure can also be used as component (d1). Examples of polymerizable compounds having a boiling point of 80° C. or higher and lower than 250° C. under normal pressure include the following: Cyclohexyl acrylate (198°C), benzyl acrylate (229°C), isobornyl acrylate (245°C), tetrahydrofurfuryl acrylate (202°C), trimethylcyclohexyl acrylate (232°C), isooctyl acrylate (217°C), n-octyl acrylate (228°C), ethoxyethoxyethyl acrylate (boiling point 230°C), divinylbenzene (193°C), 1,3-diisopropenylbenzene (218°C), styrene (145°C), α-methylstyrene (165°C)

[0102] In the present disclosure, when the entire curable composition (A) is taken as 100% by volume, the content of the solvent (d1) is 5% by volume or more and 95% by volume or less, preferably 15% by volume or more and 85% by volume or less, and more preferably 40% by volume or more and 80% by volume or less. The entire curable composition (A) refers to the total volume of the polymerizable compound (a1), the photopolymerization initiator (b1), and the solvent (d1). For example, the content of the solvent (d1) is 40% by volume or more and 85% by volume or less. If the content of the solvent (d1) is less than 5% by volume, it is difficult to obtain a thin film after evaporation of the solvent (d1) under conditions that allow for a substantially continuous liquid film. On the other hand, if the content of the solvent (d1) is more than 95% by volume, it is difficult to obtain a thick film after evaporation of the solvent (d1) even when droplets are dropped in close-packed fashion by an inkjet method.

[0103] <Temperature when compounding the curable composition> When preparing the curable composition (A) of the present disclosure, at least components (a1), (b1), and (d1) are mixed and dissolved under a predetermined temperature condition. Specifically, the predetermined temperature condition is in the range of 0°C or higher and 100°C or lower. The same applies when the curable composition (A) also contains component (c1).

[0104] <Viscosity of Curable Composition> The curable composition (A) in the present disclosure is a liquid. This is because, in the disposing step described below, droplets of the curable composition (A) are discretely dispensed onto a substrate by an inkjet method. The viscosity of the curable composition (A) in the present disclosure, at 23°C and 1 atmosphere, is 1.3 mPa·s or more and 60 mPa·s or less, preferably 2 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less. If the viscosity of the curable composition (A) is less than 2 mPa·s, the ejection of droplets by the inkjet method may become unstable. Furthermore, if the viscosity of the curable composition (A) is greater than 60 mPa·s, it is difficult to form droplets with a volume of approximately 1.0 to 3.0 pL, which is preferred in the present disclosure.

[0105] The viscosity at 23°C and 1 atmosphere of the mixture of the components of the curable composition (A) excluding the solvent (d1) after the solvent (d1) has evaporated from the curable composition (A) is 30 mPa·s or more and 10,000 mPa·s or less. The viscosity at 23°C and 1 atmosphere of the mixture of the components of the curable composition (A) excluding the solvent (d1) is preferably 90 mPa·s or more and 2,000 mPa·s or less, for example, 120 mPa·s or more and 1,000 mPa·s or less. Furthermore, the viscosity at 23°C and 1 atmosphere of the mixture of the components of the curable composition (A) excluding the solvent (d1) is more preferably 150 mPa·s or more and 500 mPa·s or less. By setting the viscosity of the components of the curable composition (A) excluding the solvent (d2) to 1,000 mPa·s or less, spreading and filling of the curable composition (A) can be completed quickly when the curable composition (A) is brought into contact with a mold. Therefore, by using the curable composition (A) of the present disclosure, it is possible to perform imprint processing with high throughput and suppress pattern defects due to insufficient filling. Furthermore, by setting the viscosity of the components of the curable composition (A) excluding the solvent (d1) to 1 mPa·s or more, it is possible to prevent unwanted flow of droplets of the curable composition (A') after the solvent (d1) has evaporated. Furthermore, when the curable composition (A) is brought into contact with a mold, the curable composition (A) is less likely to flow out from the edges of the mold.

[0106] <Contact angle of curable composition> The present inventors have found that, with regard to the contact angle of the curable composition (A), when the contact angle of the curable composition (A) with respect to an adhesion layer or a silicon substrate is 1.8° or less, droplets of the curable composition can bond to each other on the substrate to form a continuous liquid film.

[0107] In this embodiment, the contact angle of the curable composition (A) from which the solvent (d1) has been removed with respect to the adhesion layer or silicon substrate is 11° or more and 19° or less. The inventors have found that a contact angle of 11° or more of the curable composition (A) from which the solvent (component (d1)) has been removed with respect to the surface of the adhesion layer or silicon substrate exhibits a pinning effect on the spreading of droplets. This allows the spreading of droplets on the substrate to be stopped at a desired size, and the amount of overflow of the curable composition can be suppressed. Furthermore, a contact angle of 19° or less of the curable composition (A) from which the solvent (component (d1)) has been removed with respect to the surface of the adhesion layer or silicon substrate can be suppressed from shrinking.

[0108] <Impurities contained in the curable composition> The curable composition (A) of the present disclosure preferably contains as few impurities as possible. The term "impurities" refers to substances other than the above-mentioned components (a1), (b1), (c1), and (d1). Therefore, the curable composition (A) of the present disclosure is preferably obtained through a purification process. Such a purification process is preferably filtration using a filter.

[0109] In the filtration using a filter, it is preferable to mix the above-mentioned components (a1), (b1), and (c1) and then filter the mixture using a filter with a pore size of 0.001 μm or more and 5.0 μm or less. When performing filtration using a filter, it is more preferable to perform the filtration in multiple stages or repeatedly (circulating filtration). Furthermore, the liquid filtered through the filter may be filtered again, or may be filtered using multiple filters with different pore sizes. Examples of filters used for filtration include, but are not limited to, filters made of polyethylene resin, polypropylene resin, fluororesin, and nylon resin. By undergoing such a purification step, impurities such as particles mixed in the curable composition can be removed. This prevents impurities mixed in the curable composition from accidentally causing unevenness in the cured film obtained after curing the curable composition, which can result in pattern defects.

[0110] When the curable composition according to the present disclosure is used to manufacture a semiconductor integrated circuit, it is preferable to minimize the inclusion of impurities containing metal atoms (metal impurities) in the curable composition, so as not to impair the operation of the product. The concentration of metal impurities contained in the curable composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0111] <Glass Transition Temperature of Curable Composition> If the glass transition temperature is sufficiently higher than the temperature during demolding, the cured product during demolding is in a strong glass state, i.e., exhibits high mechanical strength, making it difficult for the pattern to collapse or be damaged by the impact of demolding. Therefore, when the demolding step is carried out at room temperature, the glass transition temperature of the cured product (after curing of the polymerizable compound (a1)) is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0112] The glass transition temperature of a cured product (photocured product) can be measured using a differential scanning calorimetry (DSC) or a dynamic viscoelasticity analyzer. For example, consider measuring the glass transition temperature using a DSC. In this case, a straight line is drawn by extending the low-temperature baseline of the DSC curve of the cured product (the portion of the DSC curve in the temperature range where no transition or reaction occurs in the test specimen) toward the high-temperature side, and a tangent is drawn at the point where the gradient of the curve in the stepwise change portion of the glass transition is maximum. The extrapolated glass transition onset temperature (Tig) is then calculated from the intersection of this straight line and this tangent, and this can be used as the glass transition temperature. Typical instruments include the STA-6000 (manufactured by Perkin Eimer). On the other hand, when measuring the glass transition temperature using a dynamic viscoelasticity analyzer, the temperature at which the loss sine (tan δ) of the cured product is maximized is defined as the glass transition temperature. Typical instruments for measuring dynamic viscoelasticity include the MCR301 (manufactured by Anton Paar).

[0113] [Layer forming composition] The layer-forming composition in the present disclosure is a composition for forming an adhesive layer between a base material (substrate) and a curable composition.

[0114] The layer-forming composition contains at least a compound (a2) having at least one functional group capable of bonding to the substrate and at least one polymerizable functional group, a crosslinker (b2), and a solvent (d2). Here, "adhering the substrate and the curable composition to each other" can be defined as a state in which the substrate and the cured film are bonded via an adhesion layer with a strength greater than the force required to separate the mold from the cured film of the curable composition in a demolding step. The demolding step, which will be described later, is a step in an imprinting process in which the mold is separated from the cured film of the curable composition formed on the substrate.

[0115] The layer-forming composition according to this embodiment is particularly preferably used when forming a cured film (cured product) of a curable composition on a substrate. Furthermore, a laminate having an adhesion layer formed from the layer-forming composition according to this embodiment and a substrate can be preferably used as a substrate onto which a curable composition is disposed (supplied) to obtain a cured film. Furthermore, the layer-forming composition according to this embodiment can be used as an adhesion layer-forming composition for imprinting, and is particularly useful as an adhesion layer-forming composition for photo-nanoimprinting. Here, this embodiment will describe an example in which a photocurable composition having the property of being cured by irradiation with light is used as the curable composition. However, the curable composition is not limited to a photocurable composition, and a thermosetting composition having the property of being cured by heating may also be used.

[0116] Each component of the layer-forming composition according to this embodiment will be described in detail below. As described above, the layer-forming composition according to this embodiment contains the compound (a2), the crosslinking agent (b2), and the solvent (d2).

[0117] <Compound (a2)> The compound (a2) has at least one functional group that bonds to the substrate and at least one polymerizable functional group that bonds to the curable composition. Here, the "functional group that bonds" refers to a functional group that forms a chemical bond such as a covalent bond, an ionic bond, a hydrogen bond, or an intermolecular force. The compound (a2) is contained in an amount of less than 1% by mass when the entire layer-forming composition is taken as 100% by mass. The type of compound (a2) that can be used in this embodiment is not particularly limited, and a wide variety of known compounds can be used.

[0118] The compound (a2) according to this embodiment has at least one hydroxyl group, carboxyl group, thiol group, amino group, epoxy group, or (blocked) isocyanate group in one molecule. Examples of the compound (a2) include a compound having an ethylenically unsaturated bond-containing group, a compound having an epoxy group, and a compound having a vinyl ether group.

[0119] Specific examples of the compound (a2) having an ethylenically unsaturated bond-containing group include the following: Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, N-vinylpyrrolidinone, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (Meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylic acid dimer, benzyl (meth)acrylate, 1- or 2-naphthyl (meth)acrylate, butoxyethyl (meth)acrylate, cetyl (meth)acrylate, ethylene oxide-modified (hereinafter referred to as "EO") cresol (meth)acrylate, dipropylene glycol (meth)acrylate, ethoxylated phenyl (meth)acrylate, isooctyl (meth)acrylate, cyclohexyl (meth)acrylate , isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isomyristyl (meth)acrylate, lauryl (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, neopentyl glycol benzoate (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, octyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate,Polyethylene glycol-polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, stearyl (meth)acrylate, EO-modified succinic acid (meth)acrylate, tribromophenyl (meth)acrylate, EO-modified tribromophenyl (meth)acrylate, tridodecyl (meth)acrylate, p-isopropenylphenol, N-vinylpyrrolidone, N-vinylcaprolactam, diethylene glycol monoethyl ether (meth)acrylate, dimethyloldicyclopentane di(meth)acrylate, Di(meth)acrylated isocyanurate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, EO-modified 1,6-hexanediol di(meth)acrylate, ECH-modified 1,6-hexanediol di(meth)acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanediol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, modified bisphenol A di(meth)acrylate, EO-modified bisphenol F di(meth)acrylate, ECH-modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, EO-modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO")-modified neopentyl glycol diacrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol, stearic acid-modified pentaerythritol di(meth)acrylate, ECH-modified phthalic acid di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, polyester(di)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ECH-modified propylene glycol di(meth)acrylate, silicone di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate,Neopentyl glycol modified trimethylolpropane di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO modified tripropylene glycol di(meth)acrylate, triglycerol di(meth)acrylate, dipropylene glycol di(meth)acrylate, divinylethylene urea, divinylpropylene urea, o-, m-, p-xylylene di(meth)acrylate, 1,3-adamantane diacrylate, norbornane dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ECH modified glycerol tri(meth)acrylate, EO modified glycerol tri(meth)acrylate, PO modified glycerol tri(meth)acrylate, pentaerythritol triacrylate, EO modified phosphate triacrylate, trimethylolpropane tri(meth)acrylate acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.

[0120] Examples of the compound (a2) having an epoxy group include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to phenol, cresol, butylphenol, or these; and glycidyl esters of higher fatty acids.

[0121] Examples of the compound (a2) having a vinyl ether group include the following: 2-Ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, penta Erythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1-tris[4-(2-vinyloxyethoxy)phenyl]ethane, bisphenol A divinyloxyethyl ether

[0122] A preferred example is a poly(meth)acrylate compound having an ethylenically unsaturated group (P) and a hydrophilic group (Q). Examples of the ethylenically unsaturated group (P) include a (meth)acryloyloxy group, a (meth)acryloylamino group, a maleimide group, an allyl group, and a vinyl group. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methacryloyl group having an equivalent alcohol residue. Examples of the hydrophilic group (Q) include an alcoholic hydroxyl group, a carboxyl group, a phenolic hydroxyl group, an ether group (preferably a polyoxyalkylene group), an amino group, an amide group, an imide group, a ureido group, a urethane group, a cyano group, a sulfonamide group, a lactone group, and a cyclocarbonate group. When the hydrophilic group is a urethane group, it is preferred that the group adjacent to the urethane group be present in the resin as an oxygen atom, for example, "-OC(=O)-NH-."

[0123] The poly(meth)acrylate compound (acrylic resin) may contain a repeating unit containing an ethylenically unsaturated group (P) and a repeating unit containing a hydrophilic group (Q) in the same repeating unit or in separate repeating units. However, the poly(meth)acrylate compound (acrylic resin) preferably contains these repeating units in a proportion of 20 to 100 mol %. Furthermore, the poly(meth)acrylate compound (acrylic resin) may contain other repeating units that do not contain both an ethylenically unsaturated group (P) and a hydrophilic group (Q), and the proportion of such other repeating units is preferably 50 mol % or less in the acrylic resin.

[0124] The poly(meth)acrylate compound (acrylic resin) preferably contains repeating units represented by the following general formulas (I) and (II). [ka] (In general formulas (I) and (II), R 1 and R 2 respectively represent a hydrogen atom, a methyl group, or a hydroxymethyl group. 1 represents a trivalent linking group, and L2a represents a single bond or a divalent linking group, L 2b represents a single bond, a divalent linking group, or a trivalent linking group; P represents an ethylenically unsaturated group; Q represents a hydrophilic group; and n is 1 or 2.

[0125] R 1 and R 2 R each independently represents a hydrogen atom, a methyl group, or a hydroxymethyl group. 1 and R 2 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0126] L 1 represents a trivalent linking group. The trivalent linking group is an aliphatic group, an alicyclic group, an aromatic group, or a trivalent group formed by combining these groups, and may contain an ester bond, an ether bond, a sulfide bond, and a nitrogen atom. The trivalent linking group preferably has 1 to 9 carbon atoms.

[0127] L 2a represents a single bond or a divalent linking group. The divalent linking group is an alkylene group, a cycloalkylene group, an arylene group, or a divalent group formed by combining these groups, and may contain an ester bond, an ether bond, or a sulfide bond. The divalent linking group preferably has 1 to 8 carbon atoms.

[0128] L 2b represents a single bond, a divalent linking group, or a trivalent linking group. 2b The divalent linking group represented by L 2a The meaning and preferred range of L are the same as those of the divalent linking group represented by 2b The trivalent linking group represented by L 1 The meaning and preferred range of the trivalent linking group are the same as those of the trivalent linking group represented by the formula (I), and the preferred range is also the same.

[0129] P represents an ethylenically unsaturated group. The ethylenically unsaturated group represented by P has the same meaning as the ethylenically unsaturated group exemplified above, and the preferred ethylenically unsaturated group is also the same. Furthermore, Q represents a hydrophilic group. The hydrophilic group represented by Q has the same meaning as the hydrophilic group exemplified above, and the preferred hydrophilic group is also the same.

[0130] n is 1 or 2, with 1 being preferred.

[0131] In addition, L 1 , L 2a and L 2b does not contain an ethylenically unsaturated group or a hydrophilic group.

[0132] The poly(meth)acrylate compound (acrylic resin) may further have repeating units represented by the following general formula (III) and / or general formula (IV). [ka] (In general formulas (III) and (IV), R 3 and R 4 respectively represent a hydrogen atom, a methyl group, or a hydroxymethyl group. 3 and L 4 represents a single bond or a divalent linking group. Q represents a hydrophilic group. R 5 represents an aliphatic group having 1 to 12 carbon atoms, an alicyclic group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms.

[0133] R 3 and R 4 R represents a hydrogen atom, a methyl group, and a hydroxymethyl group, respectively. 3 and R 4 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0134] L 3 and L 4 Each of L represents a single bond or a divalent linking group. 3 and L 4 The divalent linking group represented by each of the formulas is L 2a The meaning and preferred range of the divalent linking group are the same as those of the divalent linking group represented by the formula (I), and the preferred range is also the same.

[0135] Q represents a hydrophilic group. The hydrophilic group represented by Q has the same meaning as the hydrophilic groups exemplified above, and preferred hydrophilic groups are also the same.

[0136] R 5 represents an aliphatic group, alicyclic group, or aromatic group having 1 to 12 carbon atoms. Examples of the aliphatic group having 1 to 12 carbon atoms include alkyl groups having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3,3,5-trimethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, and dodecyl group). Examples of the alicyclic group having 3 to 12 carbon atoms include cycloalkyl groups having 3 to 12 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, and tricyclodecanyl group). Examples of aromatic groups having 6 to 12 carbon atoms include phenyl, naphthyl, and biphenyl groups. Of these, phenyl and naphthyl groups are preferred. The aliphatic, alicyclic, and aromatic groups may have a substituent.

[0137] Specific examples of acrylic resins that can be used in this embodiment are shown below. In the following specific examples, x represents 0 to 50 mol %, y represents 0 to 50 mol %, and z represents 20 to 100 mol %. [ka]

[0138] Other examples of the compound (a2) that can be used in this embodiment include compounds whose main chain contains an aromatic ring. Examples of the compound (a2) containing an aromatic ring include compounds whose main chain consists of an aromatic ring and an alkylene group, and whose main chain has a structure in which benzene rings and methylene groups are alternately bonded. This compound (a2) preferably has a reactive group in its side chain, more preferably a (meth)acryloyl group in its side chain, and even more preferably an acryloyl group in its side chain.

[0139] The compound (a2) whose main chain contains an aromatic ring is preferably a polymer mainly composed of a structural unit represented by the following general formula (a2-1), and more preferably a polymer in which the structural unit represented by the following general formula (a2-1) accounts for 90 mol % or more. [ka] (In the general formula (a2-1), R is an alkyl group, and L 1 and L 2 are each a divalent linking group, and P is a polymerizable group. n is an integer of 0 to 3.

[0140] R is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. 1 is preferably an alkylene group, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably "-CH2-". 2 is preferably "-CH2-", "-O-", "-CHR (R is a substituent)-", or a divalent linking group formed by a combination of two or more of these. R is preferably an OH group. P is preferably a (meth)acryloyl group, more preferably an acryloyl group. n is preferably an integer of 0 to 2, more preferably 0 or 1.

[0141] Other examples of the compound (a2) that can be used in this embodiment include epoxy poly(meth)acrylate compounds. Other examples of the compound (a2) include those described in paragraphs 0040 to 0056 of JP-A-2009-503139, the contents of which are incorporated herein by reference.

[0142] Among the compounds (a2) described above, those having a functional group that has a high bonding strength with the substrate are preferred. The functional group that has a high bonding strength with the substrate is selected from the group consisting of a hydroxyl group, a carboxyl group, a thiol group, an amino group, an epoxy group, and a (blocked) isocyanate group, with a hydroxyl group or a carboxyl group being particularly preferred.

[0143] Compound (a2) may be a low-molecular-weight compound or a polymer, but is preferably a polymer. The molecular weight is usually 200 to 100,000, preferably 500 to 50,000, and more preferably 1,000 to 10,000. If the molecular weight of compound (a2) is 200 or less, it may volatilize during the baking process, while if it is 100,000 or more, it may easily leave bubbles during the spin coating process.

[0144] The compound (a2) may be composed of one type of compound or a plurality of types of compounds.

[0145] <Crosslinking agent (b2)> The crosslinking agent (b2) according to this embodiment is a compound having a total of at least five alkoxyalkyl groups or alkylol groups, or both, in one molecule (hereinafter referred to as "functional groups a").

[0146] The functional group a possessed by the crosslinking agent (b2) according to this embodiment is a functional group that reacts with a hydroxyl group or a carboxyl group possessed by the compound (a2) in the adhesion layer forming step described below. As a result, a bond is formed between the compound (a2) and the crosslinking agent (b2). Since the crosslinking agent (b2) has a plurality of functional groups a in one molecule, the crosslinking agent (b2) can form bonds with each of the plurality of compounds (a2). By the crosslinking agent (b2) forming bonds with each of the plurality of compounds (a2), a structure (crosslinked structure) can be formed in which the compounds constituting the adhesion layer are crosslinked to each other.

[0147] The reaction between the functional group a of the crosslinking agent (b2) according to this embodiment and the hydroxyl group or carboxyl group of the compound (a2) preferably occurs during a heating process in the adhesion layer forming step described below.

[0148] By forming an adhesive layer having such a crosslinked structure, the amount of free, unreacted compound (a2) or crosslinking agent (b2) not bonded to the substrate can be reduced, thereby improving the film strength of the adhesive layer.

[0149] If unreacted compound (a2) or crosslinking agent (b2) is present in a free state in the adhesive layer, there is a possibility that these compounds will elute into the curable composition during the step of disposing the curable composition, which will be described later. As a result, the composition of the curable composition will change, and the properties of the curable composition will also change, resulting in, for example, peeling defects in the pattern of the cured film obtained by curing the curable composition.

[0150] On the other hand, when the layer-forming composition according to this embodiment is used, the amount of free compound (a2) or crosslinking agent (b2) not connected to the substrate in the adhesive layer can be significantly reduced compared to conventional methods. This also significantly reduces the elution of compound (a2) or crosslinking agent (b2) into the curable composition during the curable composition application step. As a result, the occurrence of defects such as peeling of the cured film pattern described above can be suppressed.

[0151] Furthermore, the functional group a of the crosslinking agent (b2) may form a chemical bond or interaction, such as a covalent bond, an ionic bond, a hydrogen bond, or an intermolecular force, with a functional group present on the surface of the substrate. For example, when a substrate having hydroxyl groups such as silanol groups on its surface is used as the substrate, a dealcoholization reaction occurs between the alkoxyalkyl group and the silanol group. As a result, a covalent bond can be formed between the crosslinking agent (b2) and the substrate. This can improve the adhesion between the adhesive layer and the substrate.

[0152] Furthermore, the crosslinking agent (b2) is preferably a compound represented by the following general formula (b2-1). [ka] In general formula (b2-1), R1 to R6 each independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an alkylol group, provided that at least five of R1 to R6 are alkoxyalkyl groups or alkylol groups.

[0153] The compound represented by the general formula (b2-1) above is a melamine derivative having a triazine ring at the center of its structure. That is, the compound represented by the general formula (1) has a structure in which nitrogen atoms are bonded to the 2nd, 4th, and 6th positions of 1,3,5-triazine. Furthermore, the compound represented by the general formula (1) has five or six functional groups a. That is, the compound represented by the general formula (b2-1) above has more functional groups a than urea-based compounds such as glycoluril derivatives.

[0154] The type of alkoxyalkyl group or alkylol group contained in the crosslinking agent (b2) is not particularly limited, but the alkoxyalkyl group is preferably a methoxymethyl group, and the alkylol group is preferably a methylol group. By using a functional group with a small formula weight as the alkoxyalkyl group or alkylol group, the crosslink density per unit mass in the adhesive layer 101 can be improved. As a result, the film strength of the adhesive layer 101 can be improved.

[0155] Specific examples of the crosslinking agent (b2) include pentamethoxymethylmelamine, hexamethoxymethylmelamine, (hydroxymethyl)pentakis(methoxymethyl)melamine, hexaethoxymethylmelamine, hexabutoxymethylmelamine, pentamethylolmelamine, hexamethylolmelamine, etc. The crosslinking agent (b2) may include at least one selected from these, but is not limited thereto.

[0156] Alternatively, a urea-based compound may be used as the crosslinking agent (b2).Specific examples of such a crosslinking agent include methylated urea-based crosslinking agents, such as tetrakis(methoxymethyl)glycoluril, 4,5-dimethoxy-1,3-bis(methoxymethyl)imidazolidin-2-one, tetrakis(butoxymethyl)glycoluril, tetrakis(ethoxymethyl)glycoluril, tetrakis(isopropoxymethyl)glycoluril, tetrakis(amyloxymethyl)glycoluril, and tetrakis(hexoxymethyl)glycoluril.

[0157] As commercially available urea compounds, Nikalac MX-270, Nikalac MX-280, and Nikalac MX-290 available from Sanwa Chemical Co., Ltd., Powderlink 1174 available from American Cyanamid Co., and Cymel 1170 available from Cytec Industries, Inc. can be preferably used.

[0158] Furthermore, monomers of the above resins can also be used, and examples thereof include the following compounds, dimethoxymethylurea, etc. [ka]

[0159] The crosslinking agent (b2) may be composed of one type of compound or a plurality of types of compounds.

[0160] <Mixing ratio of compound (a2) and crosslinking agent (b2)> If the blending ratio of either the compound (a2) or the crosslinking agent (b2) in the layer-forming composition is extremely small, the crosslink density of the adhesive layer 101 will be low, resulting in insufficient film strength and curability. Therefore, assuming that the weight fractions of the compound (a2) and the crosslinking agent (b2) relative to the total weight of the layer-forming composition are α and β, respectively, α:β is preferably 1:9 to 9:1, and more preferably 1:5 to 5:1. That is, α / β is preferably 0.11 or more and 9 or less, and more preferably 0.2 or more and 5 or less. The optimal blending ratio varies depending on the number of functional groups, molecular weight, and reactivity of the compound (a2) and the crosslinking agent (b2), but by maintaining the blending ratio within the above-mentioned range, the curability of the layer-forming composition can be improved.

[0161] The blending ratio (the sum of α and β) of the compound (a2) and the crosslinking agent (b2) in the layer-forming composition can be adjusted as appropriate depending on the viscosity of the layer-forming composition, the intended film thickness of the adhesive layer, and the like. The sum of α and β is preferably 0.01 to 10, more preferably 0.1 to 10, and even more preferably 0.1 to 7, relative to the total weight of the layer-forming composition. By setting the blending ratio of the compound (a2) and the crosslinking agent (b2) in the layer-forming composition within the above range, the viscosity of the layer-forming composition can be reduced, and the film thickness of the adhesive layer 101 that is formed can be made smaller.

[0162] <Volatile solvent (d2)> The layer-forming composition according to this embodiment contains a volatile solvent (d2) (hereinafter simply referred to as "solvent (d2)"). By containing the solvent (d2), the viscosity of the layer-forming composition can be reduced. As a result, the coatability of the layer-forming composition to a substrate can be improved.

[0163] The solvent (d2) may be a mixture of a first solvent (d2-1) having a boiling point at normal pressure of 80 to 200° C. and a second solvent (d2-2) having a boiling point at normal pressure of 200 to 300° C. Alternatively, the solvent (d2) may be a mixture of the first solvent (d2-1) alone or the second solvent (d2-2) alone.

[0164] The first solvent (d2-1) is not particularly limited as long as it can dissolve the compound (a2) and the crosslinking agent (b2), but a solvent having a boiling point of 80 to 200°C at normal pressure is preferred. The first solvent (d2-1) is also preferably an organic solvent having at least one of a hydroxyl group, an ether structure, an ester structure, and a ketone structure. These solvents are excellent in solubility of the compound (a2) and the crosslinking agent (b2), wettability to the substrate, etc.

[0165] Specific examples of solvents that can be used as the first solvent (d1-1) according to this embodiment include the following. n-Propanol, iso-Propanol, n-Butanol, iso-Butanol, sec-Butanol, tert-Butanol, n-Pentanol, iso-Pentanol, 2-Methylbutanol, sec-Pentanol, tert-Pentanol, 3-Methoxybutanol, n-Hexanol, 2-Methylpentanol, sec-Hexanol, 2-Ethylbutanol, sec-Heptanol, 3-Heptanol, n-Octanol, 2-Ethylhexanol, sec-Octanol, 2,6-Dimethyl Alcohol-based solvents such as 4-heptanol, sec-undecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, diacetone alcohol, ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, and propylene glycol; n-butyl ether, 2-ethylhexyl ether, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, and ethylene glycol diethyl ether. Ether solvents such as butyl acetate, 2-n-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, 1-n-butoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and 2-methyltetrahydrofuran; ester solvents such as butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, and fenchone;Acetic acid solvents such as diethyl carbonate, amyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, glycol diacetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, and diethyl malonate; amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methylpropionamide, either alone or in combination;

[0166] Among these, propylene glycol monomethyl ether acetate or a mixed solution thereof is particularly preferred from the viewpoint of coatability.

[0167] The second solvent (d2-2) is not particularly limited as long as it can dissolve the compound (a2) and the crosslinking agent (b2), but a solvent with a boiling point of 200 to 300°C at normal pressure is preferred. The second solvent (d2-2) is also preferably an organic solvent having at least one of a hydroxyl group, an ether structure, an ester structure, and a ketone structure. These solvents are excellent in solubility of the compound (a2) and the crosslinking agent (b2), wettability to the substrate, etc.

[0168] Specific examples of solvents that can be used as the second solvent (d2-2) according to this embodiment include the following. Alcohol-based solvents such as n-nonyl alcohol, n-decanol, sec-tetradecyl alcohol, benzyl alcohol, phenylmethylcarbinol, 1,3-butylene glycol, 2,4-pentanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, and tripropylene glycol; n-hexyl ether, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, and diethylene glycol mono-n-butyl ether. ether-based solvents such as ethylene glycol monopropyl ether, ethylene glycol monomethyl ether, propylene glycol mono-n-hexyl ether, ethoxytriglycol, 1-phenoxy-2-propanol, dipropylene glycol monopropyl ether, and tripropylene glycol monomethyl ether; ketone-based solvents such as acetophenone; acetic acid-based solvents such as γ-butyrolactone, γ-valerolactone, benzyl acetate, n-nonyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, di-n-butyl oxalate, n-amyl lactate, dimethyl phthalate, and diethyl phthalate; and amide-based solvents such as acetamide, N-methylacetamide, and N-methylpyrrolidone, either alone or in combination.

[0169] As described above, the solvent (d2) may contain two types of solvents: a first solvent (d2-1) and a second solvent (d2-2). In this case, when the total of the first solvent (d2-1) and the second solvent (d2-2) is 100 parts by mass, the second solvent (d2-2) is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and even more preferably 5 to 25 parts by mass. By setting the parts by mass of the second solvent (d2-2) within the above range, the in-plane uniformity of the film thickness and the defect density are improved. The solvent (d2) may contain three or more types of solvents.

[0170] The blending ratio of the solvent (d2) in the layer-forming composition according to this embodiment can be appropriately adjusted depending on the viscosity and coatability of the compound (a2) and the crosslinking agent (b2), the film thickness of the adhesive layer 101 to be formed, and the like. The blending ratio (content) of the solvent (d2) in the layer-forming composition, when the entire layer-forming composition is taken as 100% by mass, is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. The greater the blending ratio of the solvent (d2) in the layer-forming composition, the thinner the film thickness of the adhesive layer to be formed, making it preferable as an adhesive layer-forming composition for imprinting. If the blending ratio of the solvent (d2) in the layer-forming composition is less than 70% by mass, sufficient coatability may not be obtained. The upper limit of the blending ratio of the solvent (d2) is not particularly limited, but is preferably 99.9% by mass or less, and more preferably 99.5% by mass or less.

[0171] <Other ingredients (e2)> In addition to the aforementioned compound (a2), crosslinker (b2), and solvent (d2), the layer-forming composition according to this embodiment may contain an additional additive component (e2) depending on various purposes, provided that the effects of the present invention are not impaired. Examples of such additive component (e2) include a crosslinker, a polymer component, an antioxidant, a polymerization inhibitor, and a surfactant. After being disposed on a substrate, the layer-forming composition is cured by heating while volatilizing the solvent (d2), thereby reducing the thickness of the adhesive layer formed on the substrate. Therefore, the layer-forming composition according to this embodiment preferably does not contain a photopolymerization initiator, which is added for purposes such as curing the layer-forming composition by light irradiation. If the layer-forming composition contains a photopolymerization initiator, photopolymerization may occur during the formation of the adhesive layer, causing the layer-forming composition to cure before the solvent (d2) has completely volatilized, potentially making it difficult to reduce the thickness of the adhesive layer 101.

[0172] <Viscosity of Adhesion Layer-Forming Composition> The viscosity of the layer-forming composition according to this embodiment at 23° C. is preferably 0.5 mPa·s or more and 20 mPa·s or less, more preferably 1 mPa·s or more and 10 mPa·s or less, and even more preferably 1 mPa·s or more and 5 mPa·s or less. However, the viscosity of the layer-forming composition at 23° C. may vary depending on the types and blending ratios of each component, such as compound (a2), crosslinking agent (b2), solvent (d2), and other component (e2) added as needed.

[0173] By setting the viscosity of the layer-forming composition at 23°C to 20 mPa·s or less, the applicability of the layer-forming composition to the substrate 102 can be improved, and the film thickness of the layer-forming composition on the substrate can be easily adjusted.

[0174] <Impurities contained in the adhesion layer-forming composition> The layer-forming composition according to this embodiment preferably contains as few impurities as possible. The term "impurities" used herein refers to all components other than the aforementioned compound (a2), crosslinking agent (b2), solvent (d2), and other components (e2) added as needed. When the layer-forming composition is used in an imprint process, it is particularly preferable that the composition does not contain particles or solid components. Here, "particles" refers to gel-like or solid granular substances typically having a particle size (diameter) of several nanometers to several micrometers. Therefore, when the entire layer-forming composition is taken as 100% by mass, the content of particles having a particle size of more than 0.2 μm is preferably 0% by mass or more and less than 3% by mass. Alternatively, when the entire layer-forming composition is taken as 100% by mass, the content of particles having a particle size of more than 0.2 μm is preferably less than 1 particle / mL.

[0175] Therefore, the layer-forming composition according to this embodiment is preferably obtained through a purification process. Such a purification process is preferably filtration using a filter. Specifically, after mixing the compound (a2), the crosslinking agent (b2), the solvent (d2), and the other component (e2) added as needed, the mixture is preferably filtered, for example, through a filter having a pore size of 0.001 μm or more and 5.0 μm or less. It is more preferable to filter through a filter having a pore size of 0.001 μm or more and 0.2 μm or less. It is even more preferable to perform filtration through a filter in multiple stages or repeatedly multiple times. The filtered liquid may also be filtered again. Filtration may also be performed using multiple filters with different pore sizes. Filters used for filtration may be made of polyethylene resin, polypropylene resin, fluororesin, nylon resin, or the like, but are not particularly limited.

[0176] By undergoing such a purification step, impurities such as particles mixed in the layer-forming composition can be removed, thereby preventing impurities such as particles from inadvertently causing defects in the adhesion layer obtained after coating the layer-forming composition.

[0177] When the layer-forming composition is used to manufacture a circuit board for use in a semiconductor element, such as a semiconductor integrated circuit, it is preferable to minimize the inclusion of impurities containing metal atoms (metal impurities) in the layer-forming composition. This is to prevent impurities such as metals from interfering with the operation of the circuit board. In such cases, the concentration of metal impurities contained in the layer-forming composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0178] Therefore, it is preferable that the layer-forming composition be prepared without contacting metal during its production process. That is, it is preferable not to use metallic weighing tools or containers when weighing or mixing the raw materials, including compound (a2), crosslinker (b2), solvent (d2), and other components (e2) added as needed. Furthermore, it is preferable to further filter the mixture using a metal impurity removal filter during the purification process. Filters made of cellulose and diatomaceous earth, ion exchange resins, etc., can be used as the metal impurity removal filter, but are not particularly limited thereto. It is preferable to wash these metal impurity removal filters before use. The washing method is preferably performed in the order of washing with ultrapure water, washing with alcohol, and co-washing with the layer-forming composition.

[0179] [Adhesion layer formation process] In the adhesion layer forming step, as shown in FIG. 1(a), an adhesion layer containing a polymer compound (polymer) as a main component is formed on a substrate using the layer forming composition described above.

[0180] The substrate on which the curable composition is disposed is a substrate or support, and any substrate can be selected depending on various purposes. Examples of substrates that can be used include semiconductor device substrates such as silicon wafers, aluminum, titanium-tungsten alloys, aluminum-silicon alloys, aluminum-copper-silicon alloys, silicon oxide, and silicon nitride; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe; polymer substrates such as paper, polyester films, polycarbonate films, and polyimide films; TFT array substrates, PDP electrode plates, plastic substrates; conductive substrates such as ITO and metals; and insulating substrates. The substrate may be one of the above substrates on which one or more films, such as spin-on glass, organic materials, metals, oxides, and nitrides, are formed.

[0181] In this embodiment, it is particularly preferable to use a substrate having hydroxyl groups (OH groups) such as silanol groups (SiOH groups) on its surface. Examples of such substrates include silicon wafers, quartz, and glass. By using a substrate having hydroxyl groups on its surface, it is believed that the hydroxyl groups on the substrate surface and the functional groups of the compound (a2) in the layer-forming composition will form chemical bonds through heat treatment. Furthermore, when the crosslinking agent (b2) has an alkoxyalkyl group, it is believed that a chemical bond will be formed with the hydroxyl groups.

[0182] Examples of methods that can be used to apply the layer-forming composition to a substrate include inkjet coating, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scanning. Among these methods, spin coating is particularly preferred from the viewpoint of coatability, particularly film thickness uniformity.

[0183] After the layer-forming composition is applied (placed) on the substrate, the solvent (d2) contained in the layer-forming composition is evaporated by drying, forming an adhesive layer on the substrate. At this time, while the solvent (d2) is being evaporated, the substrate is reacted with the compound (a2) or the crosslinking agent (b2), and the compound (a2) is reacted with the crosslinking agent (b2). This forms a bond between the substrate and the adhesive layer, and a bond between the compound (a2) and the crosslinking agent (b2) in the adhesive layer. It is presumed that a crosslinked structure is formed by the bond between the compound (a2) and the crosslinking agent (b2).

[0184] To effectively volatilize and react, the substrate coated with the layer-forming composition is preferably subjected to a heat treatment (baking treatment). The temperature of the heat treatment can be appropriately selected based on the reactivity of compound (a2) or crosslinking agent (b2) with the substrate, the reactivity of compound (a2) with crosslinking agent (b2), the boiling points of compound (a2), crosslinking agent (b2), solvent (d2), and other components (e2), etc. The temperature of the heat treatment is preferably 70°C or higher and 250°C or lower, more preferably 100°C or higher and 220°C or lower, and even more preferably 140°C or higher and 220°C or lower. The drying of solvent (d2), the reaction between substrate 102 and compound (a2) or crosslinking agent (b2), and the crosslinking reaction between compound (a2) and crosslinking agent (b2) may be carried out at the same temperature or at different temperatures. That is, these reactions may be carried out simultaneously or sequentially.

[0185] The thickness of the adhesion layer formed on the substrate by the adhesion layer forming process varies depending on the application, but is, for example, 0.1 nm or more and 100 nm or less, more preferably 0.5 nm or more and 60 nm or less, and even more preferably 1 nm or more and 10 nm or less.

[0186] When applying a layer-forming composition to a substrate to form an adhesive layer, a second adhesive layer may be formed on the first adhesive layer using an additional layer-forming composition. This method may be called multiple coating. Furthermore, it is preferable that the surface of the adhesive layer formed on the substrate is as flat as possible. It is preferable that the surface roughness is 1 nm or less.

[0187] By such an adhesion layer forming step, a laminate having a substrate and a polymer layer (adhesion layer) laminated on the substrate can be formed. As described above, the polymer layer forms a crosslinked structure by the reaction between the alkoxyalkyl group or alkylol group of the crosslinking agent (b2) and the hydroxyl group or carboxyl group of the compound (a2).

[0188] [Pattern formation method] The pattern formation method according to the present disclosure will be described with reference to FIGS. 1(a) to 1(g). The cured film formed by the present disclosure preferably has a pattern of 1 nm to 10 mm, more preferably 10 nm to 100 μm. Generally, a film formation method that uses light to form a film having a nano-sized (1 nm to 100 nm) pattern (relief structure) is called a photoimprinting method. The film formation method according to the present disclosure uses photoimprinting to form a film of a curable composition in the space between a mold and a substrate. However, the curable composition may also be cured by other energy (e.g., heat or electromagnetic waves). Furthermore, the film formation method according to the present disclosure may be implemented as a method for forming a patterned film, i.e., a pattern formation method, or as a method for forming a film without a pattern (e.g., a planarized film), i.e., a planarized film formation method.

[0189] An example in which the film formation method of the present disclosure is applied to a pattern formation method will be described below. The pattern formation method includes, for example, a forming step, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step (separating step). The forming step is a step of forming an underlayer. The disposing step is a step of discretely disposing droplets of the curable composition (A) on the underlayer. The waiting step is a step of waiting until the droplets of the curable composition (A) bond together and the solvent (d1) evaporates. The contacting step is a step of bringing the curable composition (A) into contact with a mold. The curing step is a step of curing the curable composition (A). The demolding step is a step of separating the mold from the cured film of the curable composition (A). The disposing step is performed after the forming step, the waiting step is performed after the disposing step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0190] <Placement process> In the disposing step, as shown in Fig. 1(a), droplets 102 of the curable composition (A) are discretely disposed on a substrate 101. In the disposing step, droplets 102 of the curable composition (A) having a volume of 1.0 pL or more are dispersed at a density of 80 droplets / mm 2 The layers are arranged at a density equal to or greater than the above. A substrate having a base layer laminated thereon may be used as the substrate 101. The surface of the substrate 101 is preferably coated with the above-mentioned layer-forming composition, and the adhesion to the curable composition (A) may be improved by surface treatment such as silane coupling agent treatment, silazane treatment, or formation of an organic thin film.

[0191] As the silane coupling agent, a known silane coupling agent having an acrylic group can be used.The method of applying the silane coupling agent can be, for example, an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, a vapor deposition method, etc.Among these methods, the vapor deposition method is particularly preferred from the viewpoint of application property, particularly film thickness uniformity.

[0192] Alternatively, the substrate 101 may be a silicon substrate that has not been surface-treated.

[0193] The inkjet method is particularly preferred as a method for disposing droplets 102 of the curable composition (A) on the substrate. The droplets 102 of the curable composition (A) are preferably densely disposed on regions of the substrate 101 facing regions where the recesses constituting the pattern of the mold 106 are densely present, and sparsely disposed on regions of the substrate 101 facing regions where the recesses constituting the pattern of the mold 106 are sparsely present. This allows a film (residual film) 109 of the curable composition (A) described below formed on the substrate 101 to be controlled to a uniform thickness regardless of the density of the pattern of the mold 106.

[0194] To determine the volume of the curable composition (A) to be deposited, an index called the average remaining liquid film thickness is defined. The average remaining liquid film thickness is the value obtained by dividing the volume of the curable composition (A') (excluding the solvent (d1)) deposited in the deposition step by the area of ​​the film-forming region of the mold. The volume of the curable composition (A') (excluding the solvent (d1)) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (d1) has evaporated. This definition allows the average remaining liquid film thickness to be determined regardless of the state of the unevenness, even when the substrate surface is uneven. Here, the average remaining liquid film thickness may be understood as the value obtained by dividing the volume of the curable composition (A) remaining after the waiting step described below by the area of ​​the film-forming region of the mold, and is preferably 20 nm or less.

[0195] <Standby process> In the present disclosure, a waiting step is provided after the placing step and before the contacting step. Here, the average initial liquid film thickness is defined as the total volume of the droplets of curable composition (A) dispensed in one pattern formation divided by the total area of ​​the region where a pattern is formed in one pattern formation (pattern formation region). In the waiting step, the droplets 102 of the curable composition (A) spread on the substrate 101, as schematically shown in FIG. 1(b). As a result, the entire pattern formation region of the substrate 101 is covered with the curable composition (A).

[0196] According to the examples described later, for example, a case is selected in which the solvent (d1) is a highly volatile solvent with a non-volatile component volume ratio of 20%, and the droplet pitch is 88 μm, i.e., the average initial liquid film thickness is 13 nm or more. In this case, as shown schematically in FIG. 1(c), numerical calculations have shown that the droplets of the curable composition (A) combine with each other on the substrate to form a substantially continuous liquid film 103. This is also true when droplets of the curable composition (A) with a volume of 1.0 pL or more are deposited at a density of 130 droplets / mm 2 This means that the elements are arranged at a density of at least 100 sq. m.

[0197] Referring to Figures 3(a) to 3(d), the flow behavior of droplets of the curable composition (A) placed on a substrate during the waiting process will be described. As shown in Figure 3(a), droplets 102 of the curable composition (A) are discretely placed on the substrate 101. As shown in Figure 3(b), each droplet 102 gradually spreads on the substrate. Then, as shown in Figure 3(c), the droplets of the curable composition (A) on the substrate begin to combine with each other to form a liquid film, which then becomes a continuous liquid film as shown in Figure 3(d) (the surface of the substrate 101 is covered with the curable composition (A), with no exposed surface). The state of the curable composition (A) as shown in Figure 3(d) is referred to as a "substantially continuous liquid film."

[0198] Furthermore, in the waiting step, as shown schematically in FIG. 1(d), the solvent 105 (solvent (d1)) contained in the liquid film 104 is volatilized. The amount of solvent (d1) remaining in the liquid film 103 after the waiting step (for example, at the start of the contacting step) is preferably 10% by volume or less, assuming that the total weight of the components other than solvent (d1) is 100% by volume. If the amount of solvent (d1) remaining is more than 10% by volume, the mechanical properties of the cured film may be reduced.

[0199] In the waiting step, a baking step may be performed to heat the substrate 101 and the curable composition (A) or to ventilate the ambient gas around the substrate 101 in order to accelerate the evaporation of the solvent (d1). Heating is performed, for example, at a temperature of 30°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 110°C. The heating time may be 10 seconds or higher and 600 seconds or lower. The baking step may be performed using a known heater such as a hot plate or an oven.

[0200] The waiting step is, for example, 0.1 to 600 seconds, preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 second, the droplets of the curable composition (A) will not bond sufficiently, and a substantially continuous liquid film will not be formed. If the waiting step exceeds 600 seconds, productivity will decrease. Therefore, to prevent a decrease in productivity, substrates that have completed the placement step may be sequentially transferred to the waiting step, and the waiting step may be performed on multiple substrates in parallel, and the substrates that have completed the waiting step may be sequentially transferred to the contacting step. Note that in conventional technology, it theoretically takes several thousand to tens of thousands of seconds for a substantially continuous liquid film to be formed, but in reality, the spreading of the droplets of the curable composition stagnates due to volatilization, making it impossible to form a continuous liquid film.

[0201] In the waiting step, when the solvent (d1) volatilizes, a substantially continuous liquid film 104 consisting of the components (a1), (b1), and (c1) remains. The average remaining liquid film thickness of the substantially continuous liquid film 104 from which the solvent (d1) has been volatilized (removed) is thinner than the liquid film 103 by the amount of solvent (d1) that has been volatilized. The entire pattern formation region of the substrate 101 remains covered with the substantially continuous liquid film 104 of the curable composition (A') from which the solvent (d1) has been removed.

[0202] <Contact process> In the contacting step, as schematically shown in FIG. 1( e), a substantially continuous liquid film 104 of the curable composition (A) from which the solvent (d1) has been removed is brought into contact with the mold 106. The contacting step includes a step of changing a state in which the curable composition (A) and the mold 106 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. As a result, the liquid of the curable composition (A) fills the recesses of the fine pattern on the surface of the mold 106, and the liquid becomes a liquid film that fills the fine pattern of the mold 106.

[0203] A comparison of the gas trapped between the mold 106 and the substrate 101 in the contact step between the conventional technology (for example, Japanese Patent No. 6584578) and this embodiment is shown in Figure 4. According to this embodiment, in the waiting step, the curable composition (A) becomes a substantially continuous liquid film 104 from which the solvent (d1) has been removed, so the volume of gas trapped between the mold 106 and the substrate 101 is smaller than in the conventional technology. Therefore, spreading of the curable composition (A) in the contact step is completed quickly.

[0204] If the spreading and filling of the curable composition (A) is completed quickly in the contacting step, the time required to maintain the mold 106 in contact with the curable composition (A) (the time required for the contacting step) can be shortened. Furthermore, shortening the time required for the contacting step leads to a shortening of the time required for pattern formation (film formation), thereby improving productivity. The contacting step is preferably from 0.1 to 3 seconds, and particularly preferably from 0.1 to 1 second. If the contacting step is shorter than 0.1 seconds, spreading and filling will be insufficient, and defects known as unfilled defects tend to occur frequently.

[0205] When the curing process includes a light irradiation process, a mold made of a light-transmitting material is used as the mold 106 in consideration of this. Specific examples of materials for the mold 106 include glass, quartz, light-transmitting resins such as PMMA and polycarbonate resin, transparent metal vapor deposition films, flexible films such as polydimethylsiloxane, light-curing films, and metal films. However, when a light-transmitting resin is used as the material for the mold 106, a resin that is insoluble in the components contained in the curable composition is selected. Quartz is suitable as a material for the mold 106 because it has a small thermal expansion coefficient and small pattern distortion.

[0206] The pattern formed on the surface of the mold 106 has a height of, for example, 4 nm or more and 200 nm or less. The lower the height of the pattern of the mold 106, the smaller the force required to separate the mold 106 from the cured film of the curable composition during the demolding process, i.e., the demolding force, and the fewer demolding defects remaining on the mold 106 due to the curable composition pattern being torn off. Furthermore, the impact of demolding the mold may cause elastic deformation of the curable composition pattern, which may result in adjacent pattern elements coming into contact with each other, resulting in adhesion or breakage. However, it is advantageous to have the height of the pattern elements be approximately twice or less the width of the pattern elements (aspect ratio of 2 or less) to avoid these problems. On the other hand, if the height of the pattern elements is too low, the processing accuracy of the substrate 101 decreases.

[0207] The mold 106 may be subjected to a surface treatment before the contact step in order to improve the releasability of the mold 106 from the curable composition (A). Examples of surface treatments include applying a release agent to the surface of the mold 106 to form a release agent layer. Examples of release agents that can be applied to the surface of the mold 106 include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. For example, commercially available coating release agents such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd. can also be suitably used. One type of release agent may be used alone, or two or more types may be used in combination. Of the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0208] In the contacting step, when the mold 106 is brought into contact with the curable composition (A), the pressure applied to the curable composition (A) is not particularly limited, and is, for example, 0 MPa or more and 100 MPa or less. Note that when the mold 106 is brought into contact with the curable composition (A), the pressure applied to the curable composition (A) is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0209] The contacting step can be carried out under any of the following conditions: air, reduced pressure, or inert gas; however, a reduced pressure or inert gas atmosphere is preferred because it can prevent the curing reaction from being affected by oxygen or moisture. Specific examples of inert gases used when carrying out the contacting step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, or mixtures thereof. Gases containing 10% or more carbon dioxide or helium by molar ratio are preferred, and gases containing 10% or more carbon dioxide by molar ratio are particularly preferred. Helium gas easily diffuses into the mold, substrate, curable composition, etc., so atmospheric gas trapped in the mold pattern, etc., quickly dissipates. Carbon dioxide easily dissolves in the curable composition and the underlayer on the substrate, so atmospheric gas trapped in the mold pattern, etc., quickly dissipates. Furthermore, the solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m 3 ·ATM or more 10kg / m 3 1 atm or less. Details of these are disclosed in JP 2022-99271 A. When the contact step is carried out under a specific gas atmosphere, including air, the preferred pressure is 0.0001 atmospheres or more and 10 atmospheres or less.

[0210] <Curing process> In the curing step, as schematically shown in FIG. 1( f), the curable composition (A) is irradiated with irradiation light 107 as curing energy, thereby curing the curable composition (A) and forming a cured film. In the curing step, for example, the curable composition (A) is irradiated with irradiation light 107 through a mold 106. More specifically, the curable composition (A) filled in the fine pattern of the mold 106 is irradiated with irradiation light 107 through the mold 106. As a result, the curable composition (A) filled in the fine pattern of the mold 106 is cured to form a cured film 108 having the pattern.

[0211] The irradiation light 107 is selected according to the wavelength to which the curable composition (A) is sensitive. Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, electron beams, or the like having a wavelength of 150 nm or more and 400 nm or less. It is particularly preferable that the irradiation light 107 be ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are compounds that are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. However, ultra-high-pressure mercury lamps are particularly preferable as the light source that emits ultraviolet light. The number of light sources may be one or more. The entire area of ​​the curable composition (A) filled into the fine pattern of the mold may be irradiated with light, or only a limited area (a limited area) may be irradiated with light. Light irradiation may be performed intermittently multiple times over the entire area of ​​the substrate, or continuously over the entire area of ​​the substrate. Furthermore, light may be irradiated over a first area of ​​the substrate in a first irradiation process, and over a second area of ​​the substrate different from the first area in a second irradiation process.

[0212] <Mold release process> In the demolding step, as shown schematically in FIG. 1( g), the mold 106 is separated from the cured film 108. By separating the patterned cured film 108 from the mold 106, a free-standing cured film 108 having a pattern that is an inverse of the fine pattern of the mold 106 is obtained. Here, the cured film remains in the recesses of the patterned cured film 108. This film is called a residual film.

[0213] The method for separating the mold 106 from the patterned cured film 108 is not particularly limited as long as a portion of the patterned cured film 108 is not physically damaged during separation. For example, the substrate 101 may be fixed, and the mold 106 may be moved away from the substrate 101. Alternatively, the mold 106 may be fixed, and the substrate 101 may be moved away from the mold 106. The mold 106 may be separated from the patterned cured film 108 by moving both the mold 106 and the substrate 101 in opposite directions.

[0214] <Repeat> A series of steps (manufacturing process) including the above-mentioned placement step through demolding step in this order can produce a cured film having the desired uneven pattern shape (a pattern shape that follows the uneven shape of the mold 106) in the desired position.

[0215] In the pattern formation method of the present disclosure, the repeating unit (shot) from the placement process to the demolding process can be repeated multiple times on the same substrate, and a cured film 108 having multiple desired patterns at desired positions on the substrate can be obtained.

[0216] [Method for forming reverse imprint patterns] Another example of a pattern formation method will be described with reference to FIGS. 2(a) to 2(g). The cured film formed by the present disclosure is preferably a film having a pattern of 1 nm to 10 mm in size, and more preferably a film having a pattern of 10 nm to 100 μm in size. Generally, a film formation method that uses light to form a film having a nano-sized (1 nm to 100 nm) pattern (relief structure) is called a photoimprinting method. The film formation method of the present disclosure uses photoimprinting to form a film of a curable composition in the space between a mold and a substrate. However, the curable composition may also be cured by other energy (e.g., heat, electromagnetic waves). Furthermore, the film formation method of the present disclosure may be implemented as a method for forming a patterned film, i.e., a pattern formation method, or as a method for forming a film without a pattern (e.g., a planarized film), i.e., a planarized film formation method.

[0217] An example in which the film formation method of the present disclosure is applied to a pattern formation method will be described below. The pattern formation method includes, for example, a forming step, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step. The forming step is a step of forming an underlayer. The disposing step is a step of discretely disposing droplets of the curable composition (A) on the underlayer. The waiting step is a step of waiting until the droplets of the curable composition (A) bond together and the solvent (d1) evaporates. The contacting step is a step of contacting the curable composition (A) with a mold. The curing step is a step of curing the curable composition (A). The demolding step is a step of separating the mold from the cured film of the curable composition (A). The disposing step is performed after the forming step, the waiting step is performed after the disposing step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0218] <Placement process> 2(a) to 2(g) differ from FIGS. 1(a) to 1(g) in that the positional relationship between the mold and the substrate is reversed. Therefore, the method shown in FIGS. 2(a) to 2(g) can be called "reverse imprinting." In one example, the mold can be a blank template that serves as the basis for a replica mold. In the disposing step, as shown schematically in FIG. 2(a), droplets 102 of the curable composition (A) are discretely disposed on the mold 201. In the disposing step, droplets 102 of the curable composition (A) having a volume of 1.0 pL or more are dispersed at a density of 80 droplets / mm 2 They are arranged at a density of more than 1000.

[0219] When the curing step includes a light irradiation step, a mold made of a light-transmitting material is used as the mold 201 in consideration of this. Specific examples of materials for the mold 201 include glass, quartz, light-transmitting resins such as PMMA and polycarbonate resin, transparent metal vapor deposition films, flexible films such as polydimethylsiloxane, light-curing films, and metal films. However, when a light-transmitting resin is used as the material for the mold 106, a resin that is insoluble in the components contained in the curable composition is selected. Quartz is suitable as a material for the mold 201 because it has a small thermal expansion coefficient and little pattern distortion.

[0220] The inkjet method is particularly preferred as a method for arranging droplets 102 of the curable composition (A) on the mold. The droplets 102 of the curable composition (A) are preferably arranged densely on regions of the substrate 206 facing regions where the recesses constituting the pattern of the mold 201 are densely present, and sparsely on regions of the mold 201 facing regions where the recesses constituting the pattern of the substrate 206 are sparsely present. This allows the film (residual film) 109 of the curable composition (A) described below formed on the substrate 101 to be controlled to a uniform thickness regardless of the density of the pattern of the substrate 206.

[0221] To determine the volume of the curable composition (A) to be deposited, an index called the average remaining liquid film thickness is defined. The average remaining liquid film thickness is the value obtained by dividing the volume of the curable composition (A') (excluding the solvent (d1)) deposited in the deposition step by the area of ​​the film-forming region of the mold. The volume of the curable composition (A') (excluding the solvent (d1)) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (d1) has evaporated. This definition allows the average remaining liquid film thickness to be determined regardless of the state of the unevenness, even when the substrate surface is uneven. Here, the average remaining liquid film thickness may be understood as the value obtained by dividing the volume of the curable composition (A) remaining after the waiting step described below by the area of ​​the film-forming region of the mold, and is preferably 20 nm or less.

[0222] <Standby process> In the present disclosure, a waiting step is provided after the placing step and before the contacting step. Here, the average initial liquid film thickness is defined as the total volume of the droplets of curable composition (A) dispensed in one pattern formation divided by the total area of ​​the region where a pattern is formed in one pattern formation (pattern formation region). In the waiting step, the droplets 102 of the curable composition (A) spread on the mold 201, as schematically shown in FIG. 2(b). As a result, the entire pattern formation region of the mold 201 is covered with the curable composition (A).

[0223] According to the examples described later, for example, a case is selected in which the solvent (d1) is a highly volatile solvent with a non-volatile component volume ratio of 20%, and the droplet pitch is 88 μm, i.e., the average initial liquid film thickness is 13 nm or more. In this case, as shown schematically in FIG. 2(c), numerical calculations have shown that the droplets of the curable composition (A) combine with each other on the substrate to form a substantially continuous liquid film 103. This is also true when droplets of the curable composition (A) with a volume of 1.0 pL or more are deposited at a density of 130 droplets / mm 2 This means that the elements are arranged at a density of at least 100 sq. m.

[0224] With reference to Figures 3(a) to 3(d), the flow behavior of the droplets of the curable composition (A) placed on the substrate during the waiting step is as described with reference to Figures 3(a) to 3(d).

[0225] Furthermore, in the waiting step, as shown schematically in Fig. 2(d), the solvent 105 (solvent (d1)) contained in the liquid film 104 is volatilized. The amount of solvent (d1) remaining in the liquid film 103 after the waiting step (for example, at the start of the contacting step) is preferably 10% by volume or less, assuming that the total weight of the components other than solvent (d1) is 100% by volume. If the amount of solvent (d1) remaining is more than 10% by volume, the mechanical properties of the cured film may be reduced.

[0226] During the waiting step, a baking step may be performed to heat the mold 201 and the curable composition (A) or to ventilate the atmospheric gas around the mold 201 in order to accelerate the evaporation of the solvent (d1). Heating is performed, for example, at a temperature of 30°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 110°C. The heating time may be 10 seconds or higher and 600 seconds or lower. The baking step may be performed using a known heater such as a hot plate or an oven.

[0227] The waiting step is, for example, 0.1 to 600 seconds, preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 second, the droplets of the curable composition (A) will not bond sufficiently, and a substantially continuous liquid film will not be formed. If the waiting step exceeds 600 seconds, productivity will decrease. Therefore, to prevent a decrease in productivity, substrates that have completed the placement step may be sequentially transferred to the waiting step, and the waiting step may be performed on multiple substrates in parallel, and the substrates that have completed the waiting step may be sequentially transferred to the contacting step. Note that in conventional technology, it theoretically takes several thousand to tens of thousands of seconds for a substantially continuous liquid film to be formed, but in reality, the spreading of the droplets of the curable composition stagnates due to volatilization, making it impossible to form a continuous liquid film.

[0228] In the waiting step, when the solvent (d1) volatilizes, a substantially continuous liquid film 104 consisting of the components (a1), (b1), and (c1) remains. The average remaining liquid film thickness of the substantially continuous liquid film 104 from which the solvent (d1) has been volatilized (removed) is thinner than the liquid film 103 by the amount of solvent (d1) that has been volatilized. The entire pattern formation region of the substrate 101 remains covered with the substantially continuous liquid film 104 of the curable composition (A') from which the solvent (d1) has been removed.

[0229] <Contact process> In the contacting step, as schematically shown in Figure 2(e), a substantially continuous liquid film 104 of the curable composition (A) from which the solvent (d1) has been removed is brought into contact with a substrate 206. The contacting step includes a step of changing a state in which the curable composition (A) and the substrate 206 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. As a result, the liquid of the curable composition (A) fills the recesses of the fine pattern on the surface of the substrate 206, and this liquid becomes a liquid film that fills the fine pattern of the mold 106.

[0230] A comparison of the gas trapped between the mold 106 and the substrate 101 in the contact step between the conventional technology (for example, Japanese Patent No. 6584578) and this embodiment is shown in Figure 4. According to this embodiment, in the waiting step, the curable composition (A) becomes a substantially continuous liquid film 104 from which the solvent (d1) has been removed, so the volume of gas trapped between the mold 106 and the substrate 101 is smaller than in the conventional technology. Therefore, spreading of the curable composition (A) in the contact step is completed quickly.

[0231] If the spreading and filling of the curable composition (A) is completed quickly in the contacting step, the time required to maintain the substrate 206 in contact with the curable composition (A) (the time required for the contacting step) can be shortened. Furthermore, shortening the time required for the contacting step leads to a shortening of the time required for pattern formation (film formation), thereby improving productivity. The contacting step is preferably from 0.1 to 3 seconds, and particularly preferably from 0.1 to 1 second. If the contacting step is shorter than 0.1 seconds, spreading and filling will be insufficient, and defects known as unfilled defects tend to occur frequently.

[0232] A substrate having a base layer laminated thereon may be used as the substrate 206. The surface of the substrate 261 is preferably coated with the above-mentioned layer-forming composition, and the adhesion to the curable composition (A) may be improved by surface treatment such as silane coupling agent treatment, silazane treatment, or formation of an organic thin film. As the silane coupling agent, a known silane coupling agent having an acrylic group can be used.The method of applying the silane coupling agent can be, for example, an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, a vapor deposition method, etc.Among these methods, the vapor deposition method is particularly preferred from the viewpoint of application property, particularly film thickness uniformity.

[0233] Alternatively, the substrate 206 may be a silicon substrate that has not been surface-treated.

[0234] The pattern formed on the surface of the substrate 206 has a height of, for example, 4 nm or more and 200 nm or less. The lower the height of the pattern on the substrate 206, the smaller the force required to separate the substrate 206 from the cured film of the curable composition during the demolding process, i.e., the demolding force, and the fewer demolding defects remaining on the substrate 206 due to the curable composition pattern being torn off. Furthermore, the impact of demolding the mold may cause elastic deformation of the curable composition pattern, resulting in contact between adjacent pattern elements, resulting in adhesion or breakage. However, to avoid these problems, it is advantageous for the height of the pattern elements to be approximately twice or less the width of the pattern elements (aspect ratio of 2 or less). On the other hand, if the height of the pattern elements is too low, the processing accuracy of the mold 201 decreases.

[0235] The substrate 206 may be subjected to a surface treatment before the contact step in order to improve the releasability of the substrate 206 from the curable composition (A). Examples of surface treatments include applying a release agent to the surface of the substrate 206 to form a release agent layer. Examples of release agents that can be applied to the surface of the substrate 206 include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. Commercially available coating-type release agents, such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd., can also be suitably used. One type of release agent may be used alone, or two or more types may be used in combination. Of the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0236] In the contacting step, the pressure applied to the curable composition (A) when the substrate 206 is brought into contact with the curable composition (A) is not particularly limited, and is, for example, 0 MPa or more and 100 MPa or less. The pressure applied to the curable composition (A) when the substrate 206 is brought into contact with the curable composition (A) is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0237] The contacting step can be carried out under any of the following conditions: air, reduced pressure, or inert gas; however, a reduced pressure or inert gas atmosphere is preferred because it can prevent the curing reaction from being affected by oxygen or moisture. Specific examples of inert gases used when carrying out the contacting step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, or mixtures thereof. Gases containing 10% or more carbon dioxide or helium by molar ratio are preferred, and gases containing 10% or more carbon dioxide by molar ratio are particularly preferred. Helium gas easily diffuses into the mold, substrate, curable composition, etc., so atmospheric gas trapped in the mold pattern, etc., quickly dissipates. Carbon dioxide easily dissolves in the curable composition and the underlayer on the substrate, so atmospheric gas trapped in the mold pattern, etc., quickly dissipates. Furthermore, the solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m 3 ·ATM or more 10kg / m 3 1 atm or less. Details of these are disclosed in JP 2022-99271 A. When the contact step is carried out under a specific gas atmosphere, including air, the preferred pressure is 0.0001 atmospheres or more and 10 atmospheres or less.

[0238] <Curing process> In the curing step, as schematically shown in FIG. 2(f), the curable composition (A) is irradiated with irradiation light 107 as curing energy, thereby curing the curable composition (A) and forming a cured film. In the curing step, for example, the curable composition (A) is irradiated with irradiation light 107 through a substrate 206. More specifically, the curable composition (A) filled in a fine pattern on the substrate 206 is irradiated with irradiation light 107 through the substrate 206. As a result, the curable composition (A) filled in the fine pattern on the substrate 206 is cured to form a cured film 108 having the pattern.

[0239] The irradiation light 107 is selected according to the wavelength to which the curable composition (A) is sensitive. Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, electron beams, or the like having a wavelength of 150 nm or more and 400 nm or less. It is particularly preferable that the irradiation light 107 be ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are compounds that are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. However, ultra-high-pressure mercury lamps are particularly preferable as the light source that emits ultraviolet light. The number of light sources may be one or more. The entire area of ​​the curable composition (A) filled into the fine pattern of the mold may be irradiated with light, or only a limited area (a limited area) may be irradiated with light. Light irradiation may be performed intermittently multiple times over the entire area of ​​the substrate, or continuously over the entire area of ​​the substrate. Furthermore, light may be irradiated over a first area of ​​the substrate in a first irradiation process, and over a second area of ​​the substrate different from the first area in a second irradiation process.

[0240] <Mold release process> In the demolding step, as shown schematically in FIG. 2(g), the substrate 206 is separated from the cured film 108. By separating the patterned cured film 108 from the substrate 206, a free-standing cured film 108 having a pattern that is an inverse of the fine pattern of the substrate 206 is obtained. Here, the cured film remains in the recesses of the patterned cured film 108. This film is called a residual film.

[0241] The method for separating the substrate 206 from the patterned cured film 108 is not particularly limited as long as a portion of the patterned cured film 108 is not physically damaged during separation. For example, the mold 201 may be fixed, and the substrate 206 may be moved away from the mold 201. Alternatively, the substrate 206 may be fixed, and the mold 201 may be moved away from the substrate 206. The substrate 206 may be separated from the patterned cured film 108 by moving both the substrate 206 and the mold 201 in opposite directions.

[0242] <Repeat> By carrying out a series of steps (manufacturing process) from the above-mentioned placement step to the demolding step in this order, a cured film having the desired uneven pattern shape (a pattern shape that follows the uneven shape of the substrate 206) at the desired position can be obtained.

[0243] In the pattern formation method of the present disclosure, the repeating unit (shot) from the placement process to the demolding process can be repeated multiple times on the same mold, and a cured film 108 having multiple desired patterns at desired positions on the mold can be obtained.

[0244] [Planarization film formation method] Hereinafter, an example in which the film formation method according to the present disclosure is applied to a planarization film formation method will be described. The planarization film formation method includes, for example, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step. The disposing step is a step of disposing droplets of the curable composition (A) on a substrate. The waiting step is a step of waiting until the droplets of the curable composition (A) bond together and the solvent (d1) evaporates. The contacting step is a step of contacting the curable composition (A) with a mold. The curing step is a step of curing the curable composition (A). The demolding step is a step of separating the mold from the cured film of the curable composition (A). In the planarization film formation method, a substrate having irregularities with a height difference of about 10 to 1,000 nm is used as the substrate, and a mold having a flat surface is used as the mold. A cured film having a surface conforming to the flat surface of the mold is formed through the contacting step, curing step, and demolding step. In the disposing step, droplets of the curable composition (A) are densely disposed in the recessed portions of the substrate, and the curable composition (A) is sparsely disposed in the protruding portions of the substrate. The waiting step is performed after the disposing step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0245] In the planarization film formation method, a mold including a flat surface is used as described above. Such a mold may also be called a superstrate. In such a mold, the entire area in contact with the curable composition may be a flat surface without a pattern. However, alignment marks or patterns may be formed in part of the area in contact with the curable composition. Therefore, for example, 90% or more of the area in contact with the curable composition may be a flat surface.

[0246] [Product manufacturing method] The method for manufacturing an article includes a forming step of forming a film of a curable composition on a substrate using the above-mentioned film forming method, a processing step of processing the substrate on which the film of the curable composition has been formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. As described above, the film forming method is a pattern forming method or a planarizing film forming method.

[0247] Furthermore, the cured film 108 having a pattern formed by the pattern formation method of the present disclosure is used as is as at least a part of a constituent member of various articles. The cured film 108 having a pattern formed by the pattern formation method of the present disclosure is temporarily used as a mask for etching or ion implantation of the substrate 101 (or the layer to be processed if the substrate 101 has a layer to be processed). After etching or ion implantation is performed in the processing step of the substrate 101, the mask is removed. This allows various articles to be manufactured.

[0248] When removing the cured material in recesses of the cured material pattern by etching, the specific method is not particularly limited, and known methods, such as dry etching, can be used. A known dry etching apparatus can be used for dry etching. The source gas for dry etching is appropriately selected depending on the elemental composition of the cured material to be etched. Specifically, halogen-based gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2 can be used as the source gas. Other examples of source gases that can be used include gases containing oxygen atoms such as O2, CO, and CO2, inert gases such as He, N2, and Ar, and gases such as H2 and NH3. A mixture of these gases can also be used as the source gas. In this case, a high dry etching resistance is required for the photocured film in order to process the base substrate with a high yield.

[0249] The article may be an electric circuit element, an optical element, a MEMS, a recording element, a sensor, or a mold. Examples of the electric circuit element include volatile or non-volatile semiconductor memory such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensor, and FPGA. Examples of the optical element include a microlens, a light guide, a waveguide, an anti-reflection film, a diffraction grating, a polarizing element, a color filter, a light-emitting element, a display, and a solar cell. Examples of the MEMS include a DMD, a microchannel, and an electromechanical conversion element. Examples of the recording element include an optical disk such as a CD or a DVD, a magnetic disk, a magneto-optical disk, and a magnetic head. Examples of the sensor include a magnetic sensor, an optical sensor, and a gyro sensor. Examples of the mold include an imprint mold.

[0250] Furthermore, known photolithography processes such as imprint lithography and extreme ultraviolet (EUV) exposure can be performed on the planarization film formed by the planarization film formation method of the present disclosure. Alternatively, a spin-on-glass (SOG) film and / or a silicon oxide layer can be laminated, and then a curable composition can be applied thereon to perform a photolithography process. This allows devices such as semiconductor devices to be manufactured. Furthermore, electronic devices including such devices, such as displays, cameras, and medical devices, can also be formed. Examples of such devices include LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and NAND flash memory.

[0251] [Example] Examples will be described in detail below, but the technical scope of the present invention is not limited to the following examples. Note that "parts" and "%" used below are all by weight unless otherwise specified.

[0252] [Preparation of Curable Composition] The following polymerizable compound (a1), photopolymerization initiator (b1), solvent (d1), and surfactant (c1) were mixed to the weight percentages (%) shown in Table 1, and the mixture was filtered through a polyethylene filter with a pore size of 0.005 μm, thereby preparing curable compositions 1 to 6. [Table 1]

[0253] The abbreviations shown in Table 1 are as follows: DCPDA: Dimethylol-tricyclodecane diacrylate (Kyoeisha Chemical Co., Ltd.) Omnirad 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (IGM Resin) PGMEA: Propylene glycol monomethyl ether acetate (Kanto Chemical) FS2000M1: Fluorine-based surfactant (manufactured by CHANGZHOU FOREIGN CO., LTD.)

[0254] [Preparation of Layer-Forming Composition 1] The compound (a2-1) and the crosslinking agent (b2-1) were dissolved in a volatile solvent (d2-1) so as to obtain the weight percentages shown below. ·Compound (a2-1) 0.2775 Crosslinking agent (b2-1) 0.0692 Volatile solvent (d2-1) 99.6533

[0255] Next, the resulting mixed solution was filtered through a polyethylene filter with a pore size of 0.005 μm, thereby preparing layer-forming composition 1. The abbreviations are as follows: (Compound (a2-1)) Carboxylic acid anhydride-modified cresol novolac epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: EA-7140) (formula (1)) [ka] (Crosslinking agent (b2-1)) 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine (Tokyo Chemical Industry Co., Ltd.) (Formula (2)) [ka] (Volatile solvent (d2-1)) Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.)

[0256] [Layer forming composition 2] Layer-forming composition 2 used was layer-forming composition FULS-013D manufactured by Fujifilm.

[0257] [Formation of Adhesion Layers 1 and 2] The layer-forming compositions 1 and 2 were each applied to a 2-inch silicon wafer by spin coating. Then, the wafer was baked at 220° C. for 90 seconds to form adhesion layers 1 and 2, respectively.

[0258] [Contact angle of curable composition to adhesive layer] The contact angle of the curable composition with the adhesive layer was measured using an industrial material printer DMP-2850 (Fujifilm). The droplet volume was set to 1 to 2 μL, and the droplet was photographed with the top camera of the device immediately after landing on the adhesive layer. The contact angle was calculated using Equation 4 and Equation 5 from the droplet diameter measured by image analysis.

[0259] Assuming that the droplet spreads while maintaining its spherical shape, the relationship between the droplet radius r and height h can be expressed as follows: The abbreviations shown in the following formula are as follows: r: Droplet radius V: droplet volume h: droplet height r0: Radius when the initial shape is a hemisphere (Formula 4)

number

number

[0260] [Contact angle of the curable composition after removing the solvent to the adhesive layer] The contact angle was measured using an automatic static contact angle measuring device, Dropmaster 300 (Kyowa Interface Science Co., Ltd.), with a droplet volume of 1 μL. The equilibrium contact angle (e.g., the contact angle 15 seconds after the droplet was deposited) was measured after the solvent had completely evaporated.

[0261] Example 1 In Example 1, the measurement results of the droplet diameter measured above, the contact angle of curable composition 1 to adhesive layer 1, and the contact angle of a composition obtained by removing the solvent from the curable composition to adhesive layer 1 are shown.

[0262] <Examples 2 to 24> The curable composition and adhesive layer used in Example 1 were changed as shown in Table 2, and Examples 2 to 24 were carried out. [Table 2]

[0263] <Evaluation of inkjet ejection> The inkjet discharge was evaluated using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). Cartridges were filled with the curable compositions of Examples 1 to 24 and Comparative Examples 1 to 3 shown in Table 2. The droplet discharge was observed with a built-in discharge observation camera, and the inkjet discharge was evaluated according to the following evaluation criteria.

[0264] (Evaluation criteria) AAA: At ejection speeds (flight speeds) of 5 m / sec or more, no deviation (distortion) of the impact position was observed. AA: At ejection speeds of 5 m / sec or more, a very slight deviation in the impact position was observed that had no practical effect. A: At a discharge speed of 3 m / sec or more, a very slight deviation in the impact position was observed that had no practical effect. B: No discharge.

[0265] <Evaluation of liquid film formation> A commercially available industrial material printer, DMP-2850 (manufactured by Fujifilm), was used to evaluate liquid film formation. The curable compositions of Examples 1 to 24 and Comparative Examples 1 to 3 shown in Table 2 were each filled into a cartridge. Approximately 2 pL of liquid droplets were dropped (arranged) on an adhesive layer or a silicon substrate in an array of six rows at four different pitches (35, 50, 70, and 122 μm) such that the film thickness after evaporation of the solvent (d1) would be 160 nm or less. Liquid film formation was then evaluated using the following evaluation criteria.

[0266] (Evaluation criteria) AAA: A substantially continuous liquid film was formed at all pitch intervals. AA: A substantially continuous liquid film was formed at pitch intervals of 35, 50, and 70 μm. A: At pitch intervals of 35 and 50 μm, a substantially continuous liquid film was formed. B: At a pitch of 35 μm, a substantially continuous liquid film was formed. C: A substantially continuous liquid film was not formed at any pitch interval.

[0267] <Evaluation of liquid film stability> The liquid film stability was evaluated using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). In the evaluation of liquid film formation described above, the time during which the liquid film was maintained without shrinkage after formation was measured, and the liquid film stability was evaluated according to the following evaluation criteria. "Shrinkage" is defined as the length of the liquid film becoming shorter than the designed liquid film area.

[0268] (Evaluation criteria) AAA: No contraction for more than 600 seconds. AA: No contraction for 300 seconds or more but less than 600 seconds. A: No contraction for 180 seconds or more but less than 300 seconds. B: Contraction occurred within 180 seconds.

[0269] <Evaluation of overhang amount> The amount of overflow was evaluated using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). In the evaluation of liquid film formation described above, after 180 seconds had passed since the liquid film was formed, it was confirmed that the liquid film had formed a substantially continuous liquid film, and the amount of overflow was measured. The amount of overflow of the liquid film was defined as the length of the liquid film minus 70 × 6 μm (designed liquid film area), and the amount of overflow was evaluated according to the following evaluation criteria. (Evaluation criteria) AAA: The amount of protrusion was 50 μm or less. AA: The amount of protrusion was 70 μm or less. A: The amount of protrusion was 100 μm or less. B: The amount of protrusion was greater than 100 μm.

[0270] The evaluation results to date are shown in Table 3. [Table 3]

[0271] It can be seen that if the viscosity of the curable composition at 23°C is 1.9 mPa·s or more and 60 mPa·s or less, inkjet (IJ) ejection is good, and a viscosity of 3 mPa·s or more and 60 mPa·s or less is preferable, and a viscosity of 8 mPa·s or more and 60 mPa·s or less is even more preferable.

[0272] It can be seen that the liquid film formation is good when the contact angle of the curable composition to the adhesive layer or silicon substrate is 1.8° or less, preferably 1.1° or less, and more preferably 0.6° or less.

[0273] It can be seen that the liquid film stability is good if the contact angle of the composition obtained by removing the solvent from the curable composition with respect to the adhesive layer or silicon substrate is 19° or less, preferably 15° or less, and more preferably 11° or less.

[0274] It can be seen that the amount of overflow is good if the contact angle of the composition obtained by removing the solvent from the curable composition with respect to the adhesive layer or silicon substrate is 11° or more, preferably 13° or more, and even more preferably 17° or more.

[0275] The disclosure of this specification includes the following techniques. (Item 1) A material kit including a curable composition and a layer-forming composition for forming an adhesion layer that adheres a substrate to the curable composition, The curable composition contains a polymerizable compound (a1), a photopolymerization initiator (b1), and a solvent (d1), the viscosity of the curable composition at 23°C and 1 atmosphere is 1.3 mPa s or more and 60 mPa s or less; the content of the solvent (d1) relative to the total volume of the polymerizable compound (a1), the photopolymerization initiator (b1), and the solvent (d1) is 5% by volume or more and 95% by volume or less; The boiling point of the solvent (d1) is less than 250°C at 1 atmosphere, the contact angle of the curable composition with the adhesive layer is 1.8° or less, the contact angle of the curable composition from which the solvent (d1) has been removed to the adhesive layer is 11° or more and 19° or less; A material kit characterized by: (Item 2) 2. The material kit according to item 1, wherein the contact angle of the curable composition with respect to the adhesive layer is 1.0° or less. (Item 3) 3. The material kit according to item 1 or 2, wherein the composition, from which the solvent (d1) has been removed, has a viscosity of 30 mPa s or more and 10,000 mPa s or less at 23°C and 1 atmosphere. (Item 4) 4. The material kit according to any one of items 1 to 3, wherein the curable composition is a curable composition for inkjet printing. (Item 5) 5. The material kit according to any one of items 1 to 4, wherein the solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m3·atm or more and 10 kg / m3·atm or less. (Item 6) the layer-forming composition comprises a solvent (d2), 6. The material kit according to any one of items 1 to 5, wherein the content of the solvent (d2) is 70% by mass or more and 99.5% by mass or less when the entire layer-forming composition is taken as 100% by mass. (Item 7) 7. The material kit according to any one of items 1 to 6, wherein the layer-forming composition does not contain a photopolymerization initiator. (Item 8) 8. The material kit according to any one of items 1 to 7, wherein the content of particles having a particle size of more than 0.2 μm is less than 1 particle / mL when the entire layer-forming composition is taken as 100% by mass. (Item 9) The layer-forming composition comprises a compound (a2) having at least one functional group capable of bonding to the substrate and at least one polymerizable functional group, a crosslinking agent (b2), and a solvent (d2). (Item 10) When R1 to R6 each independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an alkylol group, The crosslinking agent (b2) is a compound represented by the following formula: [ka] is a compound represented by At least five of R1 to R6 are alkoxyalkyl groups or alkylol groups. 10. The material kit according to item 9, (Item 11) 11. The material kit according to item 9 or 10, characterized in that the crosslinking agent (b2) includes at least one selected from pentamethoxymethylmelamine, hexamethoxymethylmelamine, (hydroxymethyl)pentakis(methoxymethyl)melamine, hexaethoxymethylmelamine, hexabutoxymethylmelamine, pentamethylolmelamine, and hexamethylolmelamine. (Item 12) 12. The material kit according to any one of items 9 to 11, wherein the crosslinking agent (b2) is a compound having a total of at least five alkoxyalkyl groups or alkylol groups or both in one molecule. (Item 13) 13. The material kit according to any one of items 9 to 12, wherein the compound (a2) has at least one hydroxyl group, carboxyl group, thiol group, amino group, epoxy group, or (blocked) isocyanate group in one molecule as a functional group that bonds to the substrate. (Item 14) 14. The material kit according to any one of items 9 to 13, wherein α / β is 0.11 or more and 9 or less, where α and β are weight fractions of the compound (a2) and the crosslinking agent (b2) relative to the total weight of the layer-forming composition, respectively. (Item 15) 15. The material kit according to any one of items 9 to 14, wherein the sum of α and β is 0.01 or more and 10 or less, where α and β are weight fractions of the compound (a2) and the crosslinking agent (b2) relative to the total weight of the layer-forming composition, respectively. (Item 16) 16. The material kit according to any one of items 9 to 15, wherein the layer-forming composition is a curable composition for imprinting. (Item 17) A curable composition comprising a polymerizable compound (a1), a photopolymerization initiator (b1), and a solvent (d1), the viscosity of the curable composition at 23°C and 1 atmosphere is 1.3 mPa s or more and 60 mPa s or less; the content of the solvent (d1) relative to the total volume of the polymerizable compound (a1), the photopolymerization initiator (b1), and the solvent (d1) is 5% by volume or more and 95% by volume or less; The boiling point of the solvent (d1) is less than 250°C at 1 atmosphere, the contact angle of the curable composition with respect to the silicon substrate is 1.8° or less; the contact angle of the curable composition from which the solvent (d1) has been removed to the silicon substrate is 11° or more and 19° or less; A curable composition characterized by: (Item 18) Item 18. The curable composition according to item 17, wherein the contact angle of the curable composition with respect to the silicon substrate is 1.0° or less. (Item 19) Item 19. The curable composition according to item 17 or 18, wherein the composition from which the solvent (d1) has been removed has a viscosity of 30 mPa s or more and 10,000 mPa s or less at 23°C and 1 atmosphere. (Item 20) A film-forming method for forming a film of a curable composition in a space between a mold and a substrate, comprising: A disposing step of discretely disposing a plurality of droplets of the curable composition according to any one of items 17 to 19 on the substrate; a waiting step of waiting until each of the plurality of droplets discretely arranged on the substrate combines with an adjacent droplet to form a continuous liquid film on the substrate; a contacting step of contacting the mold with the liquid film after the waiting step; A film forming method comprising the steps of: (Item 21) 21. The film forming method according to item 20, wherein the waiting step waits until the solvent contained in the liquid film evaporates and the content of the solvent becomes 10% by volume or less with respect to the entire liquid film. (Item 22) 22. The film forming method according to item 20 or 21, wherein in the waiting step, the substrate is heated at a temperature of 30° C. or higher and 200° C. or lower for 10 seconds or higher and 600 seconds or lower. (Item 23) In the disposing step, droplets of the curable composition having a volume of 1.0 pL or more are deposited on the substrate at a density of 80 droplets / mm 2 23. The film forming method according to any one of items 20 to 22, wherein the particles are arranged at a density of at least 1000 nm. (Item 24) 24. The film forming method according to any one of items 20 to 23, wherein an average remaining liquid film thickness, which is a value obtained by dividing the volume of the curable composition remaining after the waiting step by the area of ​​the film-forming region, is 20 nm or less. (Item 25) the mold includes a pattern; In the contacting step, the pattern of the mold is brought into contact with the liquid film, The film forming method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a pattern corresponding to the pattern of the mold. 25. The film forming method according to any one of items 20 to 24, (Item 26) the mold includes a flat surface; In the contacting step, the flat surface of the mold is brought into contact with the liquid film, The film forming method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a surface conforming to the flat surface of the mold. 26. The film forming method according to any one of items 20 to 25, (Item 27) 27. The film forming method according to any one of items 20 to 26, wherein in the disposing step, the plurality of droplets are discretely disposed on the substrate using an inkjet method. (Item 28) 28. The film forming method according to any one of items 20 to 27, wherein in the contacting step, the gas filling the space between the mold and the substrate contains carbon dioxide at a molar ratio of 10% or more. (Item 29) A forming step of forming a film of a curable composition on a substrate using the film forming method according to any one of items 20 to 28; a processing step of processing the substrate on which the film has been formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising:

[0276] The invention is not limited to the above-described embodiments, and various changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the following claims are appended to apprise the public of the scope of the invention. [Explanation of symbols]

[0277] 101: substrate, 102: droplet, 103: liquid film, 105: solvent, 106: mold, 107: irradiated light, 108: cured film

Claims

1. A material kit including a curable composition and a layer-forming composition for forming an adhesion layer that adheres a substrate to the curable composition, The curable composition contains a polymerizable compound (a1), a photopolymerization initiator (b1), and a solvent (d1), the viscosity of the curable composition at 23°C and 1 atmosphere is 1.3 mPa s or more and 60 mPa s or less; the content of the solvent (d1) relative to the total volume of the polymerizable compound (a1), the photopolymerization initiator (b1), and the solvent (d1) is 5% by volume or more and 95% by volume or less; The boiling point of the solvent (d1) is less than 250°C at 1 atmosphere, the contact angle of the curable composition with respect to the adhesive layer is 1.8° or less, a contact angle of the curable composition, from which the solvent (d1) has been removed, with respect to the adhesive layer is 11° or more and 19° or less; A material kit characterized by:

2. The material kit according to claim 1, wherein the contact angle of the curable composition with respect to the adhesive layer is 1.0° or less.

3. 2. The material kit according to claim 1, wherein the composition, from which the solvent (d1) has been removed, has a viscosity of 30 mPa·s or more and 10,000 mPa·s or less at 23°C and 1 atmosphere.

4. The material kit according to claim 1 , wherein the curable composition is a curable composition for inkjet printing.

5. 2. The material kit according to claim 1, wherein the solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m3·atm or more and 10 kg / m3·atm or less.

6. the layer-forming composition contains a solvent (d2), 2. The material kit according to claim 1, wherein the content of the solvent (d2) is 70% by mass or more and 99.5% by mass or less when the entire layer-forming composition is taken as 100% by mass.

7. The material kit of claim 1 , wherein the layer-forming composition does not contain a photopolymerization initiator.

8. 2. The material kit according to claim 1, wherein the content of particles having a particle size of more than 0.2 μm is less than 1 particle / mL when the entire layer-forming composition is taken as 100% by mass.

9. The material kit according to claim 1, characterized in that the layer-forming composition comprises a compound (a2) having at least one functional group capable of bonding to the substrate and at least one polymerizable functional group, a crosslinker (b2), and a solvent (d2).

10. R 1 ~R 6 each independently represents a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an alkylol group, The crosslinking agent (b2) is a compound represented by the following formula: 【Chemistry 63】 is a compound represented by R 1 ~R 6 at least five of which are alkoxyalkyl or alkylol groups; 10. The material kit of claim 9.

11. 10. The material kit according to claim 9, wherein the crosslinking agent (b2) includes at least one selected from pentamethoxymethylmelamine, hexamethoxymethylmelamine, (hydroxymethyl)pentakis(methoxymethyl)melamine, hexaethoxymethylmelamine, hexabutoxymethylmelamine, pentamethylolmelamine, and hexamethylolmelamine.

12. The material kit according to claim 9, characterized in that the crosslinking agent (b2) is a compound having a total of at least five alkoxyalkyl groups or alkylol groups, or both, in one molecule.

13. The material kit according to claim 9, characterized in that the compound (a2) has at least one of a hydroxyl group, a carboxyl group, a thiol group, an amino group, an epoxy group, or a (blocked) isocyanate group in one molecule as a functional group that bonds to the substrate.

14. The material kit according to claim 9, wherein α / β is 0.11 or more and 9 or less, where α and β are weight fractions of the compound (a2) and the crosslinking agent (b2) relative to the total weight of the layer-forming composition, respectively.

15. 10. The material kit according to claim 9, wherein the sum of α and β is 0.01 or more and 10 or less, where α and β are weight fractions of the compound (a2) and the crosslinking agent (b2) relative to the total weight of the layer-forming composition, respectively.

16. The material kit of claim 9 , wherein the layer-forming composition is a curable composition for imprinting.

17. A curable composition comprising a polymerizable compound (a1), a photopolymerization initiator (b1), and a solvent (d1), the viscosity of the curable composition at 23°C and 1 atmosphere is 1.3 mPa s or more and 60 mPa s or less; the content of the solvent (d1) relative to the total volume of the polymerizable compound (a1), the photopolymerization initiator (b1), and the solvent (d1) is 5% by volume or more and 95% by volume or less; The boiling point of the solvent (d1) is less than 250°C at 1 atmosphere, the contact angle of the curable composition with respect to the silicon substrate is 1.8° or less; the contact angle of the curable composition, from which the solvent (d1) has been removed, with respect to the silicon substrate is 11° or more and 19° or less; A curable composition characterized by:

18. The curable composition according to claim 17, wherein the contact angle of the curable composition with respect to the silicon substrate is 1.0° or less.

19. 18. The curable composition according to claim 17, wherein the composition from which the solvent (d1) has been removed has a viscosity of 30 mPa·s or more and 10,000 mPa·s or less at 23°C and 1 atmosphere.

20. A film-forming method for forming a film of a curable composition in a space between a mold and a substrate, comprising: a disposing step of discretely disposing a plurality of droplets of the curable composition according to claim 17 on the substrate; a waiting step of waiting until each of the plurality of droplets discretely arranged on the substrate combines with an adjacent droplet to form a continuous liquid film on the substrate; a contacting step of contacting the mold with the liquid film after the waiting step; A film forming method comprising the steps of:

21. 21. The film forming method according to claim 20, wherein the waiting step waits until the solvent contained in the liquid film volatilizes and the content of the solvent becomes 10% by volume or less with respect to the entire liquid film.

22. 21. The film forming method according to claim 20, wherein in the waiting step, the substrate is heated at a temperature of 30° C. or higher and 200° C. or lower for a period of 10 seconds or higher and 600 seconds or lower.

23. In the disposing step, droplets of the curable composition having a volume of 1.0 pL or more are deposited on the substrate at a rate of 80 droplets / mm ２ 21. The film forming method according to claim 20, wherein the particles are arranged at a density equal to or greater than 1000 .mu.m.

24. 21. The film forming method according to claim 20, wherein an average remaining liquid film thickness, which is a value obtained by dividing the volume of the curable composition remaining after the waiting step by the area of ​​the film formation region, is 20 nm or less.

25. the mold includes a pattern; In the contacting step, the pattern of the mold is brought into contact with the liquid film, The film forming method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a pattern corresponding to the pattern of the mold.

21. The film forming method according to claim 20.

26. the mold includes a flat surface; In the contacting step, the flat surface of the mold is brought into contact with the liquid film, The film forming method further includes a curing step of curing the liquid film after the contacting step to form a cured film having a surface conforming to the flat surface of the mold.

21. The film forming method according to claim 20.

27. 21. The film forming method according to claim 20, wherein in the disposing step, the plurality of droplets are discretely disposed on the substrate using an inkjet method.

28. 21. The film forming method according to claim 20, wherein in the contacting step, the gas filling the space between the mold and the substrate contains carbon dioxide at a molar ratio of 10% or more.

29. A forming step of forming a film of a curable composition on a substrate using the film forming method according to any one of claims 20 to 28; a processing step of processing the substrate on which the film has been formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising:

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