Curable composition, film-forming method, and article manufacturing method

Abstract

a curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), wherein the curable composition has a viscosity of 2 mPa·s to 60 mPa·s at 23°C, the content of the solvent (d) relative to the total volume of the curable composition is 5 to 95 vol%, and the boiling point of the solvent (d) under atmospheric pressure is lower than 250°C, and the polymerizable compound (a) comprises a compound (a-1) comprising one or more aromatic rings or aromatic heterocycles and four or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles.

Description

[Technical Field]

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

[0002] In the photolithography process for manufacturing semiconductor devices, it is necessary to flatten 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 the projected image is formed becomes shallower as miniaturization progresses, so the unevenness of the substrate surface must be kept to a few tens of nanometers or less. In imprinting technology, the same level of flatness as EUV is required to improve the filling ability of the curable composition and line width accuracy.

[0003] As a planarization technique, a technique has been proposed in Japanese Patent No. 6584578 and Japanese Patent Laid-Open No. 2019-140394 in which droplets of a curable composition are discretely dropped (placed) on a substrate having irregularities in an amount corresponding to the irregularities, and the curable composition is cured while being brought into contact with a mold having a flat surface, thereby obtaining a flat surface. Films (flat films) formed by such planarization techniques are required not only to be flat, but also to have high heat resistance, for example, of 400°C or higher.

[0004] However, it is difficult to form a flat film with high heat resistance using the materials exemplified in Japanese Patent No. 6584578 and Japanese Patent Laid-Open No. 2019-140394. Summary of the Invention [Means for solving the problem]

[0005] The present invention provides a new technique relating to a curable composition.

[0006]

[0013] One aspect of the present invention provides a curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), wherein the curable composition has a viscosity of 2 mPa·s to 60 mPa·s at 23°C, the content of the solvent (d) relative to the total volume of the curable composition is 5 to 95 vol%, and the boiling point of the solvent (d) under atmospheric pressure is less than 250°C, and the polymerizable compound (a) comprises a compound (a-1) comprising one or more aromatic rings or aromatic heterocycles and four or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles.

[0007] 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. [Brief explanation of the drawings]

[0008] [Figure 1A] FIG. 1A is a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present invention. [Figure 1B] FIG. 1B is a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present invention. [Figure 1C] FIG. 1C is a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present invention. [Figure 1D] FIG. 1D is a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present invention. [Figure 1E] FIG. 1E is a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present invention. [Figure 1F] FIG. 1F is a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present invention. [Figure 1G] FIG. 1G is a diagram illustrating a pattern forming method (film forming method) according to one aspect of the present invention. [Figure 2A] FIG. 2A is a diagram illustrating the flow behavior of droplets of the curable composition during the waiting step. [Figure 2B]FIG. 2B is a diagram illustrating the flow behavior of the droplets of the curable composition during the waiting step. [Figure 2C] FIG. 2C is a diagram illustrating the flow behavior of the droplets of the curable composition during the waiting step. [Figure 2D] FIG. 2D is a diagram illustrating the flow behavior of the droplets of the curable composition during the waiting step. [Figure 3] FIG. 3 is a diagram showing a comparison between the contacting step in the prior art and the contacting step in the present invention. [Figure 4] FIG. 4 is a diagram for explaining the SLLOD method calculation. [Figure 5] FIG. 5 is a diagram for explaining the SLLOD method calculation. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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.

[0010] In providing a new technology related to curable compositions, the present inventors have discovered that a curable composition containing a polymerizable compound containing one or more aromatic rings or aromatic heterocycles and four or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles has high heat resistance. However, such a curable composition has high viscosity, and there is room for improvement in order to discretely drop (place) droplets of the curable composition using an inkjet method. The new technology related to curable compositions includes, for example, a curable composition and planarization technology for producing a flat film with high heat resistance.

[0011] [Curable composition] The curable composition (A) of the present invention is a curable composition for inkjet printing. The curable composition (A) of the present invention is a composition containing at least component (a) which is a polymerizable compound, component (b) which is a photopolymerization initiator, and component (d) which is a solvent. The polymerizable compound component (a) of the present invention contains at least a compound (a-1) having one or more aromatic rings or aromatic heterocycles and containing four or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles. The curable composition (A) of the present invention may further contain a non-polymerizable compound (c).

[0012] 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."

[0013] <Component (a): Polymerizable compound> Component (a) 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 (b)) to form a film made of a polymer compound through a chain reaction (polymerization reaction).

[0014] Examples of such polymerizable compounds include radically polymerizable compounds. The polymerizable compound as component (a) may be composed of only one type of polymerizable compound, or may be composed of multiple types (one or more) of polymerizable compounds.

[0015] As described above, component (a), which is a polymerizable compound in the present invention, contains at least compound (a-1) containing one or more aromatic rings or aromatic heterocycles and four or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles.

[0016] <Compound (a-1): Polymerizable compound> Specific examples of the compound (a-1) include, but are not limited to, the following:

[0017] TIFF2025540556000002.tif85140TIFF2025540556000003.tif108129TIFF2025540556000004.tif101131

[0018] Examples of the component (a) that does not fall under the category of compound (a-1) include radically polymerizable compounds such as (meth)acrylic compounds, styrene compounds, vinyl compounds, allyl compounds, fumaric compounds, and maleyl compounds.

[0019] 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,

[0020] 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)

[0021] 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

[0022] 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)

[0023] In the above-mentioned group of compounds, (meth)acrylate means acrylate or methacrylate having an equivalent alcohol residue. (Meth)acryloyl group means acryloyl group or methacryloyl group having an equivalent alcohol residue. EO stands for ethylene oxide, and EO-modified compound A refers to a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are bonded via an ethylene oxide block structure. PO stands for propylene oxide, and PO-modified compound B refers to a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are bonded via a propylene oxide block structure.

[0024] 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.

[0025] 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.

[0026] In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0027] Examples of acrylic compounds include, but are not limited to, the following: Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate

[0028] 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

[0029] 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

[0030] 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.)

[0031] When component (a) is composed of multiple compounds, the proportion of compounds corresponding to (a-1) in component (a) is preferably 20% by weight or more, more preferably 50% by weight or more, and even more preferably 90% by weight or more, because the higher the proportion of (a-1), the higher the heat resistance.

[0032] In the film-forming method of the present invention, 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 (d) must be evaporated while the polymerizable compound (a) must not be evaporated. Therefore, the boiling points of the polymerizable compounds (a), which may be present in multiple types, at normal pressure (1 atmosphere) are preferably all 250°C or higher, more preferably all 300°C or higher, and even more preferably all 350°C or higher. Furthermore, in order to obtain 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.

[0033] The boiling point of the polymerizable compound (a) generally correlates with the molecular weight. Therefore, the polymerizable compounds (a) preferably all have a molecular weight of 200 or more, more preferably all have a molecular weight of 240 or more, and even more preferably all have a molecular weight of 250 or more. However, even if the molecular weight is 200 or less, if the boiling point is 250°C or more, it can be preferably used as the polymerizable compound (a) of the present invention.

[0034] The vapor pressure of the polymerizable compound (component (a)) at 80° C. is preferably 0.001 mmHg or less. This is because, although it is preferable to heat the curable composition to accelerate the evaporation of the solvent (component (d)) described below, the evaporation of the polymerizable compound (a) is suppressed during such heating.

[0035] 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.

[0036] <Oonishi parameters for component (a)> 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 It is known that the relationship between the two is expressed by the following formula (1) (see Document A). Document A: Proc. SPIE 11324-11 (2020) V ∝ N / (N C -N O ) Formula (1)

[0037] where N / (N C -N O ) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, JP-A-2009-503139 discloses a technology for obtaining a photocurable composition having high dry etching resistance by using a polymerizable compound component having a small OP.

[0038] 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.

[0039] In the curable composition used in the present invention, the OP of the component (a) is preferably 1.80 or more and 2.70 or less, more preferably 2.00 or more and 2.60 or less, and even more preferably 2.30 or more and 2.60 or less. By making the OP of the component (a) 2.70 or less, the cured film of the curable composition (A) has high dry etching resistance. Furthermore, by making the OP of the component (a) 1.80 or more, it becomes easy to remove the cured film of the curable composition (A) after processing the underlying layer using the cured film of the curable composition (A). When the component (a) is composed of multiple types of polymerizable compounds a1, a2, ..., a n When the composition is as follows, OP is calculated as a weighted average value based on the molar fraction (molar fraction weighted average value) as shown in the following formula (2).

[0040] TIFF2025540556000005.tif15122

[0041] Here, OP n is component a n OP of n n is component a n This is the mole fraction of the total component (a).

[0042] <Compound (a-2): Polymerizable compound having a boiling point of 250°C or higher> The component (a) which is a polymerizable compound in the present invention may contain a compound (a-2) which has two or more cyclic structures, at least one of which is an aromatic or heteroaromatic ring structure.

[0043] The cyclic structure may be an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0044] 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

[0045] 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.

[0046] The number of carbon atoms in the aromatic heterocyclic structure is preferably 1 to 12, 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

[0047] 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

[0048] Specific examples of the compound (a-2) 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)

[0049] TIFF2025540556000006.tif2871

[0050] 1-Naphthyl acrylate (NaA, OP 2.27, boiling point 317°C, vapor pressure at 80°C 0.0422mmHg, molecular weight 198)

[0051] TIFF2025540556000007.tif3929

[0052] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2°C, vapor pressure at 80°C 0.0006mmHg, molecular weight 268.3)

[0053] TIFF2025540556000008.tif3556

[0054] 1-Naphthylmethyl acrylate (Na1MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2)

[0055] TIFF2025540556000009.tif3929

[0056] 2-Naphthylmethyl acrylate (Na2MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2)

[0057] TIFF2025540556000010.tif2853

[0058] 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

[0059] TIFF2025540556000011.tif3553

[0060] 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

[0061] TIFF2025540556000012.tif2362

[0062] FLMA (OP 2.20, boiling point 349.3°C, vapor pressure 0.0018mmHg at 80°C, molecular weight 250.3) shown in the formula below

[0063] TIFF2025540556000013.tif3145

[0064] ATMA (OP2.13, boiling point 414.9°C, vapor pressure 0.0001mmHg at 80°C, molecular weight 262.3) shown in the formula below

[0065] TIFF2025540556000014.tif4042

[0066] 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

[0067] TIFF2025540556000015.tif4748

[0068] BPh44DA (OP 2.63, boiling point 444°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below

[0069] TIFF2025540556000016.tif2291

[0070] 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

[0071] TIFF2025540556000017.tif2487

[0072] DPhEDA (OP 2.63, boiling point 410°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below

[0073] TIFF2025540556000018.tif4846

[0074] BPMDA (OP 2.68, boiling point 465.7°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 364.4) shown in the formula below

[0075] TIFF2025540556000019.tif24101

[0076] Na13MDA (OP 2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 296.3) shown in the formula below

[0077] TIFF2025540556000020.tif4648

[0078] Formula (a-2-1) below (OP 2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181mmHg, molecular weight 199.2)

[0079] TIFF2025540556000021.tif3135

[0080] Formula (a-2-2) below (OP 2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181mmHg, molecular weight 199.2)

[0081] TIFF2025540556000022.tif3135

[0082] The following formula (a-2-3) (OP 1.86, boiling point 369.5°C, vapor pressure at 80°C 0.0053mmHg, molecular weight 193.3)

[0083] TIFF2025540556000023.tif2533

[0084] The following formula (a-2-4) (OP 2.85, boiling point 438.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 296.3)

[0085] TIFF2025540556000024.tif3456

[0086] The following formula (a-2-5) (OP 2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 296.3)

[0087] TIFF2025540556000025.tif3838

[0088] The following formula (a-2-6) (OP 2.87, boiling point 421.0°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 338.4)

[0089] TIFF2025540556000026.tif3366

[0090] The following formula (a-2-7) (OP 2.87, boiling point 465.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4)

[0091] TIFF2025540556000027.tif2487

[0092] The following formula (a-2-8) (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4)

[0093] TIFF2025540556000028.tif2887

[0094] The following formula (a-2-9) (OP 2.50, boiling point 433.1°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 320.3)

[0095] TIFF2025540556000029.tif3856

[0096] The following formula (a-2-10) (OP 2.64, boiling point 468.1°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 326.4)

[0097] TIFF2025540556000030.tif1877

[0098] The following formula (a-2-11) (OP 3.25, boiling point 553.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 358.4)

[0099] TIFF2025540556000031.tif2577

[0100] The following formula (a-2-12) (OP 2.63, boiling point 443.9°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.4)

[0101] TIFF2025540556000032.tif4166

[0102] The following formula (a-2-13) (OP 2.89, boiling point 509.3℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 406.4)

[0103] TIFF2025540556000033.tif6167

[0104] The following formula (a-2-14) (OP 2.63, boiling point 450.0°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.4)

[0105] TIFF2025540556000034.tif3541

[0106] The following formula (a-2-15) (OP 3.00, boiling point 476.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 366.4)

[0107] TIFF2025540556000035.tif5184

[0108] The following formula (a-2-16) (OP 2.68, boiling point 447.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4)

[0109] TIFF2025540556000036.tif5056

[0110] The following formula (a-2-17) (OP 2.36, boiling point 543.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 398.5)

[0111] TIFF2025540556000037.tif3477

[0112] The following formula (a-2-18) (OP 3.27, boiling point 526.9°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 396.4)

[0113] TIFF2025540556000038.tif5567

[0114] The following formula (a-2-19) (OP 2.71, boiling point 333.7°C, vapor pressure 0.0302mmHg at 80°C, molecular weight 244.3)

[0115] TIFF2025540556000039.tif3156

[0116] The following formula (a-2-20) (OP 2.73, boiling point 333.7℃, vapor pressure 0.0134mmHg at 80℃, molecular weight 258.3)

[0117] TIFF2025540556000040.tif3157

[0118] The following formula (a-2-21) (OP 2.71, boiling point 319.2°C, vapor pressure at 80°C 0.0566mmHg, molecular weight 262.3)

[0119] TIFF2025540556000041.tif3157

[0120] The following formula (a-2-22) (OP 2.71, boiling point 336.9°C, vapor pressure 0.0055mmHg at 80°C, molecular weight 244.3)

[0121] TIFF2025540556000042.tif3157

[0122] The following formula (a-2-23) (OP 3.00, boiling point 370.9°C, vapor pressure at 80°C 0.0021mmHg, molecular weight 274.4)

[0123] TIFF2025540556000043.tif3266

[0124] The following formula (a-2-24) (OP 3.00, boiling point 376.4℃, vapor pressure 0.0005mmHg at 80℃, molecular weight 274.4)

[0125] TIFF2025540556000044.tif3166

[0126] The following formula (a-2-25) (OP 3.00, boiling point 379.4℃, vapor pressure at 80℃ 0.0002mmHg, molecular weight 288.4)

[0127] TIFF2025540556000045.tif3267

[0128] The following formula (a-2-26) (OP 2.33, boiling point 360.8°C, vapor pressure 0.0006mmHg at 80°C, molecular weight 252.3)

[0129] TIFF2025540556000046.tif2262

[0130] The following formula (a-2-27) (OP 2.54, boiling point 371.5°C, vapor pressure 0.0003mmHg at 80°C, molecular weight 254.3)

[0131] TIFF2025540556000047.tif2562

[0132] The following formula (a-2-28) (OP 2.57, boiling point 381.2℃, vapor pressure 0.0001mmHg at 80℃, molecular weight 268.3)

[0133] TIFF2025540556000048.tif3267

[0134] The following formula (a-2-29) (OP 2.57, boiling point 381.8°C, vapor pressure at 80°C 0.0004mmHg, molecular weight 268.3)

[0135] TIFF2025540556000049.tif3167

[0136] The following formula (a-2-30) (OP 2.50, boiling point 487.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 374.4)

[0137] TIFF2025540556000050.tif3467

[0138] The following formula (a-2-31) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3)

[0139] TIFF2025540556000051.tif5238

[0140] The following formula (a-2-32) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3)

[0141] TIFF2025540556000052.tif1758

[0142] The following formula (a-2-33) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3)

[0143] TIFF2025540556000053.tif3549

[0144] The following formula (a-2-34) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3)

[0145] TIFF2025540556000054.tif3641

[0146] The following formula (a-2-35) (OP 2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 296.3)

[0147] TIFF2025540556000055.tif3757

[0148] The blending ratio of component (a) in the curable composition (A) is preferably 40% by weight or more and 99% by weight or less, based on the total weight of component (a), component (b) described below, and component (c) described below, i.e., the total mass of all components excluding solvent (d). Furthermore, a blending ratio of 50% by weight or more and 95% by weight or less is more preferable, and a blending ratio of 60% by weight or more and 90% by weight or less is even more preferable. By making the blending ratio of component (a) 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 (a) 99% by weight or less, the blending ratios of components (b) and (c) can be increased, resulting in properties such as a fast photopolymerization rate.

[0149] The multiple additive components that may be added as at least a part of component (a) of the present invention may be polymers having polymerizable functional groups. Such polymers preferably contain at least a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0150] For example, it is preferable to include at least one of the constitutional units represented by any of the following structures (1) to (6).

[0151] TIFF2025540556000056.tif29130

[0152] In the structures (1) to (6), the substituents R are each independently a substituent containing a partial structure containing an aromatic ring, and R 1 is 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.

[0153] The polymer having a polymerizable functional group is typically a compound having 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. In the present invention, the weight-average molecular weight (Mw) refers to that measured by gel permeation chromatography (GPC), unless otherwise specified.

[0154] 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.

[0155] When a polymer having a polymerizable functional group is added as at least a part of component (a), its blending ratio 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 (d). By setting the blending ratio 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 blending ratio 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.

[0156] <Component (b): Photopolymerization initiator> Component (b) is a photopolymerization initiator. In this specification, a photopolymerization initiator is a compound that senses light of a predetermined wavelength and generates the above-mentioned polymerization factor (radical). 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 (b) may be composed of only one type of photopolymerization initiator, or may be composed of multiple types of photopolymerization initiators.

[0157] 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;

[0158] 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)

[0159] Of the above-mentioned radical generators, the component (b) 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

[0160] The blending ratio of component (b) in the curable composition (A) is preferably 0.1% by weight to 50% by weight, based on the total weight of components (a), (b), and (c) described below, i.e., the total weight of all components excluding solvent (d). Furthermore, the blending ratio of component (b) 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 (d). By incorporating component (b) 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 (b) in a ratio of 50% by weight or less, a cured film with a certain level of mechanical strength can be obtained.

[0161] <Component (c): Non-polymerizable compound> In addition to the above-described components (a) and (b), the curable composition (A) of the present invention may further contain a non-polymerizable compound as component (c) depending on various purposes, as long as the effects of the present invention are not impaired. Examples of such component (c) 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, internal mold release agents, antioxidants, polymer components, and other additives. Component (c) may contain multiple types of the above-described compounds.

[0162] 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.

[0163] 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 (b). Here, the interaction refers to energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator, component (b). 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

[0164] The hydrogen donor is a compound that reacts with the initiating radical generated from the photopolymerization initiator (component (b)) or the radical at the polymer growth terminal to generate a radical with higher reactivity. When the photopolymerization initiator (component (b)) is a photoradical generator, it is preferable to add a hydrogen donor.

[0165] 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.

[0166] The hydrogen donor may be used alone or in combination of two or more kinds. The hydrogen donor may also function as a sensitizer.

[0167] An internal mold release agent can be added to the curable composition to reduce the interfacial bonding strength between the mold and the curable composition, i.e., to reduce the mold release force in the mold release step described below. In this specification, "internal mold release agent" means that the agent is added to the curable composition in advance before the curable composition placement step. As the internal mold release agent, surfactants such as silicon-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants can be used. However, in the present invention, as described below, there is a limit to the amount of fluorine-based surfactants that can be added. The internal mold release agent in the present invention is not polymerizable. One type of internal mold release agent may be used alone, or two or more types may be mixed together.

[0168] 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

[0169] 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.

[0170] 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)

[0171] The internal release agent may also be a hydrocarbon surfactant. Examples of hydrocarbon surfactants include alkyl alcohol polyalkylene oxide adducts and polyalkylene oxides, which are alkyl alcohols having 1 to 50 carbon atoms and alkylene oxides having 2 to 4 carbon atoms.

[0172] 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

[0173] 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.

[0174] 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

[0175] 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.

[0176] Alternatively, commercially available polyalkylene oxides may be used, such as BASF's ethylene oxide-propylene oxide copolymer (Pluronic PE6400).

[0177] Fluorine-based surfactants are effective as internal mold release agents because they exhibit an excellent effect of reducing mold release force. The blending ratio of component (c) excluding the fluorine-based surfactant in the curable composition (A) is preferably 0% by weight or more and 50% by weight or less, based on the total weight of components (a), (b), and (c), i.e., the total weight of all components excluding solvent (d). Furthermore, the blending ratio of component (c) excluding the fluorine-based surfactant in the curable composition (A) is more preferably 0.1% by weight or more and 50% by weight or less, and even more preferably 0.1% by weight or more and 20% by weight or less, based on the total weight of all components excluding solvent (d). By setting the blending ratio of component (c) excluding the fluorine-based surfactant to 50% by weight or less, a cured film with a certain level of mechanical strength can be obtained.

[0178] <Component (d): Solvent> The curable composition of the present invention contains, as component (d), a solvent having a boiling point of 80°C or higher and lower than 250°C under normal pressure. Examples of component (d) include solvents in which components (a), (b), and (c) dissolve, such as alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. Component (d) can be used alone or in combination of two or more. The boiling point of component (d) under normal pressure is 80°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of component (d) under normal pressure is lower than 250°C and preferably lower than 200°C. Therefore, the boiling point of component (d) under normal pressure is preferably 80°C or higher and lower than 200°C. If the boiling point of component (d) under normal pressure is less than 80°C, the evaporation rate in the waiting step described below will be too fast, and component (d) will evaporate before the droplets of curable composition (A) combine together, which may prevent the droplets of curable composition (A) from combining together. Also, if the boiling point of component (d) under normal pressure is 250°C or higher, evaporation of solvent (d) will be insufficient in the waiting step described below, and component (d) may remain in the cured product of curable composition (A).

[0179] 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.

[0180] 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

[0181] 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

[0182] 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

[0183] 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

[0184] 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.

[0185] 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

[0186] Furthermore, particularly preferred is propylene glycol monomethyl ether acetate. Other examples include ethyl isocyanurate di(meth)acrylate.

[0187] In the present invention, 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.

[0188] In the present invention, 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 (d). 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)

[0189] In the present invention, when the entire curable composition (A) is taken as 100% by volume, the content of solvent (d) is 5% by volume or more and 95% by volume or less, preferably 30% by volume or more and 85% by volume or less, and more preferably 70% by volume or more and 80% by volume or less. If the content of solvent (d) is less than 5% by volume, a thin film cannot be obtained after evaporation of solvent (d) under conditions that allow for a substantially continuous liquid film to be obtained. On the other hand, if the content of solvent (d) is more than 95% by volume, a thick film cannot be obtained after evaporation of solvent (d) even when droplets are dropped (disposed) in a close-packed manner by an inkjet method.

[0190] <Temperature when compounding the curable composition> In preparing the curable composition (A) of the present invention, at least components (a), (b), and (d) 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 (c).

[0191] <Viscosity of Curable Composition> The curable composition (A) in the present invention is liquid. This is because droplets of the curable composition (A) are discretely dropped onto a substrate by an inkjet method in the disposing step described below. The viscosity of the curable composition (A) in the present invention at 23°C is 2 mPa·s to 60 mPa·s, preferably 5 mPa·s to 30 mPa·s, and more preferably 5 mPa·s to 15 mPa·s. If the viscosity of the curable composition (A) is less than 2 mPa·s, the ejection of droplets by the inkjet method becomes unstable. On the other hand, if the viscosity of the curable composition (A) is greater than 60 mPa·s, it is not possible to form droplets with a volume of approximately 1.0 to 3.0 pL, which is preferred in the present invention.

[0192] The viscosity at 23°C of the mixture of the components of the curable composition (A) excluding the solvent (d) after the solvent (d) 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 of the mixture of the components of the curable composition (A) excluding the solvent (d) 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, 150 mPa·s or more and 500 mPa·s or less is more preferred. By setting the viscosity of the components of the curable composition (A) excluding the solvent (d) to 1,000 mPa·s or less, spreading and filling are completed quickly when the curable composition (A) is brought into contact with a mold. Therefore, by using the curable composition (A) of the present invention, imprint processing can be performed with high throughput and pattern defects due to poor filling can be suppressed. Furthermore, by setting the viscosity of the components of the curable composition (A) excluding the solvent (d) to 1 mPa s or more, unwanted flow of droplets of the curable composition (A) after the solvent (d) has evaporated can be prevented. 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.

[0193] <Surface tension of curable composition> Regarding the surface tension of the curable composition (A) of the present invention, the surface tension at 23°C of the composition of components excluding the solvent (component (d)) is preferably 5 mN / m or more and 70 mN / m or less. Furthermore, the surface tension at 23°C of the composition of components excluding the solvent (component (d)) is more preferably 7 mN / m or more and 50 mN / m or less, and even more preferably 10 mN / m or more and 40 mN / m or less. Note that the higher the surface tension, for example, 5 mN / m or more, the stronger the capillary force, and therefore, when the curable composition (A) is brought into contact with a mold, filling (spreading and filling) is completed in a short time. Furthermore, by setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition has a smooth surface.

[0194] <Contact angle of curable composition> The contact angle of the curable composition (A) of the present invention, excluding the solvent (component (d)), is preferably 0° to 90°, particularly preferably 0° to 10°, with respect to both the surface of the substrate and the surface of the mold. If the contact angle is greater than 90°, capillary force acts in the negative direction (the direction that shrinks the contact interface between the mold and the curable composition) inside the pattern of the mold or in the gap between the substrate and the mold, which may result in failure to fill. The smaller the contact angle, the stronger the capillary force, resulting in a faster filling speed.

[0195] <Impurities contained in the curable composition> The curable composition (A) of the present invention preferably contains as few impurities as possible. Here, impurities refer to components other than the above-mentioned components (a), (b), (c), and (d). Therefore, the curable composition (A) of the present invention is preferably obtained through a purification step. Such a purification step is preferably filtration using a filter.

[0196] In the filtration using a filter, it is preferable to mix the above-mentioned components (a), (b), and (c) 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 multiple times (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 process, 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.

[0197] When the curable composition of the present invention 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, more preferably 100 ppb or less.

[0198] <Glass transition temperature of curable composition after curing> If the glass transition temperature is sufficiently higher than the temperature during demolding, the cured product will be in a strong glassy state during demolding, i.e., will exhibit high mechanical strength, making it less likely for the pattern to collapse or break due to the impact of demolding. Therefore, when the demolding step is carried out at room temperature, the glass transition temperature of the cured product is preferably 70°C or higher, more preferably 100°C or higher, and even more preferably 150°C or higher.

[0199] The glass transition temperature of the cured product can be measured using a differential scanning calorimetry (DSC) or a dynamic viscoelasticity apparatus.

[0200] For example, let us explain the case where measurement is performed using DSC. In this case, the extrapolated glass transition onset temperature (Tig) is determined from the intersection of a straight line extending the low-temperature baseline of the DSC curve of the cured product toward the high-temperature side and a tangent to the point where the gradient of the curve of the stepwise change in glass transition is maximum. Here, the low-temperature baseline refers to the portion of the DSC curve in the temperature range where no transition or reaction occurs in the test piece. The extrapolated glass transition onset temperature (Tig) is then taken as the glass transition temperature of the cured product. A typical device used for this purpose is the STA-6000 (manufactured by Perkin Elmer).

[0201] On the other hand, the case where measurement is performed using a dynamic viscoelasticity apparatus will be explained. In this case, the temperature at which the loss tangent (tanδ) of the cured product is maximum is defined as the glass transition temperature of the cured product. The main apparatus capable of measuring dynamic viscoelasticity is the MCR301 (manufactured by Anton Paar).

[0202] <Heat resistance of curable composition after curing> The heat resistance of the curable composition after curing can be measured using thermogravimetric analysis (TGA) or the like.

[0203] For example, when measuring using TGA, the cured curable composition is placed in a nitrogen atmosphere with a flow rate of 5 L / hour to 6 L / hour, and the temperature is raised to n°C at a heating rate of 20°C / min, and the thermal weight loss rate is measured to determine whether the composition has heat resistance to n°C. Typical devices include STA 1000 (manufactured by Linseis).

[0204] Regarding the heat resistance of the cured product, when the temperature is increased from 260°C at a heating rate of 20°C / min, the temperature at which the thermal weight loss rate first reaches 2% is preferably 350°C or higher, more preferably 400°C or higher, and even more preferably 450°C or higher.

[0205] [substrate] In this specification, the member onto which droplets of the curable composition (A) are discretely dropped (placed) is referred to as a substrate.

[0206] The substrate is a workpiece substrate, typically a silicon wafer. The substrate may have a workpiece layer on its surface. The substrate may also have other layers formed below the workpiece layer. Furthermore, by using a quartz substrate as the substrate, a replica of a mold for imprinting (a replica mold) can be produced. However, the substrate is not limited to a silicon wafer or a quartz substrate. The substrate can be selected from any substrate known as a substrate for semiconductor devices, such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, or silicon nitride. The surface of the substrate or workpiece layer may be subjected to a surface treatment, such as a silane coupling treatment, a silazane treatment, or the formation of an organic thin film, to improve adhesion to the curable composition (A). A specific example of an organic thin film formed as a surface treatment is the adhesion layer described in JP-A-2009-503139.

[0207] The film formation method of the present invention may be implemented as a method for forming a film having a pattern, i.e., a pattern formation method, or as a method for forming a film without a pattern (e.g., a planar film), i.e., a planarization film formation method.

[0208] [Pattern formation method] The pattern formation method of the present invention will be described with reference to FIGS. 1A to 1G. When the film formation method of the present invention is implemented as a pattern formation method, the cured film 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. In general, 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 invention 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 (for example, heat or electromagnetic waves).

[0209] An example in which the film formation method of the present invention 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 (d) 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.

[0210] <Placement process> In the disposing step, as shown in FIG. 1A, droplets 102 of the curable composition (A) are discretely disposed on a substrate 101. A substrate having a base layer laminated thereon may be used as the substrate 101. The surface of the substrate 101 may be subjected to a surface treatment such as a silane coupling treatment, a silazane treatment, or the formation of an organic thin film to improve adhesion to the curable composition (A).

[0211] 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.

[0212] To define 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 (d)) 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 (d)) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (d) has evaporated. According to this definition, even if the substrate surface is uneven, the average remaining liquid film thickness can be defined regardless of the state of the unevenness.

[0213] <Standby process> In the present invention, 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. 1B. As a result, the entire pattern formation region of the substrate 101 is covered with the curable composition (A).

[0214] The present inventors have confirmed that when the average initial liquid film thickness is 80 nm or more, droplets of the curable composition (A) combine with each other on the substrate to form a substantially continuous liquid film 103, as shown schematically in FIG. 1C. The present inventors have also confirmed that when the average initial liquid film thickness is 89 nm or more, the surface of the liquid film becomes flat. A liquid film with an average initial liquid film thickness of 80 nm or more is formed by depositing droplets of the curable composition (A) with a volume of 1.0 pL or more at a thickness of 80 droplets / mm. 2 Similarly, a liquid film having an average initial liquid film thickness of 89 nm can be obtained by disposing droplets of the curable composition (A) having a volume of 1.0 pL or more at a density of 89 droplets / mm 2 This can be achieved by arranging the particles at a density of

[0215] The flow behavior of droplets of the curable composition (A) placed on the substrate during the waiting step will be described with reference to FIGS. 2A to 2D. As shown in FIG. 2A, droplets of the curable composition (A) are discretely placed on the substrate, and as shown in FIG. 2B, each droplet gradually spreads on the substrate. Then, as shown in FIG. 2C, the droplets of the curable composition (A) on the substrate begin to combine to form a liquid film, which then becomes a continuous liquid film as shown in FIG. 2D (the surface of the substrate is covered with the curable composition (A), with no exposed surface). The state of the curable composition (A) as shown in FIG. 2D is referred to as a "substantially continuous liquid film."

[0216] 1D, the solvent (d) 105 contained in the liquid film 104 is evaporated. The amount of solvent (d) remaining in the liquid film 104 after the waiting step is preferably 10% by volume or less, assuming that the total weight of the components other than solvent (d) is 100% by volume. If the amount of solvent (d) remaining is more than 10% by volume, the mechanical properties of the cured film may be reduced.

[0217] 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 (d). 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.

[0218] 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.

[0219] In the waiting step, when the solvent (d) volatilizes, a substantially continuous liquid film 104 consisting of the components (a), (b), and (c) remains. The average remaining liquid film thickness of the substantially continuous liquid film 104 from which the solvent (d) has been volatilized (removed) is thinner than the liquid film 103 by the amount of solvent (d) 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 (d) has been removed.

[0220] <Contact process> 1E, the contacting step involves bringing a substantially continuous liquid film 104 of the curable composition (A) from which the solvent (d) has been removed 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.

[0221] In the present invention, in the waiting step, the curable composition (A) becomes a substantially continuous liquid film 104 from which the solvent (d) has been removed, thereby reducing the volume of gas trapped between the mold 106 and the substrate 101. Therefore, the filling of the curable composition (A) in the contacting step is completed quickly. A comparison (difference) between the contacting step in the prior art disclosed in Patent Document 1 and the contacting step in the present invention is shown in Figure 3.

[0222] If the filling of the curable composition (A) is completed quickly in the contacting step, the time required for maintaining 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 0.1 seconds or more and 3 seconds or less, and particularly preferably 0.1 seconds or more and 1 second or less. If the contacting step is shorter than 0.1 seconds, the filling is insufficient, and defects known as unfilled defects tend to occur frequently.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] The contacting step can be carried out under any of the conditions of air, reduced pressure, and inert gas atmosphere, but a reduced pressure or inert gas atmosphere is preferred because it can prevent the influence of oxygen and moisture on the curing reaction. Specific examples of the inert gas used when the contacting step is carried out under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, and mixtures of these. When the contacting 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.

[0228] <Curing process> In the curing step, as schematically shown in FIG. 1F, 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.

[0229] 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.

[0230] <Mold release process> In the demolding step, as shown schematically in FIG. 1G, 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.

[0231] 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.

[0232] <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.

[0233] In the pattern formation method of the present invention, 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 can be obtained at desired positions on the substrate.

[0234] [Planarization film formation method] Hereinafter, an example in which the film formation method of the present invention 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) combine with each other and the solvent (d) 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.

[0235] [Production method] A cured film having a pattern formed by the pattern forming method of the present invention is used as it is as at least a part of a constituent member of various articles. Furthermore, a cured film having a pattern formed by the pattern forming method of the present invention is temporarily used as a mask for etching or ion implantation of a substrate (or the substrate having a processable layer, if the substrate has such a layer). After etching or ion implantation is performed in the substrate processing step, the mask is removed. This allows various articles to be manufactured.

[0236] When removing the cured material in recesses of the cured material pattern by etching, the specific method is not particularly limited, and conventional methods, such as dry etching, can be used. Conventional dry etching equipment can be used for dry etching. The source gas used in dry etching is appropriately selected depending on the elemental composition of the cured material to be etched. Examples of source gases that can be used include halogen gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2. 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 H2 and NH3 gases. These gases can also be used in combination. In this case, the cured film must have high dry etching resistance to process the underlying substrate with high yield.

[0237] 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.

[0238] 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 invention. 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.

[0239] [Example] To supplement the above-described embodiment, a more specific example will be described.

[0240] <Viscosity calculation method> In this example, the viscosity of the curable composition (A) was calculated by molecular dynamics calculation (see Literature B) for a molecular assembly containing 10 gas molecules per 250 molecules constituting the curable composition. Literature B: MP Allen, Computational soft matter: from synthetic polymers to proteins, 23(1), 1-28 (2004).

[0241] In this example, molecular dynamics calculations were performed using LAMMPS-12Dec2018 (Copyright (2003) Sandia Corporation.).

[0242] Molecular dynamics calculations consist of four stages: compression process calculations, relaxation process calculations, equilibration process calculations, and SLLOD calculations. The compression process calculations are performed to form appropriate molecular aggregates. The equilibration process calculations are performed to bring the molecular aggregates into a thermodynamic equilibrium state. The simulation box for the calculations up to this point is a cube. The SLLOD calculations are a nonequilibrium molecular dynamics method that applies frictional forces between molecules by forcibly inducing Couette flow (steady simple shear flow) within the molecular aggregate (see references C and D). Document C: PJ Daivis and BD Todd, J. Chem. Phys, 124, 194103(2006). Document D: BJ Edwards, C. Baig, and DJ Keffer, J. Chem.Phys. 124, 194104 (2006).

[0243] In this example, we assume that the simulation box is a cube with a side length of L immediately before the SLLOD calculation begins, as shown in Figure 4. We also assume that the Cartesian coordinate axes within the simulation box are set so that one vertex of the cube is the origin and each side is parallel to the X, Y, and Z axes. After the SLLOD calculation begins, we assume that a Couette flow is induced, with the flow direction parallel to the X axis and the velocity field gradient direction parallel to the Y axis. To induce such a Couette flow, as shown in Figure 5, the face of the simulation box at Y = 0 is fixed, and the face at Y = L is moved in the X direction at a constant velocity v, continuously distorting the simulation box itself. The calculated viscosity value before correction, η, can be calculated from the frictional force acting between molecules using the formula: η = -<σxy> / s. Here, s is a quantity called the strain rate, and σxy represents the x and y components of the stress tensor acting on the molecules, representing both statistical and time averages.

[0244] The strain rate s is calculated using the formula s = v / L, where L is the length of one side of the cubic simulation box at the start of the calculation. However, to predict actual viscosity, the calculated value must be corrected using the formula η = η0 × 2.270 + 1.722. The calculated value after correction is η. This formula assumes units of mPa·s.

[0245] The details of the calculation conditions are as follows: Periodic boundary conditions are imposed in all calculations. To efficiently calculate long-range electrostatic forces, the PPPM (particle-particle-particle-mesh Ewald) method (see Reference E) is used. To achieve stable calculations, the SHAKE algorithm (see Reference F), which imposes constraints on specific bond angles and bond lengths, is used. Document E: JW Eastwood, RW Hockney, DN Lawrence, ComputerPhysics Communications 35, 618 (1984). Literature F: J.-P. Ryckaert, G. Ciccotti and HJC Berendsen, J of Comp Phys, 23, 327-341 (1977).

[0246] The calculation conditions used for the compression process calculation were a temperature setting of 700 K, a pressure setting of 10,000 atm, a simulation time of 10 ps, ​​a step time of 0.5 fs, a temperature relaxation time of 10 fs, and a compressibility relaxation time of 100 ps. The simulation was performed at constant temperature and pressure using the Nose-Hoover method (see references G and H). Document G:Nose ’ , Shuichi (1984). “A unified formulation of the constant temperature molecular-dynamics methods”. Journal of Chemical Physics 81 (1): 511-519. Reference H: Hoover, William G. (1985). “Canonical dynamics: Equilibrium phase-space distributions”. Phys. Rev. A 31 (3): 1695-1697.

[0247] The calculation conditions used for the relaxation process calculation were a temperature setting of 700 K, a pressure setting of 1 atm, a simulation time of 100 ps, ​​a temperature relaxation time of 10 fs, and a compressibility relaxation time of 100 ps. The simulation was performed at constant temperature and pressure using the Nose-Hoover method.

[0248] The calculation conditions used for the equilibration process calculation are a temperature setting of 300 K, a pressure setting of 1 atm, a simulation time of 2 ns, a temperature relaxation time of 10 fs, and a compressibility relaxation time of 100 ps. The simulation is performed at constant temperature and pressure using the Nose-Hoover method.

[0249] The calculation conditions used for the SLLOD method calculation are a temperature setting of 300 K, a simulation time of 8.5 ns, and a temperature relaxation time of 10 fs.

[0250] The Nose-Hoover method is used for constant temperature simulation. The speed of straining the simulation box is 1 nm / ns. When taking the time average, the stress tensor value from 7.5 nm to 8 ns is used.

[0251] To perform molecular dynamics calculations, it is necessary to set in advance the parameters that define the interactions between atoms, called force field parameters. Force field parameters consist of two types: electrostatic force field parameters and non-electrostatic force field parameters.

[0252] The electrostatic force field parameters used were as follows: The charge assigned to each atom is obtained by charge fitting using points based on the MERZ-Singh-Killmans scheme (see References I and J) to the electrostatic potential calculated by the Kohn-Sham method (exchange-correlation functional is B3LYP, basis set 6-31g*), which is a quantum chemical calculation method. Document I: BH Besler, KM Merz Jr., and PA Kollman, J. Comp. Chem. 11, 431 (1990). Reference J: UC Singh and PA Kollman, J. Comp. Chem. 5, 129 (1984).

[0253] The holiday home is a great deal of snowflakes Copyright © 2013 Gaussian Code Gaussian 09,Revision D.01(Gaussian 09,Revision D.01, MJ Frisch, GWTrucks, HBSchlegel, GEScuseria, MARobb, JRCheeseman, G. Scalmani, V. Barone, B. Mennucci, GPetersson, H. Nakatsuji, M. Caricato, X. Li, HHPratchian, AFI zmaylov,J.Bloino,G.Zheng,JLSonnenberg,M.Hada,M.Ehara,K.Toyota,R.Fukuda,J.Hasegawa,M.Ishida,T.Nakajima,Y.Honda,O.Kitao,H.Nakai,T.Vreven,JAMontgomery,Jr. ,JEPeralta,F.Ogliaro,M.Bearpark,JJHeyd,E.Brothers,KNKudin,VNStaroverov,T.Keith,R.Kobayashi,J.Normand,K.Raghavachari,A.Rendell,JCBurant,SSIyengar,J.Tom asi, M. Cossi, N. Rega, JMMillam, M. Klene, JEKnox, JBCross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, REStratmann, O. Yazyev, AJAustin, R. Cammi, C. Pomelli, JWOchterski, RLMartin,K.Morokuma,VGZakrzewski,GAVoth,P.Salvador,JJDannenberg,S.Dapprich,ADDaniels,OFarkas,JBForesman,JVOrtiz,JCioslowski,andDJFox,Gaussian,Inc.,Wallingford CT,2013.)

[0254] The non-electrostatic force field parameters used were the general Amber force field (GAFF, Ref. K), which is commonly used for organic molecules. Reference K: Wang, J., Wolf, RM, Caldwell, JW, Kollman, PA, Case, DA, J. Comp. Chem. 25, 1157(2004).

[0255] The viscosity calculation results obtained by the above-mentioned viscosity calculation method are shown in Table 1 below. However, the viscosity values ​​shown are those after the above-mentioned correction. [Table 1] Viscosity calculation results TIFF2025540556000057.tif163155

[0256] The polymerizable compounds calculated in the examples are as follows:

[0257] TIFF2025540556000058.tif85140TIFF2025540556000059.tif109130TIFF2025540556000060.tif102130

[0258] [Example 1, Comparative Example 1, Comparative Example 2] <Preparation of Curable Composition> As Example 1, Comparative Example 1, and Comparative Example 2, curable compositions S1, S2, and S3 were prepared, respectively.

[0259] The curable composition S1 contains, as component (a-1), a polymerizable compound having four vinyl groups directly bonded to an aromatic ring and represented by the following formula:

[0260] TIFF2025540556000061.tif4083

[0261] The curable composition S2 contains, as component (a-1), a polymerizable compound having three vinyl groups directly bonded to an aromatic ring and represented by the following formula:

[0262] TIFF2025540556000062.tif3987

[0263] The curable composition S3 contains, as component (a-1), a polymerizable compound having two vinyl groups directly bonded to an aromatic ring and represented by the following formula:

[0264] TIFF2025540556000063.tif3782

[0265] Curable compositions S1, S2, and S3 contain 2.91 wt. % of the photoinitiator IGM Omnirad 819 (formerly Irgacure 819) as component (b) based on the weight of the main polymerizable compound, and further contain 0.97 wt. % of a surfactant (Chemguard S554) as component (c) based on the weight of the main polymerizable compound.

[0266] <Curing> The curing was carried out by applying a liquid film of the curable composition to a thickness of about 100 nm onto a glass substrate and applying a 25 mW / cm 2 This was achieved by exposing the sample to UV light with an intensity of 2.4 J / cm for 80 seconds. 2 This corresponds to the amount of curing energy.

[0267] <Heat treatment> After curing, the cured layer was subjected to two heat treatments. In the first heat treatment, the layer was heated to 250°C at a rate of 10°C / min and held at 250°C for 1 hour. In the second heat treatment, the layer was cooled to 0°C after the first heat treatment and then heated to 450°C at a rate of 20°C / min. The second heat treatment focused on the range from 260°C to 450°C, which is higher than the maximum temperature (250°C) in the first heat treatment and just before the temperature at which significant weight loss occurs due to complete decomposition of the polymer material.

[0268] <Heat resistance measurement> Heat resistance was measured during the second heat treatment by TGA using a Linseis STA 1000 instrument under a nitrogen atmosphere with a flow rate of 5 L / h to 6 L / h and a heating rate of 20°C / min. Heat resistance to 450°C was determined to be present when the weight loss rate was 2% or less when the temperature was increased from 260°C to 450°C.

[0269] [Example 1] The curable composition S1 was cured and heat treated by the method described above, and the heat resistance was measured. As a result, the curable composition S1 showed a heat resistance of 450°C.

[0270] [Comparative Example 1] Curable composition S2 was cured and heat treated by the method described above, and the heat resistance was measured. As a result, it did not exhibit heat resistance up to 450°C.

[0271] Comparative Example 2 Curable composition S3 was cured and heat treated by the method described above, and the heat resistance was measured. As a result, it did not exhibit heat resistance up to 450°C.

[0272] This application claims the benefit of U.S. Patent Application No. 17 / 991,098, filed November 21, 2022, the contents of which are incorporated by reference in their entirety into this application.

Claims

1. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (c), The curable composition has a viscosity of 2 mPa·s or more and 60 mPa·s or less at 23°C, the content of the solvent (d) relative to the entire curable composition is 5% by volume or more and 95% by volume or less, The boiling point of the solvent (d) under normal pressure is less than 250°C, The polymerizable compound (a) includes a compound (a-1) containing one or more aromatic rings or aromatic heterocycles and four or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles. A curable composition characterized by:

2. 2. The curable composition according to claim 1, wherein the proportion of the compound (a-1) in the polymerizable compound (a) is 20% by weight or more.

3. 2. The curable composition according to claim 1, wherein the proportion of the compound (a-1) in the polymerizable compound (a) is 50% by weight or more.

4. 2. The curable composition according to claim 1, wherein the proportion of the compound (a-1) in the polymerizable compound (a) is 90% by weight or more.

5. 2. The curable composition according to claim 1, wherein a cured product of the compound (a-1) loses weight by 2% or less when the temperature is increased from 260°C to 350°C at a heating rate of 20°C / min.

6. 2. The curable composition according to claim 1, wherein a cured product of the compound (a-1) loses weight by 2% or less when the temperature is increased from 260°C to 400°C at a heating rate of 20°C / min.

7. 2. The curable composition according to claim 1, wherein a cured product of the compound (a-1) loses weight by 2% or less when the temperature is increased from 260°C to 450°C at a heating rate of 20°C / min.

8. The polymerizable compound (a) contains one or more polymerizable compounds, the boiling point of each of the one or more polymerizable compounds under normal pressure is 250°C or higher; The curable composition according to claim 1 .

9. The polymerizable compound includes one or more polymerizable compounds, Each of the one or more polymerizable compounds has a molecular weight of 200 or more. The curable composition according to claim 1 .

10. The solvent (d) includes one or more solvents, The boiling point of each of the one or more solvents under normal pressure is 80°C or higher and lower than 250°C. The curable composition according to claim 1 .

11. The curable composition according to claim 1 , wherein the solvent (d) contains a polymerizable compound having a boiling point of 80° C. or higher and lower than 250° C. under normal pressure.

12. The solvent (d) includes one or more solvents, The boiling point of each of the one or more solvents under normal pressure is 150°C or higher and lower than 200°C. The curable composition according to claim 1 .

13. The curable composition according to claim 1 , wherein the polymerizable compound (a) comprises at least a polymer having a polymerizable functional group.

14. 2. The curable composition according to claim 1, wherein a glass transition temperature of a cured product obtained by curing the polymerizable compound (a) in a state in which the solvent (d) is excluded is 70°C or higher.

15. the polymerizable compound (a) contains a plurality of types of polymerizable compounds, the vapor pressure of each of the plurality of polymerizable compounds at 80°C is 0.001 mmHg or less; The curable composition according to claim 1 .

16. 2. The curable composition according to claim 1, wherein the content of the solvent (d) relative to the entire curable composition is 70% by volume or more and 85% by volume or less.

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

18. 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 1 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 and until a solvent contained in the liquid film evaporates; a contacting step of contacting the mold with the liquid film on the substrate after the waiting step; A film forming method comprising the steps of:

19. 19. The film forming method according to claim 18, wherein the waiting step waits until the content of the solvent becomes 10% by volume or less with respect to the entire liquid film.

20. 20. The film forming method according to claim 18, wherein the waiting step comprises heating the substrate at a temperature of 30° C. or higher and 200° C. or lower for 10 seconds or higher and 600 seconds or lower.

21. 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 19. The film forming method according to claim 18, wherein the particles are arranged at a density of at least 1000 sq. m.

22. 19. The film forming method according to claim 18, 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 of the mold, is 20 nm or less.

23. the mold includes a pattern; In the contacting step, the pattern of the mold is brought into contact with the liquid film on the substrate; The 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.

19. The film forming method according to claim 18.

24. the mold includes a flat surface; In the contacting step, the flat surface of the mold is brought into contact with the liquid film on the substrate, The 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.

19. The film forming method according to claim 18.

25. 20. The film forming method according to claim 18, wherein in the disposing step, the plurality of droplets are discretely disposed on the substrate using an inkjet method.

26. forming a film of a curable composition on a substrate using the film-forming method according to claim 18; a step of treating the substrate on which the film has been formed in the step; manufacturing an article from the processed substrate; A method for manufacturing an article, comprising:

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