Curable composition, film forming method, and method for producing article

Abstract

The present invention provides a curable composition which contains a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), the curable composition being characterized by having a viscosity of 1.3 mPa∙s to 60 mPa∙s inclusive at 23°C and 1 atm, and being also characterized in that: the content of the solvent (d) relative to the entire curable composition is more than 5% by volume but not more than 95% by volume; the boiling point of the solvent (d) is less than 250°C at 1 atm; and if α1 (°) is the contact angle, with respect to a substrate, of a composition obtained by removing the solvent (d) and the surfactant (c1) from the curable composition, and α2 (°) is the contact angle, with respect to the substrate, of a composition obtained by removing the solvent (d) from the curable composition, α2 is greater than α1.

Description

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

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

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

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

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

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

[0006] Japanese Patent Application Laid-Open No. 2022-188736

[0007] However, in the technology disclosed in Patent Document 1, droplets of the curable composition dropped onto the substrate spread at such a high speed that they join together, which can cause the curable composition to overflow from the desired region (pattern formation region). The length by which the curable composition overflows from the desired region is called the "overflow amount."

[0008] Furthermore, in the technology disclosed in Patent Document 1, when the mold is brought into contact with the curable composition on the substrate, the curable composition has fluidity, and therefore the curable composition may overflow from the contact surface of the mold and adhere (creep up) to the sidewall (side surface) of the mold. This phenomenon in which the curable composition creeps up and adheres to the sidewall of the mold is called "exudation." The cured product of the curable composition that has adhered to the sidewall of the mold may remain on the substrate as unwanted matter or may fall from the sidewall of the mold onto the substrate at an unintended time, causing major defects on the substrate.

[0009] The present invention provides a new technique relating to a curable composition.

[0010]

[0013] One aspect of the present invention provides a curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), wherein the curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atmospheric pressure, the content of the solvent (d) relative to the entire curable composition is more than 5% by volume and 95% by volume or less, and the boiling point of the solvent (d) is less than 250°C at 1 atmospheric pressure, and wherein when the contact angle of a composition obtained by excluding the solvent (d) and the surfactant (c1) from the curable composition with a substrate is α1 [°] and the contact angle of a composition obtained by excluding the solvent (d) from the curable composition with the substrate is α2 [°], α2 is larger than α1.

[0011] According to the present invention, for example, a new technique relating to a curable composition can be provided.

[0012] Other features and advantages of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings, in which the same or similar elements are designated by the same reference numerals.

[0013] The accompanying drawings are included in the specification and constitute a part thereof, illustrate embodiments of the present invention, and are used, together with the description, to explain the principles of the present invention.

[0023] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0024] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0025] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0026] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0027] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0028] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0029] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0030] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0031] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0032] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0033] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0034] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0035] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention.

[0036] Figures are for explaining a pattern formation method (film formation method) according to one aspect of the present invention. 1 is a diagram for explaining the flow behavior of a droplet of a curable composition during a waiting process. FIG. 2 is a diagram for explaining the flow behavior of a droplet of a curable composition during a waiting process. FIG. 3 is a diagram for explaining the flow behavior of a droplet of a curable composition during a waiting process. FIG. 4 is a diagram comparing a contacting process in the prior art with a contacting process in the present invention. FIG. 5 is a diagram for explaining the concept of the seepage phenomenon. FIG. 6 is a diagram showing a state in which a curable composition has crawled up the side wall of a mold. FIG. 7 is a diagram showing the results of measuring a contact angle with respect to a substrate. FIG. 8 is a diagram showing the results of measuring surface tension. FIG. 9 is a diagram showing the change in the radius of a droplet over time. FIG. 10 is a diagram showing the results of measuring the amount of overflow of a liquid film. FIG. 11 is a diagram showing a state in which a droplet is isolated on a substrate. FIG. 12 is a diagram showing a state in which a substantially continuous liquid film has been formed on a substrate. FIG. 13 is a diagram summarizing experimental results for three types of compositions. FIG. 14 is a diagram showing the dependence of the maximum radius of a droplet on Δγ. FIG. 15 is a diagram showing the results of measuring a contact angle with respect to a mold. FIG. 16 is a diagram showing the results of calculating the seepage height by numerical calculation.

[0014] 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.

[0015] In providing a new technology related to a curable composition, the present inventors have discovered a curable composition and process conditions therefor that allow droplets of the curable composition that have been discretely dropped (arranged) on a substrate to bond together and that allow a solvent contained in the curable composition to volatilize.

[0016] [Curable Composition] The curable composition (A) of the present invention is a curable composition for inkjet printing, and 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.

[0017] 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 of the cured film of the curable composition (the protruding portions of the mold pattern) and the substrate is referred to as the "residual film."

[0018] <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).

[0019] Examples of such polymerizable compounds include radically polymerizable compounds. The polymerizable compound of 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.

[0020] Examples of the radically polymerizable compound include (meth)acrylic compounds, styrene compounds, vinyl compounds, allyl compounds, fumaric compounds, and maleyl compounds.

[0021] The (meth)acrylic compound refers to 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 methyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, 1- or 2-naphthyl (meth)acrylate, 1- or 2-naphthylmethyl (meth)acrylate, 3- or 4-phenoxybenzyl (meth)acrylate, chinoabenzyl (meth)acrylate, naphthalenemethyl (meth)acrylate. Examples of commercially available products of the above-mentioned 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 Co., Ltd.), 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 Co., Ltd.), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kohjin Co., Ltd.), HRD-01 (all manufactured by Nippon Shokubai Co., Ltd.). 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 ) 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. Examples of commercially available products of the above-mentioned 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 Co., Ltd.), Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei Co., Ltd.), Lipoxy (registered trademark) VR-77, VR-60, VR-90 (all manufactured by Showa Polymer Co., Ltd.), Oxol EA-0200, Oxol EA-0300 (all manufactured by Osaka Gas Chemicals Co., Ltd.), SR295, SR355 (all manufactured by Sartomer Co., Ltd.) In the above-mentioned compound group, (meth)acrylate means an acrylate or a methacrylate having an alcohol residue equivalent thereto. A (meth)acryloyl group means an acryloyl group or a methacryloyl group having an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are bonded via an ethylene oxide group block structure. PO represents propylene oxide, and PO-modified compound B represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are bonded via a propylene oxide group block structure.

[0022] 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; and compounds having a styryl group as a polymerizable functional group, such as 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, and divinylbiphenyl. 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.); and compounds having a vinyl group as a polymerizable functional group such as (meth)acrylonitrile. In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0023] Examples of acrylic compounds include, but are not limited to, the following: allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate. Examples of fumaric compounds include, but are not limited to, the following: dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate. 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, and dibenzyl maleate. Other radically polymerizable compounds include, but are not limited to, the following: Dialkyl esters of itaconic acid and derivatives thereof (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 derivatives thereof (N-phenylmaleimide, N-cyclohexylmaleimide, etc.). When component (a) is composed of multiple types of compounds having one or more polymerizable functional groups, it preferably contains both a monofunctional polymerizable compound and a polyfunctional polymerizable compound. The proportion of the polyfunctional polymerizable compound in component (a) is preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably 40% by weight or more. This is because, by combining a monofunctional polymerizable compound and a polyfunctional polymerizable compound, a cured film having an excellent balance of properties such as high mechanical strength, high dry etching resistance, and high heat resistance can be obtained.

[0024] In the film-forming method of the present invention, it takes several milliseconds to several hundred seconds for the droplets of the curable composition (A) discretely arranged on the substrate to combine to form a substantially continuous liquid film, thereby necessitating a waiting step, as described below. In the waiting step, the solvent (d) is volatilized, while the polymerizable compound (a) must not volatilize. Therefore, the boiling point of each of the one or more polymerizable compounds contained in the polymerizable compound (a) under normal pressure is preferably 250°C or higher, more preferably 300°C or higher, and even more preferably 350°C or higher. Furthermore, in order to obtain high dry etching resistance and high heat resistance in the cured film of the curable composition (A), it is preferable that the cured film contains at least a compound having a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Note that normal pressure refers to 1 atmosphere (atmospheric pressure).

[0025] The boiling point of the polymerizable compound (a) generally correlates with the molecular weight. Therefore, the molecular weight of each of the one or more polymerizable compounds contained in the polymerizable compound (a) is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more. However, even if the molecular weight is 200 or less, as long as the boiling point is 250°C or higher, it can be preferably used as the polymerizable compound (a) in the present invention. Thus, it is preferable that the boiling point under normal pressure of each of the one or more polymerizable compounds contained in the polymerizable compound (a) is 250°C or higher.

[0026] Furthermore, the vapor pressure of the polymerizable compound (component (a)) at 80°C is preferably 0.001 mmHg or less. When the polymerizable compound (a) contains one or more polymerizable compounds, it is preferable that the vapor pressure of each of the one or more polymerizable compounds at 80°C is 0.001 mmHg or less. This is because, although it is preferable to heat the curable composition in order to accelerate the volatilization of the solvent (component (d)) described below, the volatilization of the polymerizable compound (a) is suppressed during such heating.

[0027] 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.

[0028] <Oonishi parameters of component (a)> Dry etching rate V of the organic compound, 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 are known to have the relationship of the following formula (1): V ∝ N / (Nc-No) Formula (1) Here, N / (Nc-No) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, U.S. Patent Application Publication No. 2020 / 0286740 discloses a technology for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP.

[0029] 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, the larger the OP and the faster the dry etching rate.

[0030] In the curable composition (A) of the present invention, the OP of the component (a) is 1.80 or more and 4.00 or less. The OP of the component (a) is more preferably 2.00 or more and 3.50 or less, and particularly preferably 2.40 or more and 3.00 or less. By making the OP of the component (a) 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. Furthermore, by making the OP of the component (a) 1.80 or more, it becomes easy to remove the cured film of the curable composition (A) after processing the underlayer using the cured film of the curable composition (A). When the component (a) is a polymerizable compound a １ , a ２ , ..., a ｎ When the component (a) is composed of the polymerizable compounds, 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). In this way, when the component (a) contains one or more polymerizable compounds, the OP of the component (a) is calculated as N / (N Ｃ -N Ｏ) values ​​are calculated as the mole fraction weighted average.

[0031]

[0032] Here, OP ｎ is component a ｎ OP of n ｎ is component a ｎ is the molar fraction of the entire component (a).

[0033] In order to set the OP of component (a) to 1.80 or more and 2.70 or less, it is preferable to include, as at least component (a), a compound (a-1) having two or more cyclic structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0034] <Compound (a-1): Polymerizable compound having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure> The polymerizable compound (a) in the present invention may contain a polymerizable compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Furthermore, the proportion of component (a-1) in component (a) is preferably 65% ​​by weight or more. By setting the proportion of component (a-1) to 65% by weight or more, it is possible to suppress the OP to 2.70 or less.

[0035] The cyclic structure may be an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0036] The aromatic structure preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples of the aromatic ring include the following: a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a fluorene ring, a benzocyclooctene ring, an acenaphthylene ring, a biphenylene ring, an indene ring, an indane ring, a triphenylene ring, a pyrene ring, a chrysene ring, a perylene ring, and a tetrahydronaphthalene ring. Of the above-mentioned aromatic rings, 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, and examples thereof include a biphenyl ring and a bisphenyl ring.

[0037] 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 heterocycle include the following: a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiadiazole ring, an oxadiazole ring, an oxazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an isoindole ring, an indole ring, an indazole ring, a purine ring, a quinolizine ring, an isoquinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a carbazole ring, an acridine ring, a phenazine ring, a phenothiazine ring, a phenoxathiin ring, and a phenoxazine ring. The 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 still more preferably 5 or less. Specific examples thereof include the following: a cyclopropane ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, a dicyclopentadiene ring, a spirodecane ring, a spirononane ring, a tetrahydrodicyclopentadiene ring, an octahydronaphthalene ring, a decahydronaphthalene ring, a hexahydroindane ring, a bornane ring, a norbornane ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring. Specific examples of the polymerizable compound (a-1) having a boiling point of 250°C or higher include, but are not limited to, the following: 3-phenoxybenzyl acrylate (mPhOBzA, OP 2.54, boiling point 367.4°C, vapor pressure at 80°C 0.0004 mmHg, molecular weight 254.3),

[0038]

[0039] 1-naphthyl acrylate (NaA, OP 2.27, boiling point 317°C, vapor pressure at 80°C 0.0422 mmHg, molecular weight 198),

[0040]

[0041] 2-phenylphenoxyethyl acrylate (PhPhOEA, OP 2.57, boiling point 364.2°C, vapor pressure at 80°C 0.0006 mmHg, molecular weight 268.3),

[0042]

[0043] 1-naphthylmethyl acrylate (Na1MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042 mmHg, molecular weight 212.2),

[0044]

[0045] 2-Naphthylmethyl acrylate (Na2MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042 mmHg, molecular weight 212.2)

[0046]

[0047] DPhPA (OP 2.38, boiling point 354.5°C, vapor pressure at 80°C 0.0022 mmHg, molecular weight 266.3) shown in the following formula:

[0048]

[0049] PhBzA (OP 2.29, boiling point 350.4°C, vapor pressure 0.0022 mmHg at 80°C, molecular weight 238.3) shown in the following formula:

[0050]

[0051] FLMA (OP 2.20, boiling point 349.3°C, vapor pressure at 80°C 0.0018 mmHg, molecular weight 250.3) shown in the following formula:

[0052]

[0053] ATMA (OP 2.13, boiling point 414.9°C, vapor pressure at 80°C 0.0001 mmHg, molecular weight 262.3) shown in the following formula:

[0054]

[0055] DNaMA (OP 2.00, boiling point 489.4°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 338.4) shown in the following formula:

[0056]

[0057] BPh44DA (OP 2.63, boiling point 444°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3) shown in the following formula:

[0058]

[0059] BPh43DA (OP 2.63, boiling point 439.5 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 322.3) shown in the following formula:

[0060]

[0061] DPhEDA (OP 2.63, boiling point 410°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3) shown in the following formula:

[0062]

[0063] BPMDA (OP 2.68, boiling point 465.7°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 364.4) shown in the following formula:

[0064]

[0065] Na13MDA (OP 2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 296.3) shown in the following formula:

[0066]

[0067] The following formula (a-1-1) (OP 2.40, boiling point 333.4 ° C, vapor pressure at 80 ° C 0.0181 mmHg, molecular weight 199.2),

[0068]

[0069] The following formula (a-1-2) (OP 2.40, boiling point 333.4 ° C, vapor pressure at 80 ° C 0.0181 mmHg, molecular weight 199.2),

[0070]

[0071] The following formula (a-1-3) (OP 1.86, boiling point 369.5 ° C, vapor pressure at 80 ° C 0.0053 mmHg, molecular weight 193.3),

[0072]

[0073] The following formula (a-1-4) (OP 2.85, boiling point 438.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 296.3),

[0074]

[0075] The following formula (a-1-5) (OP 2.71, boiling point 438.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 296.3),

[0076]

[0077] The following formula (a-1-6) (OP 2.87, boiling point 421.0 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 338.4),

[0078]

[0079] The following formula (a-1-7) (OP 2.87, boiling point 465.2 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 338.4),

[0080]

[0081] The following formula (a-1-8) (OP 2.68, boiling point 465.7 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 364.4),

[0082]

[0083] The following formula (a-1-9) (OP 2.50, boiling point 433.1 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 320.3),

[0084]

[0085] The following formula (a-1-10) (OP 2.64, boiling point 468.1 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 326.4),

[0086]

[0087] The following formula (a-1-11) (OP 3.25, boiling point 553.4 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 358.4),

[0088]

[0089] The following formula (a-1-12) (OP 2.63, boiling point 443.9 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 322.4),

[0090]

[0091] The following formula (a-1-13) (OP 2.89, boiling point 509.3 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 406.4),

[0092]

[0093] The following formula (a-1-14) (OP 2.63, boiling point 450.0 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 322.4),

[0094]

[0095] The following formula (a-1-15) (OP 3.00, boiling point 476.5 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 366.4)

[0096]

[0097] The following formula (a-1-16) (OP 2.68, boiling point 447.4 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 364.4)

[0098]

[0099] The following formula (a-1-17) (OP 2.36, boiling point 543.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 398.5),

[0100]

[0101] The following formula (a-1-18) (OP 3.27, boiling point 526.9 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 396.4),

[0102]

[0103] The following formula (a-1-19) (OP 2.71, boiling point 333.7 ° C, vapor pressure at 80 ° C 0.0302 mmHg, molecular weight 244.3),

[0104]

[0105] The following formula (a-1-20) (OP 2.73, boiling point 333.7 ° C, vapor pressure at 80 ° C 0.0134 mmHg, molecular weight 258.3),

[0106]

[0107] The following formula (a-1-21) (OP 2.71, boiling point 319.2 ° C, vapor pressure at 80 ° C 0.0566 mmHg, molecular weight 262.3),

[0108]

[0109] The following formula (a-1-22) (OP 2.71, boiling point 336.9 ° C, vapor pressure at 80 ° C 0.0055 mmHg, molecular weight 244.3),

[0110]

[0111] The following formula (a-1-23) (OP 3.00, boiling point 370.9 ° C, vapor pressure at 80 ° C 0.0021 mmHg, molecular weight 274.4),

[0112]

[0113] The following formula (a-1-24) (OP 3.00, boiling point 376.4 ° C, vapor pressure at 80 ° C 0.0005 mmHg, molecular weight 274.4),

[0114]

[0115] The following formula (a-1-25) (OP 3.00, boiling point 379.4 ° C, vapor pressure at 80 ° C 0.0002 mmHg, molecular weight 288.4),

[0116]

[0117] The following formula (a-1-26) (OP 2.33, boiling point 360.8 ° C, vapor pressure at 80 ° C 0.0006 mmHg, molecular weight 252.3),

[0118]

[0119] The following formula (a-1-27) (OP 2.54, boiling point 371.5 ° C, vapor pressure at 80 ° C 0.0003 mmHg, molecular weight 254.3),

[0120]

[0121] The following formula (a-1-28) (OP 2.57, boiling point 381.2 ° C., vapor pressure at 80 ° C. 0.0001 mmHg, molecular weight 268.3):

[0122]

[0123] The following formula (a-1-29) (OP 2.57, boiling point 381.8 ° C, vapor pressure at 80 ° C 0.0004 mmHg, molecular weight 268.3),

[0124]

[0125] The following formula (a-1-30) (OP 2.50, boiling point 487.4 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 374.4),

[0126]

[0127] The following formula (a-1-31) (OP 2.67, boiling point 417.2 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 268.3),

[0128]

[0129] The following formula (a-1-32) (OP 2.67, boiling point 417.2 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 268.3),

[0130]

[0131] The following formula (a-1-33) (OP 2.67, boiling point 417.2 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 268.3),

[0132]

[0133] The following formula (a-1-34) (OP 2.67, boiling point 417.2 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 268.3),

[0134]

[0135] The following formula (a-1-35) (OP 2.71, boiling point 438.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight 296.3),

[0136]

[0137] <Compound (a-2): Polymerizable compound containing at least Si atoms> The polymerizable compound (a) in the present invention may contain a polymerizable compound (a-2) containing at least Si atoms. Further, when the polymerizable compound (a) contains the polymerizable compound (a-2), the curable composition (A) in a state in which the solvent (d) has been removed preferably contains 10 wt % or more of Si atoms based on the entire curable composition (A).

[0138] An example of the polymerizable compound (a-2) containing at least a Si atom may be linear or branched. For example, cyclic siloxane compounds have the structures shown below. Examples of the polymerizable functional group in the group Q having a polymerizable functional group include radically polymerizable functional groups. Specific examples of radically polymerizable functional groups include (meth)acrylic groups, (meth)acrylamide groups, vinylbenzene groups, allyl ether groups, vinyl ether groups, and maleimide groups. The group Q having a polymerizable functional group may be any group having the above-mentioned polymerizable functional group.

[0139]

[0140] Other examples of the polymerizable compound (a-2) include a silsesquioxane skeleton as shown in the following chemical formula (I) and a silicone skeleton as shown in the following chemical formula (II): where m+n=8 (8≧m≧1) and R １ is a divalent organic group. ２ , R ３ are independently an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, or a hydroxyl group having 1 to 6 carbon atoms, t is an integer of 1 to 3, and at least one of A and B is a polymerizable functional group.

[0141]

[0142]

[0143] Examples of the polymerizable functional group in the groups Q, A, and B having a polymerizable functional group include radically polymerizable functional groups. Specific examples of the radically polymerizable functional group include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds. The group Q having a polymerizable functional group may be any of the groups having the above-mentioned polymerizable functional groups.

[0144] The silicon-containing (meth)acrylate compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of the monofunctional (meth)acrylate compound having one silicon-containing acryloyl group or methacryloyl group include, but are not limited to, the following: (2-acryloylethoxy)trimethylsilane, N-(3-acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, acryloxymethyltrimethoxysilane, (acryloxymethyl)phenethyltrimethoxysilane, acryloxymethyltrimethylsilane, (3-acryloxypropyl)dimethylmethoxysilane, (3-acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-acryloxypropyl)methyldichlorosilane, (3-acryloxypropyl)methyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)trichlorosilane, (3-acryloxypropyl)trimethoxysilane, (3-acryloxypropyl)tris(trimethylsiloxy)silane, acryloxytriisopropylsilane, acryloxytrimethylsilane, methacryloxymethyltrimethoxysilane, 0-(Methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloylpropyltriisopropoxysilane, 0-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyldimethylethoxysilane, (methacryloxymethyl)dimethylethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl silatrane,Methacryloxypentamethyldisiloxane, (methacryloxymethyl)phenyldimethylsilane, methacryloxytrimethylsilane, methacryloxymethyltrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropylpentamethyldisiloxane, 0-(methacryloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propylcarbamate, methacryloxymethyltris(trimethylsiloxy)silane, methacryloxyethoxytrimethylsilane, (3-methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane, methacryloxypropyltris(vinyldimethylsiloxy)silane, methacryloxypropyltris(trimethylsiloxy)silane, 3-methacryloxypropyltriacetoxysilane, methacryloxypropylmethyldichlorosilane, Methacryloxypropyltrichlorosilane, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, 3-methacryloxypropyldimethylchlorosilane, 0-methacryloxy(polyethyleneoxy)trimethylsilane, poly(methacryloxypropylsilsesquioxane), methacryloxypropylheptaisobutyl-T8-silsesquioxane, methacryloxypropyltris(trimethylsiloxy)silane Examples of commercially available products of the above-mentioned silicon-containing monofunctional (meth)acrylate compounds include, but are not limited to, the following:SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0 194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200. A1, SIA0210.0, SIA0315.0, SIA0320.0, SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481.43, SIM6482.0, SI M6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM64 86.4, SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.4 8, SIM6481.5, SIM6491.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, SIM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, SIM6486.65 (all manufactured by GELEST), TM-0701T, FM-0711, FM-0721, FM-0725 (all manufactured by JNC). Silicon-containing (meth)acrylamide compounds are compounds having one or more acrylamide groups or methacrylamide groups. Examples of monofunctional (meth)acrylamide compounds having one silicon-containing acrylamide group or methacrylamide group include, but are not limited to, the following: 3-acrylamidopropyltrimethoxysilane, 3-acrylamidopropyltris(trimethylsiloxy)silane Examples of commercially available silicon-containing monofunctional (meth)acrylamido compounds include, but are not limited to, the following: SIA0146.0, SIA0150.0 (both manufactured by GELEST)Furthermore, examples of polyfunctional (meth)acrylate compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: linear polydimethylsiloxane modified at both ends with acryloxypropyl groups, linear polydimethylsiloxane modified at both ends with methacryloxypropyl groups, cyclic siloxane modified with multiple acryloxypropyl groups, cyclic siloxane modified with multiple methacryloxypropyl groups, silsesquioxane modified with multiple acryloxypropyl groups, silsesquioxane modified with multiple methacryloxypropyl groups. Examples of commercially available products of the above-mentioned silicon-containing polyfunctional (meth)acrylate compounds include, but are not limited to, the following: SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18, DMS-R31 (all manufactured by GELEST), FM-7711, FM-7721, FM-7725 (all manufactured by JNC), X-22-2445 (Shin-Etsu Chemical), AC-SQ TA-100, MAC-SQ TM-100, AC-SQSI-20, MAC-SQ SI-20 (all manufactured by Toagosei). In addition, the following can be synthesized and / or obtained, for example, from known literature 1. Linear modified polydimethylsiloxane (MA-Si-12) modified at both ends with methacryloxypropyl groups, 8-membered ring siloxane (8-ring) modified with four methacryloxypropyl groups, 10-membered ring siloxane (10-ring) modified with five methacryloxypropyl groups, Publicly known document 1: "Ultraviolet curable branched siloxanes as low-k dielectric for imprint lithography" by Ogawa et al.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 combined weight of component (a), component (b) (described below), and component (c) (described below), i.e., the total weight 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, thereby achieving properties such as a fast photopolymerization rate. At least a portion of component (a), which contains one or more polymerizable compounds, may be a polymer having a polymerizable functional group. Such a polymer preferably contains at least a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. For example, it is preferable to contain at least one structural unit represented by any of the following structures (1) to (6).

[0145]

[0146] 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. It is practical that the upper limit of the formula weight of the substituent R is 500 or less.

[0147] 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 specified, 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.

[0148] 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.

[0149] 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 wt% to 60 wt%, more preferably 1 wt% to 50 wt%, and even more preferably 10 wt% to 40 wt%, 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 wt% 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 wt% or less, it is possible to fall within the upper limit specification of viscosity described below.

[0150] <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 in response 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.

[0151] Examples of radical generators 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 benzophenone derivatives such as 4-chloro-4,4'-diaminobenzophenone, 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-butanone, and the like; Quinones such as thiyl anthraquinone, octamethyl anthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenyl anthraquinone, 2,3-diphenyl anthraquinone, 1-chloro anthraquinone, 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethyl anthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoins benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzil derivatives such as benzil 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, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Examples of commercially available products of the radical generators described above 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) Of the above-mentioned radical generators, component (b) is preferably an acylphosphine oxide polymerization initiator. Among the above-mentioned radical generators, the acylphosphine oxide 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. The proportion of component (b) in the curable composition (A) is preferably 0.1 wt% to 50 wt% based on the total mass of components (a), (b), and (c) described below, i.e., the total mass of all components excluding the solvent (d). Furthermore, the proportion of component (b) in the curable composition (A) is more preferably 0.1 wt% to 20 wt%, and even more preferably 1 wt% to 20 wt%, based on the total mass of all components excluding the solvent (d). By making the proportion of component (b) 0.1 wt% or more, the curing rate of the composition can be increased, and the reaction efficiency can be improved. Furthermore, by adjusting the blending ratio of component (b) to 50% by weight or less, a cured film having a certain degree of mechanical strength can be obtained.

[0152] <Component (c): Non-Polymerizable Compound> In addition to the above-described components (a) and (b), the curable composition (A) of the present invention can 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 do not have the ability to sense light of a specific wavelength and generate the above-described polymerization factor (radical). Examples of non-polymerizable compounds include sensitizers, hydrogen donors, surfactants (c1), antioxidants, polymer components, and other additives. Component (c) may contain multiple types of the above-described compounds.

[0153] The sensitizer is a compound that is appropriately added 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.

[0154] 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, which is component (b). Here, the interaction refers to energy transfer or electron transfer from the excited sensitizing dye to the photopolymerization initiator, which is 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, and pyrylium salt dyes. 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 growing end, 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.

[0155] Specific examples of such hydrogen donors include, but are not limited to, the following: 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, N-phenylglycine and other amine compounds; 2-mercapto-N-phenylbenzimidazole, mercaptopropionic acid ester and other mercapto compounds. One type of hydrogen donor may be used alone, or two or more types may be used in combination. The hydrogen donor may also function as a sensitizer.

[0156] In the present invention, a surfactant (c1) is added to the curable composition (A) for the purpose of suppressing extrusion and seepage. The surfactant (c1) also functions as an internal mold release agent that reduces the interfacial bonding strength between the mold and the curable composition, i.e., reduces the mold release force in the mold release step described below. In this specification, "internal mold release" means that the surfactant is added to the curable composition in advance before the curable composition placement step. As the surfactant (c1), surfactants such as silicon-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants can be used. However, in the present invention, the surfactant (c1) has a limited amount to be added, as described below. Note that the surfactant (c1) in the present invention is not polymerizable. The surfactant (c1) may be used alone or in combination of two or more types.

[0157] Fluorine-based surfactants include the following: polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having a perfluoroalkyl group, and polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers. Note that the fluorine-based surfactants may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, etc. in part of their molecular structure (for example, a terminal group). For example, pentadecaethylene glycol mono 1H,1H,2H,2H-perfluorooctyl ether can be mentioned.

[0158] 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, Ltd.), Futergent (registered trademark) 250, 251, 222F, 208G (all manufactured by Neos). The surfactant (c1) may also be a hydrocarbon-based surfactant. Examples of the hydrocarbon-based surfactant include alkyl alcohol polyalkylene oxide adducts and polyalkylene oxides in which alkylene oxides having 2 to 4 carbon atoms are added to alkyl alcohols having 1 to 50 carbon atoms.

[0159] Examples of alkyl alcohol polyalkylene oxide adducts include: 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, and stearyl alcohol ethylene oxide / propylene oxide adduct. 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. The hydroxyl group may be substituted with other substituents, such as polar functional groups such as carboxyl groups, amino groups, pyridyl groups, thiol groups, and silanol groups, or hydrophobic functional groups such as alkyl groups and alkoxy groups.

[0160] Examples of polyalkylene oxides include: 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, and monosuccinate esters. Commercially available alkyl alcohol polyalkylene oxide adducts may be used. 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), random polymerization type polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R) manufactured by Aoki Oil & Fat Industries, polyoxyethylene methyl ether (Pluriol (registered trademark) A760E) manufactured by BASF, polyoxyethylene alkyl ether (Emulgen series) manufactured by Kao. Furthermore, commercially available polyalkylene oxides may be used, and examples thereof include ethylene oxide-propylene oxide copolymer (Pluronic PE6400) manufactured by BASF.

[0161] The surfactant (c1) may also be a silicone surfactant, such as those commercially available under the trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), Megafac Paintad 31 (manufactured by Dainippon Ink and Chemicals, Inc.), and KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0162] Furthermore, the surfactant (c1) may be a surfactant containing at least both a fluorine atom and a silicon atom. Examples of surfactants containing both a fluorine atom and a silicon atom include the following: Trade names X-70-090, X-70-091, X-70-092, and X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and trade names Megafac R-08 and XRB-4 (all manufactured by Dainippon Ink and Chemicals, Inc.). The blending ratio of component (c) excluding the surfactant in the curable composition (A) is preferably 0.01% by weight or more and 50% by weight or less, based on the total weight of components (a), (b), and (c), i.e., the total weight of all components excluding the solvent (d). Furthermore, the blending ratio of component (c) excluding the surfactant in the curable composition (A) is more preferably 0.01% by weight or more and 50% by weight or less, and even more preferably 0.01% by weight or more and 20% by weight or less, based on the total mass of all components excluding the solvent (d). By setting the blending ratio of component (c) excluding the surfactant to 50% by weight or less, a cured film having a certain degree of mechanical strength can be obtained.

[0163] The upper limit of the blending ratio of the surfactant (c1) in the present invention is determined based on the surface tension of the composition obtained by removing the solvent (d) from the curable composition (A), and the contact angle with the surface of the substrate and the surface of the mold, as described below. The effects of the present invention can be obtained by setting the blending ratio of the surfactant (c1) to 0.01 wt % or more.

[0164] <Component (d): Solvent> The curable composition of the present invention contains, as component (d), a solvent having a boiling point of 100°C or higher but 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 100°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, preferably lower than 200°C. If the boiling point of component (d) under normal pressure is lower than 100°C, the evaporation rate in the waiting step described below is too fast, which may result in component (d) volatilizing before droplets of the curable composition (A) combine with each other, preventing the droplets of the curable composition (A) from combining with each other. Furthermore, if the boiling point of component (d) under normal pressure is 250°C or higher, the solvent (d) may not volatilize sufficiently in the waiting step described below, and component (d) may remain in the cured product of the curable composition (A). Here, when component (d) contains one or more solvents, the boiling point of each of the one or more solvents under normal pressure may be 100°C or higher and lower than 250°C (e.g., 100°C or higher and lower than 200°C).

[0165] 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, and sec-tetradecyl Monoalcohol-based solvents such as alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol-based 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; and ketone-based solvents, for example, the following can be mentioned. 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, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone. Examples of ether-based 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 ethanol 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. Examples of ester-based solvents 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, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate 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 Of the above-mentioned solvents, ether-based solvents and ester-based solvents are preferred. From the viewpoint of excellent film-forming properties, ether solvents and ester solvents having a glycol structure are more preferred.

[0166] Further, 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, and particularly preferred is propylene glycol monomethyl ether acetate. In addition, examples thereof include ethyl isocyanurate di(meth)acrylate.

[0167] 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.

[0168] 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-diisopropenyl benzene (218 ° C), styrene (145 ° C), α-methylstyrene (165 ° C). In the present invention, when the entire curable composition (A) is taken as 100 vol%, the content of the solvent (d) is more than 5 vol% and not more than 95 vol%, preferably 15 vol% to 85 vol%, and more preferably 40 vol% to 80 vol%. For example, the content of the solvent (d) is 40 vol% to 85 vol%. 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, whereas 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 in close proximity by the inkjet method.

[0169] <Temperature during blending of curable composition> When preparing the curable composition (A) of the present invention, at least the components (a), (b), and (d) are mixed and dissolved under predetermined temperature conditions. Specifically, the predetermined temperature conditions are in the range of 0°C or higher and 100°C or lower. The same applies when the curable composition (A) contains the component (c).

[0170] <Viscosity of Curable Composition> The curable composition (A) in the present invention is a liquid. This is because, in the disposing step described below, droplets of the curable composition (A) are discretely dropped onto a substrate by an inkjet method. The viscosity of the curable composition (A) in the present invention is 1.3 mPa·s or more and 60 mPa·s or less, preferably 2 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less, at 23°C and 1 atmosphere. If the viscosity of the curable composition (A) is less than 2 mPa·s, the ejection of droplets by the inkjet method becomes unstable. Furthermore, if the viscosity of the curable composition (A) is greater than 60 mPa·s, it is impossible to form droplets with a volume of about 1.0 to 3.0 pL, which is preferred in the present invention.

[0171] The viscosity at 23°C and 1 atmosphere 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 and 1 atmosphere 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, the viscosity at 23°C and 1 atmosphere of the mixture of the components of the curable composition (A) excluding the solvent (d) is more preferably 150 mPa·s or more and 500 mPa·s or less. By making the viscosity of the components of the curable composition (A) excluding the solvent (d) 1,000 mPa·s or less, spreading and filling are quickly completed when the curable composition (A) is brought into contact with a mold. Therefore, by using the curable composition (A) of the present invention, it is possible to perform imprint processing with high throughput and suppress pattern defects due to insufficient filling. Furthermore, by making the viscosity of the components of the curable composition (A) excluding the solvent (d) 1 mPa s or more, it is possible to prevent unwanted flow of droplets of the curable composition (A) after the solvent (d) has evaporated. Furthermore, when the curable composition (A) is brought into contact with a mold, the curable composition (A) is less likely to flow out from the edge of the mold.

[0172] <Surface tension of curable composition> The surface tension γ1 of the curable composition (A) of the present invention after the solvent (d) has evaporated is preferably 5 mN / m or more and 70 mN / m or less at 23°C and 1 atmosphere. Furthermore, for a composition of components excluding the solvent (component (d)), the surface tension at 23°C and 1 atmosphere 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. 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 surface smoothness.

[0173] In the present invention, when the surface tension of the curable composition at 23°C from which the solvent (d) has been removed is γ1 [mN / m] and the surface tension of the solvent (d) at 23°C is γ2 [mN / m], the curable composition is configured so that γ1 is greater than γ2. In other words, when Δγ = γ1 - γ2, the curable composition is configured so that Δγ is greater than zero. Specifically, the solvent (d) is selected so that Δγ is greater than zero. When Δγ is greater than zero, the Marangoni effect accelerates the spreading of droplets of the curable composition in the waiting step described below, causing the droplets to quickly combine with each other and form a continuous liquid film. Furthermore, the rapid spreading of the droplets accelerates the evaporation of the solvent, thereby achieving effects such as completing the waiting step described below in a short time and relaxing or eliminating the conditions for the baking step. Δγ is preferably 0.1 or greater, particularly preferably 1.0 or greater, and even more preferably 2.0 or greater. Note that γ1 and γ2 are surface tensions under normal pressure (1 atmosphere).

[0174] <Contact angle of curable composition> The contact angle of the curable composition (A) of the present invention is preferably 0° or more and 90° or less with respect to both the surface of the substrate and the surface of the mold, for a composition of components excluding the solvent (component (d)). If the contact angle is greater than 90°, capillary force acts in the negative direction (a 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, and the curable composition (A) may not fill the mold. The smaller the contact angle, the stronger the capillary force, and the faster the filling speed.

[0175] Regarding the contact angle of the curable composition (A) in the present invention, the contact angle of the composition of components excluding the solvent (component (d)) and surfactant (c1) with respect to the surface of the substrate is defined as α1 [°], and the contact angle of the composition of components excluding the solvent (component (d)) with respect to the surface of the substrate is defined as α2 [°]. In this case, the type and amount of surfactant (c1) are selected so that α2 is larger than α1. Specifically, by selecting surfactant (c1) so that α2 is larger than α1, a pinning effect is exerted on the spreading of the droplets, making it possible to stop the spreading of the droplets on the substrate at a desired size and suppress the amount of overflow of the curable composition.

[0176] Furthermore, with regard to the contact angle of the curable composition (A) in the present invention, when the composition of components excluding the solvent (component (d)) is expressed as β [°] with respect to the surface of the mold, the type and amount of surfactant (c1) are selected so that β is 25° or greater. Specifically, by selecting surfactant (c1) so that β is 25° or greater, a pinning effect is exerted on the spreading of droplets, and seepage can be suppressed. β is preferably 30° or greater, and more preferably 40° or greater.

[0177] <Impurities Contained in the Curable Composition> The curable composition (A) of the present invention preferably contains as few impurities as possible. Here, the impurities refer to substances 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.

[0178] 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 having 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.

[0179] 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, and more preferably 100 ppb or less.

[0180] <Glass Transition Temperature of Curable Composition> When the glass transition temperature is sufficiently higher than the temperature during demolding, the cured product during demolding is in a strong glassy state, i.e., exhibits high mechanical strength, making it difficult for the pattern to collapse or be damaged by the impact of demolding. Therefore, when the demolding step is performed at room temperature, the glass transition temperature of the cured product (after curing of the polymerizable compound (a)) is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0181] As a method for measuring the glass transition temperature of a cured product (photocured product), it is possible to apply a method using differential scanning calorimetry (DSC) or a dynamic viscoelasticity apparatus. For example, consider the case where the glass transition temperature is measured using DSC. In this case, a straight line is obtained by extending the low-temperature baseline of the DSC curve of the cured product (the portion of the DSC curve in the temperature range where transition and reaction do not occur in the test specimen) toward the high-temperature side, and a tangent line is drawn at the point where the gradient of the curve of the stepwise change in the glass transition is maximum. The extrapolated glass transition onset temperature (Tig) is then determined from the intersection of this straight line and this tangent line, and this can be determined as the glass transition temperature. Typical devices include the STA-6000 (manufactured by Perkin Eimer). On the other hand, when measuring the glass transition temperature using a dynamic viscoelasticity apparatus, the temperature at which the loss sine (tan δ) of the cured product is maximized is defined as the glass transition temperature. Typical devices for measuring dynamic viscoelasticity include the MCR301 (manufactured by Anton Paar).

[0182] [Substrate] In this specification, the member onto which droplets of the curable composition (A) are discretely dropped is referred to as a substrate.

[0183] The substrate is a workpiece substrate, and is 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 (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 silane coupling treatment, silazane treatment, or 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.

[0184] [Pattern Forming Method] The pattern forming method of the present invention will be described with reference to FIGS. 1A to 1G. The cured film formed by the present invention is preferably a film having a pattern of 1 nm to 10 mm in size, and more preferably a film having a pattern of 10 nm to 100 μm in size. Generally, a film formation method that uses light to form a film having a nano-sized (1 nm to 100 nm) pattern (relief structure) is called a photoimprinting method. The film formation method of the present invention uses the photoimprinting method to form a film of a curable composition in the space between a mold and a substrate. However, the curable composition may be cured by other energy (e.g., heat, electromagnetic waves). Furthermore, the film formation method of the present invention may be implemented as a method for forming a patterned film, i.e., a pattern forming method, or as a method for forming a non-patterned film (e.g., a planarized film), i.e., a planarized film forming method.

[0185] 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.

[0186] <Disposing Step> In the disposing step, as schematically shown in Fig. 1A, droplets 102 of the curable composition (A) are discretely disposed on a substrate 101. In the disposing step, droplets 102 of the curable composition (A) having a volume of 1.0 pL or more are disposed at a density of 80 droplets / mm ２The particles are arranged at a density of at least 100 μm. 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).

[0187] As a method for disposing the droplets 102 of the curable composition (A) on the substrate, an inkjet method is particularly preferred. The droplets 102 of the curable composition (A) are preferably disposed densely on regions of the substrate 101 facing regions where the recesses constituting the pattern of the mold 106 are densely present, and sparsely 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.

[0188] In order to define the volume of the curable composition (A) to be placed, 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)) placed in the placing 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 unevenness. Here, the average remaining liquid film thickness may be understood as the value obtained by dividing the volume of the curable composition (A) remaining after the waiting step described below by the area of ​​the film-forming region of the mold, and is preferably 20 nm or less.

[0189] <Waiting Step> 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).

[0190] As described above, in the present invention, when the surface tension of the curable composition from which the solvent (d) has been removed is γ1 [mN / m] and the surface tension of the solvent (d) is γ2 [mN / m], the curable composition (A) is configured so that γ1 is greater than γ2. Specifically, the solvent (d) is selected so that γ1 is greater than γ2, and therefore the droplets 102 of the curable composition (A) dropped onto the substrate 101 spread widely (i.e., the spreading speed of the droplets 102 increases). The reasons for this are explained below.

[0191] Since the droplets of curable composition (A) dropped onto the substrate contain volatile components, the concentration of the volatile components changes due to evaporation after dropping. Since the surface tension γ1 of the non-volatile components is greater than the surface tension γ2 of the volatile components, as the concentration of the volatile components decreases with evaporation, the surface tension increases. Generally, the dropped droplets gradually spread and stop spreading at a static contact angle. The greater the difference between the contact angle with the substrate at the edge of the droplet and the static contact angle, the greater the spreading rate. Furthermore, since the thickness of the cured film is very thin compared to the radius of the droplet, the radial concentration diffusion is much slower than the thickness concentration diffusion.

[0192] The behavior (post-drop behavior) of a droplet 102 of the curable composition (A) dropped onto a substrate 101 will be described with reference to FIG. 2 . FIG. 2 shows the spreading of the droplet 102 dropped onto the substrate. As described above, the evaporation of the solvent component progresses even while the droplet 102 is spreading. The evaporation rate is highly dependent on the surface area of ​​the droplet 102. Comparing the central portion 303 of the droplet 102 with the end portion 304 of the droplet 102, the surface area of ​​the end portion 304 of the droplet 102 is slightly larger than the surface area of ​​the central portion 303 of the droplet 102, resulting in faster evaporation. Meanwhile, the volume of the droplet 102 is smaller at the end portion 304 of the droplet 102 than at the central portion 303 of the droplet 102. Therefore, the edge 304 of the droplet 102 volatilizes faster and has a smaller volume than the central portion 303 of the droplet 102, resulting in a lower concentration of volatile components and a higher surface tension. In this way, the surface tension of the edge 304 of the droplet 102 is higher than that of the central portion 303 of the droplet 102, and therefore a force is generated from the central portion 303 of the droplet 102 toward the edge 304 due to the Marangoni effect, inducing a flow (spreading) of the droplet 102.

[0193] Fig. 3 is a diagram showing the shape of the droplet 102 when a flow of the droplet 102 is induced by the Marangoni effect. When a flow of the droplet 102 is induced toward the edge of the droplet 102, the edge of the droplet 102 becomes swollen, as shown in Fig. 4. As a result, the contact angle between the edge of the droplet 102 and the substrate 101 becomes larger than when a flow of the droplet 102 is not induced, and the spreading speed of the droplet 102 also increases.

[0194] As described above, the type and amount of surfactant (c1) are selected so that the contact angle of the curable composition (A) is such that α2 [°] is greater than α1 [°]. Here, α1 is the contact angle of the composition of components excluding the solvent (component (d)) and surfactant (c1) with respect to the surface of the substrate 101, and α2 is the contact angle of the composition of components excluding the solvent (component (d)) with respect to the surface of the substrate 101. Specifically, because the surfactant (c1) is selected so that α2 is greater than α1, a pinning effect is exerted on the spreading of the droplets 102, allowing the spreading of the droplets 102 on the substrate to be stopped at a desired size, thereby suppressing the amount of spillover. The reasons for this are explained below.

[0195] FIG. 4 is a diagram showing a state in which a droplet 102 of a curable composition (A) is dropped onto a substrate 101. The droplet 102 dropped onto the substrate 101 spreads while volatilizing. When the curable composition (A) does not contain a surfactant (c1), the droplet 102 spreads to a contact angle α1 as shown in FIG. 5. In particular, when the contact angle α1 is close to zero, the droplet 102 continues to spread over a large area. On the other hand, when the curable composition (A) contains a surfactant (c1), the droplet 102 dropped onto the substrate 101 spreads until the contact angle becomes α2 (α2 > α1), as shown in FIG. 6. Comparing FIG. 5 and FIG. 6, the surfactant (c1) increases the contact angle from α1 to α2, and the droplet 102 pins in the area determined by the contact angle α2, stopping the spreading, thereby suppressing the amount of spillover.

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

[0197] 7A to 7D, the flow behavior of droplets of the curable composition (A) placed on a substrate during the waiting process will be described. As shown in FIG. 7A, droplets 102 of the curable composition (A) are discretely placed on the substrate 101, and as shown in FIG. 7B, each droplet 102 gradually spreads on the substrate. Then, as shown in FIG. 7C, 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. 7D (the surface of the substrate 101 is covered with the curable composition (A), with no exposed surface). The state of the curable composition (A) as shown in FIG. 7D is referred to as a "substantially continuous liquid film."

[0198] Furthermore, in the waiting step, as schematically shown in Fig. 1D, the solvent 105 (solvent (d)) contained in the liquid film 104 is volatilized. The amount of solvent (d) remaining in the liquid film 103 after the waiting step (for example, at the start of the contacting step) is preferably 10% by volume or less, assuming that the total weight of the components other than solvent (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.

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

[0200] The waiting step is, for example, 0.1 to 600 seconds, preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 seconds, 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 suppress the 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 the influence of volatilization, making it impossible to form a continuous liquid film.

[0201] 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.

[0202] 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 a mold 106. The contacting step includes a step of changing a state in which the curable composition (A) and the mold 106 are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. As a result, the liquid of the curable composition (A) fills the recesses of the fine pattern on the surface of the mold 106, and the liquid becomes a liquid film that fills the fine pattern of the mold 106.

[0203] 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, spreading 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 Japanese Patent No. 6584578 and the contacting step in the present invention is shown in Figure 8.

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

[0205] As described above, a phenomenon called seepage may occur during the contact step. This is a phenomenon in which the curable composition overflows from the contact surface of the mold and adheres (creeps up) to the sidewall (side surface) of the mold. The concept of seepage will be explained with reference to FIG. 9 . As shown in FIG. 16 , the curable composition 1602 that has overflowed from the mold 106 creeps up the sidewall of the mold 106, causing unwanted cured material of the curable composition 1602 to form outside the contact surface of the mold 106, resulting in defects, or so-called seepage (defects). Here, the height to which the curable composition 1602 has crept up the sidewall of the mold 106 is defined as the seepage height 1604.

[0206] In the present invention, as described above, with respect to the contact angle of the curable composition (A), when the composition of components excluding the solvent (component (d)) with respect to the surface of the mold is expressed as β [°], the type and amount of surfactant (c1) are selected so that β is 25° or greater. The reason for this is explained with reference to FIG. 10 . As described above, the curable composition 1602 that protrudes from the mold 106 creeps up the side wall of the mold 106. When the contact angle β is less than 25°, for example, an interface 1705 as shown by the solid line in FIG. 10 is formed. The contact angle β between the mold 106 and the interface 1705 is β<25°. On the other hand, when the curable composition 1602 contains a surfactant and the contact angle β is 25° or greater, for example, an interface 1706 as shown by the dashed line in FIG. 10 is formed. The contact angle β between the mold 106 and the interface 1705 is β≧25°. Comparing interface 1705 and interface 1706, it can be seen that although the volume of curable composition 1602 that has overflowed from mold 106 is greater at interface 1706, the seepage height is lower at interface 1706. As such, by increasing the contact angle β, the dependency of the seepage height on the volume of curable composition 1602 that has overflowed from mold 106 becomes weaker, and the seepage height can be suppressed. β is preferably 30° or more, and more preferably 40° or more.

[0207] When the curing step includes a light irradiation step, 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.

[0208] 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 in 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, resulting in contact between adjacent pattern elements, 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) in order 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.

[0209] 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. Commercially available coated 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.

[0210] In the contacting step, the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the curable composition (A) is not particularly limited, and is, for example, 0 MPa or more and 100 MPa or less. Note that the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the curable composition (A) is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0211] The contacting step can be carried out under any of the following conditions: air, reduced pressure, and inert gas; however, 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 inert gases used when carrying out the contacting step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, and mixtures thereof. Gases containing 10% or more carbon dioxide or helium by molar ratio are preferred, and gases containing 10% or more carbon dioxide by molar ratio are particularly preferred. Helium gas easily diffuses into the mold, substrate, curable composition, etc., so that atmospheric gas trapped in the mold pattern, etc., quickly disappears. Carbon dioxide easily dissolves in the curable composition and the underlayer on the substrate, so that atmospheric gas trapped in the mold pattern, etc., quickly disappears. Furthermore, the solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m ３ ・ATM or more 10kg / m ３ The pressure is preferably 0.0001 atm or less. Details of these are disclosed in JP 2022-99271 A. When the contact step is carried out under a specific gas atmosphere, including air, the preferred pressure is 0.0001 atm or more and 10 atm or less.

[0212] <Curing Step> 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.

[0213] 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 having a wavelength of 150 nm or more and 400 nm or less, X-rays, electron beams, etc. It is particularly preferable that the irradiation light 107 is ultraviolet light. This is because many of the compounds commercially available as curing aids (photopolymerization initiators) 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, F ２ Examples of such a light source include a laser. However, an ultra-high pressure mercury lamp is particularly preferred as a light source emitting ultraviolet light. The number of light sources may be one or more. Furthermore, the entire area of ​​the curable composition (A) filled into the fine pattern of the mold may be irradiated with light, or only a partial area (a limited area) may be irradiated with light. Furthermore, light irradiation may be performed intermittently multiple times over the entire area of ​​the substrate, or may be performed 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 light may be irradiated over a second area of ​​the substrate different from the first area in a second irradiation process.

[0214] <Mold Release Step> In the mold release step, as schematically shown 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. Such a film is called a residual film.

[0215] 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.

[0216] <Repetition> A series of steps (manufacturing process) including the above-described placement step to demolding step in this order can provide a cured film having a desired concave-convex pattern shape (a pattern shape that follows the concave-convex shape of the mold 106) at a desired position.

[0217] In the pattern formation method of the present invention, the repeating unit (shot) from the placement step to the demolding step 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.

[0218] [Planarization Film Forming Method] An example in which the film formation method of the present invention is applied to a planarization film forming method will be described below. The planarization film forming method includes, for example, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step. The disposing step is a step of disposing droplets of the curable composition (A) on a substrate. The waiting step is a step of waiting until the droplets of the curable composition (A) bond together and the solvent (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 forming 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.

[0219] [Method for manufacturing an article] The method for manufacturing an article includes a forming step of forming a film of a curable composition on a substrate using the above-mentioned film forming method, a processing step of processing the substrate on which the film of the curable composition has been formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. As described above, the film forming method is a pattern forming method or a planarizing film forming method.

[0220] Furthermore, the cured film 108 having a pattern formed by the pattern formation method of the present invention can be used as it is as at least a part of a constituent member of various articles. The cured film 108 having a pattern formed by the pattern formation method of the present invention can be temporarily used as a mask for etching or ion implantation of the substrate 101 (or the processable layer if the substrate 101 has one). After etching or ion implantation is performed in the process of processing the substrate 101, the mask is removed. This allows various articles to be manufactured.

[0221] When removing the cured material in the recesses of the cured material pattern by etching, the specific method is not particularly limited, and a known method, for example, dry etching, can be used. A known dry etching apparatus can be used for dry etching. The source gas for dry etching is appropriately selected depending on the elemental composition of the cured material to be etched. Specifically, CF is used as the source gas. ４ , C ２ F ６ , C ３ F ８ , CCl ２ F ２ , CCl ４ , CBrF ３ , BCl ３ , PCl ３ , SF ６ , Cl ２ The source gas may be a halogen-based gas such as O ２ , CO, CO ２ Gases containing oxygen atoms such as He, N ２ , an inert gas such as Ar, H ２ , N.H. ３ These gases can also be used as a source gas. In this case, a high dry etching resistance is required for the photocured film in order to process the base substrate with a high yield.

[0222] 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 memories 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.

[0223] 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 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.

[0224] [Example] To supplement the above-described embodiment, a more specific example will be described.

[0225] Example 1 shows that by adding a surfactant to make α2 larger than α1, the spreading of the droplet on the substrate can be controlled by the pinning effect, and the amount of spillover can be reduced. Furthermore, by making γ1 larger than γ2, the amount of spillover can be reduced while still forming a liquid film due to the spreading of the droplet.

[0226] In Example 1, droplet spreading experiments were conducted using three different compositions, as shown in Table 1 below. In Table 1, FS2000M1 (manufactured by CHANGZHOU FOREIGN CO., LTD.) was the surfactant. Composition 1 was a composition containing no surfactant, Composition 2 was a composition containing 0.4 wt % of a surfactant, and Composition 3 was a composition containing 3% of a surfactant.

[0227]

[0228] First, we show that the addition of a surfactant increases α2 to α1. The contact angle was measured using a 1 μL droplet and an automatic static contact angle measuring device, Dropmaster 300 (Kyowa Interface Science Co., Ltd.). FIG. 11 shows the results of measuring the contact angle of each composition with respect to the substrate. The horizontal axis in FIG. 11 represents time, and the vertical axis represents contact angle, showing the change in contact angle of each composition over time. Referring to FIG. 11, it can be seen that at each time point, composition 2 has a larger contact angle than composition 1, and composition 3 has a larger contact angle than composition 2, and α2 is larger than α1. In FIG. 11, the contact angle of composition 2 10 seconds after the droplet of each composition was dropped was approximately 0.5° higher than composition 1.

[0229] Next, the change in surface tension with the addition of a surfactant is shown. Surface tension measurements were performed using an automatic surface tensiometer DY-300 (manufactured by Kyowa Interface Science Co., Ltd.) by the plate method using a platinum plate. Figure 12 shows the results of surface tension measurements. In Figure 12, the horizontal axis represents the amount of surfactant added, and the horizontal axis represents the surface tension value. Graph 901 is a graph showing the dependence of the surface tension of the curable composition from which the solvent (d) has been removed on the amount of surfactant added, and graph 902 is a graph showing the surface tension value of the solvent. As described above, when γ1 is greater than γ2, the droplets spread quickly and form a liquid film. This is the region where the surface tension of graph 901 is greater than the surface tension of graph 902, which is region 903 in Figure 12. According to this, for composition 2, γ1 is greater than γ2, and for composition 3, γ1 is smaller than γ2.

[0230] Next, Figure 13 shows the change in droplet radius over time when a droplet of approximately 2 pL was dropped. An industrial material printer, DMP-2850 (manufactured by Fujifilm), was used to photograph (measure) the droplet dropping and the droplet spreading. In Figure 13, the horizontal axis represents time and the vertical axis represents the droplet radius. Referring to Figure 13, it can be seen that for Composition 1, the droplet spreads over time, whereas for Composition 2, the droplet spreading stops at an appropriate radius due to the pinning effect. It can also be seen that for Composition 3, the droplet shrinks due to the pinning effect and Marangoni effect. Thus, by exerting the pinning effect through the addition of a surfactant, it is possible to control the droplet spreading.

[0231] Next, the amount of overflow of the liquid film was measured using an industrial material printer DMP-2850 (manufactured by Fujifilm) when droplets of approximately 2 pL were arranged in a 6-row array with a 70 μm pitch. The overflow amount of the liquid film was defined as the length of the liquid film minus 70 × 6 μm. In Figure 14, the horizontal axis represents time, and the vertical axis represents the amount of overflow. Composition 3 failed to form a substantially continuous liquid film due to excessive shrinkage, defeating the purpose of the waiting step and being deemed unsuitable. Typically, with composition 3, droplets 1302 are isolated on substrate 1301, as shown in Figure 15. On the other hand, with compositions 1 and 2, a substantially continuous liquid film can be formed, and typically, droplets merge to form liquid film 1202 on substrate 1201, as shown in Figure 16.

[0232] With respect to compositions 1 and 2 other than composition 3, which was judged to be unsuitable, referring to FIG. 14 , it can be seen that composition 1 had a large amount of protrusion that increased with time, whereas composition 2 had a small amount of protrusion and little dependency on time.

[0233] A summary of the experimental results for Compositions 1, 2, and 3 is shown in Figure 17. Figure 17 shows the amount of overflow after 600 seconds. Referring to Figure 17, it can be seen that by making α2 larger than α1, as in the case of Compositions 1 and 2, it is possible to suppress the amount of overflow from 120 μm to 48 μm. It can also be seen that by making γ1 larger than γ2, as in the case of Compositions 3 and 2, it is possible to achieve compatibility with liquid film formation.

[0234] As described above, it was shown that the amount of overflow can be suppressed by making α2 larger than α1. Also, it was shown that it is possible to achieve compatibility with liquid film formation by making γ1 larger than γ2. As shown in Figure 11, it is clear that it is preferable for the contact angle 10 seconds after the droplet is dropped to be α2-α1>0.5°.

[0235] Next, a preferred Δγ defined by the following formula (3) will be described.

[0236] Δγ = γ1 - γ2 Equation (3) Figure 18 is a diagram showing the dependence of the maximum radius of a droplet on Δγ when a droplet of approximately 1 pL is dropped. Figure 18 shows the results of numerical calculations obtained by solving the Navier-Stokes equations approximated by a thin film (lubrication theory) with a free surface. In Figure 18, the horizontal axis is Δγ [mN / m], and the vertical axis is Δr [μm]. Here, Δr is defined by the following equation (4):

[0237] Δr = r - r ０ In equation (4), r is the maximum radius of the droplet, and r ０ is the maximum radius of the droplet when Δγ=0.

[0238] 18, when Δγ > 0.1 mN / m, Δr > 1 μm, and it is clear that the droplet spreads more than when Δγ = 0. Furthermore, when Δγ > 1 mN / m, Δr > 10 μm, and it is clear that the droplet spreads more significantly than when Δγ = 0. Therefore, in order to see an effect on the maximum radius of the droplet, it is clear that Δγ > 0.1 mN / m is preferable, and Δγ > 1 mN / m is more preferable.

[0239] Example 2 shows that by adding a surfactant to increase β to more than 25°, it is possible to control the spreading of droplets on the surface of the mold through a pinning effect, thereby suppressing the height of seepage onto the side wall of the mold. In Example 2, experiments were also conducted using the three compositions shown in Table 1.

[0240] First, it shows that β (contact angle) increases with the addition of surfactant. The contact angle measurement was performed in the same manner as in Example 1. FIG. 19 is a diagram showing the results of measuring the contact angle with respect to the mold for each of Compositions 1, 2, and 3. In FIG. 19, the horizontal axis represents time and the vertical axis represents contact angle, showing the change in contact angle with respect to the mold surface for each composition over time. Referring to FIG. 19, it can be seen that at each time point after 1 second, the contact angle for Composition 2 is larger than that for Composition 1, and the contact angle for Composition 3 is larger than that for Composition 2, and β increases. In FIG. 19, the contact angle 10 seconds after the droplets of each composition were dropped was approximately 14° for Composition 1 and approximately 31° for Composition 2.

[0241] Next, the results of numerical calculations of the exudation height for different contact angles are shown in Figure 20. Figure 20 shows the results obtained by approximating the substrate and mold as rigid bodies and solving the Navier-Stokes equations with thin film approximation. In Figure 20, the horizontal axis represents the contact angle, and the vertical axis represents the exudation height.

[0242] 20, it can be seen that the exudation height for composition 1, which has a contact angle of about 14°, is about 95 nm, and the exudation height for composition 2, which has a contact angle of about 31°, is about 70 nm. Therefore, it can be seen that it is possible to suppress the exudation height by selecting composition 2 rather than composition 1. Note that composition 3 has a higher contact angle, so it is possible to further suppress the exudation height, but it can be seen from Example 1 that composition 2, in which γ1 is larger than γ2, is required to be compatible with liquid film formation.

[0243] According to the abbreviations shown in Table 2 below, curable compositions (A) were mixed so that the total of components (a), (b), (c), and (d) was 100% by weight, as shown in Table 3 below. Curable compositions (A) were also mixed without component (d). The viscosities of these curable compositions (A) at 23°C were measured, and the Si atom content and post-cured Tg of the curable compositions when component (d) was removed were calculated using the method described above. The results are shown in Table 4 below. In addition, in the component (d) shown in Table 3, PGEA is an abbreviation for propylene glycol monomethyl ether, and Gly is an abbreviation for glycerin.

[0244]

[0245]

[0246]

[0247] <Evaluation of Inkjet Discharge> A commercially available industrial material printer DMP-2850 (manufactured by Fujifilm) was used to evaluate inkjet discharge. The curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3 were filled into cartridges. The state of droplet discharge was observed with a built-in discharge observation camera, and inkjet discharge was evaluated according to the following evaluation criteria. (Evaluation criteria) AAA: At a discharge speed (flight speed) of 6 m / sec or more, no deviation (distortion) of the landing position was observed. AA: At a discharge speed of 6 m / sec or more, very slight deviation of the landing position was observed, which was at a level that had no practical effect. A: At a discharge speed of 4 m / sec or more, very slight deviation of the landing position was observed, which was at a level that had no practical effect. B: No discharge.

[0248] <Evaluation of Overflow Amount> The overflow amount was evaluated using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). Cartridges were filled with the curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3. Approximately 2 pl of droplets were dispensed and arranged in an array of six rows at a 70 μm pitch. In all Examples and Comparative Examples, after 600 seconds, it was confirmed that the liquid film had formed a substantially continuous liquid film, and the overflow amount was measured. The overflow amount of the liquid film was defined as the length of the liquid film minus 70 × 6 μm, and the overflow amount was evaluated according to the following evaluation criteria: (Evaluation Criteria) AAA: The overflow amount was 50 μm or less. AA: The overflow amount was 70 μm or less. A: The overflow amount was 100 μm or less. B: The overflow amount was greater than 100 μm.

[0249] <Evaluation of the Amount of Exudation> The amount of exudation was evaluated using a commercially available industrial material printer DMP-2850 (manufactured by Fujifilm). The curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3 were filled into cartridges at 1 pL. A pattern array was created using the DMP-2850's pattern editor software, with the X width set to 25.5 mm, the Y height set to 32.5 mm, and the drop spacing set to 50 μm. Then, droplets were dropped onto a silicon substrate, and a placement step, a waiting step, and a contacting step were performed using a quartz blank mold. The placement step, waiting step, and contacting step were performed in a carbon dioxide atmosphere, and the outer periphery of the plain mold after the steps was photographed at 500 μm intervals to obtain a total of 232 images. All images were observed, and the amount of exudation was evaluated using the following evaluation criteria. (Evaluation criteria) AAA: Exudation was observed in less than 1% of the images. AA: Seepage was confirmed in 3% or less of the total number of images. A: Seepage was confirmed in 5% or less of the total number of images. B: Seepage was confirmed in more than 5% of the total number of images.

[0250] <Evaluation of Drop Bonding> The curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3 were discretely dropped (placed) onto a silicon substrate under conditions such that the thickness of the liquid film before the solvent (d) volatilized was 80 nm. The time until a substantially continuous liquid film was formed was then measured, and the drop bonding was evaluated according to the following evaluation criteria. (Evaluation criteria) AAA: A substantially continuous liquid film was formed within less than 100 seconds. AA: A substantially continuous liquid film was formed within 100 seconds or more but less than 200 seconds. A: A substantially continuous liquid film was formed within 200 seconds or more but less than 300 seconds. B: A substantially continuous liquid film was not formed even after 300 seconds had passed.

[0251] <Evaluation of Pattern Collapse> For the curable compositions of Examples 3 to 28 and Comparative Examples 1 and 2 shown in Table 3, a placement step, a waiting step, a contact step, a curing step, and a demolding step were carried out using a quartz mold in which a line-and-space (L / S) pattern with a depth of 50 nm and a width of 20 nm was formed over the entire area. The patterns obtained through these steps were then observed, and pattern collapse was evaluated according to the following evaluation criteria. (Evaluation Criteria) AAA: Pattern collapse was observed in less than 0.5% of the pattern-formed area. AA: Pattern collapse was observed in less than 1% of the pattern-formed area. A: Pattern collapse was observed in less than 10% of the pattern-formed area. B: Pattern collapse was observed in 10% or more of the pattern-formed area.

[0252] <Evaluation of dry etching resistance> The cured films obtained from the curable compositions of Examples 3 to 22 and Comparative Examples 1 and 2 shown in Table 3 were exposed to oxygen plasma in a dry etching apparatus. In addition, the cured films obtained from the curable compositions of Examples 23 to 28 shown in Table 3 were exposed to CF ４The film was exposed to plasma. The change in weight of the remaining cured film after exposure was measured, and the dry etching resistance was evaluated according to the following evaluation criteria. (Evaluation criteria) AAA: The weight of the remaining cured film was 46% or more of the weight before etching. AA: The weight of the remaining cured film was 42% or more of the weight before etching. A: The weight of the remaining cured film was 38% or more of the weight before etching. B: The weight of the remaining cured film was less than 38% of the weight before etching.

[0253] The evaluation results so far are shown in Table 5 below.

[0254]

[0255] It can be seen that when the viscosity of the curable composition at 23°C is 2 mPa·s or more and 60 mPa·s or less, inkjet ejection is favorable, and a viscosity of 5 mPa·s or more and 30 mPa·s or less is preferable, and a viscosity of 5 mPa·s or more and 15 mPa·s or less is even more preferable.

[0256] When the contact angle of the composition excluding the solvent (d) and the surfactant (c1) with respect to the substrate is α1 [°] and the contact angle of the composition excluding the solvent (d) with respect to the substrate is α2 [°], it can be seen that the amount of overflow is good if α2 is larger than α1. It can also be seen that α2 - α1 > 0.5 is preferable, and α2 - α1 ≥ 3.0 is even more preferable.

[0257] It can be seen that the amount of seepage is good when the contact angle β [°] of the composition excluding the solvent (d) with quartz is β≧25°, preferably β≧30°, and even more preferably β≧40°.

[0258] It can be seen that drop bonding is favorable if γ1 is greater than γ2, where γ1 [mN / m] is the surface tension of the composition from which solvent (d) has been removed at 23°C, and γ2 [mN / m] is the surface tension of solvent (d) at 23°C. It can also be seen that γ1 - γ2 ≧ 1.0 is preferable, and γ1 - γ2 ≧ 2.0 is even more preferable.

[0259] It can be seen that the pattern collapse occurs when the glass transition temperature of the curable composition after curing is preferably 70° C. or higher, more preferably 100° C. or higher, and even more preferably 130° C. or higher.

[0260] It can be seen from Examples 3 to 22 and Comparative Examples 1 and 2 that the dry etching resistance is preferably such that the OP of the polymerizable compound (a) is 1.80 or more and 4.00 or less, more preferably such that the OP is 2.00 or more and 3.50 or less, and even more preferably such that the OP is 2.40 or more and 3.00 or less. It can also be seen from Examples 3 to 28 that the dry etching resistance is preferably such that the Si content of the polymerizable compound (a) is 10 wt % or more, more preferably such that the Si content is 15 wt % or more, and even more preferably such that the Si content is 20 wt % or more.

[0261] The invention is not limited to the above-described embodiments, and various changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the following claims are appended to apprise the public of the scope of the invention.

[0262] This application claims priority based on Japanese Patent Application No. 2023-119299, filed on July 21, 2023, the entire contents of which are incorporated herein by reference.

Claims

1. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), wherein the curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atmospheric pressure, the content of the solvent (d) relative to the entire curable composition is more than 5 volume% and less than 95 volume%, the boiling point of the solvent (d) is less than 250°C at 1 atmospheric pressure, and when the contact angle of a composition obtained by excluding the solvent (d) and the surfactant (c1) from the curable composition with a substrate is α1 [°] and the contact angle of a composition obtained by excluding the solvent (d) from the curable composition with the substrate is α2 [°], α2 is greater than α1.

2. The curable composition according to claim 1, characterized in that α2-α1>0.5[°].

3. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), wherein the curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atmospheric pressure, the content of the solvent (d) relative to the entire curable composition is more than 5 volume% and 95 volume% or less, the boiling point of the solvent (d) is less than 250°C at 1 atmospheric pressure, and the contact angle β [°] of the composition obtained by removing the solvent (d) from the curable composition with respect to a mold is 25° or more.

4. The curable composition according to claim 1 or 3, characterized in that, when the surface tension of the composition obtained by removing the solvent (d) from the curable composition at 23°C and 1 atmospheric pressure is γ1 [mN / m], and the surface tension of the solvent (d) at 23°C and 1 atmospheric pressure is γ2 [mN / m], γ1 is greater than γ2.

5. The curable composition according to claim 4, characterized in that γ1-γ2>0.1 [mN / m].

6. The curable composition according to claim 4, characterized in that γ1-γ2>1 [mN / m].

7. The curable composition according to claim 1 or 3, characterized in that the surfactant (c1) contains a fluorine atom.

8. The curable composition according to claim 1 or 3, characterized in that the surfactant (c1) contains a silicon atom.

9. The curable composition according to claim 1 or 3, characterized in that the composition obtained by removing the solvent (d) from the curable composition has a viscosity of 30 mPa·s or more and 10,000 mPa·s or less at 23°C and 1 atmospheric pressure.

10. The curable composition according to claim 1 or 3, characterized in that the solvent (d) contains one or more solvents, and each of the one or more solvents has a boiling point at 1 atmospheric pressure of 100°C or higher and lower than 250°C.

11. The curable composition according to claim 1 or 3, characterized in that the solvent (d) contains a polymerizable compound having a boiling point at 1 atmospheric pressure of 100°C or higher and lower than 250°C.

12. The curable composition according to claim 1 or 3, characterized in that the solvent (d) contains one or more solvents, and the boiling point of each of the one or more solvents at 1 atmospheric pressure is 100°C or higher and lower than 200°C.

13. The curable composition according to claim 1 or 3, characterized in that the content of the solvent (d) in the entire curable composition is 40 volume % or more and 85 volume % or less.

14. The curable composition according to claim 1 or 3, characterized in that the ratio of the polyfunctional polymerizable compound in the polymerizable compound (a) is 20% by weight or more.

15. The curable composition described in claim 1 or 3, characterized in that the polymerizable compound (a) contains one or more types of polymerizable compounds, and each of the one or more types of polymerizable compounds has a boiling point at 1 atmosphere of 250°C or higher.

16. The curable composition according to claim 1 or 2, characterized in that the polymerizable compound (a) contains one or more types of polymerizable compounds, and each of the one or more types of polymerizable compounds has a molecular weight of 200 or more.

17. The curable composition according to claim 1 or 2, characterized in that the polymerizable compound (a) includes a polymer having a polymerizable functional group.

18. The curable composition according to claim 1 or 3, characterized in that the polymerizable compound (a) has a glass transition temperature of 70° C. or higher after curing.

19. The curable composition described in claim 1 or 3, characterized in that the polymerizable compound (a) contains one or more types of polymerizable compounds, and each of the one or more types of polymerizable compounds has a vapor pressure of 0.001 mmHg or less at 80°C and 1 atmosphere.

20. The curable composition according to claim 1 or 3, characterized in that the polymerizable compound (a) includes a compound (a-1) having an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure.

21. The curable composition according to claim 1 or 3, characterized in that the polymerizable compound (a) contains one or more types of polymerizable compounds, and the Ohnishi parameter (OP) of the polymerizable compound (a) is 1.80 or more and 4.00 or less, and is a mole fraction weighted average value of the N / (Nc-No) value of each molecule of the one or more types of polymerizable compounds, where N is the total number of atoms in the molecule, Nc is the number of carbon atoms in the molecule, and No is the number of oxygen atoms in the molecule.

22. The curable composition according to claim 1 or 3, characterized in that the polymerizable compound (a) includes a compound (a-2) containing a silicon atom.

23. The curable composition according to claim 22, wherein the compound (a-2) includes a polymerizable compound having a silsesquioxane skeleton or a cyclic siloxane compound.

24. The curable composition according to claim 1 or 3, characterized in that the composition obtained by removing the solvent (d) from the curable composition contains 10% by weight or more of Si atoms.

25. The curable composition according to claim 1 or 3, characterized in that the curable composition is a curable composition for inkjet.

26. The solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m ３ ・ATM or more 10kg / m ３ 4. The curable composition according to claim 1, wherein the viscosity is equal to or less than 0.5 atm.

27. A film formation method for forming a film of a curable composition in a space between a mold and a substrate, comprising: an arrangement step of discretely arranging a plurality of droplets of the curable composition according to claim 1 or 3 on the substrate; a waiting step of waiting until the plurality of droplets combine with adjacent droplets to form a liquid film; and a contacting step of bringing the mold into contact with the liquid film after the waiting step.

28. The film forming method described in Claim 27, characterized in that in the waiting step, waiting is continued until the solvent contained in the liquid film evaporates and the content of the solvent becomes 10 volume % or less with respect to the entire liquid film.

29. The film forming method according to claim 27, wherein in the waiting step, the substrate is heated at 30° C. or higher and 200° C. or lower for 10 seconds or higher and 600 seconds or lower.

30. In the disposing step, droplets of the curable composition having a volume of 1.0 pL or more are applied onto the substrate at a rate of 80 droplets / mm ２ 28. The film forming method according to claim 27, wherein the particles are arranged at a density of at least 100 nm.

31. The film forming method according to claim 27, characterized in that the average remaining liquid film thickness, which is the volume of the curable composition remaining after the waiting step divided by the area of ​​the film formation region, is 20 nm or less.

32. The film formation method according to claim 27, characterized in that the mold includes a pattern, the contacting step involves contacting the pattern of the mold with the liquid film, and the film formation method further includes a hardening step, after the contacting step, of hardening the liquid film to form a hardened film having a pattern corresponding to the pattern of the mold.

33. The film formation method according to claim 27, characterized in that the mold includes a flat surface, and in the contacting step, the flat surface of the mold is brought into contact with the liquid film, and the film formation method further includes a hardening step, after the contacting step, of hardening the liquid film to form a hardened film having a surface conforming to the flat surface of the mold.

34. The film forming method according to claim 27, characterized in that in the disposing step, the plurality of droplets are discretely disposed on the substrate by using an inkjet method.

35. The film forming method according to claim 27, wherein in the contacting step, the gas filling the space between the mold and the substrate contains carbon dioxide at a molar ratio of 10% or more.

36. A method for producing an article, comprising: a forming step of forming a film of a curable composition on a substrate by using the film forming method described in claim 27; a processing step of processing the substrate on which the film has been formed in the forming step; and a manufacturing step of producing an article from the substrate processed in the processing step.

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