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

Abstract

Providing new technologies related to curable compositions. [Solution] 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 to 60 mPa·s at 23°C and 1 atm, the content of solvent (d) relative to the total curable composition is greater than 5 vol% and 95 vol% or less, the boiling point of solvent (d) is less than 250°C at 1 atm, and the polymerizable compound (a) and solvent (d) have an SP value of 17 MPa 1 / 2 More than 25MPa 1 / 2 It has less than 11 MPa, and the surfactant (c1) does not contain fluorine atoms or silicon atoms, and has an SP value of 11 MPa. 1 / 2 17 MPa or more 1 / 2 A liquid-repellent atomic group having less than 25 MPa SP value 1 / 2 Above 35 MPa 1 / 2 The composition contains a hydrophilic atomic group having less than , and the surfactant (c1) content relative to the entire curable composition is 0.1% by weight or more and 10% by weight or less.

Description

[Technical Field]

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

[0002] In semiconductor devices and MEMS, the demand for miniaturization is increasing, and imprint technology (optical imprint technology) is attracting attention as a microfabrication technology. In imprint technology, a mold with a fine uneven pattern formed on its surface is brought into contact with a curable composition supplied (coated) onto a substrate, and the curable composition is cured. This transfers the pattern of the mold to the cured film of the curable composition, forming the pattern on the substrate. According to imprint technology, it is possible to form fine patterns (structures) on the order of a few nanometers on a substrate.

[0003] An example of a pattern formation method using imprint technology is described below. First, liquid curable material is discretely dropped (placed) onto the pattern formation area on the substrate. The droplets of curable composition placed on the pattern formation area spread on 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 curable composition spread throughout the entire gap between the substrate and the mold by capillary action. This phenomenon is called spreading. The curable composition is also filled into the recesses that make up the pattern of the mold by capillary action. This phenomenon is called filling. The time until spreading and filling are completed is called the filling time. Once the filling of the curable composition is complete, light is irradiated onto the curable composition to cure it. 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, and a pattern of the curable composition is formed. Here, the pattern of the curable composition formed on the substrate includes a residual film. The residual film is the cured film that remains between the recesses (protrusions in the mold pattern) of the cured film of the curable composition and the substrate.

[0004] Furthermore, in the photolithography process for manufacturing semiconductor devices, it is also necessary to planarize the substrate. For example, in extreme ultraviolet (EUV) lithography, a photolithography technique that has attracted attention in recent years, the depth of focus at which the projected image is formed becomes shallower as miniaturization progresses, so the surface irregularities of the substrate to which the curable composition is supplied must be kept to tens of nanometers or less. In imprint technology, a level of flatness similar to that of EUV is also required to improve the packing efficiency and line width accuracy of the curable composition. As a planarization technique, a technique is known in which droplets of curable composition corresponding to the irregularities are discretely dropped onto a substrate with irregularities, and the curable composition is cured while a mold with a flat surface is in contact with it, thereby obtaining a flat surface.

[0005] In pattern formation and planarization techniques using imprint technology, the mold is brought into contact with the substrate while the droplets of the curable composition dropped onto the substrate are not in contact with each other. Consequently, air bubbles are inevitably trapped between the mold, the substrate, and the curable composition. Therefore, it takes a long time for these air bubbles to diffuse into the mold and substrate and disappear, which is one of the factors that reduces productivity (throughput). To address this, a technique has been proposed to bond the droplets of the curable composition together before bringing the curable composition on the substrate into contact with the mold (see Patent Document 1). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-188736 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, in the technology disclosed in Patent Document 1, a mold release defect occurs in the mold release step, in which the mold is separated from the hardened curable composition on the substrate, and the hardened curable composition peels off from the substrate and adheres to the mold.

[0008] This invention has been made in view of the problems of the prior art, and its exemplary objective is to provide a new technology relating to curable compositions. [Means for solving the problem]

[0009] To achieve the above objective, a curable composition as one aspect of the present invention is 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 atm, the content of the solvent (d) in the total curable composition is greater than 5 volume% and 95 volume% or less, the boiling point of the solvent (d) is less than 250°C at 1 atm, and the polymerizable compound (a) and solvent (d) have an SP value of 17 MPa 1 / 2 More than 25MPa 1 / 2 It has less than 11 MPa, and the surfactant (c1) does not contain fluorine atoms or silicon atoms, and has an SP value of 11 MPa. 1 / 2 17 MPa or more 1 / 2 A liquid-repellent atomic group having less than 25 MPa SP value 1 / 2 Above 35 MPa 1 / 2 The curable composition is characterized by containing a hydrophilic atomic group having the following properties, and the content of the surfactant (c1) relative to the total curable composition being 0.1% by weight or more and 10% by weight or less.

[0010] Further objects or other aspects of the present invention will be revealed by embodiments described below with reference to the accompanying drawings. [Effects of the Invention]

[0011] According to the present invention, for example, a new technology relating to curable compositions can be provided. [Brief explanation of the drawing]

[0012] [Figure 1] This figure illustrates a pattern formation method (film formation method) as one aspect of the present invention. [Modes for carrying out the invention]

[0013] The embodiments will be described in detail below with reference to the attached drawings. Note that the following embodiments do not limit the invention as defined in the claims. While the embodiments describe multiple features, not all of these features are essential to the invention, and the features may be combined in any way. Furthermore, in the attached drawings, identical or similar configurations are given the same reference numerals, and redundant descriptions are omitted.

[0014] In providing a new technology relating to curable compositions, the present inventors have found conditions that improve the adhesion between the substrate and the cured curable composition, and reduce the adhesion between the mold and the cured curable composition, in the process of separating the mold from the cured curable composition on the substrate.

[0015] [Curable composition] The curable composition (A) in the present invention is useful as a curable composition for inkjet printing. It is also useful as a curable composition for photoimprinting. The curable composition (A) in the present invention is a composition comprising at least a component (a) which is a polymerizable compound, a component (b) which is a photopolymerization initiator, and a component (d) which is a solvent.

[0016] In this specification, "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 may have a pattern shape on its surface. Furthermore, the cured film remaining between the recesses (protrusions of the pattern) of the cured film of the curable composition and the substrate is referred to as the residual film.

[0017] <Component (a): Polymerizable compound> Component (a) is a polymerizable compound. In this specification, a polymerizable compound is a compound that reacts with polymerization factors (such as radicals) generated from a photopolymerization initiator (component (b)) to form a film made of a polymer compound through a chain reaction (polymerization reaction).

[0018] Such polymerizable compounds have an SP value of 17 MPa.1 / 2 25 MPa or less, for example, a radically polymerizable compound. The polymerizable compound as the component (a) may be composed of only one kind of polymerizable compound or may be composed of a plurality of kinds (one or more kinds) of polymerizable compounds. 1 / 2 The SP value δ (J / cm

[0019] 3 ) 1 / 2 = MPa 1 / 2 is described in TABLE 7.3 on pages 195 to 197 of "Properties of Polymers" 4th Edition (2009) by D.W. van Krevelen and K. te Nijenhuis, and is the cohesive energy E i (J / mol) of each atomic group of Fedors and the molar volume V(cm i (cm 3 / mol), and can be calculated by the formula (1) of the atomic group contribution method.

[0020]

Number

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

[0022] (Meth)acrylic compounds refer to compounds having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or 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 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 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, cynoabenzyl(meth)acrylate, naphthalenemethyl(meth)acrylate,

[0023] Examples of commercially available monofunctional (meth)acrylic compounds mentioned above 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), Light Acrylate BO-A, EC-A, DJ / CM3, 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), KAYARAD (registered trademark) TC110S, R-564, R-128H (all manufactured by Nippon Kayaku), NK ester AMP-10G, AMP-20G, A-LEN-10 (all manufactured by Shin Nakamura Chemical Industry), FA-511A, 512A, 513A (all manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Daiichi Kogyo Seiyaku), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kojin), HRD-01 (all manufactured by Nippon Shokubai)

[0024] Furthermore, examples of polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following. Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, 1,3-Adamantane dimethanol di(meth)acrylate, Tris(2-Hydoxyethyl)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-Benzene di(meth)acrylate, o-, m- or p-Xylylene di(meth)acrylate

[0025] Examples of commercially available polyfunctional (meth)acrylic compounds mentioned above include, but are not limited to, the following: Yupimer® UV SA1002, SA2007 (both 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® PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku), Aronix® M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei), Lipoxy® VR-77, VR-60, VR-90 (all manufactured by Showa Polymer), Ogusol EA-0200, Ogusol EA-0300 (all manufactured by Osaka Gas Chemical), SR295, SR355 (all manufactured by Sartomer)

[0026] In the above-mentioned group of compounds, (meth)acrylate means acrylate or methacrylate having an equivalent alcohol residue. (meth)acryloyl group means acryloyl group or methacryloyl group having an equivalent alcohol residue. EO 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 linked via a block structure of ethylene oxide group. Furthermore, 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 linked via a block structure of propylene oxide group.

[0027] Specific examples of styrene 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 iodose Halide styrenes such as ethylene; 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.

[0028] Specific examples of vinyl compounds include, but are not limited to, the following. Compounds having a vinyl group as a polymerizable functional group, such as 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; vinylidenes such as vinylidene chloride; vinyl esters of organic carboxylic acids and their derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, etc., (meth)acrylonitrile, etc.)

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

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

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

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

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

[0034] When component (a) is composed of multiple types of compounds having one or more polymerizable functional groups, it is preferable to include both monofunctional polymerizable compounds and polyfunctional polymerizable compounds. The proportion of polyfunctional polymerizable compounds 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 combining monofunctional polymerizable compounds and polyfunctional polymerizable compounds yields a cured film with an excellent balance of performance, such as high mechanical strength, high dry etching resistance, and high heat resistance.

[0035] In the film formation method of the present invention, it takes several milliseconds to several hundred seconds for droplets of the curable composition (A) discretely arranged on the substrate to bond together and form a substantially continuous liquid film, so a waiting step described later is necessary. In the waiting step, the solvent (d) is allowed to volatilize, while the polymerizable compound (a) must not volatilize. Therefore, the boiling point of one or more polymerizable compounds contained in the polymerizable compound (a) at atmospheric 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 to include at least one compound having a ring structure such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Atmospheric pressure is defined as 1 atmosphere (atmospheric pressure).

[0036] The boiling point of polymerizable compound (a) generally correlates with its molecular weight. Therefore, the molecular weight of each of the one or more polymerizable compounds contained in 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, if the boiling point is 250°C or higher, it can be preferably used as polymerizable compound (a) in the present invention. Thus, it is preferable that the boiling point of each of the one or more polymerizable compounds contained in polymerizable compound (a) under normal pressure is 250°C or higher.

[0037] Furthermore, the vapor pressure of the polymerizable compound (component (a)) at 80°C is preferably 0.001 mmHg or less. If 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 it is preferable to heat the curable composition in order to accelerate the volatilization of the solvent (component (d)) described later, and this heating suppresses the volatilization of polymerizable compound (a).

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

[0039] <Parameters for component (a) of Onishi> V is the dry etching rate of the organic compound, N is the total number of atoms in the organic compound, and N is the total number of carbon atoms in the composition. C , and the total number of oxygen atoms in the composition N O It is known that the following relationship (2) holds true. V∝N / (Nc-No) Equation (2)

[0040] Here, N / (Nc-No) is also called the "Onishi parameter" (hereinafter referred to as "OP"). For example, U.S. Patent Application Publication No. 2020 / 0286740 discloses a technique for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP.

[0041] According to equation (1), organic compounds with a higher oxygen content or fewer aromatic or alicyclic structures in the molecule have a larger OP value and a faster dry etching rate.

[0042] In the present invention, the curable composition (A) has an OP of component (a) of 1.80 to 4.00. More preferably, the OP of component (a) is 2.00 to 3.50, and particularly preferably 2.40 to 3.00. By setting the OP of component (a) to 4.00 or less, the cured film of curable composition (A) has high dry etching resistance. Furthermore, by setting the OP of component (a) to 1.80 or more, it becomes easy to remove the cured film of curable composition (A) after processing the underlying layer using the cured film of curable composition (A). Component (a) is a plurality of polymerizable compounds a1, a2, ..., a n When it is composed of these, OP is calculated as a weighted average value based on mole fractions (mole fraction weighted average value) as shown in equation (3) below. Thus, when component (a) contains one or more polymerizable compounds, the OP of component (a) is N / (N) of each molecule of the one or more polymerizable compounds. C -N O It is calculated as the mole fraction-weighted average of the values.

[0043]

number

[0044] Here's the OP n is component a n It is the OP, n n is component a n This is the mole fraction of component (a) in the whole.

[0045] In order to make the OP of component (a) 1.80 or more and 2.70 or less, it is preferable to include at least one compound (a-1) as component (a), which has two or more cyclic structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0046] <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 include polymerizable compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. Furthermore, it is preferable that the proportion of component (a-1) in component (a) is 65% by weight or more. By setting the proportion of component (a-1) to 65% by weight or more, it is possible to keep the OP to 2.70 or less.

[0047] Examples of cyclic structures include aromatic structures, aromatic heterocyclic structures, and alicyclic structures.

[0048] The aromatic structure preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Specific examples of aromatic rings are as follows: Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indan ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring

[0049] Of the aromatic rings mentioned above, benzene rings or naphthalene rings are preferred, and benzene rings are more preferred. The aromatic rings may have a structure in which multiple rings are linked together, for example, biphenyl rings or bisphenyl rings.

[0050] The aromatic heterocyclic structure preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples of aromatic heterocyclic structures are as follows: Thiofen ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, quinoridine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, sinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxatiin ring, phenoxazine ring

[0051] For alicyclic structures, the number of carbon atoms is preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. Furthermore, for alicyclic structures, the number of carbon atoms is preferably 22 or less, more preferably 18 or less, even more preferably 6 or less, and even more preferably 5 or less. Specific examples include the following. Cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, spirodecane ring, spirononane ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindan ring, bornane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring

[0052] A specific example of a polymerizable compound (a-1) having a boiling point of 250°C or higher is an SP value of 17 MPa. 1 / 2 More than 25MPa 1 / 2 It includes, but is not limited to, the following:

[0053] 3-Phenoxybenzylacrylate (mPhOBzA, OP2.54, boiling point 367.4℃, vapor pressure at 80℃ 0.0004mmHg, molecular weight 254.3, SP value 22.0MPa) 1 / 2 ),

[0054] [ka]

[0055] 1-Naphthyl acrylate (NaA, OP2.27, boiling point 317°C, vapor pressure at 80°C 0.0422 mmHg, molecular weight 198, SP value 22.5 MPa) 1 / 2 ),

[0056] [ka]

[0057] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2℃, vapor pressure at 80℃ 0.0006mmHg, molecular weight 268.3, SP value 21.7MPa) 1 / 2 ),

[0058] [ka]

[0059] 1-Naphthylmethyl acrylate (Na1MA, OP2.33, boiling point 342.1℃, vapor pressure at 80℃ 0.042 mmHg, molecular weight 212.2, SP value 22.0 MPa) 1 / 2 ),

[0060] [ka]

[0061] 2-Naphthylmethyl acrylate (Na2MA, OP2.33, boiling point 342.1℃, vapor pressure at 80℃ 0.042mmHg, molecular weight 212.2, SP value 22.0MPa) 1 / 2 )

[0062] [ka]

[0063] The following formula shows DPhPA (OP2.38, boiling point 354.5°C, vapor pressure at 80°C 0.0022 mmHg, molecular weight 266.3, SP value 21.1 MPa) 1 / 2 ),

[0064] [ka]

[0065] The following formula shows PhBzA(OP2.29, boiling point 350.4°C, vapor pressure at 80°C 0.0022 mmHg, molecular weight 238.3, SP value 21.9 MPa) 1 / 2 ),

[0066] [ka]

[0067] The following formula shows FLMA (OP2.20, boiling point 349.3°C, vapor pressure at 80°C 0.0018 mmHg, molecular weight 250.3, SP value 22.6 MPa) 1 / 2 ),

[0068] [ka]

[0069] ATMA(OP2.13, boiling point 414.9°C, vapor pressure at 80°C 0.0001 mmHg, molecular weight 262.3, SP value 22.9 MPa) 1 / 2 ),

[0070] [ka]

[0071] The following formula shows DNaMA(OP2.00, boiling point 489.4°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 338.4, SP value 23.1 MPa) 1 / 2 ),

[0072] [ka]

[0073] The following formula shows BPh44DA(OP2.63, boiling point 444°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3, SP value 22.2 MPa) 1 / 2 ),

[0074] [ka]

[0075] The following formula shows BPh43DA(OP2.63, boiling point 439.5°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3, SP value 22.2 MPa) 1 / 2 ),

[0076] [ka]

[0077] The following formula shows DPHEDA (OP2.63, boiling point 410°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3, SP value 21.8 MPa) 1 / 2 ),

[0078] [ka]

[0079] The following formula shows BPMDA (OP2.68, boiling point 465.7°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 364.4, SP value 21.3 MPa) 1 / 2 ),

[0080] [ka]

[0081] The following formula shows Na13MDA (OP2.71, boiling point 438.8°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 296.3, SP value 22.4 MPa) 1 / 2),

[0082] [ka]

[0083] The following formula (a-1-1)(OP2.40, boiling point 333.4℃, vapor pressure at 80℃ 0.0181mmHg, molecular weight 199.2, SP value 24.1MPa) 1 / 2 ),

[0084] [ka]

[0085] The following formula (a-1-2) (OP2.40, boiling point 333.4℃, vapor pressure at 80℃ 0.0181mmHg, molecular weight 199.2, SP value 24.1MPa) 1 / 2 ),

[0086] [ka]

[0087] 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, SP value 22.5 MPa) 1 / 2 ),

[0088] [ka]

[0089] The following formula (a-1-4) (OP2.85, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3, SP value 22.4MPa) 1 / 2 ),

[0090] [ka]

[0091] The following formula (a-1-5) (OP2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3, SP value 22.0MPa) 1 / 2 ),

[0092] [ka]

[0093] The following formula (a-1-6) (OP2.87, boiling point 421.0℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4, SP value 22.4MPa) 1 / 2 ),

[0094] [ka]

[0095] The following formula (a-1-7) (OP2.87, boiling point 465.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4, SP value 22.4MPa) 1 / 2 ),

[0096] [ka]

[0097] The following formula (a-1-8) (OP2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4, SP value 21.3MPa) 1 / 2 ),

[0098] [ka]

[0099] The following formula (a-1-9) (OP2.50, boiling point 433.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 320.3, SP value 23.1MPa) 1 / 2 ),

[0100] [ka]

[0101] The following formula (a-1-10) (OP2.64, boiling point 468.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 326.4, SP value 23.5MPa) 1 / 2 ),

[0102] [ka]

[0103] The following formula (a-1-11) (OP3.25, boiling point 553.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 358.4),

[0104] [ka]

[0105] The following formula (a-1-12) (OP2.63, boiling point 443.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.4, SP value 21.5MPa) 1 / 2 ),

[0106] [ka]

[0107] The following formula (a-1-13) (OP2.89, boiling point 509.3℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 406.4, SP value 22.5MPa) 1 / 2 ),

[0108] [ka]

[0109] The following formula (a-1-14) (OP2.63, boiling point 450.0℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.4, SP value 21.8MPa) 1 / 2 ),

[0110] [ka]

[0111] The following formula (a-1-15) (OP3.00, boiling point 476.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 366.4, SP value 23.0MPa) 1 / 2 )

[0112] [ka]

[0113] The following formula (a-1-16) (OP2.68, boiling point 447.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4, SP value 21.4MPa) 1 / 2 )

[0114] [ka]

[0115] The following formula (a-1-17) (OP2.36, boiling point 543.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 398.5, SP value 22.4MPa) 1 / 2 ),

[0116] [ka]

[0117] The following formula (a-1-18) (OP3.27, boiling point 526.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 396.4, SP value 21.8MPa) 1 / 2 ),

[0118] [ka]

[0119] The following formula (a-1-19) (OP2.71, boiling point 333.7℃, vapor pressure at 80℃ 0.0302mmHg, molecular weight 244.3, SP value 20.1MPa) 1 / 2 ),

[0120] [ka]

[0121] The following formula (a-1-20) (OP2.73, boiling point 333.7℃, vapor pressure at 80℃ 0.0134mmHg, molecular weight 258.3, SP value 20.0MPa) 1 / 2 ),

[0122] [ka]

[0123] The following formula (a-1-21) (OP2.71, boiling point 319.2℃, vapor pressure at 80℃ 0.0566mmHg, molecular weight 262.3, SP value 20.6MPa) 1 / 2 ),

[0124] [ka]

[0125] The following formula (a-1-22) (OP2.71, boiling point 336.9℃, vapor pressure at 80℃ 0.0055mmHg, molecular weight 244.3, SP value 20.3MPa) 1 / 2 ),

[0126] [ka]

[0127] The following formula (a-1-23) (OP3.00, boiling point 370.9℃, vapor pressure at 80℃ 0.0021mmHg, molecular weight 274.4, SP value 20.1MPa) 1 / 2 ),

[0128] [ka]

[0129] The following formula (a-1-24) (OP3.00, boiling point 376.4℃, vapor pressure at 80℃ 0.0005mmHg, molecular weight 274.4, SP value 20.3MPa) 1 / 2 ),

[0130] [ka]

[0131] The following formula (a-1-25) (OP3.00, boiling point 379.4℃, vapor pressure at 80℃ 0.0002mmHg, molecular weight 288.4, SP value 20.2MPa) 1 / 2 ),

[0132] [ka]

[0133] The following formula (a-1-26) (OP2.33, boiling point 360.8℃, vapor pressure at 80℃ 0.0006mmHg, molecular weight 252.3, SP value 21.6MPa) 1 / 2 ),

[0134] [ka]

[0135] The following formula (a-1-27) (OP2.54, boiling point 371.5℃, vapor pressure at 80℃ 0.0003mmHg, molecular weight 254.3, SP value 22.0MPa) 1 / 2 ),

[0136] [ka]

[0137] The following formula (a-1-28) (OP2.57, boiling point 381.2℃, vapor pressure at 80℃ 0.0001mmHg, molecular weight 268.3, SP value 21.7MPa) 1 / 2 ),

[0138]

Chem.

[0139] 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, SP value 21.7 MPa 1 / 2 )

[0140]

Chem.

[0141] 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, SP value 22.2 MPa 1 / 2 )

[0142]

Chem.

[0143] 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, SP value 23.1 MPa 1 / 2 )

[0144]

Chem.

[0145] 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, SP value 23.1 MPa 1 / 2 )

[0146]

Chem.

[0147] The following formula (a-1-33) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3, SP value 23.1MPa) 1 / 2 ),

[0148] [ka]

[0149] The following formula (a-1-34) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3, SP value 23.1MPa) 1 / 2 ),

[0150] [ka]

[0151] The following formula (a-1-35) (OP2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3, SP value 22.4MPa) 1 / 2 ),

[0152] [ka]

[0153] <Compound (a-2): Polymerizable compound containing at least one Si atom> The polymerizable compound (a) in the present invention may include polymerizable compound (a-2) which contains at least Si atoms. Furthermore, if polymerizable compound (a) contains polymerizable compound (a-2), it is preferable that the curable composition (A) in the state from which the solvent (d) has been removed contains 10% by weight or more of Si atoms relative to the total amount of such curable composition (A).

[0154] As an example of the polymerizable compound (a-2) containing at least Si atoms, it may be linear or branched. For example, as the cyclic siloxane compound and the like, structures as shown below can be mentioned. As the polymerizable functional group in the group Q having a polymerizable functional group, for example, a radical polymerizable functional group can be mentioned. Specifically, as the radical polymerizable functional group, a (meth)acryl group, a (meth)acrylamide group, a vinylbenzene group, an allyl ether group, a vinyl ether group, and a maleimide group are included. The group Q having a polymerizable functional group may be any group having the polymerizable functional group described above.

[0155]

Chemical formula

[0156] As other examples of the polymerizable compound (a-2), for example, a silsesquioxane skeleton as shown in the following chemical formula (I) and a silicone skeleton as shown in the following chemical formula (II) can be mentioned. Here, in chemical formula (I), m + n = 8 (8 ≥ m ≥ 1), and R1 is a divalent organic group. In chemical formula (II), A, B, R2, and R3 are independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an alkoxy group, a phenyl group, or a hydroxyl group, t is an integer from 1 to 3, and at least one of A and B is a polymerizable functional group.

[0157]

Chemical formula

[0158]

Chemical formula

[0159] Examples of polymerizable functional groups in groups Q, A, and B include radical polymerizable functional groups. Specifically, radical polymerizable functional groups include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds. Group Q, which has a polymerizable functional group, can be any group having one of the polymerizable functional groups described above.

[0160] Silicon-containing (meth)acrylate compounds are compounds having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylate compounds having one silicon-containing acryloyl group or methacryloyl group include, but are not limited to, the following. (2-Acryloylethoxy)trimethylsilane, N-(3-acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, Acryloxymethyltrimethoxysilane, (Acryloxymethyl)phenethyltrimethoxysilane, Acryloxymethyltrimethylsilane, (3-Acryloxypropyl)dimethylmethoxysilane, (3-Acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-Acryloxypropyl)methyldichlorosilane, (3-Acryloxypropyl)methyldiethoxysilane, (3-Acryloxypropyl)methyldimethoxysilane, (3-Acryloxypropyl)trichlorosilane, (3-Acryloxypropyl)trimethoxysilane, (3-Acryloxypropyl)tris(trimethylsiloxy)silane, Acryloxytriisopropylsilane, Acryloxytrimethylsilane, Methacryloxymethyltrimethoxysilane, 0-(methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, Methacryloxymethyltriethoxysilane, Methacryloxypropyltrimethoxysilane, Methacryloylpropyltriisopropoxysilane, 0-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, Methacryloxypropylmethyldimethoxysilane, Methacryloxypropylmethyldiethoxysilane, Methacryloxypropyldimethylmethoxysilane, Methacryloxypropyldimethylethoxysilane, (methacryloxymethyl)dimethylethoxysilane, Methacryloxypropyltriethoxysilane, Methacryloxypropyl silatoran, 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-Methacluroxypropylbis(trimethylsiloxy)methylsilane, 3-Methacluroxypropyldimethylchlorosilane, 0-Methacryloxy(polyethyleneoxy)trimethylsilane, Poly(methacluroxypropylsilsesquioxane), Methacryloxypropylheptaisorbyl-T8-silsesquioxane, Methacryloxypropyltris(trimethylsiloxy)silane

[0161] Examples of commercially available silicon-containing monofunctional (meth)acrylate compounds mentioned above include, but are not limited to, the following. SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200.A1, SIA0210.0, SIA0315.0, SIA0320.0 , SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481 .43, SIM6482.0, SIM6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM648 6.4, SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.48, SIM6481.5, SIM6 491.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, S IM6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, SIM6486.65 (all manufactured by GELEST), TM-0701T, FM-0711, FM-0721, FM-0725 (all manufactured by JNC)

[0162] 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

[0163] Examples of commercially available silicon-containing monofunctional (meth)acreamide compounds mentioned above include, but are not limited to, the following. SIA0146.0, SIA0150.0 (both manufactured by GELEST)

[0164] Furthermore, examples of polyfunctional (meth)acrylate compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following. A linear polydimethylsiloxane modified at both ends with acryloxypropyl groups, A linear polydimethylsiloxane modified at both ends with methacryloxypropyl groups, Cyclic siloxanes modified with multiple acryloxypropyl groups, Cyclic siloxanes modified with multiple methacryloxypropyl groups, Silsesquioxane modified with multiple acryloxypropyl groups, Silsesquioxane modified with multiple methacryloxypropyl groups

[0165] Examples of commercially available silicon-containing polyfunctional (meth)acrylate compounds mentioned above 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)

[0166] Furthermore, for example, the following can be synthesized and / or obtained from known reference 1. A linear modified polydimethylsiloxane (MA-Si-12) modified at both ends with methacryloxypropyl groups, An 8-ring siloxane modified with four methacryloxypropyl groups, A 10-membered ring siloxane modified with five methacryloxypropyl groups (10-ring), Publicly known reference 1: "Ultraviolet curable branched siloxanes as low-k dielectric for imprint lithography" by Ogawa et al.

[0167] The proportion of component (a) in the curable composition (A) is preferably 40% to 99% by weight of the total mass of all components excluding the solvent (d), i.e., the synthesis of component (a), component (b) described later, and component (c) described later. It is more preferably 50% to 95% by weight, and even more preferably 60% to 90% by weight. By increasing the proportion of component (a) to 40% by weight or more, the mechanical strength of the cured film of the curable composition is increased. Furthermore, by increasing the proportion of component (a) to 99% by weight or less, the proportions of components (b) and (c) can be increased, and properties such as a fast photopolymerization rate can be obtained. At least a portion of component (a), which contains one or more polymerizable compounds, may be a polymer having polymerizable functional groups. 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 of the following structural units represented by structures (1) to (6).

[0168] [ka]

[0169] In structures (1) to (6), each substituent R is a substituent that independently contains a substructure containing an aromatic ring, 1This is a hydrogen atom or a methyl group. In this specification, the portion of the structural unit represented by structures (1) to (6), excluding R, is used as the main chain of a specific polymer. The formula weight of substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and even more preferably 150 or more. In practice, the upper limit of the formula weight of substituent R is 500 or less.

[0170] Polymers having polymerizable functional groups are typically compounds with a weight-average molecular weight of 500 or more, preferably 1000 or more, and more preferably 2000 or more. There is no specific upper limit for the weight-average molecular weight, but for example, 50000 or less is preferred. By setting the weight-average molecular weight above the lower limit mentioned above, the boiling point can be set to 250°C or higher, and the mechanical properties after curing can be further improved. Furthermore, by setting the weight-average molecular weight below the upper limit mentioned above, solubility in solvents is high, the fluidity of discretely arranged droplets is maintained without excessive viscosity, and the flatness of the liquid film plane can be further improved. In this invention, unless otherwise specified, the weight-average molecular weight (Mw) refers to that measured by gel permeation chromatography (GPC).

[0171] Specific examples of polymerizable functional groups in polymers include (meth)acryloyl groups, epoxy groups, oxetane groups, methylol groups, methylol ether groups, and vinyl ether groups. From the viewpoint of ease of polymerization, (meth)acryloyl groups are particularly preferred.

[0172] When a polymer having polymerizable functional groups is added as at least a portion of component (a), its blending ratio can be freely set as long as it falls within the viscosity specifications described later. For example, it is preferable that the blending ratio be 0.1% to 60% by weight, more preferably 1% to 50% by weight, and even more preferably 10% to 40% by weight, based on the total mass of all components excluding solvent (d). By blending the polymer having polymerizable functional groups at a ratio of 0.1% by weight or more, heat resistance, dry etching resistance, mechanical strength, and low volatility can be improved. Furthermore, by blending the polymer having polymerizable functional groups at a ratio of 60% by weight or less, the viscosity can be kept within the upper limit specifications described later.

[0173] <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 polymerization factors (radicals) described above. 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, X-rays, charged particle beams such as electron beams, and radiation). Component (b) may consist of only one type of photopolymerization initiator or may consist of multiple types of photopolymerization initiators.

[0174] Examples of radical generators include, but are not limited to, the following: 2,4,5-triarylimidazole dimers which may have substituents 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, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone Benzophenone derivatives such as 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, and 1,2-benz Quinones such as anthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantaraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl Benzyl derivatives such as dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone;Acyl phosphine 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-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one;

[0175] Examples of commercially available radical generators mentioned 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), Yubekrill P36 (manufactured by UCB)

[0176] Of the radical generators mentioned above, component (b) is preferably an acylphosphine oxide polymerization initiator. The acylphosphine oxide polymerization initiators among the radical generators mentioned above are as follows: Acyl phosphine 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.

[0177] The blending ratio of component (b) in the curable composition (A) is preferably 0.1% by weight or more and 50% by weight or less, relative to the total mass of component (a), component (b), and component (c) described later, i.e., the total mass of all components excluding solvent (d). Furthermore, the blending ratio of component (b) in the curable composition (A) is more preferably 0.1% by weight or more and 20% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less, relative to the total mass of all components excluding solvent (d). By setting the blending ratio of component (b) to 0.1% by weight or more, the curing rate of the composition can be increased and the reaction efficiency can be improved. Furthermore, by setting the blending ratio of component (b) to 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0178] <Component (c): Non-polymerizable compound> In addition to components (a) and (b) described above, the curable composition (A) in the present invention may further contain a non-polymerizable compound as component (c), to the extent that it does not impair the effects of the present invention, depending on the purpose. Examples of such component (c) include compounds that do not have polymerizable functional groups such as (meth)acryloyl groups and do not have the ability to sense light of a predetermined wavelength and generate the polymerization factors (radicals) described above. 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 compounds described above.

[0179] Sensitizers are compounds added as needed to accelerate polymerization reactions or improve the conversion rate. Sensitizers may be used individually or in combination of two or more types.

[0180] 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, 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 are listed below, but are not limited to these. Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphaquinone derivatives, acridine dyes, thiopyrillium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes

[0181] The hydrogen donor is a compound that reacts with the initiation radicals and polymerization growth end radicals generated from the photopolymerization initiator (component (b)) to generate more reactive radicals. It is preferable to add the hydrogen donor when the photopolymerization initiator (component (b)) is a photoradical generator.

[0182] Specific examples of such hydrogen donors include, but are not limited to, the following. Amine compounds such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethanolamine, N-phenylglycine, and other amine compounds, as well as mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

[0183] The hydrogen donor may be used individually or in a mixture of two or more types. Furthermore, the hydrogen donor may also function as a sensitizer.

[0184] In this invention, a surfactant (c1) is added to the curable composition (A) for the purpose of suppressing overflow and seepage. The surfactant (c1) also functions as an internal release agent that reduces the interfacial bonding force between the mold and the curable composition, that is, the release force in the release step described later. In this specification, "internal addition" means that it is added to the curable composition in advance before the curable composition placement step. As the surfactant (c1), a surfactant that does not contain fluorine atoms and silicon atoms can be used. However, in this invention, there are restrictions on the amount of surfactant (c1) that can be added, as described later. The surfactant (c1) in this invention is assumed to be nonpolymerizable. One type of surfactant (c1) may be used alone, or two or more types may be used in mixture form.

[0185] Furthermore, the surfactant (c1) does not contain fluorine atoms or silicon atoms, and has an SP value of 11 MPa. 1 / 2 17 MPa or more 1 / 2 A liquid-repellent atomic group having less than 25 MPa SP value 1 / 2 Above 35 MPa 1 / 2 It includes a hydrophilic atomic group having less than [amount missing].

[0186] The molecular weight of the surfactant (c1) is 200 or more and less than 2000, preferably 210 or more and less than 1970.

[0187] The molar volume ratio of the liquid-repellent atomic group to the hydrophilic atomic group of the surfactant (c1) is 1.5 or more and less than 5, preferably 1.6 or more and less than 4.7.

[0188] Furthermore, it is preferable that the liquid-repellent atomic group of the surfactant (c1) has two or more methyl groups.

[0189] The liquid-repellent atomic group of the surfactant (C1), as a specific example, has an SP value close to 11.9 MPa of nitrogen, which is the main component of air, in the placement process and the standby process described later. 1 / 2 (quoted from page 252, TABLE 13.4 of "Hansen Solubility Parameters: A User's Handbook" 2nd Edition (2007) written by Charles M. Hansen) and preferably has an atomic group with a small SP value in order to reduce the release force in the release process described later. The SP value is preferably 11 MPa 1 / 2 or more and 17 MPa 1 / 2 or less. For example, a methyl group (CH3-, molar volume 33.5 cm 3 / mol, SP value 11.9 MPa 1 / 2 ), an ethyl group (CH3-CH2-, molar volume 49.6 cm 3 / mol, SP value 13.9 MPa 1 / 2 ), a propyl group (CH3-(CH2)2-, molar volume 65.7 cm 3 / mol, SP value 14.9 MPa 1 / 2 ), a butyl group (CH3-(CH2)3-, molar volume 81.8 cm 3 / mol, SP value 15.5 MPa 1 / 2 ), a pentyl group (CH3-(CH2)4-, molar volume 97.9 cm 3 / mol, SP value 15.8 MPa 1 / 2 ), a hexyl group (CH3-(CH2)5-, molar volume 114.0 cm 3 / mol, SP value 16.1 MPa 1 / 2 ), a heptyl group (CH3-(CH2)6-, molar volume 130.1 cm 3 / mol, SP value 16.2 MPa 1 / 2 , an octyl group (CH3-(CH2)7-, molar volume 146.2 cm 3 / mol, SP value 16.4 MPa 1 / 2 ), a nonyl group (CH3-(CH2)8-, molar volume 162.3 cm 3 / mol, SP value 16.5 MPa 1 / 2 ), a decyl group (CH3-(CH2)9-, molar volume 178.4 cm 3 / mol, SP value 16.6 MPa 1 / 2), dodecyl group (CH3-(CH2) 11 - Molar volume 210.6 cm³ 3 / mol, SP value 16.7MPa 1 / 2 ), tridecyl group (CH3-(CH2) 12 - Molar volume 226.7 cm³ 3 / mol, SP value 16.8MPa 1 / 2 ), myristyl group (CH3-(CH2) 13 - Molar volume 242.8 cm³ 3 / mol, SP value 16.8MPa 1 / 2 ), isopropyl group ((CH3)2CH-, molar volume 66.0 cm³ 3 / mol, SP value 14.0 MPa 1 / 2 ), isobutyl group ((CH3)2CH-CH2-, molar volume 82.1 cm³ 3 / mol, SP value 14.7 MPa 1 / 2 ), isopentyl group ((CH3)2CH-(CH2)2-, molar volume 98.2 cm³ 3 / mol, SP value 15.2 MPa 1 / 2 ), isodecyl group ((CH3)2CH-(CH2)7-, molar volume 178.7 cm³ 3 / mol, SP value 16.3MPa 1 / 2 ), tert-butyl group ((CH3)3C-, molar volume 81.3 cm³ 3 / mol, SP value 13.9 MPa 1 / 2 ), 2-ethylhexyl group (CH3-(CH2)3-CH(-CH2-CH3)-CH2-, molar volume 146.5 cm³ 3 / mol, SP value 15.8 MPa 1 / 2 ), 3,5-dimethyl-1-(2-methylpropyl)hexyl group (CH3-CH(CH3)-CH2-CH(CH3)-CH2-CH(CH2-CH(CH3)2)-, molar volume 211.8 cm³ 3 / mol, SP value 15.7 MPa 1 / 2 Examples include, ), and so on.

[0190] A specific example of a hydrophilic atomic group of surfactant (c1) is the SP value of quartz constituting type 106, which is 33.0 MPa, in the contact process described later. 1 / 2Atomic groups with an SP value close to (calculated from Fedors' atomic group SiO4) are preferred, with an SP value of 25 MPa. 1 / 2 Above 35 MPa 1 / 2 Preferably less than 4.0 cm³, for example, hydroxyl-terminated ethylene oxide (-O-CH2-CH2-OH, molar volume 49.0 cm³). 3 / mol, SP value 26.8MPa 1 / 2 ), carboxyl-terminated ethylene oxide (-O-CH2-CH2-COOH, molar volume 64.5 cm³) 3 / mol, SP value 25.2 MPa 1 / 2 ), cyano-terminated ethylene oxide (-O-CH2-CH2-CN, molar volume 60.0 cm³) 3 / mol, SP value 25.4 MPa 1 / 2 ), acetylene group (-C≡C-, molar volume 13.0 cm³) 3 / mol, SP value 33.0 MPa 1 / 2 ), amide ethylene oxide (-CO-NH-CH2-CH2-O-, molar volume 51.3 cm³) 3 / mol, SP value 27.6MPa 1 / 2 ), hydroxyl-terminated amide ethylene oxide (-CO-NH-CH2-CH2-OH, molar volume 60.5 cm³) 3 / mol, SP value 30.8 MPa 1 / 2 ), hydroxyl-terminated N-methylamide ethylene oxide (-CO-N(CH3)-CH2-CH2-OH, molar volume 80.5 cm³ 3 / mol, SP value 26.8MPa 1 / 2 ), monoglyceride (-COO-CH2-CH(OH)-CH2-OH, molar volume 79.0 cm³ 3 / mol, SP value 31.5 MPa 1 / 2 ), diglyceride (-COO-CH2-CH(-COO-)-CH2-OH, molar volume 84.0 cm³ 3 / mol, SP value 29.8 MPa 1 / 2 ), triglyceride (-COO-CH2-CH(-COO-)-CH2-COO-, molar volume 89.0 cm³ 3 / mol, SP value 28.2 MPa 1 / 2 ), glyceride (-COO-CH2-CH(OH)-CH2-O-, molar volume 69.8 cm³ 3 / mol, SP value 29.3 MPa 1 / 2 ), polyglycerin (-CH2-CH(OH)-CH2-O-, molar volume 48.0 cm³ 3 / mol, SP value 28.3MPa 1 / 2 ), hydroxyl-terminated polyglycerin (-CH2-CH(OH)-CH2-OH, molar volume 57.2 cm³ 3 / mol, SP value 31.6MPa 1 / 2 ), anhydrosorbitol (C4H5O(OH)2-CH(OH)-CH2-O-, molar volume 101.6 cm³) 3 / mol, SP value 32.7 MPa 1 / 2 Examples include:

[0191] Examples of preferred products include ethylene oxide adducts of acetylene glycol, ethylene oxide / propylene oxide adducts of acetylene glycol, alkyl polyethylene oxide adducts, polyoxyethylene 2-ethylhexyl ether, and alkyl polyethylene oxide propylene oxide adducts.

[0192] Ethylene oxide adduct of acetylene glycol SURFYNOL 420 (molecular weight 284, liquid-repellent atomic group ((CH3)2CH-CH2-C(CH3)<(×2)) manufactured by Nisshin Chemical Industry Co., Ltd., molar volume 192.8 cm³) 3 / mol, hydrophilic atomic groups (-O-CH2-CH2-OH (×2), -C≡C- (×1)), molar volume 111.0 cm³ 3 / mol, molar volume ratio 1.7), SURFYNOL 440 (molecular weight 381, molar volume ratio 1.7), SURFYNOL 465 (molecular weight 667, molar volume ratio 1.7), SURFYNOL 485 (molecular weight 1548, molar volume ratio 1.7),

[0193] [ka]

[0194] OLFINE E1004C (molecular weight 381, liquid-repellent atomic group ((CH3)2CH-CH2-C(CH3)<(×2)) manufactured by Nisshin Chemical Industry Co., Ltd., molar volume 192.8 cm³) 3 / mol, hydrophilic atomic groups (-O-CH2-CH2-OH (×2), -C≡C- (×1)), molar volume 111.0 cm³ 3 / mol, molar volume ratio 1.7), OLFINE E1004 (molecular weight 403, molar volume ratio 1.7), OLFINE E1006 (molecular weight 491, molar volume ratio 1.7), OLFINE E1010 (molecular weight 667, molar volume ratio 1.7), OLFINE E1020 (molecular weight 1107, molar volume ratio 1.7), OLFINE E1030W (molecular weight 1548, molar volume ratio 1.7), OLFINE E1204C (molecular weight 403, molar volume ratio 1.7), DYNOL 604 manufactured by Nisshin Chemical Industry Co., Ltd. (molecular weight 431, number of Fedors methyl groups in the liquid-repellent atomic group 6, liquid-repellent atomic group ((CH3)2CH-CH2-CH2-C(CH3)<(×2)), molar volume 225.0 cm³) 3 / mol, hydrophilic atomic groups (-O-CH2-CH2-OH (×2), -C≡C- (×1)), molar volume 111.0 cm³ 3 / mol, molar volume ratio 2.0), DYNOL 607 (molar volume ratio 2.0),

[0195] [ka]

[0196] Ethylene oxide / propylene oxide adduct of acetylene glycol SURFYNOL 2502 (liquid-repellent atomic group ((CH3)2CH-CH2-C(CH3)<(×2)) manufactured by Nisshin Chemical Industry Co., Ltd., molar volume 192.8 cm³ 3 / mol, hydrophilic atomic groups (-O-CH2-CH2-OH (×2), -C≡C- (×1)), molar volume 111.0 cm³ 3 / mol, molar volume ratio 1.7), Alkyl polyethylene oxide adducts TERGITOL 15-S-3 (molecular weight 333, number of Fedors methyl groups in the liquid-repellent atomic group 2, liquid-repellent atomic group (CH3-(CH2)6-CH((CH2)4-CH3)-(×1)) manufactured by Dow Chemical, molar volume 227.0 cm³ 3 / mol, hydrophilic group (-O-CH2-CH2-OH(×1)), molar volume 49.0 cm³ 3 / mol, molar volume ratio 4.6), TERGITOL 15-S-5 (molecular weight 421, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6), TERGITOL 15-S-7 (molecular weight 509, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6), TERGITOL 15-S-9 (molecular weight 597, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6), TERGITOL 15-S-12 (molecular weight 729, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6), TERGITOL 15-S-15 (molecular weight 861, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6), TERGITOL 15-S-20 (molecular weight 1081, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6), TERGITOL 15-S-30 (molecular weight 1522, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6), TERGITOL 15-S-40 (molecular weight 1962, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 4.6),

[0197] [ka]

[0198] TERGITOL TMN-3 (molecular weight 318, number of Fedors methyl groups in the liquid-repellent atomic group 5, liquid-repellent atomic group (CH3-CH(CH3)-CH2-CH(CH3)-CH2-CH(-CH2-CH(CH3)2)-(×1)) manufactured by Dow Chemical, molar volume 211.8 cm³ 3 / mol, hydrophilic group (-O-CH2-CH2-OH(×1)), molar volume 49.0 cm³ 3 / mol, molar volume ratio 4.3), TERGITOL TMN-6 (molecular weight 539, number of Fedors methyl groups in the liquid-repellent atomic group 5, molar volume ratio 4.3), TERGITOL TMN-10 (molecular weight 671, number of Fedors methyl groups in the liquid-repellent atomic group 5, molar volume ratio 4.3),

[0199] [ka]

[0200] Polyoxyethylene 2-ethylhexyl ether BLAUNON EH-2 (molecular weight 218, number of Fedors methyl groups in the liquid-repellent atomic group 2, liquid-repellent atomic group (CH3-(CH2)3-CH(-CH2-CH3)-CH2-(×1)) manufactured by Aoki Oil & Fat Industry Co., Ltd.) molar volume 146.5 cm³ 3 / mol, hydrophilic group (-O-CH2-CH2-OH(×1)), molar volume 49.0 cm³ 3 / mol, molar volume ratio 3.0), BLAUNON EH-4 (molecular weight 306, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 3.0), BLAUNON EH-6 (molecular weight 395, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 3.0), BLAUNON EH-11 (molecular weight 615, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 3.0), BLAUNON EH-30 (molecular weight 1452, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 3.0),

[0201] [ka]

[0202] Alkyl polyethylene oxide propylene oxide adduct ECOSURF EH-3 (molecular weight 553, number of Fedors methyl groups in the liquid-repellent atomic group 2, liquid-repellent atomic group (CH3-(CH2)3-CH(-CH2-CH3)-CH2-(×1))) manufactured by Dow Chemical, molar volume 146.5 cm³ 3 / mol, hydrophilic group (-O-CH2-CH2-OH(×1)), molar volume 49.0 cm³ 3 / mol, molar volume ratio 3.0. Propylene oxide chains with 2 or more repeating units, those having 2 or more methyl groups, are not included in the preferred liquid-repellent atomic group. ), ECOSURF EH-6 (molecular weight 685, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 3.0), ECOSURF EH-9 (molecular weight 817, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 3.0), ECOSURF EH-14 (molecular weight 1037, number of Fedors methyl groups in the liquid-repellent atomic group 2, molar volume ratio 3.0),

[0203] [ka]

[0204] The proportion 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, relative to the total mass of component (a), component (b), and component (c), i.e., the total mass of all components excluding the solvent (d). Furthermore, the proportion 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 0.1% by weight or more and 10% by weight or less, relative to the total mass of all components excluding the solvent (d). By setting the proportion of component (c) excluding the surfactant to 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0205] The upper limit of the surfactant (c1) blending ratio in this invention is determined, as described later, by the surface tension of the composition obtained by removing the solvent (d) from the curable composition (A), and the contact angles with the surface of the substrate and the surface of the mold. The effects of this invention can be obtained by blending the surfactant (c1) at a ratio of 0.1% by weight or more.

[0206] <Component (d): Solvent> The curable composition in the present invention contains, as component (d), a solvent with a boiling point of 100°C or higher and less than 250°C under normal pressure, and has an SP value of 17 MPa. 1 / 2 More than 25MPa 1 / 2 It has less than . Component (d) is a solvent in which components (a), components (b), and components (c) dissolve, such as alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, nitrogen-containing solvents, etc. Component (d) can be used alone or in combination of two or more types. The boiling point of component (d) at 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) at normal pressure is less than 250°C, preferably less than 200°C. If the boiling point of component (d) at normal pressure is less than 100°C, the volatilization rate in the waiting step described later will be too fast, and component (d) may volatilize before the droplets of curable composition (A) can bond together, potentially preventing the droplets of curable composition (A) from bonding. Furthermore, if the boiling point of component (d) at atmospheric pressure is 250°C or higher, the volatilization of solvent (d) may be insufficient during the waiting process described later, and component (d) may remain in the cured product of the curable composition (A). Here, if component (d) contains one or more types of solvents, the boiling point of each of the one or more solvents at atmospheric pressure should be between 100°C and 250°C (for example, between 100°C and 200°C).

[0207] Examples of alcohol-based solvents include the following: Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl Monoalcohol solvents such as alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol 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.

[0208] Examples of ketone solvents include the following: Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, phenthone

[0209] Examples of ether-based solvents include the following: Ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol Diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran

[0210] Examples of ester solvents include the following: Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl 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 ether acetate Ethers, diethylene glycol acetate mono-n-butyl ether, propylene glycol acetate monomethyl ether, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether, propylene glycol acetate monobutyl ether, dipropylene glycol acetate monomethyl ether, dipropylene glycol acetate monoethyl ether, 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

[0211] 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

[0212] Of the solvents mentioned above, ether-based solvents and ester-based solvents are preferred. More preferably, from the viewpoint of excellent film-forming properties, are ether-based solvents and ester-based solvents having a glycol structure.

[0213] Furthermore, a more preferable option is an SP value of 17 MPa. 1 / 2 More than 25MPa1 / 2 Less than is preferable, and the following are examples: Propylene glycol monomethyl ether (boiling point 120°C, SP value 20.8MPa) 1 / 2 ), propylene glycol monoethyl ether (boiling point 133°C, SP value 20.4MPa) 1 / 2 ), propylene glycol monopropyl ether (boiling point 149°C, SP value 20.1MPa) 1 / 2 ), propylene glycol monomethyl ether acetate (boiling point 146°C, SP value 17.9MPa) 1 / 2 ), propylene glycol monoethyl ether acetate (boiling point 160℃, SP value 17.8MPa) 1 / 2 ), propylene glycol monopropyl ether acetate (SP value 17.8 MPa) 1 / 2 )

[0214] Furthermore, particularly preferred is propylene glycol monomethyl ether acetate (boiling point 146°C, SP value 17.9 MPa). 1 / 2 ) are some examples.

[0215] In the present invention, preferred solvents are those having at least one of the following: an ester structure, a ketone structure, a hydroxyl group, or an ether structure. Specifically, propylene glycol monomethyl ether acetate (boiling point 146°C, SP value 17.9 MPa) 1 / 2 ), propylene glycol monomethyl ether (boiling point 120°C, SP value 20.8MPa) 1 / 2 ), cyclohexanone (boiling point 156℃, SP value 20.0MPa) 1 / 2 ), 2-heptanone (boiling point 151℃, SP value 18.1MPa) 1 / 2 ), γ-butyrolactone (boiling point 204℃, SP value 20.3MPa) 1 / 2 ), ethyl lactate (boiling point 154℃, SP value 22.6MPa) 1 / 2 ) are selected from a single solvent or a mixture thereof.

[0216] Furthermore, in the present invention, a polymerizable compound having a boiling point of 80°C or higher and less than 250°C under normal pressure can also be used as component (d). A polymerizable compound having a boiling point of 80°C or higher and less than 250°C under normal pressure is an SP value of 17 MPa. 1 / 2 More than 25MPa 1 / 2 Less than is preferable, for example, the following: Cyclohexyl acrylate (boiling point 198°C, SP value 18.9MPa) 1 / 2 ), benzyl acrylate (boiling point 229℃, SP value 20.7MPa) 1 / 2 ), isobornyl acrylate (boiling point 245℃, SP value 17.8MPa) 1 / 2 ), tetrahydrofurfuryl acrylate (boiling point 202℃, SP value 19.5MPa) 1 / 2 ), trimethylcyclohexyl acrylate (boiling point 232°C, SP value 17.9MPa) 1 / 2 ), isooctyl acrylate (boiling point 217℃, SP value 17.6MPa) 1 / 2 ), n-octyl acrylate (boiling point 228℃, SP value 17.9MPa) 1 / 2 ), ethoxyethoxyethyl acrylate (boiling point 230℃, SP value 18.7MPa) 1 / 2 ), divinylbenzene (boiling point 193°C, SP value 19.0 MPa) 1 / 2 ), 1,3-diisopropenylbenzene (boiling point 218℃, SP value 18.8MPa) 1 / 2 ), styrene (boiling point 145℃, SP value 18.9MPa) 1 / 2 ), α-methylstyrene (boiling point 165℃, SP value 18.8MPa) 1 / 2 )

[0217] In this invention, when the total volume of the curable composition (A) is 100 vol%, the content of solvent (d) is greater than 5 vol% and 95 vol% or less, preferably 15 vol% to 85 vol%, and more preferably 40 vol% to 80 vol%. For example, the content of solvent (d) is 40 vol% to 85 vol%. If the content of solvent (d) is less than 5 vol%, a thin film cannot be obtained after the evaporation of solvent (d) under conditions in which a substantially continuous liquid film can be obtained. Also, if the content of solvent (d) is greater than 95 vol%, a thick film cannot be obtained after the evaporation of solvent (d), even if the liquid droplets are dropped as densely as possible by the inkjet method.

[0218] <Temperature during compounding of curable composition> When preparing the curable composition (A) in the present invention, at least 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 to 100°C. The same applies when the curable composition (A) contains component (c).

[0219] <Viscosity of curable composition> The curable composition (A) in this invention is a liquid. This is because, in the placement step described later, droplets of the curable composition (A) are discretely dropped onto the substrate by an inkjet method. The viscosity of the curable composition (A) in this invention is 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atm, preferably 2 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less. If the viscosity of the curable composition (A) is less than 2 mPa·s, the droplet ejection by the inkjet method becomes unstable. Also, if the viscosity of the curable composition (A) is greater than 60 mPa·s, it is not possible to form droplets with a volume of about 1.0 to 3.0 pL, which is preferred in this invention.

[0220] The viscosity of the mixture of components of the curable composition (A) excluding solvent (d) at 23°C and 1 atm after solvent (d) has evaporated is 30 mPa·s or more and 10,000 mPa·s or less. Preferably, the viscosity of the mixture of components of the curable composition (A) excluding solvent (d) at 23°C and 1 atm is 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. Even more preferably, the viscosity of the mixture of components of the curable composition (A) excluding solvent (d) at 23°C and 1 atm is 150 mPa·s or more and 500 mPa·s or less. By making the viscosity of the components of the curable composition (A) excluding solvent (d) 1,000 mPa·s or less Therefore, by using the curable composition (A) of the present invention, imprint processing can be carried out with high throughput, and pattern defects due to insufficient filling can be suppressed. Furthermore, by making the viscosity of the components of the curable composition (A) excluding the solvent (d) 1 mPa·s or higher, unwanted flow of droplets of the curable composition (A) after the solvent (d) has evaporated can be prevented. In addition, when the curable composition (A) is brought into contact with the mold, it becomes less likely for the curable composition (A) to flow out from the edges of the mold.

[0221] <Surface tension of curable compositions> Regarding the surface tension γ1 of the curable composition (A) after the solvent (d) has evaporated, it is preferable that it is 5 mN / m or more and 70 mN / m or less at 23°C and 1 atm. Furthermore, for the composition of components other than the solvent (component (d)), it is more preferable that the surface tension at 23°C and 1 atm is 7 mN / m or more and 50 mN / m or less, and even more preferable that it is 10 mN / m or more and 40 mN / m or less. Note that the higher the surface tension, for example, if it is 5 mN / m or more, the stronger the capillary force, so that when the curable composition (A) is brought into contact with the mold, filling (spreading and filling) can be completed in a short time. In addition, by making the surface tension 70 mN / m or less, the cured film obtained by curing the curable composition becomes a cured film with a smooth surface.

[0222] <Contact angle of curable composition> Regarding the contact angle of the curable composition (A) in the present invention, it is preferable that the contact angle of the composition of components other than the solvent (component (d)) is 0° or more and 90° or less with respect to both the surface of the substrate and the surface of the mold. If the contact angle is greater than 90°, capillary forces act in a negative direction (a direction that causes contraction of the contact interface between the mold and the curable composition) inside the mold pattern and in the gap between the substrate and the mold, which may prevent the curable composition (A) from filling the mold. The smaller the contact angle, the stronger the capillary forces act, resulting in a faster filling speed.

[0223] <Impurities present in the curable composition> The curable composition (A) in the present invention is preferably free of impurities as much as possible. Impurities refer to substances other than the components (a), (b), (c), and (d) described above. Therefore, the curable composition (A) in the present invention is preferably obtained through a purification process. Such a purification process is preferably filtration using a filter.

[0224] For filtration using a filter, it is preferable to mix components (a), (b), and (c) described above and then filter them using, for example, a filter with a pore size of 0.001 μm to 5.0 μm. When performing filtration using a filter, it is even more preferable to perform it in multiple stages or repeat it many times (circulating filtration). The liquid filtered by the filter may be filtered again, or multiple filters with different pore sizes may be used for filtration. Examples of filters used for filtration include, but are not particularly limited to, filters made of polyethylene resin, polypropylene resin, fluororesin, and nylon resin. By going through such a purification process, impurities such as particles mixed into the curable composition can be removed. This prevents impurities mixed into the curable composition from unintentionally causing irregularities in the cured film obtained after curing the curable composition, resulting in pattern defects.

[0225] Furthermore, when using the curable composition of the present invention to manufacture semiconductor integrated circuits, it is preferable to avoid, as much as possible, the inclusion of metal atoms (metallic impurities) in the curable composition in order to avoid interfering with the operation of the product. The concentration of metal impurities in the curable composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0226] <Glass transition temperature of curable composition> If the glass transition temperature is sufficiently higher than the release temperature, the cured product at the time of release will be in a rigid glassy state, i.e., will exhibit high mechanical strength, making it less likely for the pattern to collapse or break due to the impact of release. Therefore, when the release process is carried out at room temperature, the glass transition temperature of the cured product (after curing of polymerizable compound (a)) is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0227] Methods for measuring the glass transition temperature of a cured material (photocured material) include differential scanning calorimetry (DSC) and dynamic viscoelasticity measurement. For example, consider measuring the glass transition temperature using DSC. In this case, a straight line is obtained by extending the low-temperature baseline (the portion of the DSC curve in the temperature range where no transition or reaction occurs in the specimen) of the cured material's DSC curve toward the high-temperature side, and a tangent line is drawn at the point where the slope of the curve representing the stepwise change portion of the glass transition is maximum. The extrapolated glass transition onset temperature (Tig) can then be determined from the intersection of this straight line and the tangent line, and this can be considered the glass transition temperature. A major instrument for this method is the STA-6000 (manufactured by Perkin Eimer). On the other hand, when measuring the glass transition temperature using a dynamic viscoelasticity measurement device, the temperature at which the loss sine (tanδ) of the cured material is maximum is defined as the glass transition temperature. A major instrument for measuring dynamic viscoelasticity is the MCR301 (manufactured by Anton Paar).

[0228] [substrate] In this specification, a component on which droplets of the curable composition (A) are discretely dropped is described as a substrate.

[0229] The substrate is the substrate to be processed, and typically a silicon wafer is used. The substrate may have a layer to be processed on its surface. The substrate may also have other layers formed beneath the layer to be processed. Furthermore, if a quartz substrate is used as the substrate, a replica of the mold for imprinting (replica mold) can be manufactured. However, the substrate is not limited to silicon wafers or quartz substrates. The substrate can be arbitrarily selected from those known as semiconductor device substrates, such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, and silicon nitride. It is preferable to improve the adhesion to the curable composition (A) by surface treatment of the substrate or the layer to be processed, such as silane coupling treatment, silazane treatment, or deposition of an organic thin film. The surface SP value of the organic thin film deposited as a surface treatment is 17 MPa. 1 / 2 More than 25MPa 1 / 2 A value less than is preferable, and as a specific example, for example, the adhesion layer described in Japanese Patent Publication No. 2009-503139 can be used.

[0230] [Pattern formation method] The pattern formation method in the present invention will be described with reference to Figures 1(a) to 1(g). The cured film formed by the present invention is preferably a film having a pattern of size 1 nm to 10 mm, and more preferably a film having a pattern of size 10 nm to 100 μm. Generally, a film formation method that uses light to form a film having a nano-sized pattern (uneven structure) of 1 nm to 100 nm is called an optical imprint method. The film formation method in the present invention uses an optical imprint 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 in the present invention may be implemented as a method for forming a film having a pattern, i.e., as a pattern formation method, or as a method for forming a film without a pattern (e.g., a planarized film), i.e., as a planarized film formation method.

[0231] The following describes an example in which the film-forming method of the present invention is applied to a pattern-forming method. The pattern-forming method includes, for example, a forming step, a placement step, a waiting step, a contact step, a curing step, and a demolding step. The forming step is a step of forming a base layer. The placement step is a step of discretely placing droplets of the curable composition (A) on the base layer. The waiting step is a step of waiting until the droplets of the curable composition (A) combine with each other and the solvent (d) evaporates. The contact step is a step of bringing the curable composition (A) into contact with a mold. The curing step is a step of curing the curable composition (A). The demolding step is a step of separating the mold from the cured film of the curable composition (A). The placement step is performed after the forming step, the waiting step is performed after the placement step, the contact step is performed after the waiting step, the curing step is performed after the contact step, and the demolding step is performed after the curing step.

[0232] <Placement process> In the placement process, droplets 102 of the curable composition (A) are discretely placed on the substrate 101, as schematically shown in Figure 1(a). In the placement process, 80 droplets / mm of the curable composition (A) having a volume of 1.0 pL or more are placed. 2 The substrates are arranged at the above density. A substrate with a laminated underlayer may be used as the substrate 101. Furthermore, the surface of the substrate 101 may be treated with a silane coupling treatment, silazane treatment, or organic thin film deposition to achieve a surface SP value of 17 MPa. 1 / 2 More than 25MPa 1 / 2 Adhesion to the curable composition (A) may be improved by a surface treatment having a value less than .

[0233] As a method for arranging droplets 102 of the curable composition (A) on the substrate, the inkjet method is particularly preferred. It is preferable that the droplets 102 of the curable composition (A) be densely arranged on the region of the substrate 101 facing the region where the recesses constituting the pattern of the mold 106 are densely present, and sparsely arranged on the region of the substrate 101 facing the region where the recesses constituting the pattern of the mold 106 are sparsely present. As a result, the film (residual film) 109 of the curable composition (A), which will be described later, formed on the substrate 101 is controlled to have a uniform thickness regardless of the density of the pattern of the mold 106.

[0234] To define the volume of curable composition (A) to be placed, an index called the average residual liquid film thickness is defined. The average residual liquid film thickness is the value obtained by dividing the volume of curable composition (A) (excluding solvent (d)) placed in the placement process by the area of ​​the film formation region of the mold. The volume of curable composition (A) (excluding solvent (d)) is the sum of the volumes of individual droplets of curable composition (A) after the solvent (d) has evaporated. According to this definition, even if there are irregularities on the substrate surface, the average residual liquid film thickness can be defined regardless of the irregularity. Here, the average residual liquid film thickness may be understood as the value obtained by dividing the volume of curable composition (A) remaining after the waiting process described later by the area of ​​the film formation region of the mold, and it is preferable that it be 20 nm or less.

[0235] <Standby process> In this invention, a waiting step is provided between the placement step and the contact step. Here, the average initial liquid film thickness is defined as the value obtained by dividing the total volume of droplets of curable composition (A) dropped in one pattern formation by the total area of ​​the region where a pattern is formed in one pattern formation (pattern formation region). During the waiting step, the droplets 102 of curable composition (A) spread out on the substrate 101, as schematically shown in Figure 1(b). As a result, the entire pattern formation region of the substrate 101 is covered with curable composition (A).

[0236] Furthermore, during the waiting process, the solvent 105 (solvent (d)) contained in the liquid film 104 is evaporated, as schematically shown in Figure 1(d). The amount of solvent (d) remaining in the liquid film 103 after the waiting process (for example, at the start of the contact process) is preferably 10% by volume or less, assuming the total weight of components other than solvent (d) is 100% by volume. If the amount of solvent (d) remaining is greater than 10% by volume, the mechanical properties of the cured film may be reduced.

[0237] During the waiting process, a baking process may be carried out to accelerate the volatilization of solvent (d), by heating the substrate 101 and the curable composition (A), or by ventilating the atmospheric gas around the substrate 101. The heating is carried out, for example, at a temperature of 30°C to 200°C, preferably 80°C to 150°C, and particularly preferably 90°C to 110°C. The heating time can be 10 seconds to 600 seconds. The baking process can be carried out using a known heating device such as a hot plate or an oven.

[0238] The waiting period is, for example, 0.1 seconds to 600 seconds, preferably 10 seconds to 300 seconds. If the waiting period is shorter than 0.1 seconds, the bonding between droplets of the curable composition (A) will be insufficient, and a substantially continuous liquid film will not be formed. If the waiting period exceeds 600 seconds, productivity will decrease. Therefore, in order to suppress the decrease in productivity, substrates that have completed the placement process may be sequentially moved to the waiting process, and the waiting process may be carried out in parallel for multiple substrates, with substrates that have completed the waiting process being sequentially moved to the contact process. In the prior art, theoretically, it takes several thousand to tens of thousands of seconds for a substantially continuous liquid film to be formed, but in reality, the spreading of droplets of the curable composition is delayed due to the effect of volatilization, making it impossible to form a continuous liquid film.

[0239] During the waiting process, when solvent (d) evaporates, a substantially continuous liquid film 104 consisting of components (a), (b), and (c) remains. The average remaining liquid film thickness of the substantially continuous liquid film 104 from which solvent (d) has evaporated (removed) is thinner than the liquid film 103 by the amount of solvent (d) that has evaporated. The pattern formation region of the substrate 101 remains covered throughout by a substantially continuous liquid film 104 of the curable composition (A) from which solvent (d) has been removed.

[0240] The SP value of nitrogen, the main component of air, is 11.9 MPa. 1 / 2 (Quoted from Charles M. Hansen, "Hansen Solubility Parameters: A User's Handbook," 2nd Edition (2007), p. 252, TABLE 13.4) It has an SP value close to that of an SP value of 11 MPa. 1 / 2 17 MPa or more 1 / 2 The liquid-repellent atomic group of surfactant (c1) having less than is segregated towards the air side.

[0241] <Contact process> In the contact step, as schematically shown in Figure 1(e), a substantially continuous liquid film 104 of the curable composition (A), from which the solvent (d) has been removed, is brought into contact with the mold 106. The contact step includes a step of changing the state from one in which the curable composition (A) and the mold 106 are not in contact to a state in which they are in contact, and a step of maintaining the state in which they are in contact. 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 this liquid becomes a liquid film that fills the fine pattern of the mold 106.

[0242] If the spreading and filling of the curable composition (A) is completed quickly during the contact process, the time required to maintain the mold 106 in contact with the curable composition (A) (the time required for the contact process) can be shortened. Shortening the time required for the contact process leads to a reduction in the time required for pattern formation (film formation), thus improving productivity. The contact process is preferably 0.1 seconds or more and 3 seconds or less, and particularly preferably 0.1 seconds or more and 1 second or less. If the contact process is shorter than 0.1 seconds, the spreading and filling will be insufficient, and defects called unfilled defects tend to occur frequently.

[0243] If the curing process includes a light irradiation process, the mold 106 should be made of a light-transmitting material, taking this into consideration. Specifically, preferred materials for the mold 106 include glass, quartz, light-transmitting resins such as PMMA and polycarbonate resin, transparent metal vapor-deposited films, flexible films such as polydimethylsiloxane, photocurable films, and metal films. However, if a light-transmitting resin is used as the material for the mold 106, a resin that does not dissolve in the components of the curable composition should be selected. Quartz is suitable as a material for the mold 106 because it has a low coefficient of thermal expansion and low pattern distortion.

[0244] The SP value of quartz is 33.0 MPa. 1 / 2 (Calculated from Fedors' atomic group SiO4) It has an SP value close to 25 MPa. 1 / 2 Above 35 MPa 1 / 2 The hydrophilic atomic group of surfactant (c1) having less than is segregated towards the quartz side.

[0245] The pattern formed on the surface of mold 106 has a height of, for example, 4 nm to 200 nm. The lower the height of the pattern on mold 106, the smaller the force required to separate mold 106 from the cured film of the curable composition during the release process, i.e., the release force, which reduces the number of release defects remaining on mold 106 due to the pattern of the curable composition being torn off. Also, the impact when separating the mold can cause elastic deformation of the pattern of the curable composition, which can cause adjacent pattern elements to come into contact, resulting in adhesion or damage. However, it is advantageous to have a pattern element height of approximately twice the width of the pattern element (aspect ratio of 2 or less) to avoid these problems. On the other hand, if the height of the pattern elements is too low, the processing accuracy of the substrate 101 will be reduced.

[0246] The mold 106 may be surface-treated before the contact process to improve its release properties from the curable composition (A). For example, surface treatment may involve applying a release agent to the surface of the mold 106 to form a release agent layer. Examples of release agents to be applied to the surface of the mold 106 include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. For example, commercially available coating-type release agents such as Optool® DSX manufactured by Daikin Industries, Ltd. can also be suitably used. The release agent may be used alone or in combination of two or more types. Among the above-mentioned release agents, one that does not contain fluorine atoms or silicon atoms and has an SP value of 11 MPa is suitable. 1 / 2 17 MPa or more 1 / 2 A liquid-repellent atomic group having less than 25 MPa SP value 1 / 2 Above 35 MPa 1 / 2 Hydrocarbon-based release agents containing a hydrophilic group having less than 1 / 2 are particularly preferred.

[0247] In the contact process, 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, but for example, it may be 0 MPa or more and 100 MPa or less. However, 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.

[0248] The contact process can be carried out under any of the following conditions: under an atmospheric atmosphere, under a reduced pressure atmosphere, or under an inert gas atmosphere. However, it is preferable to use a reduced pressure atmosphere or an inert gas atmosphere because it prevents the influence of oxygen and moisture on the curing reaction. Specific examples of inert gases used when carrying out the contact process under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various fluorocarbon gases, or mixtures thereof. A gas containing 10% or more carbon dioxide or helium by molar ratio is preferred, and a gas containing 10% or more carbon dioxide by molar ratio is particularly preferred. Helium gas diffuses easily into the mold, substrate, and curable composition, so atmospheric gas trapped in the mold pattern, etc., disappears quickly. Carbon dioxide dissolves easily in the curable composition and the underlying layer on the substrate, so atmospheric gas trapped in the mold pattern, etc., disappears quickly. The solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m³. 3 ·ATM or more 10kg / m 3 It is preferable that the pressure be below atm. Details of these are disclosed in Japanese Patent Publication No. 2022-99271. When the contact process is carried out in a specific gas atmosphere, including an atmospheric atmosphere, the preferred pressure is 0.0001 atmospheres or more and 10 atmospheres or less.

[0249] <Curing process> In the curing process, as schematically shown in Figure 1(f), the curable composition (A) is cured by irradiating it with irradiation light 107 as curing energy to form a cured film. In the curing process, for example, the curable composition (A) is irradiated with irradiation light 107 through the 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 hardens to form a cured film 108 having a pattern.

[0250] The irradiation light 107 is selected according to the sensitivity wavelength of the curable composition (A). Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, or electron beams with a wavelength of 150 nm to 400 nm. It is particularly preferable that the irradiation light 107 be ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are compounds that are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. However, ultra-high-pressure mercury lamps are particularly preferred as light sources that emit ultraviolet light. There may be one or more light sources. Furthermore, the entire surface of the curable composition (A) filled in the fine pattern of the mold may be irradiated with light, or only a portion of it may be irradiated (limited to a specific area). Additionally, the light irradiation may be performed intermittently over the entire surface of the substrate multiple times, or continuously over the entire surface of the substrate. Moreover, in the first irradiation process, a first region of the substrate may be irradiated with light, and in the second irradiation process, a second region of the substrate different from the first region may be irradiated with light.

[0251] <Mold release process> In the demolding process, the mold 106 is separated from the cured film 108, as schematically shown in Figure 1(g). By separating the patterned cured film 108 from the mold 106, a self-supporting cured film 108 with a pattern that is an inversion of the fine pattern of the mold 106 is obtained. Here, some of the cured film remains in the recesses of the patterned cured film 108. This film is called residual film.

[0252] The SP value of the adhesive layer surface between the curable composition (A) is 17 MPa. 1 / 2 More than 25MPa 1 / 2 Because it has less than 11 MPa, the adhesion between the curable composition (A) and the adhesion layer is improved. Furthermore, the SP value of the liquid-repellent atomic group of the surfactant (c1) is 11 MPa. 1 / 2 17 MPa or more 1 / 2 Because it has less than [a certain value] and a small SP value, the release force is reduced.

[0253] The method for separating the mold 106 from the patterned cured film 108 is not limited to any particular conditions, as long as no part of the patterned cured film 108 is 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 also be separated from the patterned cured film 108 by moving both the mold 106 and the substrate 101 in opposite directions.

[0254] <Repeat> By a series of steps (manufacturing process) including the above-described placement step and demolding step in this order, a cured film having a desired uneven pattern shape (a pattern shape corresponding to the uneven shape of the mold 106) at a desired position can be obtained.

[0255] In the pattern formation method of the present invention, the repeating units (shots) 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 at desired positions on the substrate can be obtained.

[0256] [Planarization film formation method] The following describes an example in which the film formation method of the present invention is applied to a planarization film formation method. The planarization film formation method includes, for example, a placement step, a waiting step, a contact step, a curing step, and a release step. The placement step is a step of placing droplets of the curable composition (A) on a substrate. The waiting step is a step of waiting until the droplets of the curable composition (A) combine with each other and the solvent (d) evaporates. The contact step is a step of bringing the curable composition (A) into contact with a mold. The curing step is a step of curing the curable composition (A). The release step is a step of separating the mold from the cured film of the curable composition (A). In the planarization film formation method, a substrate having irregularities with a height difference of about 10 to 1,000 nm is used as the substrate, and a mold having a flat surface is used as the mold. After the contact step, curing step and release step, a cured film having a surface that conforms to the flat surface of the mold is formed. In the placement process, droplets of the curable composition (A) are densely arranged in the recesses of the substrate, and the curable composition (A) is sparsely arranged in the protrusions of the substrate. The waiting process is performed after the placement process, the contact process is performed after the waiting process, the curing process is performed after the contact process, and the demolding process is performed after the curing process.

[0257] [Method of manufacturing articles] The method for manufacturing an article includes a forming step of forming a film of a curable composition on a substrate using the film forming method described above, a processing step of processing the substrate on which the film of the curable composition was formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. The film forming method is, as described above, a pattern forming method or a planarization film forming method.

[0258] Furthermore, the cured film 108 having a pattern formed by the pattern forming method of the present invention can be used as is as a component of at least a part of various articles. The cured film 108 having a pattern formed by the pattern forming method of the present invention is temporarily used as a mask for etching, ion implantation, etc., on the substrate 101 (or the layer to be processed if the substrate 101 has a layer to be processed). After etching, ion implantation, etc., is performed in the processing process of the substrate 101, the mask is removed. This makes it possible to manufacture various articles.

[0259] When removing hardened material from recesses in the pattern of a hardened material by etching, the specific method is not particularly limited, and known methods, such as dry etching, can be used. Known dry etching apparatus can be used for dry etching. The source gas for dry etching is appropriately selected according to the elemental composition of the hardened material to be etched. Specifically, halogen-based gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2 can be used as source gases. In addition, gases containing oxygen atoms such as O2, CO, and CO2, inert gases such as He, N2, and Ar, and gases such as H2 and NH3 can also be used as source gases. These gases can also be mixed and used as a source gas. In this case, in order to process the substrate with good yield, the photocured film requires high dry etching resistance.

[0260] Articles include electrical circuit elements, optical elements, MEMS, recording elements, sensors, or molds. Electrical circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, as well as semiconductor elements such as LSI, CCD, image sensors, and FPGA. Optical elements include microlenses, light guides, waveguides, anti-reflective coatings, diffraction gratings, polarizing elements, color filters, light-emitting elements, displays, and solar cells. MEMS include DMDs, microfluidics, and electromechanical conversion elements. Recording elements include optical discs such as CDs and DVDs, magnetic discs, magneto-optical discs, and magnetic heads. Sensors include magnetic sensors, optical sensors, and gyro sensors. Molds include molds for imprinting.

[0261] Furthermore, known photolithography processes such as imprint lithography and extreme ultraviolet (EUV) exposure can be performed on the planarized film formed by the planarized 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 for photolithography. This makes it possible to manufacture devices such as semiconductor devices. It is also possible to form devices including such devices, such as electronic devices such as displays, cameras, and medical devices. Examples of devices include LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and NAND flash memory.

[0262] [Examples] To supplement the embodiments described above, more specific examples will be explained. Experiments were conducted using four different compositions, as shown in Table 1 below. The polymerizable compound was 1-naphthylmethyl acrylate (Na1MA, OP2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042 mmHg, molecular weight 212.2, SP value 22.0 MPa). 1 / 2) and tricyclodecanedimethanol diacrylate (DCPDA, OP 3.29, boiling point 342℃, 80℃, vapor pressure 0.0024 mmHg, molecular weight 304, SP value 20.3MPa) 1 / 2 The solvent used was propylene glycol monomethyl ether acetate (PGMEA, boiling point 146°C, SP value 17.9 MPa). 1 / 2 ) was used.

[0263] <Example 1> In Example 1, Table 1 shows that the surfactant used was DYNOL 604 (manufactured by Nisshin Chemical Industry Co., Ltd., molecular weight 431, liquid-repellent atomic group ((CH3)2CH-CH2-CH2-C(CH3)<) SP value 16.0 MPa). 1 / 2 The hydrophilic group (-O-CH2-CH2-OH) has an SP value of 26.8 MPa. 1 / 2 Fedors methyl group number 6 in the liquid-repellent atomic group, hydrophilic atomic group (-C≡C-) SP value 33.0 MPa 1 / 2 This composition is achieved by adding 3 parts by weight of ).

[0264] [ka]

[0265] <Comparative Example 1> Comparative Example 1, as shown in Table 1, is a composition without the addition of a surfactant.

[0266] <Comparative Example 2> In Comparative Example 2, Table 1 shows that the surfactant is FS2000M1 (manufactured by CHANGZHOU FOREIGN, molecular weight 2680, liquid-repellent atomic group (CF3-(CF2)7-CH2-CH2-) SP value 13.3 MPa) 1 / 2 The number of Fedors methyl groups in the liquid-repellent atomic group is 0, and the SP value of the liquid-hydrophilic atomic group (-O-CH2-CH2-OH) is 26.8 MPa. 1 / 2 The composition is obtained by adding 3 parts by weight of propylene oxide chains with two or more repeating units, those having two or more methyl groups, and those not included in the preferred liquid-repellent atomic group.

[0267] [ka]

[0268] <Comparative Example 3> In Comparative Example 3, Table 1 shows that the surfactant is random polymerization type polyoxyethylene polyoxypropylene stearyl ether BLAUNON SA-30 / 70 2000R (manufactured by Aoki Oil & Fat Industry Co., Ltd., molecular weight 2000, liquid-repellent atomic group (CH3-(CH2) 17 -) SP value 17.0 MPa 1 / 2 The liquid-repellent atomic group has 1 Fedors methyl group, and the liquid-hydrophilic atomic group (-O-CH2-CH2-OH) has an SP value of 26.8 MPa. 1 / 2 The composition is obtained by adding 3 parts by weight of propylene oxide chains with two or more repeating units, those having two or more methyl groups, and those not included in the preferred liquid-repellent atomic group.

[0269] [ka]

[0270] [Table 1]

[0271] <Evaluation of pattern failure> For the curable compositions of the examples shown in Table 1 and Comparative Examples 1-3, a quartz mold with a line-and-space (L / S) pattern of 50 nm depth and 20 nm width formed throughout the entire surface was used to perform the placement, waiting, contact, curing, and demolding steps. The patterns obtained after these steps were observed, and the pattern collapse was evaluated according to the following evaluation criteria.

[0272] (Evaluation Criteria) AAA: Pattern collapse was observed in less than 0.5% of the pattern-forming region. AA: Pattern collapse was observed in less than 1% of the pattern-forming region. A: Pattern collapse was observed in less than 10% of the pattern formation region. B: Pattern collapse was observed in 10% or more of the pattern formation area.

[0273] <Evaluation of LPOS Defects> For the curable compositions of the examples shown in Table 1 and Comparative Examples 1 to 3, using a quartz mold in which line-and-space (L / S) patterns with a depth of 50 nm and a width of 20 nm were formed in the entire area, an arrangement process, a standby process, a contact process, a curing process, and a mold release process were carried out. Then, the patterns obtained through these processes were observed, and longitudinal position (LPOS) defects were evaluated according to the following evaluation criteria.

[0274] (Evaluation Criteria) A: No LPOS defects were observed in the pattern formation area. B: LPOS defects were observed in the pattern formation area.

[0275] The evaluation results so far are shown in Table 2 below.

[0276]

Table 2

[0277] The disclosure of this specification includes the following curable compositions, film formation methods, and article manufacturing methods.

[0278] (Item 1) A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a surfactant (c1), wherein the polymerizable compound (a) has an SP value of 17 MPa 1 / 2 or more and less than 25 MPa 1 / 2 and the surfactant (c1) does not contain a fluorine atom and a silicon atom, has a liquid-repellent atomic group with an SP value of 11 MPa 1 / 2 or more and less than 17 MPa 1 / 2 and has an SP value of 25 MPa 1 / 2 or more and 35 MPa or less1 / 2 It includes a hydrophilic atomic group having less than The content of the surfactant (c1) relative to the total curable composition is 0.1% by weight or more and 10% by weight or less. A curable composition characterized by the following features.

[0279] (Item 2) A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), The curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atm. The content of the solvent (d) relative to the total curable composition is greater than 5% by volume and 95% by volume or less. The boiling point of solvent (d) is less than 250°C at 1 atmosphere. Polymerizable compound (a) and solvent (d) have an SP value of 17 MPa. 1 / 2 More than 25MPa 1 / 2 Having less than, The surfactant (c1) does not contain fluorine atoms or silicon atoms. PL value 11 MPa 1 / 2 17 MPa or more 1 / 2 A liquid-repellent atomic group having less than, SP value 25MPa 1 / 2 Above 35 MPa 1 / 2 It includes a hydrophilic atomic group having less than The content of the surfactant (c1) relative to the total curable composition is 0.1% by weight or more and 10% by weight or less. A curable composition characterized by the following features.

[0280] (Item 3) The curable composition according to item 1 or 2, characterized in that the molecular weight of the surfactant (c1) is 200 or more and less than 2000.

[0281] (Item 4) A curable composition according to any one of items 1 to 3, characterized in that the molar volume ratio of the liquid-repellent atomic group to the hydrophilic atomic group of the surfactant (c1) is 1.5 or more and less than 5.

[0282] (Item 5) A curable composition according to any one of items 1 to 4, characterized in that the liquid-repellent atomic group of the surfactant (c1) has two or more methyl groups.

[0283] (Item 6) The curable composition according to any one of items 1 to 5, characterized in that the curable composition is a curable composition for inkjet printing.

[0284] (Item 7) The curable composition according to any one of items 1 to 6, characterized in that the curable composition is a curable composition for photoimprinting.

[0285] (Item 8) A method for forming a film of a curable composition on a substrate, A placement step of discretely arranging a plurality of droplets of the curable composition described in any one of items 1 to 7 on the substrate, A waiting step in which the plurality of droplets wait until they combine with adjacent droplets to form a liquid film, A film formation method characterized by having the following:

[0286] (Item 9) The film formation method according to item 8, characterized in that the arrangement step involves discretely arranging the plurality of liquid droplets on the substrate using an inkjet method.

[0287] (Item 10) The film-forming method according to item 8 or 9, characterized in that the waiting step is performed until the solvent contained in the liquid film evaporates and the solvent content is 10% by volume or less relative to the entire liquid film.

[0288] (Item 11) A film forming method according to any one of items 8 to 10, further comprising a contact step of bringing the liquid film into contact with the mold after the waiting step.

[0289] (Item 12) The aforementioned type includes a pattern, In the contact step, the pattern of the type and the liquid film are brought into contact. The process further includes a curing step, in which the liquid film is cured after the contact step to form a cured film having a pattern corresponding to the pattern of the mold. The film formation method according to item 11, characterized by the features described herein.

[0290] (Item 13) The aforementioned type includes a flat surface, In the contact step, the flat surface of the mold and the liquid film are brought into contact. The process further includes a curing step, in which the liquid film is cured after the contact step to form a cured film having a surface that conforms to the flat surface of the mold. The film formation method according to item 11, characterized by the features described herein.

[0291] (Item 14) A forming step of forming a film of a curable composition on a substrate using a film forming method described in any one of items 8 to 13, A processing step for processing the substrate on which the film has been formed in the forming step, A manufacturing process for producing an article from the substrate processed in the above-mentioned processing step, A method for manufacturing an article, characterized by having the following:

[0292] The invention is not limited to the embodiments described above, and various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, claims are attached to disclose the scope of the invention. [Explanation of Symbols]

[0293] 101 circuit board 102 Droplet 103 Liquid film 104 Liquid film 105 Solvent Type 106 107 Irradiation light 108 Cured film

Claims

1. A polymerizable compound (a), a photopolymerization initiator (b), and a surfactant (c1), A curable composition comprising, Polymerizable compound (a) has an SP value of 17 MPa. １／２ 25MPa or more １／２ Having less than, The surfactant (c1) does not contain fluorine atoms or silicon atoms. SP value 11 MPa １／２ Above 17 MPa １／２ A liquid-repellent atomic group having less than, SP value 25 MPa １／２ Above 35 MPa １／２ It includes a hydrophilic atomic group having less than The content of the surfactant (c1) relative to the total curable composition is 0.1% by weight or more and 10% by weight or less. A curable composition characterized by the following features.

2. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), a solvent (d), and a surfactant (c1), The curable composition has a viscosity of 1.3 mPa·s or more and 60 mPa·s or less at 23°C and 1 atm. The content of the solvent (d) in the total curable composition is greater than 5% by volume and 95% by volume or less. The boiling point of the solvent (d) is less than 250°C at 1 atmosphere. Polymerizable compound (a) and solvent (d) have an SP value of 17 MPa. １／２ 25MPa or more １／２ Having less than, The surfactant (c1) does not contain fluorine atoms or silicon atoms. SP value of 11 MPa １／２ 17 MPa or more １／２ a liquid-repellent atomic group having less than... SP value 25 MPa １／２ Above 35 MPa １／２ It includes a hydrophilic atomic group having less than The content of the surfactant (c1) relative to the total curable composition is 0.1% by weight or more and 10% by weight or less. A curable composition characterized by the following features.

3. The curable composition according to claim 1 or 2, characterized in that the molecular weight of the surfactant (c1) is 200 or more and less than 2000.

4. The curable composition according to claim 1 or 2, characterized in that the molar volume ratio of the liquid-repellent atomic group to the hydrophilic atomic group of the surfactant (c1) is 1.5 or more and less than 5.

5. The curable composition according to claim 1 or 2, characterized in that the liquid-repellent atomic group of the surfactant (c1) has two or more methyl groups.

6. The curable composition according to claim 1 or 2, characterized in that the curable composition is a curable composition for inkjet printing.

7. The curable composition according to claim 1 or 2, characterized in that the curable composition is a curable composition for photoimprinting.

8. A method for forming a film of a curable composition on a substrate, A placement step of discretely arranging a plurality of droplets of the curable composition according to claim 1 or 2 on the substrate, A waiting step in which the plurality of droplets wait until they combine with adjacent droplets to form a liquid film, A film formation method characterized by having the following:

9. The film formation method according to claim 8, characterized in that the arrangement step involves discretely arranging the plurality of liquid droplets on the substrate using an inkjet method.

10. The film forming method according to claim 8, characterized in that the waiting step is performed until the solvent contained in the liquid film evaporates and the solvent content is 10% by volume or less relative to the entire liquid film.

11. The film forming method according to claim 8, further comprising a contact step of bringing the liquid film into contact with a mold after the waiting step.

12. The aforementioned type includes a pattern, In the contact step, the pattern of the type and the liquid film are brought into contact. The process further includes a curing step, in which the liquid film is cured after the contact step to form a cured film having a pattern corresponding to the pattern of the mold. The film formation method according to feature 11.

13. The aforementioned type includes a flat surface, In the contact step, the flat surface of the mold and the liquid film are brought into contact. The process further includes a curing step, in which the liquid film is cured after the contact step to form a cured film having a surface that conforms to the flat surface of the mold. The film formation method according to feature 11.

14. A forming step of forming a film of a curable composition on a substrate using the film forming method described in claim 8, A processing step for processing the substrate on which the film has been formed in the forming step, A manufacturing process for producing an article from the substrate processed in the above-mentioned processing step, A method for manufacturing an article, characterized by having the following:

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