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

Abstract

This invention provides novel technologies relating to curable compositions, film-forming methods, and methods for manufacturing articles. [Solution] A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), The viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less. 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 the solvent (d) is less than 250°C. The viscosity of the curable composition after the solvent (d) has been removed is 8 mPa·s or more and 30 mPa·s or less at 23°C and 1 atm. A curable composition characterized by the following features.

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 contact 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, the mold is brought into contact with the curable composition on the substrate (pressed against it). 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 a 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 (see Patent Document 1).

[0005] In pattern formation and planarization techniques using imprint technology, the mold is brought into contact with the substrate while the droplets of 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 curable composition together before bringing the curable composition on the substrate into contact with the mold (see Patent Document 2). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2019-140394 [Patent Document 2] Japanese Patent Publication No. 2022-188736 [Overview of the project] [Problems that the invention aims to solve]

[0007] In the technology described in Patent Document 2, it is necessary to fill the liquid film of the curable composition, formed by the spreading of droplets, with the curable composition by bringing the mold into contact with (pressing) the liquid film, thereby filling the edges of the contact area (pattern formation area) between the mold and the substrate. This phenomenon is called edge filling. The speed at which edge filling occurs is called the edge filling speed. In pattern formation methods and planarization technologies using imprint technology, it takes time to fill the edges of the desired area (pattern formation area) with the curable composition because the mold is brought into contact with the liquid droplets of curable composition dropped onto the substrate. As a result, this is one of the factors that reduces productivity (throughput).

[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] The first aspect of the present invention is, A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), The viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less. 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 the solvent (d) is less than 250°C. The viscosity of the curable composition after the solvent (d) has been removed is 8 mPa·s or more and 30 mPa·s or less at 23°C and 1 atm. It is characterized by the following:

[0010] Furthermore, a second aspect of the present invention is, A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), a surfactant (c), and a solvent (d), The viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less. The content of the solvent (d) in the whole of the curable composition is more than 5% by volume and 95% by volume or less, the boiling point of the solvent (d) is less than 250 ° C, the viscosity of the surfactant (c) at 23 ° C and 1 atmosphere is 500 mPa·s or less, which is characterized by.

[0011] A further object or other aspect of the present invention will be clarified by embodiments described below with reference to the accompanying drawings.

Effects of the Invention

[0012] According to the present invention, for example, a new technology regarding a curable composition can be provided.

Brief Description of the Drawings

[0013] [Figure 1] A diagram for explaining a pattern forming method (film forming method) as one aspect of the present invention. [Figure 2] A diagram for explaining the flow behavior during the standby process of droplets of the curable composition. [Figure 3] A diagram for explaining the segregation of the surfactant in the contact process. [Figure 4] A diagram for explaining the contact process. [Figure 5] A diagram showing the change in the edge filling rate when the viscosity coefficient of the liquid film is changed. [Figure 6] A diagram showing the calculation result with the horizontal axis as time / viscosity coefficient for FIG. 5. [Figure 7] A diagram showing the change in the edge filling rate when the average liquid film thickness is changed. [Figure 8] A diagram showing the relationship between the average liquid film thickness and the edge filling rate.

Embodiments for Carrying Out the Invention

[0014] 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.

[0015] [Curable composition] The curable composition (A) in the present invention is a curable composition for inkjet printing. The curable composition (A) in the present invention comprises at least a polymerizable compound component (a), a photopolymerization initiator component (b), and a solvent component (d), and may also comprise a surfactant component (c) and other components (e). In this specification, the non-volatile composition (A') is defined as the composition of the curable composition (A) excluding component (d).

[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] Examples of such polymerizable compounds include radical polymerizable compounds. The polymerizable compound that is component (a) may consist of only one type of polymerizable compound, or it may consist of multiple types (one or more types) of polymerizable compounds.

[0019] Examples of radical polymerizable compounds include (meth)acrylic compounds, styrene compounds, vinyl compounds, allyl compounds, fuma compounds, and maleyl compounds.

[0020] (Meth)acrylic compounds are 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,

[0021] 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, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, Epoxy Ester M-600A, POB-A, OPP-EA (all manufactured by Kyoeisha Chemical), 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)

[0022] 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

[0023] 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)

[0024] 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.

[0025] 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.

[0026] 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.)

[0027] In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0028] Examples of acrylic compounds include, but are not limited to, the following: Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, diallyl phthalate

[0029] 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

[0030] 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

[0031] 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.)

[0032] 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.

[0033] 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).

[0034] 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.

[0035] 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).

[0036] 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.

[0037] <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 (1) holds true. V∝N / (Nc-No) Equation (1)

[0038] Here, N / (Nc - No) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, in U.S. Patent Application Publication No. 2020 / 0286740, a technique for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP is disclosed.

[0039] According to formula (1), it is suggested that the more oxygen atoms in the molecule, or the fewer aromatic ring structures and alicyclic ring structures, the larger the OP and the faster the dry etching rate of the organic compound.

[0040] Among the curable composition (A) in the present invention, the OP of component (a) is 1.80 or more and 4.00 or less. The OP of component (a) is more preferably 2.00 or more and 3.50 or less, and particularly preferably 2.40 or more and 3.00 or more. By setting the OP of component (a) to 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. Also, by setting the OP of component (a) to 1.80 or more, after processing the underlying layer using the cured film of the curable composition (A), it becomes easy to remove the cured film of the curable composition (A). When component (a) is composed of a plurality of types of polymerizable compounds a1, a2, ···, a n in the case, as shown in the following formula (2), OP is calculated as a weighted average value based on the molar fraction (molar fraction weighted average value). Thus, when component (a) contains one or more types of polymerizable compounds, the OP of component (a) is the molar fraction weighted average value of the N / (N C -N O ) values of each molecule of one or more types of polymerizable compounds.

[0041]

Number

[0042] Here, OP n is the OP of component a n and n n is the molar fraction of component a n in the whole component (a).

[0043] 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.

[0044] <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.

[0045] Examples of cyclic structures include aromatic structures, aromatic heterocyclic structures, and alicyclic structures.

[0046] 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

[0047] 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.

[0048] 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

[0049] 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

[0050] Specific examples of polymerizable compounds (a-1) having a boiling point of 250°C or higher include, but are not limited to, the following.

[0051] 3-Phenoxybenzylacrylate (mPhOBzA, OP2.54, boiling point 367.4℃, vapor pressure 0.0004mmHg at 80℃, molecular weight 254.3),

[0052] [ka]

[0053] 1-Naphthyl acrylate (NaA, OP2.27, boiling point 317°C, vapor pressure 0.0422 mmHg at 80°C, molecular weight 198),

[0054] [ka]

[0055] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2℃, vapor pressure at 80℃ 0.0006 mmHg, molecular weight 268.3),

[0056] [ka]

[0057] 1-Naphthylmethyl acrylate (Na1MA, OP2.33, boiling point 342.1℃, vapor pressure 0.042 mmHg at 80℃, molecular weight 212.2),

[0058] [ka]

[0059] 2-Naphthylmethyl acrylate (Na2MA, OP2.33, boiling point 342.1℃, vapor pressure 0.042 mmHg at 80℃, molecular weight 212.2)

[0060] [ka]

[0061] DPhPA (OP2.38, boiling point 354.5°C, vapor pressure 0.0022 mmHg at 80°C, molecular weight 266.3), as shown in the following formula,

[0062] [ka]

[0063] The following formula shows PhBzA (OP2.29, boiling point 350.4℃, vapor pressure at 80℃ 0.0022mmHg, molecular weight 238.3),

[0064] [ka]

[0065] FLMA (OP2.20, boiling point 349.3°C, vapor pressure 0.0018 mmHg at 80°C, molecular weight 250.3) as shown in the following formula,

[0066] [ka]

[0067] ATMA (OP2.13, boiling point 414.9°C, vapor pressure 0.0001 mmHg at 80°C, molecular weight 262.3), as shown in the following formula,

[0068] [ka]

[0069] The following formula represents DNaMA (OP2.00, boiling point 489.4°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 338.4),

[0070] [ka]

[0071] BPh44DA (OP2.63, boiling point 444°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3), as shown in the following formula,

[0072] [ka]

[0073] BPh43DA (OP2.63, boiling point 439.5℃, vapor pressure <0.0001mmHg at 80℃, molecular weight 322.3), as shown in the following formula,

[0074] [ka]

[0075] The following formula shows DPhEDA (OP2.63, boiling point 410°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 322.3),

[0076] [ka]

[0077] The following formula shows BPMDA (OP2.68, boiling point 465.7°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 364.4),

[0078] [ka]

[0079] Na13MDA (OP2.71, boiling point 438.8°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 296.3), as shown in the following formula,

[0080] [ka]

[0081] The following formula (a-1-1) (OP2.40, boiling point 333.4℃, vapor pressure at 80℃ 0.0181mmHg, molecular weight 199.2),

[0082] [ka]

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

[0084] [ka]

[0085] 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),

[0086] [ka]

[0087] The following formula (a-1-4) (OP2.85, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0088] [ka]

[0089] The following formula (a-1-5) (OP2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001 mmHg, molecular weight 296.3),

[0090] [ka]

[0091] The following formula (a-1-6) (OP2.87, boiling point 421.0℃, vapor pressure at 80℃ <0.0001 mmHg, molecular weight 338.4),

[0092] [ka]

[0093] The following formula (a-1-7) (OP2.87, boiling point 465.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4),

[0094] [ka]

[0095] The following formula (a-1-8) (OP2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4),

[0096] [ka]

[0097] The following formula (a-1-9) (OP2.50, boiling point 433.1℃, vapor pressure at 80℃ <0.0001 mmHg, molecular weight 320.3),

[0098] [ka]

[0099] The following formula (a-1-10) (OP2.64, boiling point 468.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 326.4),

[0100] [ka]

[0101] The following formula (a-1-11) (OP3.25, boiling point 553.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 358.4),

[0102] [ka]

[0103] The following formula (a-1-12) (OP2.63, boiling point 443.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.4),

[0104] [ka]

[0105] The following formula (a-1-13) (OP2.89, boiling point 509.3℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 406.4),

[0106] [ka]

[0107] The following formula (a-1-14) (OP2.63, boiling point 450.0℃, vapor pressure at 80℃ <0.0001 mmHg, molecular weight 322.4),

[0108] [ka]

[0109] The following formula (a-1-15) (OP3.00, boiling point 476.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 366.4)

[0110] [ka]

[0111] The following formula (a-1-16) (OP2.68, boiling point 447.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4)

[0112] [ka]

[0113] The following formula (a-1-17) (OP2.36, boiling point 543.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 398.5),

[0114] [ka]

[0115] The following formula (a-1-18) (OP3.27, boiling point 526.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 396.4),

[0116] [ka]

[0117] The following formula (a-1-19) (OP2.71, boiling point 333.7℃, vapor pressure at 80℃ 0.0302 mmHg, molecular weight 244.3),

[0118] [ka]

[0119] The following formula (a-1-20) (OP2.73, boiling point 333.7℃, vapor pressure at 80℃ 0.0134mmHg, molecular weight 258.3),

[0120] [ka]

[0121] The following formula (a-1-21) (OP2.71, boiling point 319.2℃, vapor pressure at 80℃ 0.0566 mmHg, molecular weight 262.3),

[0122] [ka]

[0123] The following formula (a-1-22) (OP2.71, boiling point 336.9℃, vapor pressure at 80℃ 0.0055mmHg, molecular weight 244.3),

[0124] [ka]

[0125] The following formula (a-1-23) (OP3.00, boiling point 370.9℃, vapor pressure at 80℃ 0.0021mmHg, molecular weight 274.4),

[0126] [ka]

[0127] The following formula (a-1-24) (OP3.00, boiling point 376.4℃, vapor pressure at 80℃ 0.0005mmHg, molecular weight 274.4),

[0128] [ka]

[0129] The following formula (a-1-25) (OP3.00, boiling point 379.4℃, vapor pressure at 80℃ 0.0002mmHg, molecular weight 288.4),

[0130] [ka]

[0131] The following formula (a-1-26) (OP2.33, boiling point 360.8℃, vapor pressure at 80℃ 0.0006mmHg, molecular weight 252.3),

[0132] [ka]

[0133] The following formula (a-1-27) (OP2.54, boiling point 371.5℃, vapor pressure at 80℃ 0.0003mmHg, molecular weight 254.3),

[0134] [ka]

[0135] The following formula (a-1-28) (OP2.57, boiling point 381.2℃, vapor pressure at 80℃ 0.0001mmHg, molecular weight 268.3),

[0136] [ka]

[0137] The following formula (a-1-29) (OP2.57, boiling point 381.8℃, vapor pressure at 80℃ 0.0004mmHg, molecular weight 268.3),

[0138] [ka]

[0139] The following formula (a-1-30) (OP2.50, boiling point 487.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 374.4),

[0140] [ka]

[0141] The following formula (a-1-31) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0142] [ka]

[0143] The following formula (a-1-32) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0144] [ka]

[0145] The following formula (a-1-33) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0146] [ka]

[0147] The following formula (a-1-34) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0148] [ka]

[0149] The following formula (a-1-35) (OP2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0150] [ka]

[0151] The following formula shows mXDA (OP3.20, boiling point 335.9°C, vapor pressure 0.0043 mmHg at 80°C, molecular weight 246.26, viscosity 13 mPa·s at 23°C),

[0152] [ka]

[0153] The following formula shows PhEDA (OP3.20, boiling point 327.8°C, vapor pressure 0.0057 mmHg at 80°C, molecular weight 246.26, viscosity 23 mPa·s at 23°C),

[0154] [ka]

[0155] The following formula shows PhPDA (OP3.18, boiling point 339.7°C, vapor pressure 0.0017 mmHg at 80°C, molecular weight 260.29, viscosity 38 mPa·s at 23°C),

[0156] [ka]

[0157] Na26MDA (OP2.71, boiling point °C, vapor pressure mmHg at 80°C, molecular weight 296.32, viscosity 117 mPa·s at 23°C), as shown in the following formula,

[0158] [ka]

[0159] The following formula represents TMD47DA (OP3.38, boiling point 365.4℃, vapor pressure 0.0035mmHg at 80℃, molecular weight 334.4, viscosity 20mPa·s at 23℃),

[0160] [ka]

[0161] The following formula shows NDODA (OP3.91, boiling point 322.2℃, vapor pressure 0.0174 mmHg at 80℃, molecular weight 268.35, viscosity 8 mPa·s at 23℃),

[0162] [ka]

[0163] DDODA (OP3.83, boiling point 338.5℃, vapor pressure 0.00067mmHg at 80℃, molecular weight 282.38, viscosity 9mPa·s at 23℃), as shown in the following formula,

[0164] [ka]

[0165] DA1 (molecular weight 258.27) is shown in the following formula.

[0166] [ka]

[0167] DA2 (molecular weight 268.35) is shown in the following formula.

[0168] [ka]

[0169] DA3 (molecular weight 252.31) is shown in the following formula.

[0170] [ka]

[0171] DA4 (molecular weight 250.29) is shown in the following formula.

[0172] [ka]

[0173] DA5 (molecular weight 262.31) as shown in the following formula,

[0174] [ka]

[0175] DA6 (molecular weight 252.31) as shown in the following formula,

[0176] [ka]

[0177] DA7 (molecular weight 252.31) is shown in the following formula.

[0178] [ka]

[0179] DA8 (molecular weight 252.31) is shown in the following formula.

[0180]

Chem.

[0181] DA9 (molecular weight 304.39) shown in the following formula,

[0182]

Chem.

[0183] MA1 (molecular weight 236.27) shown in the following formula,

[0184]

Chem.

[0185] MA2 (molecular weight 238.29) shown in the following formula,

[0186]

Chem.

[0187] <Compound (a-2): A polymerizable compound containing at least a Si atom> The polymerizable compound (a) in the present invention may contain a polymerizable compound (a-2) containing at least a Si atom. Further, when the polymerizable compound (a) contains the polymerizable compound (a-2), it is preferable that the curable composition (A) in a state where the solvent (d) is removed contains Si atoms of 10% by weight or more with respect to the whole of such curable composition (A).

[0188] An example of a polymerizable compound (a-2) containing at least one Si atom may be linear or branched. For example, a cyclic siloxane compound may have the structure shown below. A polymerizable functional group in group Q may be, for example, a radical polymerizable functional group. Specifically, radical polymerizable functional groups include (meth)acrylic group, (meth)acrylamide group, vinylbenzene group, allyl ether group, vinyl ether group, and maleimide group. Group Q having a polymerizable functional group may be any group having one of the polymerizable functional groups described above.

[0189] [ka]

[0190] Examples of polymerizable compounds (a-2) include, for example, the silsesquioxane skeleton shown in the following chemical formula (I), and the silicone skeleton shown in the following chemical formula (II). 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 alkyl groups, cycloalkyl groups, alkoxy groups, phenyl groups, and hydroxyl groups having 1 to 6 carbon atoms, t is an integer from 1 to 3, and at least one of A and B is a polymerizable functional group.

[0191] [ka]

[0192] [ka]

[0193] Examples of the polymerizable functional groups in the groups Q, A, and B having a coincident functional group include, for example, radical polymerizable functional groups. Specific examples of the radical polymerizable functional group include (meth)acrylate compounds, (meth)acrylamide compounds, vinylbenzene compounds, allyl ether compounds, vinyl ether compounds, and maleimide compounds. The group Q having a polymerizable functional group may be any group having the above-described polymerizable functional group.

[0194] The silicon-containing (meth)acrylate compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of the monofunctional (meth)acrylate compound having one silicon-containing acryloyl group or methacryloyl group include, but are not limited to, the following. (2-Acryloylethoxy)trimethylsilane, N-(3-Acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, Acryloxymethyltrimethoxysilane, (Acryloxymethyl)phenethyltrimethoxysilane, Acryloxymethyltrimethylsilane, (3-Acryloxypropyl)dimethylmethoxysilane, (3-Acryloxypropyl)methylbis(trimethylsiloxy)silane, (3-Acryloxypropyl)methyldichlorosilane, (3-Acryloxypropyl)methyldiethoxysilane, (3-Acryloxypropyl)methyldimethoxysilane, (3-Acryloxypropyl)trichlorosilane, (3-Acryloxypropyl)trimethoxysilane, (3-Acryloxypropyl)tris(trimethylsiloxy)silane, Acryloxytriisopropylsilane, Acryloxytrimethylsilane, Methacryloxymethyltrimethoxysilane, 0-(methacryloxyethoxy)carbamoylpropylmethyldimethoxysilane, (methacryloxymethyl)bis(trimethylsiloxy)methylsilane, N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)methyldiethoxysilane, Methacryloxymethyltriethoxysilane, Methacryloxypropyltrimethoxysilane, Methacryloylpropyltriisopropoxysilane, 0-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate, Methacryloxypropylmethyldimethoxysilane, Methacryloxypropylmethyldiethoxysilane, Methacryloxypropyldimethylmethoxysilane, Methacryloxypropyldimethylethoxysilane, (methacryloxymethyl)dimethylethoxysilane, Methacryloxypropyltriethoxysilane, Methacryloxypropyl 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

[0195] 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)

[0196] 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

[0197] 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)

[0198] 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

[0199] 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)

[0200] 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.

[0201] The proportion of component (a) in the curable composition (A) is preferably 40% to 99% by weight relative to the mass of component (A'). More preferably, the proportion of component (a) in the curable composition (A) is 50% to 95% by weight relative to the mass of component (A'), 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), (c), and (e) 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).

[0202] [ka]

[0203] 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.

[0204] Polymers having polymerizable functional groups are typically compounds with a weight-average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. There is no specific upper limit for the weight-average molecular weight, but for example, 50,000 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).

[0205] 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.

[0206] 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.

[0207] <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.

[0208] 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;

[0209] 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)

[0210] 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.

[0211] 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 mass of component (A'). 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 mass of component (A'). By increasing 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 increasing 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.

[0212] <Ingredients (c): Surfactants> Component (c) is a surfactant. In this specification, a surfactant is a compound that reduces the interfacial bonding force between the mold and the curable composition, that is, reduces the release force in the mold release step described later. As the surfactant, you can use surfactants such as silicone-based surfactants, fluorine-based surfactants and hydrocarbon-based surfactants. Component (c) may be used alone or as a mixture of two or more types.

[0213] Fluorine-based surfactants include the following: Polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having perfluoroalkyl groups, and polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers.

[0214] Furthermore, fluorinated surfactants may have hydroxyl groups, alkoxy groups, alkyl groups, amino groups, thiol groups, etc., in part of their molecular structure (for example, terminal groups). Examples include pentadecaethylene glycol mono-1H,1H,2H,2H-perfluorooctyl ether.

[0215] Commercially available fluorinated surfactants may be used. Examples of commercially available fluorinated surfactants include the following: Megafac® F-444, TF-2066, TF-2067, TF-2068, abbreviated DEO-15 (all manufactured by DIC), Florard FC-430, FC-431 (all manufactured by Sumitomo 3M), Surflon® S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all manufactured by Tochem Products), PF-636, PF-6320, PF-656, PF-6520 (all manufactured by OMNOVA Solutions), Unidyne® DS-401, DS-403, DS-451 (all manufactured by Daikin Industries), Futergent® 250, 251, 222F, 208G (all manufactured by Neos)

[0216] Furthermore, surfactant (c) may be a hydrocarbon surfactant. Examples of hydrocarbon surfactants include alkyl alcohol polyalkylene oxide adducts and polyalkylene oxides, which are obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms.

[0217] Examples of alkyl alcohol polyalkylene oxide adducts include the following: Methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide / propylene oxide adduct

[0218] Furthermore, the terminal group of an alkyl alcohol polyalkylene oxide adduct is not simply limited to a hydroxyl group that can be produced by adding a polyalkylene oxide to an alkyl alcohol. Such a hydroxyl group may be substituted with other substituents, such as polar functional groups like carboxyl groups, amino groups, pyridyl groups, thiol groups, or silanol groups, or hydrophobic functional groups like alkyl groups or alkoxy groups.

[0219] Examples of polyalkylene oxides include the following: Polyethylene glycol, polypropylene glycol, their mono or dimethyl ethers, mono or dioctyl ethers, mono or dinonyl ethers, mono or didecyl ethers, monoadipic acid esters, monooleic acid esters, monostearate esters, monosuccinate esters

[0220] Commercially available alkyl alcohol polyalkylene oxide adducts may be used. Examples of commercially available alkyl alcohol polyalkylene oxide adducts include the following: Polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Oil & Fat Industry Co., Ltd., polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310) manufactured by Aoki Oil & Fat Industry Co., Ltd., polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oil & Fat Industry Co., Ltd., polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Oil & Fat Industry Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), random polymerization type polyoxyethylene polyoxypropylene alkyl ethers from Aoki Oil & Fat Industry (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R, WONDERSURF 140, FineSurf TDP-0633K), polyoxyethylene methyl ether from BASF (Pluriol® A760E), polyoxyethylene alkyl ethers from Kao (Emulgen series), polyoxypropylene-polyoxypropylene block polymers from ADEKA (Pluronic® L-44, L-43, L-42, L-31, 17R2, 25R1), polyoxyethylene alkyl ethers from DOW (Briji S10), polyoxyethylene alkyl ethers from Aoki Oil & Fat Industry (BLAUNON EN-1504, EL-1502.Polyoxypropylene polyoxyethylene 2-ethylhexyl ether (TERGITOL EH-9, EH-6, EH-3) manufactured by DOW, polyoxyethylene 2-ethylhexyl ether (BLAUNON EH-2, EH-4) manufactured by Aoki Oil & Fat Industry, polyethylene glycol trimethylnonyl ether (TERGITOL HW-1000, TMN-3) manufactured by DOW, polyoxyethylene tert-octylphenyl ether (TRITON® X-15, X-45) manufactured by DOW, ethoxylated acetylene diol (Dynol-604) manufactured by Evonik, acetylenol E100, E13T) manufactured by Kawaken Fine Chemical, and Surfinol SE, 420 manufactured by Nisshin Chemical.

[0221] Furthermore, commercially available polyalkylene oxides may be used, such as BASF's ethylene oxide-propylene oxide copolymer (Pluronic PE6400).

[0222] Examples of silicone-based surfactants include the following: for example, the SI-10 series (manufactured by Takemoto Oil & Fat Co., Ltd.), Megafac Paintad 31 (manufactured by Dainippon Ink and Chemicals, Inc.), and KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0223] Furthermore, the surfactant may contain at least both fluorine atoms and silicon atoms. Examples of surfactants containing both fluorine atoms and silicon atoms include the following: Product names X-70-090, X-70-091, X-70-092, X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), Product names Megafaac R-08, XRB-4 (both manufactured by Dainippon Ink and Chemicals, Inc.)

[0224] As a result of diligent research, the inventors of the present invention have found that, as described later, component (c) segregates at the edges of the liquid film of the curable composition (A), causing the edges of the liquid film to become specifically more viscous and reducing the edge filling speed. Therefore, the viscosity of surfactant (c) in the present invention is preferably 500 mPa·s or less, more preferably 400 mPa·s or less, and even more preferably 300 mPa·s or less at 23°C and 1 atm. As shown in Figure 3, in the interface region 111 near the interface between the liquid film and the atmospheric gas, the concentration (c) increases due to the action of the surfactant, i.e., surfactant (c) is unevenly distributed. Here, if the viscosity of surfactant (c) is greater than 500 mPa·s, the fluidity of the liquid in this interface region 111 becomes relatively low. For this reason, when the non-volatile composition (A') after the solvent (d) has evaporated is brought into contact with the mold, the edge filling speed slows down. Therefore, by using the curable composition (A) of this embodiment to which a surfactant (c) with a viscosity of 500 mPa·s or less is applied, the imprint process can be carried out with high throughput.

[0225] The surfactants (c) that have a pressure of 500 mPa·s or less at 23℃ and 1 atm include ADEKA's Pluronic L-44 (435.4 mPa·s), ADEKA's Pluronic 17R2 (407.1 mPa·s), Aoki Oil & Fat Industry's WONDERSURF140 (146.6 mPa·s), Aoki Oil & Fat Industry's Brownon SA-50 / 50 1000R (114.6 mPa·s), Aoki Oil & Fat Industry's Brownon SA-30 / 70 2000R (217.0 mPa·s), Dow's TERGITOL EH-9 (101.8 mPa·s), Dow's TERGITOL HW-1000 (41.2 mPa·s), Dow's TERGITOL TMN-3 (22.4 mPa·s), and Dow's TRITON (registered trademark). X-45 (374.0 mPa·s), Evonik Dynol-604 (340.45 mPa·s), Kawaken Fine Chemical Acetylenel E100 (171.3 mPa·s), Nisshin Chemical Surfinol 420 (295.6 mPa·s), and Kawaken Fine Chemical Acetylenel E13T (295.6 mPa·s) can be used.

[0226] The blending ratio of component (c) in the curable composition (A) is preferably 0.01% by weight or more and 10% by weight or less relative to the mass of component (A'). Furthermore, the blending ratio of component (c) in the curable composition (A) is more preferably 0.1% by weight or more and 5% by weight or less, and even more preferably 0.5% by weight or more and 3% by weight or less, relative to the mass of component (A'). By setting the blending ratio of component (c) to 0.01% by weight or more, the interfacial bonding force between the mold and the curable composition is reduced, and the release force in the release process described later is reduced. In addition, by setting the blending ratio of component (c) to 10% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0227] <Component (e): Non-polymerizable compound> In addition to components (a), (b), and (c) described above, the curable composition (A) in the present invention may further contain a non-polymerizable compound as component (e), to the extent that it does not impair the effects of the present invention, depending on the purpose. Examples of such component (e) 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, antioxidants, polymer components, and other additives. Component (e) may contain multiple types of the compounds described above.

[0228] 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.

[0229] 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

[0230] 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.

[0231] 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.

[0232] 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.

[0233] The blending ratio of component (e) in the curable composition (A) is preferably 0.01% by weight or more and 50% by weight or less relative to the mass of component (A'). Furthermore, the blending ratio of component (e) in the curable composition (A) is more preferably 0.01% by weight or more and 50% by weight or less relative to the mass of component (A'), and even more preferably 0.01% by weight or more and 20% by weight or less. By setting the blending ratio of component (e) to 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0234] <Component (d): Solvent> The curable composition (A) in the present invention may contain, as component (d), a solvent having a boiling point of 100°C or higher and less than 250°C under normal pressure. Component (d) can be a solvent in which components (a), (b), (c), and (e) dissolve, such as an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, or a nitrogen-containing solvent. Component (d) can be used alone or in combination of two or more types. The boiling point of component (d) under normal pressure should be 100°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of component (d) under normal pressure should be less than 250°C, preferably less than 200°C. If the boiling point of component (d) at atmospheric pressure is less than 100°C, the evaporation 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 evaporation of solvent (d) will be insufficient in the waiting step described later, potentially leaving residual component (d) in the cured product of curable composition (A). Here, if component (d) contains one or more solvents, the boiling points of each of these solvents at atmospheric pressure should ideally be between 100°C and 250°C (for example, between 100°C and 200°C).

[0235] 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.

[0236] 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

[0237] 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

[0238] 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

[0239] 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

[0240] 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.

[0241] Furthermore, the following are even more desirable: Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol acetate monomethyl ether, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether

[0242] Furthermore, propylene glycol monomethyl ether acetate is particularly preferred. Ethyl)isocyanurate di(meth)acrylate is also a good example.

[0243] 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, these are solvents selected individually or in mixtures thereof from propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate.

[0244] 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). Examples of polymerizable compounds having a boiling point of 80°C or higher and less than 250°C under normal pressure include the following: Cyclohexyl acrylate (boiling point 198°C), benzyl acrylate (boiling point 229°C), isobornyl acrylate (boiling point 245°C), tetrahydrofurfuryl acrylate (boiling point 202°C), trimethylcyclohexyl acrylate (boiling point 232°C), isooctyl acrylate (boiling point 217°C), n-octyl acrylate (boiling point 228°C), ethoxyethoxyethyl acrylate (boiling point 230°C), divinylbenzene (boiling point 193°C), 1,3-diisopropenylbenzene (boiling point 218°C), styrene (boiling point 145°C), α-methylstyrene (boiling point 165°C)

[0245] 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.

[0246] <Temperature when compounding the curable composition> When preparing the curable composition (A) in the present invention, at least components (a), (b), (c), 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 (e).

[0247] <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.

[0248] As a result of diligent research, the inventors of the present invention have found that the viscosity of the non-volatile composition dominantly determines the edge filling speed. Therefore, the viscosity of the non-volatile composition (A') in the present invention is preferably 8 mPa·s or more and 70 mPa·s or less at 23°C and 1 atm. Furthermore, the viscosity of the non-volatile composition (A') at 23°C and 1 atm is more preferably 8 mPa·s or more and 30 mPa·s or less, and even more preferably 8 mPa·s or more and 20 mPa·s or less. Note that if the viscosity is greater than 70 mPa·s, the fluidity of the non-volatile composition (A') is low, and therefore the edge filling speed is slow when the non-volatile composition (A') is brought into contact with the mold. Therefore, by using the curable composition (A) of the present invention in which the viscosity of the non-volatile composition (A') is adjusted to 70 mPa·s or less, the imprint process can be carried out with high throughput.

[0249] <Surface tension of curable compositions> Regarding the surface tension γ1 of the non-volatile composition (A') in the present invention, 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 excluding 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 non-volatile composition (A') is brought into contact with the mold, filling (spreading and filling) is completed in a short time. In addition, by setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition becomes a cured film with a smooth surface.

[0250] <Contact angle of curable composition> In the present invention, the contact angle of the curing composition (A) is preferably 0° or more and 90° or less with respect to the surface of the substrate. If the contact angle is greater than 90°, the droplets on the substrate will not come into contact with each other, and a continuous liquid film cannot be formed.

[0251] In this invention, the contact angle of the non-volatile composition (A') is preferably 0° to 90° with respect to both the surface of the substrate and the surface (contact 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 non-volatile composition (A') from filling the mold. The smaller the contact angle, the stronger the capillary forces, resulting in a faster filling speed.

[0252] <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), (e), and (d) described above. Therefore, the curable composition (A) in the present invention is preferably obtained through a purification process. Such a purification process may include filtration using a filter.

[0253] For filtration using a filter, it is preferable to mix components (a), (b), (c), and (e) as described above, and then filter the mixture 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 through 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.

[0254] 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.

[0255] <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 strong 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 of non-volatile composition (A') is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0256] 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).

[0257] [substrate] In this specification, a component on which droplets of the curable composition (A) are discretely dropped is described as a substrate.

[0258] 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 of the substrate or the layer to be processed to the curable composition (A) by surface treatment such as silane coupling treatment, silazane treatment, or deposition of an organic thin film. As a specific example of the organic thin film deposited as a surface treatment, for example, the adhesion layer described in Japanese Patent Publication No. 2009-503139 can be used.

[0259] [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 a nanoimprint method. The film formation method in the present invention uses a photoimprint 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.

[0260] 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.

[0261] <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 materials are arranged at the above density. A substrate 101 may be a substrate with a laminated underlayer. Furthermore, the surface of the substrate 101 may have improved adhesion to the curable composition (A) through surface treatment such as silane coupling treatment, silazane treatment, or deposition of an organic thin film.

[0262] 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.

[0263] To define the volume of the non-volatile composition (A') to be placed, an index called the average liquid film thickness is defined. The average liquid film thickness is the value obtained by dividing the volume of the non-volatile composition (A') placed in the placement process by the area of ​​the film formation region of the mold. The volume of the non-volatile composition (A') is the sum of the volumes of individual droplets of the curable composition (A) after the solvent (d) has evaporated. According to this definition, the average liquid film thickness can be defined regardless of the surface irregularities of the substrate. Here, the average liquid film thickness may be understood as the value obtained by dividing the volume of the non-volatile composition (A') remaining after the waiting process described later by the area of ​​the film formation region of the mold, and is preferably between 5 nm and 170 nm.

[0264] <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).

[0265] Referring to Figures 2(a) to 2(d), the flow behavior of droplets of the curable composition (A) placed on the substrate during the waiting process will be explained. As shown in Figure 2(a), droplets 102 of the curable composition (A) are discretely arranged on the substrate 101, and as shown in Figure 2(b), each droplet 102 gradually expands on the substrate. Then, as shown in Figure 2(c), the droplets of the curable composition (A) on the substrate begin to combine to form a liquid film, and as shown in Figure 2(d), it becomes a continuous liquid film (the surface of the substrate 101 is covered with the curable composition (A), and there are no exposed surfaces). The state of the curable composition (A) as shown in Figure 2(d) is referred to as a "substantially continuous liquid film".

[0266] 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.

[0267] 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.

[0268] 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.

[0269] During the waiting process, when solvent (d) evaporates, a substantially continuous liquid film 104 of the non-volatile composition (A') consisting of components (a), (b), (c), and (e) remains. The average 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 over its entire surface by a substantially continuous liquid film 104 of the curable composition (A) from which solvent (d) has been removed.

[0270] <Contact process> In the contact step, as schematically shown in Figure 1(e), a substantially continuous liquid film 104 of the curable composition (A), i.e., the non-volatile 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 non-volatile 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 non-volatile 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.

[0271] In this invention, during the waiting step, the curable composition (A) becomes a substantially continuous liquid film 104 of the non-volatile composition (A') from which the solvent (d) has been removed, thus reducing the volume of gas trapped between the mold 106 and the substrate 101. Therefore, the spreading of the non-volatile composition (A') in the contact step is completed quickly.

[0272] If the spreading and filling of the non-volatile composition (A') is completed quickly during the contact process, the time that the mold 106 is in contact with the non-volatile 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.

[0273] In this invention, the time required to maintain the mold 106 in contact with the non-volatile composition (A') during the contact process (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 (throughput). 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, edge filling becomes insufficient, and defects called unfilled edges occur frequently. Therefore, by using the non-volatile composition (A') in this invention, the imprint process can be carried out with high productivity (throughput).

[0274] 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.

[0275] 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.

[0276] 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, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0277] In the contact process, the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the non-volatile 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 non-volatile 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.

[0278] 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 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 disappears quickly (see Japanese Patent Publication No. 2022-99271). In this case, it is preferable that the curable composition has a solubility coefficient of carbon dioxide of 0.5 kg / m3·atm or more and 10 kg / m3·atm or less. When performing a contact process under a specific gas atmosphere, including an atmospheric atmosphere, the preferred pressure is between 0.0001 atmospheres and 10 atmospheres.

[0279] <Curing process> In the curing process, as schematically shown in Figure 1(f), the non-volatile composition (A') is cured by irradiating it with irradiation light 107 as curing energy, thereby forming a cured film. In the curing process, for example, the irradiation light 107 is irradiated onto the non-volatile composition (A') through the mold 106. More specifically, the irradiation light 107 is irradiated onto the non-volatile composition (A') filled in the fine pattern of the mold 106 through the mold 106. As a result, the non-volatile composition (A') filled in the fine pattern of the mold 106 hardens, becoming a cured film 108 having a pattern.

[0280] The irradiation light 107 is selected according to the sensitivity wavelength of the non-volatile 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.

[0281] <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.

[0282] 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.

[0283] <Repeat> By a series of steps (manufacturing process) including the above-described placement step followed by the mold release step, a cured film having a desired uneven pattern shape (a pattern shape that follows the uneven shape of the mold 106) at a desired position can be obtained.

[0284] 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.

[0285] [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 non-volatile composition (A') into contact with the mold. The curing step is a step of curing the non-volatile composition (A'). The release step is a step of separating the mold from the cured film of the non-volatile 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.

[0286] [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.

[0287] 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.

[0288] 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.

[0289] 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.

[0290] 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. [Examples]

[0291] To supplement the embodiments described above, more specific examples will be explained.

[0292] (Example 1) When a mixture of a curable composition and a surfactant comes into contact with an atmospheric gas, the surfactant, which is highly hydrophobic and has a low SP value, segregates within a few nanometers near the atmospheric gas interface. The amount of segregation can be determined by applying Florey-Huggins' theory to the mixture of the curable composition, surfactant, and air, and calculating the distribution of substances when the free energy of the mixture is minimized. The distribution of substances is determined by the relative SP values ​​of the curable composition, surfactant, and air. For example, the SP value of air is 10, the SP value of the hydrophobic portion of the surfactant Surfinol is 13.8, and the SP value of the hydrophobic portion of the polymerizable compound tricyclodecanedimethanol diacrylate is 15.8. Therefore, surfactants with similar SP values ​​segregate at the air interface.

[0293] (Example 2) In this embodiment, we show that the edge filling rate v is given by (Equation 1) using the non-volatile composition viscosity μ (mPa·s) of the curable composition and the average liquid film thickness h (m) of the curable composition. (Formula 1) v(μ,h)=C×h^α×μ0 / μ,C=9.75e-2,α=0.489,μ0=50(mPa·s)

[0294] In this example, assuming a contact process, the edge filling rate was determined by solving a simultaneous equation of the Navier-Stokes equations (approximated as a thin film sandwiched between walls) and the equation for the elastic deformation of the mold. Figure 4 shows the configuration of the calculation domain. 106 is the mold, 102 is the liquid film, 101 is the substrate, 1049 is the edge of the pattern formation region, and 110 is the initial position of the liquid film edge. The x and y axes are taken as shown in the figure. The negative x-axis ends are assumed to be symmetrical boundaries, and the direction perpendicular to the plane of the paper in Figure 4 is assumed to be symmetrical, and the calculation was approximated as a two-dimensional problem.

[0295] The mold was assumed to be a linearly elastic material, with a Young's modulus of 72 GPa and a Poisson's ratio of 0.17. The surface tension coefficient of the liquid film was set to 30 mN / m. As shown in Figure 4, the initial conditions for the average liquid film thickness were uniform, and the distance between points 110 and 109 was set to 100 μm. In the case of A05, the gap between the mold and the substrate was filled with the liquid film in the negative x-axis direction, and there was no gap between the liquid film and the mold. Also, in A05, the liquid film was in contact with the mold and the substrate at a contact angle of 0°. The experiment started from a stationary state. The numerical calculation method shown in this embodiment is merely one example, and other calculation methods can also be used.

[0296] Figure 5 shows the change in edge filling speed when the viscosity coefficient of the liquid film is varied, with an average liquid film thickness of 40 nm. In Figure 5, the horizontal axis is time, and the vertical axis is the distance between the liquid film edge and the edge. Note that the downward direction on the vertical axis is positive. B01, B02, and B03 correspond to the results when the liquid film thickness is 50, 150, and 300 mPa·s, respectively. From this, it can be seen that the lower the viscosity, the faster the edge filling speed. Figure 6 shows the same calculation results, but with the horizontal axis as time / viscosity coefficient. As shown in C01, it can be seen that they overlap on the same curve. This means that the edge filling speed is inversely proportional to the viscosity coefficient. Thus, it has been shown that the flow speed of the liquid film is inversely proportional to the viscosity coefficient.

[0297] Figure 7 shows the change in edge filling speed when the average liquid film thickness is varied, while the viscosity coefficient of the liquid film is 50 mPa·s. In Figure 7, the horizontal axis is time, and the vertical axis is the distance between the edge of the liquid film and the edge. Note that the downward direction is positive on the vertical axis. D01, D02, D03, D04, and D05 correspond to the results when the average liquid film thickness is 1000, 200, 100, 80, and 40 nm, respectively. From this, it can be seen that the thicker the average liquid film thickness, the faster the edge filling speed.

[0298] Figure 8 shows a graph with the average liquid film thickness on the horizontal axis and the edge filling rate on the vertical axis. The plots represent the calculation results, and the curve is (Equation 1). In this way, the dependence of the edge filling rate on the average liquid film thickness can be expressed using (Equation 1). Furthermore, as discussed above, since the edge filling rate is inversely proportional to the viscosity coefficient, it can be seen that the dependence on the viscosity coefficient can also be expressed by (Equation 1).

[0299] As shown above, the edge filling rate can be expressed as (Equation 1) with μ and h as variables.

[0300] Table 1 shows the viscosity measurement results for surfactant (c) at 23°C and 1 atm.

[0301] [Table 1]

[0302] Table 2 shows the viscosity and edge filling rate at 23°C and 1 atm for the non-volatile component (A') obtained by mixing components (a), (b), (e), and (d) in a total of 100% by weight of curable composition (A), and by mixing curable composition (A) without component (d). In Table 2, DCPDA is an abbreviation for tricyclodecanedimethanol diacrylate in the first component (a), DDODA is an abbreviation for 1,10-decanediol diacrylate in the second component (a), and PGMEA is an abbreviation for propylene glycol monomethyl ether in component (d). The edge filling rate was evaluated using Equation 2. The edge filling rate was evaluated using the following criteria with an average liquid film thickness of 300 nm. A: Edge filling occurs at a speed of 100 μm / sec or more. B: Edges are filled at a speed of less than 100 μm / sec.

[0303] [Table 2]

[0304] As described above, the curable composition of this embodiment can provide a curable composition with a fast edge filling speed and high productivity in the imprint process.

[0305] This specification and accompanying drawings include the following disclosures:

[0306] (Item 1) A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), The viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less. 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 the solvent (d) is less than 250°C. The viscosity of the curable composition after the solvent (d) has been removed is 8 mPa·s or more and 30 mPa·s or less at 23°C and 1 atm. A curable composition characterized by the following features.

[0307] (Item 2) A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), a surfactant (c), and a solvent (d), The viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less. 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 the solvent (d) is less than 250°C. The viscosity of the surfactant (c) at 23°C and 1 atm is 500 mPa·s or less. A curable composition characterized by the following features.

[0308] (Item 3) The viscosity of the curable composition after the solvent (d) has been removed is 8 mPa·s or more and 20 mPa·s or less at 23°C and 1 atm. A curable composition according to item 1 or 2, characterized by the above.

[0309] (Item 4) The viscosity of the surfactant (c) at 23°C and 1 atm is 400 mPa·s or less. A curable composition according to any one of items 1 to 3, characterized by the above.

[0310] (Item 5) The solvent (d) comprises one or more solvents, and the boiling point of each of the one or more solvents at 1 atmosphere is 100°C or higher and less than 250°C. A curable composition according to any one of items 1 to 4, characterized by the above.

[0311] (Item 6) The polymerizable compound (a) comprises one or more polymerizable compounds, and the boiling point of each of the one or more polymerizable compounds at 1 atmosphere is 250°C or higher. A curable composition according to any one of items 1 to 5, characterized by the above.

[0312] (Item 7) The polymerizable compound (a) comprises a monofunctional polymerizable compound and a polyfunctional polymerizable compound, and the proportion of the polyfunctional polymerizable compound in the polymerizable compound (a) is 20% by weight or more. A curable composition according to any one of items 1 to 6, characterized in that it is a curable composition according to any one of items 1 to 6.

[0313] (Item 8) The polymerizable compound (a) comprises one or more polymerizable compounds, and the molecular weight of each of the one or more polymerizable compounds is 200 or more. A curable composition according to any one of items 1 to 7, characterized by the above.

[0314] (Item 9) The polymerizable compound (a) comprises a polymer having polymerizable functional groups. A curable composition according to any one of items 1 to 8, characterized by the above.

[0315] (Item 10) The glass transition temperature of the polymerizable compound (a) after curing is 70°C or higher. A curable composition according to any one of items 1 to 9, characterized by the above.

[0316] (Item 11) The polymerizable compound (a) comprises one or more polymerizable compounds, and the vapor pressure of each of the one or more polymerizable compounds at 80°C and 1 atm is 0.001 mmHg or less. A curable composition according to any one of items 1 to 10, characterized by the above.

[0317] (Item 12) The polymerizable compound (a) includes a compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. A curable composition according to any one of items 1 to 11, characterized by the above.

[0318] (Item 13) The polymerizable compound (a) comprises one or more polymerizable compounds, The Onishi parameter (OP) of the polymerizable compound (a) is 1.80 or more and 4.00 or less, and is the mole fraction weighted average of the N / (Nc-No) values ​​of each molecule of the one or more polymerizable compounds, where N is the total number of atoms in the molecule, Nc is the number of carbon atoms in the molecule, and No is the number of oxygen atoms in the molecule. A curable composition according to any one of items 1 to 12, characterized by the above.

[0319] (Item 14) The composition obtained by removing the solvent (d) from the curable composition contains 10% by weight or more silicon atoms. A curable composition according to any one of items 1 to 13, characterized by the above.

[0320] (Item 15) The solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m³. 3 ·ATM or more 10kg / m 3 • It is less than or equal to ATM. A curable composition according to any one of items 1 to 14, characterized by the above.

[0321] (Item 16) The curable composition is a curable composition for inkjet printing. A curable composition according to any one of items 1 to 15, characterized by the above.

[0322] (Item 17) A film formation method for forming a film of a curable composition on a substrate using a mold, A placement step of discretely arranging a plurality of droplets of the curable composition described in any one of items 1 to 16 on the substrate, After the arrangement step, a contact step is performed in which the plurality of liquid droplets on the substrate and the mold are brought into contact to form a liquid film between the substrate and the mold. After the contact step, a curing step is performed to harden the liquid film and form a cured film, After the curing step, a release step is performed to release the cured film from the mold, including, A film formation method characterized by the following:

[0323] (Item 18) Between the arrangement step and the contact step, droplets of the curable composition bond together on the substrate to form a substantially continuous liquid film. Furthermore, it includes a waiting step in which the solvent contained in the liquid film is allowed to evaporate. A film formation method according to item 17, characterized by the features described herein.

[0324] (Item 19) In the waiting step, the process is continued until the solvent contained in the liquid film evaporates and the solvent content becomes 10% by volume or less of the total liquid film. A film formation method according to item 18, characterized by the features described above.

[0325] (Item 20) In the aforementioned waiting step, the substrate is heated under the conditions of 30°C to 200°C and 10 seconds to 600 seconds. A film formation method according to item 18 or 19, characterized by the features described above.

[0326] (Item 21) In the above placement step, droplets of the curable composition having a volume of 1.0 pL or more are placed on the substrate at a rate of 80 droplets / mm². 2 Arrange them at the above density. A film formation method according to any one of items 17 to 20, characterized by the features described herein.

[0327] (Item 22) The aforementioned type includes an uneven pattern on the contact surface, In the contact step, the pattern of the type and the liquid film are brought into contact. The film formation method further comprises a curing step, after the contact step, in which the liquid film is cured to form a cured film having a pattern corresponding to the pattern of the mold. A film formation method according to any one of items 17 to 21, characterized by the features described herein.

[0328] (Item 23) The aforementioned type has a contact surface that is a flat surface. In the contact step, the flat surface of the mold and the liquid film are brought into contact. The film formation method further comprises a curing step, after the contact step, in which the liquid film is cured to form a cured film having a surface that conforms to the flat surface of the mold. A film formation method according to any one of items 17 to 21, characterized by the features described herein.

[0329] (Item 24) 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 17 to 23, 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, comprising:

[0330] The present 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]

[0331] 101 circuit board 102 Droplet 103 Liquid film 104 Liquid film 105 Solvent Type 106 107 Irradiation light 108 Cured film 109 Edge of the pattern formation region 110 Initial position of the liquid film edge 111 Interface region between liquid film and atmospheric gas

Claims

1. A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d), The viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less. 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 the solvent (d) is less than 250°C. The viscosity of the curable composition after the solvent (d) has been removed is 8 mPa·s or more and 30 mPa·s or less at 23°C and 1 atm. A curable composition characterized by the following features.

2. A curable composition comprising at least a polymerizable compound (a), a photopolymerization initiator (b), a surfactant (c), and a solvent (d), The viscosity of the curable composition at 23°C and 1 atm is 1.3 mPa·s or more and 60 mPa·s or less. 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 the solvent (d) is less than 250°C. The viscosity of the surfactant (c) at 23°C and 1 atm is 500 mPa·s or less. A curable composition characterized by the following features.

3. The viscosity of the curable composition after the solvent (d) has been removed is 8 mPa·s or more and 20 mPa·s or less at 23°C and 1 atm. The curable composition according to claim 1.

4. The viscosity of the surfactant (c) at 23°C and 1 atm is 400 mPa·s or less. The curable composition according to claim 1.

5. The solvent (d) comprises one or more solvents, and the boiling point of each of the one or more solvents at 1 atmosphere is 100°C or higher and less than 250°C. The curable composition according to claim 1.

6. The polymerizable compound (a) comprises one or more polymerizable compounds, and the boiling point of each of the one or more polymerizable compounds at 1 atmosphere is 250°C or higher. The curable composition according to claim 1.

7. The polymerizable compound (a) comprises a monofunctional polymerizable compound and a polyfunctional polymerizable compound, and the proportion of the polyfunctional polymerizable compound in the polymerizable compound (a) is 20% by weight or more. The curable composition according to claim 1.

8. The polymerizable compound (a) comprises one or more polymerizable compounds, and the molecular weight of each of the one or more polymerizable compounds is 200 or more. The curable composition according to claim 1.

9. The polymerizable compound (a) comprises a polymer having polymerizable functional groups. The curable composition according to claim 1.

10. The glass transition temperature of the polymerizable compound (a) after curing is 70°C or higher. The curable composition according to claim 1.

11. The polymerizable compound (a) comprises one or more polymerizable compounds, and the vapor pressure of each of the one or more polymerizable compounds at 80°C and 1 atm is 0.001 mmHg or less. The curable composition according to claim 1.

12. The polymerizable compound (a) includes a compound (a-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure. The curable composition according to claim 1.

13. The polymerizable compound (a) comprises one or more polymerizable compounds, The Onishi parameter (OP) of the polymerizable compound (a) is 1.80 or more and 4.00 or less, and is the mole fraction weighted average of the N / (Nc-No) values ​​of each molecule of the one or more polymerizable compounds, where N is the total number of atoms in the molecule, Nc is the number of carbon atoms in the molecule, and No is the number of oxygen atoms in the molecule. The curable composition according to claim 1.

14. The composition obtained by removing the solvent (d) from the curable composition contains 10% by weight or more silicon atoms. The curable composition according to claim 1.

15. The solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m³. ３ ・ATM or more 10kg / m ３ - It is less than or equal to ATM. The curable composition according to claim 1.

16. The curable composition is a curable composition for inkjet printing. The curable composition according to claim 1.

17. A film formation method for forming a film of a curable composition on a substrate using a mold, A placement step of discretely arranging a plurality of droplets of the curable composition according to any one of claims 1 to 16 on the substrate, After the arrangement step, a contact step is performed in which the plurality of liquid droplets on the substrate and the mold are brought into contact to form a liquid film between the substrate and the mold. After the contact step, a curing step is performed to harden the liquid film and form a cured film, After the curing step, a release step is performed to release the cured film from the mold, including, A film formation method characterized by the following:

18. Between the arrangement step and the contact step, droplets of the curable composition bond together on the substrate to form a substantially continuous liquid film. Furthermore, it includes a waiting step in which the solvent contained in the liquid film is allowed to evaporate. The film formation method according to feature 17.

19. In the waiting step, the process is continued until the solvent contained in the liquid film evaporates and the solvent content is reduced to 10% by volume or less relative to the entire liquid film. The film formation method according to feature 18.

20. In the aforementioned waiting step, the substrate is heated under the conditions of 30°C to 200°C and 10 seconds to 600 seconds. The film formation method according to feature 18.

21. In the above placement step, droplets of the curable composition having a volume of 1.0 pL or more are placed on the substrate at a rate of 80 droplets / mm². ２ Arrange them at the above density. The film formation method according to feature 17.

22. The aforementioned type includes an uneven pattern on the contact surface, In the contact step, the pattern of the type and the liquid film are brought into contact. The film formation method further comprises a curing step, after the contact step, in which the liquid film is cured to form a cured film having a pattern corresponding to the pattern of the mold. The film formation method according to feature 17.

23. The aforementioned type has a contact surface that is a flat surface. In the contact step, the flat surface of the mold and the liquid film are brought into contact. The film formation method further comprises a curing step, after the contact step, in which the liquid film is cured to form a cured film having a surface that conforms to the flat surface of the mold. The film formation method according to feature 17.

24. A forming step of forming a film of a curable composition on a substrate using the film forming method described in claim 17, 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, comprising:

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