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

Abstract

The purpose of the present invention is to provide a curable composition capable of maintaining a stable state as a liquid film without overflow or shrinkage of the curable composition in a desired region.　The curable composition comprises a polymerizable compound (a), a photopolymerization initiator (b), an additive (c), and a solvent (d), the curable composition being characterized in that: the content of the solvent (d) with respect to the entirety of the curable composition is more than 5 vol.% and equal to or less than 95 vol.%; the boiling point of the solvent (d) is equal to or greater than 100 °C and less than 250 °C at 1 atmospheric pressure; the additive (c) is a compound composed of carbon, oxygen, and hydrogen or a compound composed of carbon, nitrogen, oxygen, and hydrogen; and the HLB value of the additive (c), as calculated by Griffin's method, is 2.0 to 8.4.

Description

S硬化性組成物、膜形成方法及び物品の製造方法

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

[0002] In semiconductor devices, MEMS, etc., the demand for miniaturization is increasing, and as a microfabrication technique, imprint technology (photoimprint technology) has attracted attention. In imprint technology, a mold with a fine concavo-convex pattern formed on its surface is brought into contact with a curable composition supplied (applied) onto a substrate, and the curable composition is cured in this state. Thereby, the pattern of the mold is transferred to the cured film of the curable composition, and a pattern is formed on the substrate. According to imprint technology, a fine pattern (structure) on the order of several nanometers can be formed on the substrate.

[0003] An example of a pattern forming method using imprint technology will be described. First, a liquid curable composition is discretely dropped (arranged) onto a pattern forming region on a substrate. The droplets of the curable composition arranged in the pattern forming region spread on the substrate. Such a phenomenon is called presspread. Next, a mold is brought into contact with (pressed against) the curable composition on the substrate. As a result, the droplets of the curable composition spread over the entire gap between the substrate and the mold by capillary action. Such a phenomenon is called spread. Further, the curable composition is filled into the concave portions constituting the pattern of the mold by capillary action. Such a phenomenon is called filling. The time until spread and filling are completed is called the filling time. When the filling of the curable composition is completed, the curable composition is irradiated with light to cure the curable composition. Then, the mold is separated from the cured curable composition on the substrate. By performing these steps, the pattern of the mold is transferred to the curable composition on the substrate, 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 a cured film remaining between the concave portion (convex portion of the mold pattern) of the cured film of the curable composition and the substrate.

[0004] Furthermore, in the photolithography process for manufacturing semiconductor devices, it is also necessary to planarize the substrate. For example, in extreme ultraviolet (EUV) 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 in order to improve the filling ability and line width of the curable composition. As a planarization technique, a technique is known in which droplets of curable composition corresponding to the irregularities are discretely dropped onto a substrate with irregularities, and the curable composition is cured while a mold with a flat surface is in contact with it, thereby obtaining a flat surface.

[0005] In pattern formation and planarization techniques using imprint technology, the mold is brought into contact with the substrate while the droplets of the curable composition dropped onto the substrate are not in contact with each other. Consequently, air bubbles are inevitably trapped between the mold, the substrate, and the curable composition. Therefore, it takes a long time for these air bubbles to diffuse into the mold and substrate and disappear, which is one of the factors that reduces productivity (throughput). To address this, a technique has been proposed to bond the droplets of the curable composition together before bringing them into contact with the mold (see Patent Documents 1 and 2). Hereinafter, the ability of the droplets of the curable composition to bond together and form a liquid film will be referred to as "liquid film formation ability."

[0006] Japanese Patent Publication No. 2022-188736, Japanese Patent Publication No. 2010-530641

[0007] In the technologies disclosed in Patent Documents 1 and 2, by adding a solvent to the curable composition to reduce its viscosity, the droplets of the curable composition dropped onto the substrate spread rapidly enough to bond with each other, resulting in good liquid film formation. However, when a curable composition containing a solvent is used, the liquid film may extend beyond the desired area (designed liquid film area). The curable composition (liquid film) that extends beyond the desired area can erode adjacent areas and cause undesirable conditions such as adhesion to the sidewalls of the mold. Furthermore, if the "pinning effect" that appears when certain additives are added to the curable composition is too strong, the liquid film may shrink. Hereinafter, the ability to ensure (maintain) a stable state as a liquid film without overflow or shrinkage of the curable composition (liquid film) in the desired area will be referred to as "liquid film stability."

[0008] This disclosure provides a new technology relating to curable compositions.

[0009] A curable composition as one aspect of the present disclosure is a curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), an additive (c), and a solvent (d), wherein 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 100°C or more and less than 250°C at 1 atmosphere, the additive (c) is a compound consisting of carbon, oxygen and hydrogen, or a compound consisting of carbon, nitrogen, oxygen and hydrogen, and the HLB value of the additive (c) calculated by the Griffin method is 2.0 or more and 8.4 or less.

[0010] Further purposes or other aspects of this disclosure will be revealed by embodiments described below with reference to the accompanying drawings.

[0011] According to this disclosure, for example, it is possible to provide new technologies relating to curable compositions.

[0012] Other features and advantages of this disclosure will become apparent from the following description with reference to the accompanying drawings. In the accompanying drawings, the same or similar components are given the same reference numeral.

[0013] The attached drawings are included in the specification and constitute part thereof, illustrating embodiments of the present disclosure and used together with the description to explain the principles of the present disclosure. A diagram showing the process by which droplets of a curable composition placed on a substrate form a liquid film. A diagram showing the process by which droplets of a curable composition placed on a substrate form a liquid film. A diagram showing the process by which an additive component is adsorbed onto the substrate at the edge of the liquid film of the curable composition. A diagram showing the process by which an additive component is adsorbed onto the substrate at the edge of the liquid film of the curable composition. A diagram illustrating a pattern formation method (film formation method) as one aspect of the present disclosure. A diagram illustrating a pattern formation method (film formation method) as one aspect of the present disclosure. A diagram illustrating a pattern formation method (film formation method) as one aspect of the present disclosure. A diagram illustrating a pattern formation method (film formation method) as one aspect of the present disclosure. A diagram illustrating a pattern formation method (film formation method) as one aspect of the present disclosure. A diagram illustrating a pattern formation method (film formation method) as one aspect of the present disclosure. A diagram illustrating the flow behavior of droplets of a curable composition during the waiting process. This is a diagram illustrating the flow behavior of droplets of a curable composition during the waiting process. This is a diagram illustrating the flow behavior of droplets of a curable composition during the waiting process. This is a diagram illustrating the flow behavior of droplets of a curable composition during the waiting process. This is a diagram comparing the prior art with the present disclosure regarding gas containment that occurs in the contact process.

[0014] The embodiments will be described in detail below with reference to the attached drawings. Note that the following embodiments do not limit the disclosures relating to the claims. While the embodiments describe multiple features, not all of these features are necessarily essential, 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] In providing a new technology related to curable compositions, the present inventors have discovered a technology that enables both liquid film formation and liquid film stability in a curable composition containing a solvent.

[0016] [Curable Composition (A)] Curable composition (A) in this disclosure is, for example, a curable composition for inkjet printing. Curable composition (A) in this disclosure is a composition comprising at least a component (a) which is a polymerizable compound, a component (b) which is a photopolymerization initiator, a component (c) which is an additive, and a component (d) which is a solvent.

[0017] In this specification, "cured film" refers to a film obtained by polymerizing and curing a curable composition (A) 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 curable composition (A) and the substrate is referred to as the residual film.

[0018] <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)) and forms a film made of a polymer compound by a chain reaction (polymerization reaction).

[0019] 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.

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

[0021] (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, cinovabenzyl (meth)acrylate, naphthalenemethyl (meth)acrylate. Examples of commercially available monofunctional (meth)acrylic compounds as described above include, but are not limited to, the following. Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (manufactured by Toagosei), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, #2150 (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 (manufactured by Kyoeisha Chemical), KAYARAD (registered trademark) TC110S, R-564, R-128H (manufactured by Nippon Kayaku), NK ester AMP-10G, AMP-20G, A-LEN-10 (manufactured by Shin Nakamura Chemical Industry), FA-511A, 512A, 513A (manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (manufactured by Daiichi Kogyo Seiyaku), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (manufactured by Kojin), HRD-01 (manufactured by Nippon Shokubai) In addition, polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: Trimethylolpropanedi(meth)acrylate, trimethylolpropanetri(meth)acrylate, EO-modified trimethylolpropanetri(meth)acrylate, PO-modified trimethylolpropanetri(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 ) Acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,Commercially available polyfunctional (meth)acrylic compounds include, but are not limited to, the following: 2-bis(4-((meth)acryloxy)phenyl)propane, o-, m- or p-benzenedi(meth)acrylate, o-, m- or p-xylylenedi(meth)acrylate. Yupimer (registered trademark) UV SA1002, SA2007 (manufactured by Mitsubishi Chemical), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (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 (manufactured by Kyoeisha Chemical), KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (manufactured by Nippon Kayaku), Aronix® M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (manufactured by Toagosei), Lipoxy® VR-77, VR-60, VR-90 (manufactured by Showa Polymer), Ogusol EA-0200, Ogusol EA-0300 (manufactured by Osaka Gas Chemical), SR295, SR355 (manufactured by Sartomer). 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 an EO-modified compound refers to a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are linked via a block structure of the ethylene oxide group. Similarly, PO represents propylene oxide, and a PO-modified compound B refers to a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are linked via a block structure of the propylene oxide group.

[0022] Specific examples of styrene compounds include, but are not limited to, the following: 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; alkylstyrenes such as fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene , acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, divinylbiphenyl, etc., are examples of vinyl compounds having a styryl group as a polymerizable functional group, but are not limited to these.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.). In this specification, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile.

[0023] Examples of acrylic compounds include, but are not limited to, allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate. Examples of fumarate compounds include, but are not limited to, dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl maleate compounds. Examples of dibenzyl maleate compounds include, but are not limited to, dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate. 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.), maleimide and its derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.) When component (a), which is a polymerizable compound, 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 with polyfunctional polymerizable compounds results in a cured film with an excellent balance of properties, such as high mechanical strength, high dry etching resistance, and high heat resistance.

[0024] In the film formation method described herein, since it takes several milliseconds to several hundred seconds for droplets of the curable composition (A), which are discretely arranged on the substrate, to bond together and form a substantially continuous liquid film, a waiting step described later is necessary. In the waiting step, component (d), which is a solvent, is allowed to volatilize, while component (a), which is a polymerizable compound, must not volatilize. Therefore, the boiling point at atmospheric pressure of one or more polymerizable compounds contained in component (a), which is a polymerizable compound, 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).

[0025] The boiling point of component (a), which is a polymerizable compound, generally correlates with its molecular weight. For this reason, the molecular weight of each of the one or more polymerizable compounds contained in component (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 a polymerizable compound in this disclosure. Thus, it is preferable that the boiling point of each of the one or more polymerizable compounds contained in component (a) at atmospheric pressure be 250°C or higher.

[0026] Furthermore, the vapor pressure of the polymerizable compound (component (a)) at 80°C is preferably 0.001 mmHg or less. If component (a), which is a polymerizable compound, 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 (A) in order to accelerate the volatilization of the solvent (component (d)) described later, and this heating suppresses the volatilization of component (a), which is a polymerizable compound.

[0027] 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.

[0028] <Oonishi parameters for component (a)> Dry etching rate V of the organic compound, total number of atoms N in the organic compound, total number of carbon atoms N in the composition Ｃ , and the total number of oxygen atoms in the composition N Ｏ It is known that the following relationship holds: V∝N / (Nc-No) Equation (1) Here, N / (Nc-No) is also called the "Onishi parameter" (hereinafter referred to as "OP"). For example, U.S. Patent Application Publication No. 2020 / 0286740 discloses a technique for obtaining a photocurable composition with high dry etching resistance by using a polymerizable compound component with a small OP.

[0029] According to equation (1), organic compounds with a high concentration of oxygen atoms in the molecule, or with fewer aromatic or alicyclic structures, have a larger OP (Oxidation Factor) and a faster dry etching rate.

[0030] In this disclosure, the curable composition (A) has an OP of component (a), which is a polymerizable compound, of 1.80 to 4.00. More preferably, the OP of component (a) is 2.00 to 3.50, and particularly preferably 2.40 to 3.00. By setting the OP of component (a) to 4.00 or less, the cured film of the curable composition (A) has high dry etching resistance. Furthermore, by setting the OP of component (a) to 1.80 or more, it becomes easy to remove the cured film of the curable composition (A) after processing the underlying layer using the cured film of the curable composition (A). Component (a) is a polymerizable compound a of multiple types. １ a ２ , ..., a ｎ When it is composed of these, OP is calculated as a weighted average value based on mole fractions (mole fraction weighted average value) as shown in equation (2) below. Thus, when component (a) contains one or more polymerizable compounds, the OP of component (a) is N / (N) of each molecule of the one or more polymerizable compounds.Ｃ -N Ｏ is calculated as the mole fraction weighted average value of the value.

[0031]

[0032] Here, OP ｎ is the OP of component a ｎ , and n ｎ is the mole fraction in the total amount of component (a) of component a ｎ .

[0033] In order to make the OP of component (a), which is a polymerizable compound, 1.80 or more and 4.00 or less, it is preferable to contain at least a compound (a1-1) having two or more cyclic structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure, as at least component (a).

[0034] <Compound (a1-1): Polymerizable compound having an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure> Component (a), which is a polymerizable compound in the present disclosure, may contain a compound (a1-1) having an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure.

[0035] Examples of the cyclic structure include an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure.

[0036] As the aromatic structure, the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10. Specific examples of the aromatic ring include the following. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring Among the above-mentioned aromatic rings, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. The aromatic ring may have a structure in which a plurality are linked, and examples thereof include a biphenyl ring and a bisphenyl ring.

[0037] For aromatic heterocyclic structures, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples of aromatic heterocyclic structures include: thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, 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, and phenoxazine ring. 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, as for the alicyclic structure, 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. Specific examples of compounds (a1-1) having a boiling point of 250°C or higher include, but are not limited to, the following. 3-Phenoxybenzylacrylate (mPhOBzA, OP2.54, boiling point 367.4°C, vapor pressure 0.0004 mmHg at 80°C, molecular weight 254.3),

[0038]

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

[0040]

[0041] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2°C, vapor pressure 0.0006 mmHg at 80°C, molecular weight 268.3),

[0042]

[0043] 1-Naphthylmethyl acrylate (Na1MA, OP2.33, boiling point 342.1°C, vapor pressure 0.042 mmHg at 80°C, molecular weight 212.2),

[0044]

[0045] 2-Naphthylmethyl acrylate (Na2MA, OP2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042 mmHg, molecular weight 212.2),

[0046]

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

[0048]

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

[0050]

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

[0052]

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

[0054]

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

[0056]

[0057] 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.

[0058]

[0059] The following formula represents BPh43DA (OP2.63, boiling point 439.5°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.3),

[0060]

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

[0062]

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

[0064]

[0065] 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.

[0066]

[0067] The following formula (a1-1-1) (OP2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181 mmHg, molecular weight 199.2),

[0068]

[0069] The following formula (a1-1-2) (OP2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181 mmHg, molecular weight 199.2),

[0070]

[0071] The following formula (a1-1-3) (OP 1.86, boiling point 369.5°C, vapor pressure at 80°C 0.0053 mmHg, molecular weight 193.3),

[0072]

[0073] The following formula (a1-1-4) (OP2.85, boiling point 438.8°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 296.3),

[0074]

[0075] The following formula (a1-1-5) (OP2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 296.3),

[0076]

[0077] The following formula (a1-1-6) (OP2.87, boiling point 421.0°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 338.4),

[0078]

[0079] The following formula (a1-1-7) (OP2.87, boiling point 465.2°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 338.4),

[0080]

[0081] The following formula (a1-1-8) (OP2.68, boiling point 465.7°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 364.4),

[0082]

[0083] The following formula (a1-1-9) (OP2.50, boiling point 433.1°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 320.3),

[0084]

[0085] The following formula (a1-1-10) (OP2.64, boiling point 468.1°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 326.4),

[0086]

[0087] The following formula (a1-1-11) (OP3.25, boiling point 553.4°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 358.4),

[0088]

[0089] The following formula (a1-1-12) (OP2.63, boiling point 443.9°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.4),

[0090]

[0091] The following formula (a1-1-13) (OP2.89, boiling point 509.3°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 406.4),

[0092]

[0093] The following formula (a1-1-14) (OP2.63, boiling point 450.0°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 322.4),

[0094]

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

[0096]

[0097] The following formula (a1-1-16) (OP2.68, boiling point 447.4°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 364.4)

[0098]

[0099] The following formula (a1-1-17) (OP2.36, boiling point 543.8°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 398.5),

[0100]

[0101] The following formula (a1-1-18) (OP3.27, boiling point 526.9°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 396.4),

[0102]

[0103] The following formula (a1-1-19) (OP2.71, boiling point 333.7°C, vapor pressure at 80°C 0.0302 mmHg, molecular weight 244.3),

[0104]

[0105] The following formula (a1-1-20) (OP2.73, boiling point 333.7°C, vapor pressure at 80°C 0.0134 mmHg, molecular weight 258.3),

[0106]

[0107] The following formula (a1-1-21) (OP2.71, boiling point 319.2°C, vapor pressure at 80°C 0.0566 mmHg, molecular weight 262.3),

[0108]

[0109] The following formula (a1-1-22) (OP2.71, boiling point 336.9°C, vapor pressure at 80°C 0.0055 mmHg, molecular weight 244.3),

[0110]

[0111] The following formula (a1-1-23) (OP 3.00, boiling point 370.9°C, vapor pressure at 80°C 0.0021 mmHg, molecular weight 274.4),

[0112]

[0113] The following formula (a1-1-24) (OP3.00, boiling point 376.4°C, vapor pressure at 80°C 0.0005 mmHg, molecular weight 274.4),

[0114]

[0115] The following formula (a1-1-25) (OP 3.00, boiling point 379.4°C, vapor pressure at 80°C 0.0002 mmHg, molecular weight 288.4),

[0116]

[0117] The following formula (a1-1-26) (OP2.33, boiling point 360.8°C, vapor pressure at 80°C 0.0006 mmHg, molecular weight 252.3),

[0118]

[0119] The following formula (a1-1-27) (OP2.54, boiling point 371.5°C, vapor pressure at 80°C 0.0003 mmHg, molecular weight 254.3),

[0120]

[0121] The following formula (a1-1-28) (OP2.57, boiling point 381.2°C, vapor pressure at 80°C 0.0001 mmHg, molecular weight 268.3),

[0122]

[0123] The following formula (a1-1-29) (OP2.57, boiling point 381.8°C, vapor pressure at 80°C 0.0004 mmHg, molecular weight 268.3),

[0124]

[0125] The following formula (a1-1-30) (OP2.50, boiling point 487.4°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 374.4),

[0126]

[0127] The following formula (a1-1-31) (OP2.67, boiling point 417.2°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 268.3),

[0128]

[0129] The following formula (a1-1-32) (OP2.67, boiling point 417.2°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 268.3),

[0130]

[0131] The following formula (a1-1-33) (OP2.67, boiling point 417.2°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 268.3),

[0132]

[0133] The following formula (a1-1-34) (OP2.67, boiling point 417.2°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 268.3),

[0134]

[0135] The following formula (a1-1-35) (OP2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 296.3),

[0136]

[0137] The proportion of component (a) in the curable composition (A) is preferably 40% to 99% by weight of the total mass of component (a), component (b), and component (c), i.e., the total mass of all components excluding component (d). More preferably, it is 50% to 95% by weight, and even more preferably 60% to 90% by weight. As described above, component (a) is a polymerizable compound, component (b) is a photopolymerization initiator, component (c) is an additive, and component (d) is a solvent. By increasing the proportion of component (a) to 40% by weight or more, the mechanical strength of the cured film of the curable composition (A) is increased. Furthermore, by increasing the proportion of component (a) to 99% by weight or less, the proportion of component (b) 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 polymers preferably contain 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).

[0138]

[0139] In structures (1) to (6), each substituent R is a substituent that independently contains a substructure containing an aromatic ring, １ 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 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.

[0140] 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 particular upper limit to 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 the solvent 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 disclosure, unless otherwise specified, the weight-average molecular weight (Mw) refers to that measured by gel permeation chromatography (GPC).

[0141] 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.

[0142] When a polymer having polymerizable functional groups is added as at least a portion of component (a), which is a polymerizable compound, the 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% by weight or more and 60% by weight or less, more preferably 1% by weight or more and 50% by weight or less, and even more preferably 10% by weight or more and 40% by weight or less, based on the total mass of all components excluding component (d), which is a solvent. 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.

[0143] <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.

[0144] 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, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N'-tetraethyl Benzophenone derivatives such as 4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-aminoaromatic 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, and 2-t- Quinones such as thylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantaraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzo Benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl derivatives such as benzyldimethylketal; 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 benzylketal, 1-hydroxycyclohexylphenylketone, and 2,2-dimethoxy-2-phenylacetophenone;Thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime);Xanthones, fluorenones, benzaldehyde, fluorene, anthraquinones, triphenylamines, carbazoles, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Examples of commercially available radical generators mentioned above include, but are not limited to, the following. Among the radical generators listed above, component (b) is preferably an acylphosphine oxide polymerization initiator. Among the radical generators listed above, the acylphosphine oxide polymerization initiators are as follows. In a curable composition (A) of 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, the blending ratio of component (b) is preferably 0.1% by weight or more and 50% by weight or less of the total mass of component (a), component (b), and component (c) described later, i.e., the total mass of all components excluding component (d). Furthermore, the blending ratio of component (b) in the curable composition (A) is more preferably 0.1% by weight or more and 20% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less, based on the total mass of all components excluding component (d). 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 reducing the mixing ratio of component (b) to 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0145] <Component (c): Additive> In addition to component (a), which is a polymerizable compound, and component (b), which is a photopolymerization initiator, the curable composition (A) in this disclosure further includes an additive as component (c). Component (c) has the structure of a surfactant having a hydrophilic group and a hydrophobic group, and is a compound consisting of carbon, oxygen, and hydrogen, or a compound consisting of carbon, nitrogen, oxygen, and hydrogen. Thus, component (c) is a compound that does not contain fluorine or silicon. The HLB value of component (c) is 2.0 or more and 8.4 or less. The HLB value in this disclosure is a value obtained by the Griffin method, and is calculated based on HLB value = 20 × (formula weight of the hydrophilic group of the additive) / (molecular weight of the additive). The HLB value obtained by the Griffin method is a physical property value that represents the degree of hydrophilicity or lipophilicity of the surfactant, and is defined as a value from 0 to 20. The higher the HLB value, the higher the hydrophilicity, and the higher the overall polarity of the molecule compared to the lower the HLB value.

[0146] In this disclosure, the liquid film stability of the curable composition (A) is controlled by adding an additive component (c). The manifestation of liquid film stability by the additive component (c) will be explained. The curable composition (A) contains a solvent component (d) and is prepared to have low viscosity. Therefore, droplets of the curable composition (A) placed on the substrate spread easily, and good liquid film formation is obtained by the rapid bonding of the droplets to each other. On the other hand, the liquid film formed on the substrate may extend beyond the desired area (designed liquid film area) before contact with the mold, and good liquid film stability cannot be obtained.

[0147] Therefore, the inventors focused on the volatilization behavior of component (d), which is a solvent, from the time a droplet of curable composition (A) is placed (dropped) onto a substrate until a liquid film is formed. Figures 1A and 1B show the process by which a droplet of curable composition (A) placed on a substrate forms a liquid film. As shown in Figure 1A, when a droplet of curable composition (A) is placed on a substrate, the droplet wets and spreads. Then, as shown in Figure 1B, the droplets of curable composition (A) on the substrate combine and become one, forming a liquid film. At this time, component (d), which is a solvent contained in the liquid film of curable composition (A) placed on the substrate, volatilizes, but volatilization occurs more easily at the edges of the liquid film than at the center of the liquid film. This is because the surface of the edges of the liquid film of curable composition (A) is curved, so the surface area of ​​the edges of the liquid film is larger than the surface area of ​​the center of the liquid film.

[0148] Since component (d), which is a solvent, needs to sufficiently dissolve component (a), which is a polymerizable compound, a component with higher polarity than component (a) is used. Therefore, as component (d), the solvent, volatilizes, it is thought that the polarity of the curable composition (A) decreases relatively at the edges of the liquid film where component (d) volatilizes faster, compared to the center of the liquid film. Accordingly, if the decrease in polarity caused by the volatilization of component (d) at the edges of the liquid film of the curable composition (A) can be used to reduce the wettability between the substrate and the edges of the liquid film, the wetting and spreading of the liquid film can be suppressed.

[0149] The inventors investigated materials that reduce the wettability of a curable composition (A) to a substrate and found that the wettability of the curable composition (A) decreased on a substrate coated with the additive component (c). This is thought to be because the additive component (c) has a surfactant structure, resulting in a low surface energy on the surface of the substrate coated with component (c), thus reducing the wettability of the curable composition (A).

[0150] The inventors investigated a method to suppress the wettability of the curable composition (A) and improve the stability of the liquid film by adsorbing the additive component (c) onto the substrate only at the edges of the liquid film of the curable composition (A). Figures 2A and 2B show the process by which the additive component (c) is adsorbed onto the substrate at the edges of the liquid film of the curable composition (A). As shown in Figure 2A, at the edges of the liquid film of the curable composition (A), the volatilization of the solvent component (d) proceeds more rapidly than at the center of the liquid film, and the polarity of the curable composition (A) decreases. Here, the curable composition (A) contains an additive component (c) which has high polarity, i.e., a high HLB value. Therefore, as shown in Figure 2B, with the decrease in polarity at the edges of the liquid film of the curable composition (A), the adsorption of the additive component (c) onto the substrate, which has higher polarity than the edges of the liquid film, is induced. The adsorption of the additive component (c) onto the substrate reduces the wettability at the edges of the liquid film of the curable composition (A), thereby suppressing the wetting and spreading of the liquid film. The HLB value is used as a physical property value indicating the strength of the polarity of the additive component (c). A higher HLB value indicates higher polarity, and a larger amount of component (c) is adsorbed onto the substrate at the edges of the liquid film of the curable composition (A).

[0151] As a result of the inventors' investigation, it was found that by using a curable composition (A) containing component (c), an additive with a high HLB value, the shrinkage or expansion of the liquid film can be suppressed. In this disclosure, this phenomenon is referred to as the pinning effect by component (c), an additive. If the pinning effect is too weak, the wetting spread (expansion) of the liquid film of curable composition (A) cannot be suppressed, and it is difficult to obtain good liquid film stability. On the other hand, if the pinning effect is too strong, the liquid film of curable composition (A) shrinks, and it is difficult to obtain good liquid film stability.

[0152] From the viewpoint of liquid film stability, the HLB value of the additive component (c) is preferably between 2.0 and 8.4. If the HLB value is less than 2.0, the adsorption of the additive component (c) to the substrate is small, and the wetting and spreading of the liquid film cannot be sufficiently suppressed. If the HLB value is greater than 8.4, the adsorption of the additive component (c) to the substrate is large, and the liquid film may shrink.

[0153] The additive component (c) can be a surfactant consisting of carbon, nitrogen, oxygen, or hydrogen, specifically, as described above, a compound consisting of carbon, oxygen, and hydrogen, or a compound consisting of carbon, nitrogen, oxygen, and hydrogen. However, in this disclosure, there are limitations on the amount of additive component (c) that can be added, as will be described later. Furthermore, the additive component (c) is assumed to be nonpolymerizable. The additive component (c) may be used alone or in a mixture of two or more types.

[0154] Examples of additive component (c) include the following: alkyl alcohol polyalkylene oxide adducts, polyalkylene oxides, acetylene glycol polyalkylene oxide adducts, alkylamine alkylene oxide adducts, etc. Commercially available polyoxyethylene polyoxypropylene stearyl ethers include, for example, BLAUNON SA-50 / 50 1000R (HLB value = 6.2) and SA-30 / 70 2000R (HLB value = 4.2) manufactured by Aoki Oil & Fat Industry Co., Ltd.

[0155] A commercially available example of polyoxyethylene polyoxypropylene tridecyl ether is FineSurf TDP-0633K ​​(HLB value = 5.8) manufactured by Aoki Oil & Fat Industry Co., Ltd.

[0156] Examples of commercially available ethylene oxide-propylene oxide copolymers include BASF's Pluronic 17R2 (HLB value = 6.1) and Pluronic L-81 (HLB value = 2.0).

[0157] Examples of commercially available acetylene glycol polyalkylene oxide adducts include Surfinol 604 (HLB value = 8.2) and Surfinol 420 (HLB value = 4.0) manufactured by Nisshin Chemical Industry Co., Ltd.

[0158] Examples of commercially available alkylamine alkylene oxide adducts include Pelletex 4417 (HLB value = 6.3) and Pelletex 4817 (HLB value = 4.9) manufactured by Miyoshi Oil & Fat Co., Ltd.

[0159] From the viewpoint of liquid film stability, it is more preferable that the additive component (c) has the following structure: polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, acetylene glycol polyalkylene oxide adduct, or alkylamine alkylene oxide adduct. The blending ratio of the additive component (c) in the curable composition (A) differs depending on the HLB value. For example, if the total weight of all components excluding the solvent (d) from the curable composition (A) is 100 (parts by weight), and the amount of additive component (c) added is A (parts by weight), then it is preferable that the HLB value of component (c) satisfies 0.8 ≤ A × HLB value ≤ 12.6.

[0160] When the HLB value of additive component (c) is high, the pinning effect is high, so liquid film stability can be ensured with a small amount of additive. On the other hand, when the HLB value of additive component (c) is low, the pinning effect is low, so a large amount of additive is required. When the A × HLB value is less than 0.8, the pinning effect is weak, and the liquid film of the curable composition (A) wets and spreads, making it difficult to obtain good liquid film stability. When the A × HLB value is greater than 12.6, the pinning effect is strong, and the liquid film of the curable composition (A) shrinks, making it difficult to obtain good liquid film stability.

[0161] <Component (d): Solvent> The curable composition (A) in this disclosure contains, as component (d), a solvent having a boiling point of 100°C or higher and less than 250°C at normal pressure. Component (d) can be a solvent in which components (a), (b), and (c) dissolve, such as polar solvents including alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. Component (d) can be used alone or in combination of two or more types. The boiling point of component (d) at normal pressure is 100°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of component (d) at normal pressure is less than 250°C, preferably less than 200°C. If the boiling point of component (d) at atmospheric pressure is less than 100°C, the volatilization rate in the waiting step described later is too fast, causing component (d) to volatilize before the droplets of curable composition (A) can bond together, resulting in a failure of the droplets to bond and a decrease in liquid film formation. Furthermore, if the boiling point of component (d) at atmospheric pressure is 250°C or higher, component (d) remains in the liquid film even after the film has been formed, preventing sufficient pinning effect from the additive component (c) and reducing liquid film stability. Here, if component (d) contains one or more solvents, the boiling points of each of the one or more solvents at atmospheric pressure should be between 100°C and 250°C (for example, between 100°C and 200°C).

[0162] Examples of alcohol-based solvents include the following: 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 alcohol, se Examples of monoalcohol solvents include c-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol solvents include 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, and diethylene glycol; and ketone solvents include the following: Examples of solvents include 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, and acetophenone ether solvents.n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, 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 mono-n-butyl ether, di Examples of ester solvents include ethylene 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, and tripropylene glycol monomethyl ether.Diethyl carbonate, γ-valerolactone, n-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, diethylene glycol mono-n-butyl ether acetate Examples of nitrogen-containing solvents include: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, and dimethyl phthalate. N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone In this disclosure, when the total curable composition (A) is considered to be 100% by volume, the content of component (d), which is a solvent, is set to 5% by volume or more and 95% by volume or less, preferably 15% by volume or more and 85% by volume or less, and more preferably 40% by volume or more and 80% by volume or less. The total curable composition (A) refers to the total deposition of component (a), which is a polymerizable compound, component (b), which is a photopolymerization initiator, component (c), which is an additive, and component (d), which is a solvent. For example, the content of component (d) is 40% by volume or more and 85% by volume or less. If the content of component (d) is less than 5% by volume, it is difficult to obtain a thin film after the volatilization of component (d) under conditions in which a substantially continuous liquid film can be obtained.Furthermore, if the content of component (d) is greater than 95% by volume, it is difficult to obtain a thick film after the evaporation of component (d), even if the droplets are dropped as densely as possible using the inkjet method.

[0163] <Temperature during compounding of curable composition> When preparing the curable composition (A) in this disclosure, at least component (a), which is a polymerizable compound, component (b), which is a photopolymerization initiator, component (c), which is an additive, and component (d), which is a solvent, are mixed and dissolved under predetermined temperature conditions. Specifically, the predetermined temperature conditions are in the range of 0°C to 100°C.

[0164] <Viscosity of the Curable Composition> The curable composition (A) in this disclosure 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 disclosure 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 difficult to form droplets with a volume of about 1.0 to 3.0 pL, which is preferred in this disclosure.

[0165] <Contact Angle of Curable Composition> The inventors have found that when the contact angle of the curable composition (A) with respect to the adhesion layer or silicon substrate is 1.8 degrees or less, droplets of the curable composition (A) bond together on the substrate, resulting in good liquid film formation.

[0166] <Impurities in the curable composition> The curable composition (A) in this disclosure preferably contains as few impurities as possible. Impurities refer to components other than the polymerizable compound (a), the photopolymerization initiator (b), the additive (c), and the solvent (d). Therefore, the curable composition (A) in this disclosure is preferably obtained through a purification process. Such a purification process may include filtration using a filter.

[0167] For filtration using a filter, it is preferable to mix component (a), which is a polymerizable compound, component (b), which is a photopolymerization initiator, and component (c), which is an additive, and then filter the mixture using, for example, a filter with a pore size of 0.001 μm or more and 5.0 μm or less. When performing filtration using a filter, it is even more preferable to perform it in multiple stages or to repeat it many times (circulation filtration). The liquid filtered by the filter may be filtered again, or multiple filters with different pore sizes may be used for filtration. Examples of filters used for filtration include filters made of polyethylene resin, polypropylene resin, fluororesin, and nylon resin, but are not particularly limited. By going through such a purification process, impurities such as particles mixed in the curable composition (A) can be removed. This prevents impurities mixed in the curable composition (A) from unintentionally causing irregularities in the cured film obtained after curing the curable composition (A), resulting in pattern defects.

[0168] Furthermore, when the curable composition (A) in this disclosure is used 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 (A) in order to avoid interfering with the operation of the product. The concentration of metallic impurities in the curable composition (A) is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0169] <Glass transition temperature of curable composition> If the glass transition temperature is sufficiently higher than the temperature at the time of demolding, the cured product at the time of demolding 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 demolding. Therefore, when the demolding process is carried out at room temperature, the glass transition temperature of the cured product (after curing of component (a), which is a polymerizable compound) is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0170] 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 of the DSC curve of the cured material (the portion of the DSC curve in the temperature range where no transition or reaction occurs in the test specimen) toward the high-temperature side, and a tangent line is drawn at the point where the slope of the curve of the stepwise transition portion of the glass transition is maximum. Then, the extrapolated glass transition onset temperature (Tig) can be determined from the intersection of this straight line and the tangent line, and this can be determined as the glass transition temperature. A major example of such equipment 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 example of such equipment for measuring dynamic viscoelasticity is the MCR301 (manufactured by Anton Paar).

[0171] <Layer-forming composition> The layer-forming composition in this disclosure is a composition for forming an adhesion layer between a substrate (base material) and a curable composition (A).

[0172] The layer-forming composition comprises at least a compound (a2) having at least one functional group that bonds to the substrate and at least one polymerizable functional group, a crosslinking agent (b2), and a solvent (d2). Here, "to adhere the substrate and the curable composition" is defined as a state in which the substrate and the cured film are bonded via the adhesion layer with a strength greater than the force required to separate the mold from the cured film of the curable composition in the release step. The release step, as described later, is the step in the imprint process to separate the mold from the cured film of the curable composition formed on the substrate.

[0173] The layer-forming composition in this disclosure is particularly suitable for forming a cured film (cured product) of a curable composition (A) on a substrate. Furthermore, a laminate including an adhesion layer formed by the layer-forming composition in this disclosure and a substrate is suitable as a substrate on which the curable composition (A) is placed (supplied) to obtain a cured film. In addition, the layer-forming composition in this disclosure can be used as an adhesion layer-forming composition for imprinting, and is particularly useful as an adhesion layer-forming composition for photoimprinting. In this embodiment, a case in which a photocurable composition having the property of curing by irradiation with light is used as the curable composition is described. However, the curable composition is not limited to a photocurable composition, and a thermosetting composition having the property of curing by heating may also be used.

[0174] The components included in the layer-forming composition in this disclosure will be described in detail below. As described above, the layer-forming composition in this disclosure includes a compound (a2), a crosslinking agent (b2), and a solvent (d2).

[0175] <Compound (a2)> Compound (a2) has at least one functional group that bonds to the substrate and at least one polymerizable functional group that bonds to the curable composition (A). Here, "bonding functional group" means a functional group that produces chemical bonds such as covalent bonds, ionic bonds, hydrogen bonds, and intermolecular forces. Compound (a2) is included in a proportion of less than 1% by mass when the total amount of the layer-forming composition is 100% by mass. The type of compound (a2) is not particularly limited and broadly includes known compounds.

[0176] Compound (a2) has at least one hydroxyl group, carboxyl group, thiol group, amino group, epoxy group, or (blocked) isocyanate group in one molecule. Examples of compound (a2) include compounds having an ethylenically unsaturated bond-containing group, compounds having an epoxy group, and compounds having a vinyl ether group.

[0177] Examples of compounds (a2) having an ethylenically unsaturated bond-containing group include the following: methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, N-vinylpyrrolidinone, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, 2-hydroxybutyl (meth)acrylate acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylate dimer, benzyl (meth)acrylate, 1- or 2-naphthyl (meth)acrylate, butoxyethyl (meth)acrylate, cetyl (meth)acrylate, ethylene oxide modified (hereinafter, "EO") cresol (meth)acrylate, dipropylene glycol (meth)acrylate, ethoxylated phenyl (meth)acrylate, isooctyl (meth)acrylate Acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isomiristyl (meth)acrylate, lauryl (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, neopentyl Glycol benzoate (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, octyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, epichlorohydrin (hereinafter, "ECH") modified phenoxyacrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate,Phenoxytetraethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, stearyl (meth)acrylate, EO-modified succinic acid (meth)acrylate, tribromophenyl (meth)acrylate, EO-modified tribromophenyl (meth)acrylate, toridodecyl (meth)acrylate, p-isopropenylphenol, N-vinylpyrrolidone, N-vinylcaprolactam, diethylene glycol Recall monoethyl ether (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, di(meth)acrylated isocyanurate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, EO-modified 1,6-hexanediol di(meth)acrylate, ECH-modified 1,6-hexanediol di(meth)acrylate, aryloxy polyethylene glycol acrylate, 1,9-nonanediol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bi Sphenol A di(meth)acrylate, modified bisphenol A di(meth)acrylate, EO modified bisphenol F di(meth)acrylate, ECH modified hexahydrophthalate diacrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, EO modified neopentyl glycol diacrylate, propylene oxide (hereinafter, "PO") modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate neopentyl glycol, stearic acid modified Pentaerythritol di(meth)acrylate, ECH-modified phthalate di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, polyester (di)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ECH-modified propylene glycol di(meth)acrylate, silicone di(meth)acrylate, triethylene glycol di(meth)acrylate,Tetraethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO modified tripropylene glycol di(meth)acrylate, triglycerol di(meth)acrylate, dipropylene glycol di(meth)acrylate, divinylethylene urea, divinylpropylene urea, o-,m-,p-xylylene di(meth)acrylate, 1,3-adamantanediaacrylate, norbornane dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ECH modified glycerol tri(meth)acrylate, EO modified glycerol tri(meth)acrylate, PO modified glycerol tri(meth)acrylate, pentaerythritol triacrylate, EO modified phosphate triacrylate, trimethylolpropane Examples of epoxy group-containing compounds (a2) include tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, Brominated Bisphenol A diglycidyl ether, Brominated Bisphenol F diglycidyl ether, Brominated Bisphenol S diglycidyl ether, Hydrogenated Bisphenol A diglycidyl ether, Hydrogenated Bisphenol F diglycidyl ether,Examples of compounds (a2) having a vinyl ether group include: hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to phenol, cresol, butylphenol, or phenol, and glycidyl esters of higher fatty acids. 2-Ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether,Pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1-tris[4-(2-vinyloxyethoxy)phenyl]ethane, bisphenol A divinyloxyethyl ether are examples of poly(meth)acrylate compounds having an ethylenically unsaturated group (P) and a hydrophilic group (Q).

[0178] Examples of ethylenically unsaturated groups (P) include (meth)acryloyloxy groups, (meth)acryloylamino groups, maleimide groups, allyl groups, and vinyl groups. In this specification, (meth)acryloyl group means an acryloyl group or a methacryloyl group having an equivalent alcohol residue.

[0179] Examples of hydrophilic groups (Q) include: alcoholic hydroxyl groups, carboxyl groups, phenolic hydroxyl groups, ether groups (preferably polyoxyalkylene groups), amino groups, amide groups, imide groups, ureido groups, urethane groups, cyano groups, sulfonamide groups, lactone groups, and cyclocarbonate groups. When the hydrophilic group (Q) is a urethane group, it is preferable that the group adjacent to the urethane group contains an oxygen atom, for example, "-O-C(=O)-NH-" in the resin.

[0180] The poly(meth)acrylate compound (acrylic resin) may contain repeating units containing an ethylenically unsaturated group (P) and repeating units containing a hydrophilic group (Q) in the same repeating unit, or in separate repeating units. However, it is preferable that the poly(meth)acrylate compound (acrylic resin) contains these repeating units in a proportion of 20 to 100 mol%. Furthermore, the poly(meth)acrylate compound (acrylic resin) may also contain other repeating units that do not contain both an ethylenically unsaturated group (P) and a hydrophilic group (Q), and the proportion of these other repeating units is preferably 50 mol% or less of the acrylic resin.

[0181] The poly(meth)acrylate compound (acrylic resin) preferably contains repeating units represented by the following general formulas (I) and (II).

[0182]

[0183] In general formulas (I) and (II), R １ and R ２ These represent a hydrogen atom, a methyl group, or a hydroxymethyl group, respectively. １ This represents a trivalent linking group, L ２ａ represents a single bond or a divalent linking group, L ２ｂ represents a single bond, a divalent linking group, or a trivalent linking group. P represents an ethylenically unsaturated group, Q represents a hydrophilic group, and n is 1 or 2.

[0184] R １ and R ２ These represent, independently, a hydrogen atom, a methyl group, and a hydroxymethyl group. １ and R ２ Hydrogen atoms and methyl groups are preferred, with methyl groups being more preferred.

[0185] L １ As described above, represents a trivalent linking group. A trivalent linking group is an aliphatic group, an alicyclic group, an aromatic group, or a trivalent group that is a combination of these, and may contain an ester bond, an ether bond, a sulfide bond, and a nitrogen atom. The number of carbon atoms in the trivalent linking group is preferably 1 to 9.

[0186] L ２ａ As described above, represents a single bond or a divalent linking group. The divalent linking group is an alkylene group, a cycloalkylene group, an arylene group, or a divalent group that is a combination of these, and may include ester bonds, ether bonds, and sulfide bonds. The number of carbon atoms in the divalent linking group is preferably 1 to 8.

[0187] L ２ｂ As mentioned above, L represents a single bond, a divalent linking group, or a trivalent linking group. ２ｂ The divalent linking group represented by is L ２ａ This is synonymous with the divalent linking group represented by L, and the preferred range is also the same. ２ｂ The trivalent linking group represented by is L １ This is synonymous with the trivalent linking group represented by , and the preferred range is also the same.

[0188] As mentioned above, P represents an ethylenically unsaturated group. The ethylenically unsaturated group represented by P is synonymous with the ethylenically unsaturated groups exemplified so far, and the preferred ethylenically unsaturated group is also the same. Furthermore, as mentioned above, Q represents a hydrophilic group. The hydrophilic group represented by Q is synonymous with the hydrophilic groups exemplified so far, and the preferred hydrophilic group is also the same.

[0189] As described above, n is 1 or 2, and is preferably 1.

[0190] Note L １ , L ２ａ and L ２ｂ It does not contain ethylenically unsaturated groups or hydrophilic groups.

[0191] Furthermore, the poly(meth)acrylate compound (acrylic resin) may contain repeating units represented by the following general formula (III) and / or general formula (IV).

[0192]

[0193] In general formulas (III) and (IV), R ３ and R ４ These represent a hydrogen atom, a methyl group, or a hydroxymethyl group, respectively. ３ and L ４ Each represents a single bond or a divalent linking group. Q represents a hydrophilic group. R ５ This represents an aliphatic group having 1 to 12 carbon atoms, an alicyclic group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms.

[0194] R ３ and R ４ As mentioned above, these represent a hydrogen atom, a methyl group, and a hydroxymethyl group, respectively. ３ and R ４ Hydrogen atoms and methyl groups are preferred, with methyl groups being more preferred.

[0195] L ３ and L ４ As described above, each represents a single bond or a divalent linking group. ３ and L ４ The divalent linking group represented by each of these is L in general formula (I).２ａ This is synonymous with the divalent linking group represented by , and the preferred range is also the same.

[0196] As mentioned above, Q represents a hydrophilic group. The hydrophilic group represented by Q is synonymous with the hydrophilic groups exemplified so far, and the preferred hydrophilic group is also the same.

[0197] R ５ As described above, this represents an aliphatic group having 1 to 12 carbon atoms, an alicyclic group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. The aliphatic group, alicyclic group, and aromatic group may have substituents.

[0198] Examples of aliphatic groups having 1 to 12 carbon atoms include: alkyl groups having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, 3,3,5-trimethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, etc.) Examples of alicyclic groups having 3 to 12 carbon atoms include: cycloalkyl groups having 3 to 12 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecanyl group, etc.) Examples of aromatic groups having 6 to 12 carbon atoms include: phenyl group, naphthyl group, biphenyl group, etc., with phenyl group and naphthyl group being preferred.

[0199] Specific examples of acrylic resins that can be used in this disclosure are shown below. In the following examples, x represents 0 to 50 mol%, y represents 0 to 50 mol%, and z represents 20 to 100 mol%.

[0200]

[0201] Other examples of compounds (a2) that can be used in this disclosure include those whose main chain contains an aromatic ring. Examples of compounds (a2) containing an aromatic ring include those whose main chain consists of an aromatic ring and an alkylene group, and whose main chain has a structure in which benzene rings and methylene groups are alternately bonded. Such compounds (a2) preferably have a reactive group in the side chain, more preferably have a (meth)acryloyl group in the side chain, and even more preferably have an acryloyl group in the side chain.

[0202] The compound (a2) whose main chain contains an aromatic ring is preferably a polymer whose main component is a structural unit represented by the following general formula (a2-1), and more preferably a polymer in which the structural unit represented by the following general formula (a2-1) accounts for 90 mol% or more.

[0203]

[0204] In general formula (a2-1), R is an alkyl group, and L １ and L ２ Each of these is a divalent linking group, and P is a polymerizable group. n is an integer from 0 to 3.

[0205] R is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group. １ It is preferably an alkylene group, and more preferably an alkylene group having 1 to 3 carbon atoms, "-CH ２ It is more preferable to have "-". ２ is, "-CH ２ It is preferable that the linking group is a divalent group consisting of "-", "-O-", "-CHR (R is a substituent)-", and two or more combinations thereof. R is preferably an OH group. P is preferably a (meth)acryloyl group, and more preferably an acryloyl group. n is preferably an integer from 0 to 2, and more preferably 0 or 1.

[0206] Other examples of compounds (a2) that can be used in this disclosure include epoxy poly(meth)acrylate compounds. Other examples of compounds (a2) include, for example, those described in paragraphs 0040 to 0056 of Japanese Patent Publication No. 2009-503139, which are incorporated herein by reference.

[0207] Of the compounds (a2) described above, those having a functional group with high binding affinity to the substrate are preferred. Examples of functional groups with high binding affinity to the substrate include hydroxyl groups, carboxyl groups, thiol groups, amino groups, epoxy groups, and (blocked) isocyanate groups, with hydroxyl groups or carboxyl groups being particularly preferred.

[0208] Compound (a2) may be a low-molecular-weight compound or a polymer, but a polymer is preferred. The molecular weight is usually between 200 and 100,000, preferably between 500 and 50,000, and more preferably between 1,000 and 10,000. If the molecular weight of compound (a2) is 200 or less, it may volatilize during the baking process. Also, if the molecular weight of compound (a2) is 100,000 or more, bubbles may remain during the spin coating process.

[0209] Compound (a2) may consist of one type of compound or multiple types of compounds.

[0210] <Crosslinking agent (b2)> The crosslinking agent (b2) in this disclosure is a compound having a total of at least five alkoxyalkyl groups and alkylol groups (hereinafter referred to as "functional group a") in one molecule.

[0211] The functional group a of the crosslinking agent (b2) in this disclosure is a functional group that reacts with the hydroxyl group or carboxyl group of compound (a2) in the adhesion layer formation step described later. As a result, a bond is formed between compound (a2) and the crosslinking agent (b2). The crosslinking agent (b2) has multiple functional groups a in one molecule. Therefore, the crosslinking agent (b2) can create bonds with multiple compounds (a2). By creating bonds with multiple compounds (a2), the crosslinking agent (b2) can form a crosslinked structure (crosslinked structure) in which the compounds constituting the adhesion layer are crosslinked with each other.

[0212] The reaction between the functional group a of the crosslinking agent (b2) in this disclosure and the hydroxyl group or carboxyl group of the compound (a2) is preferably carried out by a heating process in the adhesion layer formation step described later.

[0213] In this way, by forming an adhesion layer having a crosslinked structure, the amount of free, unreacted compounds (a2) or crosslinking agents (b2) that are not connected to the substrate can be reduced, and the film strength of the adhesion layer can be improved.

[0214] If unreacted compounds (a2) or crosslinking agents (b2) are present in a free state within the adhesion layer, these compounds may leach into the curable composition (A) during the curing step of curable composition (A) described later. As a result, the composition of curable composition (A) changes, altering its properties, which can lead to, for example, peeling (defects) of the pattern of the cured film obtained by curing curable composition (A).

[0215] On the other hand, when using the layer-forming composition of this disclosure, the amount of free compounds (a2) and crosslinking agents (b2) in the adhesion layer that are not connected to the substrate can be significantly reduced compared to conventional methods. As a result, the elution of compounds (a2) or crosslinking agents (b2) into the curable composition (A) during the curable composition (A) placement process can also be significantly suppressed. Consequently, the occurrence of peeling (defects) of the cured film pattern described above can be suppressed.

[0216] Furthermore, the functional group a of the crosslinking agent (b2) may form any chemical bond or interaction, such as a covalent bond, ionic bond, hydrogen bond, or intermolecular force, with the functional groups present on the surface of the substrate. For example, if a substrate having hydroxyl groups such as silanol groups on its surface is used, a de-alcoholization reaction occurs between the alkoxyalkyl group and the silanol group. As a result, a covalent bond can be formed between the crosslinking agent (b2) and the substrate. This improves the adhesion between the adhesion layer and the substrate.

[0217] Furthermore, the crosslinking agent (b2) is preferably a compound represented by the following general formula (b2-1).

[0218]

[0219] In general formula (b2-1), R １ ~R ６ Each of these independently represents one of a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an alkylol group. However, R １ ~R ６ At least five of these are alkoxyalkyl groups or alkylol groups.

[0220] Compounds represented by general formula (b2-1) are derivatives of melamine having a triazine ring at the center of their structure. In other words, compounds represented by general formula (1) have a structure in which nitrogen atoms are bonded to the 2, 4, and 6 positions of 1,3,5-triazine, respectively. Furthermore, compounds represented by general formula (1) have five or six functional groups a. Therefore, compounds represented by general formula (b2-1) have more functional groups a than urea compounds such as glycoluryl derivatives.

[0221] The type of alkoxyalkyl group or alkylol group possessed by the crosslinking agent (b2) is not particularly limited, but a methoxymethyl group is preferred as the alkoxyalkyl group, and a methylol group is preferred as the alkylol group. By using a functional group with a small formula weight as the alkoxyalkyl group or alkylol group in this way, the crosslinking density per unit mass of the adhesion layer can be improved, and the film strength of the adhesion layer can be improved.

[0222] Specific examples of crosslinking agents (b2) include the following. Crosslinking agents (b2) include, but are not limited to, at least one selected from the following: pentamethoxymethylmelamine, hexamethoxymethylmelamine, (hydroxymethyl)pentakis(methoxymethyl)melamine, hexaethoxymethylmelamine, hexasubtoxymethylmelamine, pentamethylolmelamine, hexamethylolmelamine, etc. Urea-based compounds may also be used as crosslinking agents (b2), and specific examples include the following. Commercially available methylated urea crosslinking agents such as tetrakis(methoxymethyl) glycoluryl, 4,5-dimethoxy-1,3-bis(methoxymethyl)imidazolidin-2-one, tetrakis(butoxymethyl) glycoluryl, tetrakis(ethoxymethyl) glycoluryl, tetrakis(isopropoxymethyl) glycoluryl, tetrakis(amyloxymethyl) glycoluryl, and tetrakis(hexoxymethyl) glycoluryl include, for example: Nikalac MX-270, Nikalac MX-280, Nikalac MX-290 (manufactured by Sanwa Chemical Co.), Powderlink 1174 (manufactured by American Cyanamide Co.), and Cymel 1170 (manufactured by Cytec Industries). Monomers of the above-mentioned resins can also be used, for example, the following compounds and dimethoxymethylurea.

[0223]

[0224] The crosslinking agent (b2) may consist of one type of compound or multiple types of compounds.

[0225] <Mixing ratio of compound (a2) and crosslinking agent (b2)> If the mixing ratio of either compound (a2) or crosslinking agent (b2) in the layer-forming composition is extremely small, the crosslinking density of the adhesion layer will be small, resulting in insufficient film strength and curability. Therefore, if the weight fractions of compound (a2) and crosslinking agent (b2) to the total weight of the layer-forming composition are α and β, respectively, then α:β is preferably 1:9 to 9:1, and more preferably 1:5 to 5:1. In other words, α / β is preferably 0.11 to 9, and preferably 0.2 to 5. The optimal mixing ratio will vary depending on the number of functional groups, molecular weight, and reactivity of compound (a2) and crosslinking agent (b2), but generally, the curability of the layer-forming composition can be improved by using a mixing ratio within the range described above.

[0226] The blending ratio (sum of α and β) of compound (a2) and crosslinking agent (b2) in the layer-forming composition can be appropriately adjusted depending on the viscosity of the layer-forming composition and the desired thickness of the adhesion layer. The sum of α and β is preferably 0.01 to 10, more preferably 0.1 to 10, and even more preferably 0.1 to 7, relative to the total weight of the layer-forming composition. By setting the blending ratio of compound (a2) and crosslinking agent (b2) in the layer-forming composition within the above range, the viscosity of the layer-forming composition can be reduced, and the thickness of the adhesion layer formed on the substrate can be reduced.

[0227] <Volatile Solvent (d2)> The layer-forming composition in this disclosure contains a volatile solvent (d2) (hereinafter simply referred to as "solvent (d2)"). By containing a volatile solvent (d2) in the layer-forming composition, the viscosity of the layer-forming composition can be reduced, and the coatability of the layer-forming composition on the substrate can be improved.

[0228] As the volatile solvent (d2), a mixture of a first solvent (d2-1) having a boiling point of 80 to 200°C at atmospheric pressure and a second solvent (d2-2) having a boiling point of 200 to 300°C at atmospheric pressure may be used. Alternatively, the volatile solvent (d2) may be the first solvent (d2-1) alone, or the second solvent (d2-2) alone.

[0229] The first solvent (d2-1) is not particularly limited as long as it is a solvent in which compound (a2) and crosslinking agent (b2) can be dissolved, but it is preferably a solvent with a boiling point of 80 to 200°C at atmospheric pressure. Furthermore, the first solvent (d2-1) is preferably an organic solvent having at least one of a hydroxyl group, an ether structure, an ester structure, and a ketone structure. These solvents have excellent solubility of compound (a2) and crosslinking agent (b2) and wettability to the substrate.

[0230] Specific examples of solvents used as the first solvent (d1-1) are listed below, and these solvents may be used alone or in mixtures: n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, 2,6-dimethyl Alcohol-based solvents such as heptanol-4, sec-undecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, diacetone alcohol, ethylene glycol, 1,2-propylene glycol, 2-methyl-2,4-pentanediol, propylene glycol; n-butyl ether, 2-ethylhexyl ether, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether Ether-based solvents such as ether, 2-n-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, 1-n-butoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and 2-methyltetrahydrofuran; ester-based solvents such as butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate; ketone-based solvents such as 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, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, and fenthone;Diethyl carbonate, amyl acetate, 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, cyclohexyl acetate, methylcyclohexyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Acetic acid-based solvents such as ethyl ether, glycol diacetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, and diethyl malonate; and amide-based solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methylpropionamide. Of these solvents, propylene glycol monomethyl ether acetate or a mixed solution thereof is particularly preferred as the first solvent (d1-1) from the viewpoint of coatability.

[0231] The second solvent (d2-2) is not particularly limited as long as it is a solvent in which compound (a2) and crosslinking agent (b2) can be dissolved, but it is preferably a solvent with a boiling point of 200 to 300°C at atmospheric pressure. Furthermore, the second solvent (d2-2) is preferably an organic solvent having at least one of the following: a hydroxyl group, an ether structure, an ester structure, or a ketone structure. These solvents have excellent solubility of compound (a2) and crosslinking agent (b2) and wettability to the substrate.

[0232] Specific examples of solvents used as the second solvent (d2-1) include the following, and these solvents may be used alone or in mixtures: Alcohol-based solvents such as n-nonyl alcohol, n-decanol, sec-tetradecyl alcohol, benzyl alcohol, phenylmethylcarbinol, 1,3-butylene glycol, 2,4-pentanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, and tripropylene glycol; n-hexyl ether, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxyethanol Ether-based solvents such as liglycol, 1-phenoxy-2-propanol, dipropylene glycol monopropyl ether, and tripylene glycol monomethyl ether; ketone-based solvents such as acetophenone; acetic acid-based solvents such as γ-butyrolactone, γ-valerolactone, benzyl acetate, n-nonyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, di-n-butyl oxalate, n-amyl lactate, dimethyl phthalate, and diethyl phthalate; amide-based solvents such as acetamide, N-methylacetamide, and N-methylpyrrolidone. As described above, solvent (d2) may contain two types: a first solvent (d2-1) and a second solvent (d2-2). In this case, if the total amount of the first solvent (d2-1) and the second solvent (d2-2) is 100 parts by mass, the amount of the second solvent (d2-2) is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and even more preferably 5 to 25 parts by mass. By keeping the amount of the second solvent (d2-2) within the above range, the in-plane uniformity of the film thickness and the defect density are improved. Note that the solvent (d2) may contain three or more types of solvents.

[0233] The blending ratio of the volatile solvent (d2) in the layer-forming composition in this disclosure can be appropriately adjusted depending on the viscosity and coatability of the compound (a2) and crosslinking agent (b2), and the thickness of the adhesion layer to be formed on the substrate. The blending ratio (content) of the volatile solvent (d2) in the layer-forming composition is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, when the total amount of the layer-forming composition is considered to be 100% by mass. A higher blending ratio of the solvent (d2) in the layer-forming composition allows for a thinner adhesion layer to be formed on the substrate, making it preferable as an adhesion layer-forming composition for imprinting. If the blending ratio of the solvent (d2) in the layer-forming composition is less than 70% by mass, sufficient coatability may not be obtained. The upper limit of the blending ratio of the solvent (d2) is not particularly limited, but it is preferably 99.9% by mass or less, and more preferably 99.5% by mass or less.

[0234] <Other Additive Components (e2)> In addition to the compound (a2), crosslinking agent (b2), and volatile solvent (d2), the layer-forming composition in this disclosure may further contain additive components (e2) to the extent that they do not impair the effects of this disclosure, depending on the purpose. Examples of such additive components (e2) include crosslinking agents, polymer components, antioxidants, polymerization inhibitors, and surfactants. After the layer-forming composition is placed on the substrate, the thickness of the adhesion layer formed on the substrate can be reduced by curing while volatilizing the volatile solvent (d2) by heating. Therefore, it is preferable that the layer-forming composition in this disclosure does not contain a photopolymerization initiator, which is added for purposes such as curing the layer-forming composition by light irradiation. This is because if the layer-forming composition contains a photopolymerization initiator, photopolymerization may occur during the formation of the adhesion layer, and the layer-forming composition may harden before the volatile solvent (d2) has completely evaporated, making it difficult to reduce the thickness of the adhesion layer.

[0235] <Viscosity of the layer-forming composition> The viscosity of the layer-forming composition at 23°C is preferably 0.5 mPa·s or more and 20 mPa·s or less, more preferably 1 mPa·s or more and 10 mPa·s or less, and even more preferably 1 mPa·s or more and 5 mPa·s or less. However, the viscosity of the layer-forming composition at 23°C varies depending on the type and blending ratio of each component, such as the compound (a2), crosslinking agent (b2), solvent (d2), and other additive components (e2) added as needed.

[0236] By setting the viscosity of the layer-forming composition at 23°C to 20 mPa·s or less, the coatability of the layer-forming composition on the substrate is improved, and the thickness of the layer-forming composition on the substrate can be easily adjusted.

[0237] <Impurities in the Layer-Forming Composition> The layer-forming composition in this disclosure preferably contains as few impurities as possible. Impurities refer to substances other than the compound (a2), crosslinking agent (b2), volatile solvent (d2), and other additives (e2) added as needed. When the layer-forming composition is used in an imprinting process, it is particularly preferable that it does not contain particles and solid components. Here, particles are typically gel-like or solid granular substances having a particle size (diameter) of several nm to several μm. Therefore, when the entire layer-forming composition is considered as 100% by mass, the content of particles with a particle size larger than 0.2 μm is preferably 0% by mass or more and less than 3% by mass. Also, when the entire layer-forming composition is considered as 100% by mass, the content of particles with a particle size larger than 0.2 μm is preferably less than 1 particle / mL. Therefore, the layer-forming composition in this disclosure is preferably obtained through a purification process. Such a purification process may include filtration using a filter.

[0238] For filtration using a filter, it is preferable to mix the compound (a2), crosslinking agent (b2), volatile solvent (d2), and other additive components (e2) as needed, and then filter the mixture using, for example, a filter with a pore size of 0.001 μm to 5.0 μm. It is even more preferable to filter using a filter with a pore size of 0.001 μm to 0.2 μm. When performing filtration using a filter, it is even more preferable to perform it in multiple stages or repeat it many times (circulation 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 layer-forming composition can be removed. This prevents defects from occurring unintentionally in the adhesion layer obtained after coating the layer-forming composition due to impurities mixed into the layer-forming composition.

[0239] Furthermore, when using the layer-forming composition described herein to manufacture circuit boards used in semiconductor devices such as semiconductor integrated circuits, it is preferable to avoid, as much as possible, the inclusion of metal atoms (metallic impurities) in the layer-forming composition. This is to prevent metallic impurities from hindering the operation of the circuit board. The concentration of metallic impurities in the layer-forming composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

[0240] It is preferable that the layer-forming composition is prepared without contact with metal during its manufacturing process. Specifically, it is preferable not to use metal weighing instruments, containers, etc., when weighing or mixing and stirring each of the raw materials of the compound (a2), crosslinking agent (b2), volatile solvent (d2), and other additive components (e2) as needed. Furthermore, it is preferable to filter the mixture using a metal impurity removal filter in the purification process described above. As the metal impurity removal filter, cellulose and diatomaceous earth filters or ion exchange resin filters can be used, but are not particularly limited. It is preferable to wash these metal impurity removal filters before use. When washing the metal impurity removal filters, it is preferable to wash them in the following order: washing with ultrapure water, washing with alcohol, and then washing with the layer-forming composition.

[0241] <Adhesion Layer Formation Process> In the adhesion layer formation process, an adhesion layer mainly composed of polymer compounds (polymers) is formed on the substrate using the layer-forming composition described above.

[0242] The substrate (support) on which the layer-forming composition is placed can be any substrate selected according to various purposes. Examples include semiconductor device substrates such as silicon wafers, aluminum, titanium-tungsten alloys, aluminum-silicon alloys, aluminum-copper-silicon alloys, silicon oxide, and silicon nitride. Other examples include quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films, and metal substrates such as Ni, Cu, Cr, and Fe. Furthermore, examples include polymer substrates such as paper, polyester film, polycarbonate film, and polyimide film, TFT array substrates, PDP electrode plates, plastic substrates, conductive substrates such as ITO and metal, and insulating substrates. As for the substrate, one or more types of films selected from spin-on-glass, organic materials, metals, oxides, nitrides, etc., may be deposited on the above-mentioned substrates.

[0243] As the substrate, it is particularly preferable to use a substrate having hydroxyl groups (OH groups), such as silanol groups (SiOH groups), on its surface. Examples of such substrates include silicon wafers, quartz, and glass. By using a substrate having hydroxyl groups on its surface, it is thought that the hydroxyl groups on the substrate surface and the functional groups of compound (a2) of the layer-forming composition will form chemical bonds upon heat treatment. Furthermore, if the crosslinking agent (b2) has an alkoxyalkyl group, it is thought that it will form chemical bonds with the hydroxyl groups.

[0244] Methods for coating (arranging) the layer-forming composition onto a substrate include the following, but the spin coating method is particularly preferred from the viewpoint of coatability, especially uniformity of film thickness. After coating the layer-forming composition onto the substrate using methods such as inkjet, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, and slit scan, the volatile solvent (d2) contained in the layer-forming composition is evaporated by drying to form an adhesion layer on the substrate. At this time, it is preferable to react the substrate with the compound (a2) or crosslinking agent (b2) at the same time as evaporating the volatile solvent (d2), and to react the compound (a2) with the crosslinking agent (b2). This forms a bond between the substrate and the adhesion layer, and a bond is formed between the compound (a2) and the crosslinking agent (b2) in the adhesion layer. It is presumed that a crosslinked structure is formed by the bond between the compound (a2) and the crosslinking agent (b2).

[0245] To effectively carry out such volatilization and reaction, it is preferable to heat-treat (bake) the substrate coated with the layer-forming composition. The temperature of the heat treatment can be appropriately selected depending on the reactivity of the compound (a2) or crosslinking agent (b2) with the substrate, the reactivity of the compound (a2) with the crosslinking agent (b2), and the boiling points of the compound (a2), crosslinking agent (b2), volatile solvent (d2), and other additive components (e2). The temperature of the heat treatment is preferably 70°C to 250°C, more preferably 100°C to 220°C, and even more preferably 140°C to 220°C. Furthermore, the drying of the volatile solvent (d2), the reaction between the substrate and the compound (a2) or crosslinking agent (b2), and the crosslinking reaction between the compound (a2) and the crosslinking agent (b2) may be carried out at the same temperature or at different temperatures. In other words, these reactions may be carried out simultaneously or sequentially.

[0246] The thickness of the adhesion layer formed on the substrate by the adhesion layer formation process varies depending on the application, but for example, it is 0.1 nm to 100 nm, more preferably 0.5 nm to 60 nm, and even more preferably 1 nm to 10 nm.

[0247] When forming an adhesion layer by coating a substrate with a layer-forming composition, a second adhesion layer may be formed by coating the first adhesion layer with another layer of the layer-forming composition. This method is also called multiple coating. Furthermore, the surface of the adhesion layer formed on the substrate is preferably flat. Specifically, the surface roughness of the adhesion layer is preferably 1 nm or less.

[0248] Through this adhesion layer formation process, a laminate having a substrate and an adhesion layer (polymer layer) formed on the substrate can be formed. As described above, the polymer layer as the adhesion layer has a crosslinked structure due to a reaction between the alkoxyalkyl group or alkylol group of the crosslinking agent (b2) and the hydroxyl group and carboxyl group of the compound (a2).

[0249] [Pattern Formation Method] The pattern formation method in this disclosure will be described with reference to Figures 3A to 3G. The cured film formed by this disclosure 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 (1 nm to 100 nm) pattern (uneven structure) is called an optical imprint method. The film formation method in this disclosure uses an optical imprint method to form a film of a curable composition (A) in the space between a mold and a substrate. However, the curable composition (A) may be cured by other energy (e.g., heat, electromagnetic waves). Furthermore, the film formation method in this disclosure 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.

[0250] The following describes an example in which the film forming method in this disclosure 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 (separation 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 component (d) volatilizes. 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.

[0251] <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 1A. In the placement process, 80 droplets / mm of the curable composition (A) having a volume of 1.0 pL or more are placed. ２The layers are arranged at the above density. As the substrate 101, a substrate with a laminated underlayer may be used. Furthermore, it is preferable that the above-described layer-forming composition is formed on the surface of the substrate 101, and the adhesion with the curable composition (A) may be improved by surface treatment such as silane coupling treatment, silazane treatment, or deposition of an organic thin film.

[0252] As the silane coupling agent, known silane coupling agents having an acrylic group can be used. Examples of methods for applying the silane coupling agent include the following, but vapor deposition is particularly preferred from the viewpoint of coatability, especially film thickness uniformity. Examples include inkjet method, dip coat method, air knife coat method, curtain coat method, wire bar coat method, gravure coat method, extrusion coat method, spin coat method, slit scan method, vapor deposition method, etc. Furthermore, an untreated silicon substrate can be used as the substrate 101.

[0253] 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.

[0254] To define the volume of curable composition (A) to be placed on the substrate, an index called the average residual liquid film thickness is defined. The average residual liquid film thickness is the value obtained by dividing the volume of curable composition (A) (excluding the solvent component (d)) placed in the placement process by the area of ​​the film formation region of the mold. The volume of curable composition (A) (excluding the solvent component (d)) is the sum of the volumes of individual droplets of curable composition (A) after the solvent component (d) has evaporated. According to this definition, even if the substrate surface has irregularities, the average residual liquid film thickness can be defined regardless of the irregularities. Here, the average residual liquid film thickness may be understood as the value obtained by dividing the volume of curable composition (A) remaining after the waiting process described later by the area of ​​the film formation region of the mold, and it is preferable that it be 20 nm or less.

[0255] <Waiting Step> In this disclosure, 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). In the waiting step, the droplets 102 of curable composition (A) spread out on the substrate 101 as schematically shown in Figure 3(b). As a result, the pattern formation region of the substrate 101 is covered with curable composition (A) over its entire surface.

[0256] Referring to Figures 4A to 4D, 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 4A, the droplets 102 of the curable composition (A) are discretely arranged on the substrate 101, and as shown in Figure 4B, each droplet 102 gradually spreads on the substrate. Then, as shown in Figure 4C, the droplets of the curable composition (A) on the substrate begin to combine to form a liquid film, and as shown in Figure 4D, 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 4D is referred to as a "substantially continuous liquid film".

[0257] Furthermore, during the waiting process, as schematically shown in Figure 3D, the solvent 105 (solvent component (d)) contained in the liquid film 104 is evaporated. After the waiting process (for example, at the start of the contact process), the amount of solvent component (d) remaining in the liquid film 103 is preferably 10% by volume or less, assuming the total weight of components other than component (d) is 100% by volume. If the amount of solvent component (d) remaining is greater than 10% by volume, the pinning effect of the additive component (c) may not be fully exerted, and the liquid film formation ability may decrease.

[0258] In the waiting process, a baking process may be carried out to heat the substrate 101 and the curable composition (A) in order to accelerate the volatilization of component (d), which is the solvent, or the atmospheric gas around the substrate 101 may be ventilated. The heating is carried out at, for example, 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.

[0259] 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.

[0260] During the waiting process, when component (d), which is a solvent, evaporates, a substantially continuous liquid film 104 remains, consisting of component (a), which is a polymerizable compound, component (b), which is a photopolymerization initiator, and component (c), which is an additive. The average remaining liquid film thickness of the substantially continuous liquid film 104 from which component (d), which is a solvent, has evaporated (removed), is thinner than the liquid film 103 by the amount that component (d) has evaporated. The pattern formation region of the substrate 101 is maintained to be covered over its entire surface by a substantially continuous liquid film 104 of the curable composition (A) from which component (d), which is a solvent, has been removed.

[0261] <Contact Process> In the contact process, as schematically shown in Figure 3E, a substantially continuous liquid film 104 of the curable composition (A), from which component (d), which is the solvent, has been removed, is brought into contact with the mold 106. The contact process includes a step of changing the state from one in which the curable composition (A) and the mold 106 are not in contact to a state in which they are in contact, and a step of maintaining the state in which they are in contact. As a result, the liquid of the curable composition (A) fills the recesses of the fine pattern on the surface of the mold 106, and this liquid becomes a liquid film that fills the fine pattern of the mold 106.

[0262] Figure 5 shows a comparison between the prior art (e.g., Japanese Patent Publication No. 6584578) and the present disclosure regarding the gas trapped between the mold 106 and the substrate 101 during the contact process. In the present disclosure, during the waiting process, the curable composition (A) becomes a substantially continuous liquid film 104 from which the solvent component (d) has been removed, resulting in a smaller volume of gas trapped between the mold 106 and the substrate 101 compared to the prior art. Therefore, the spreading of the curable composition (A) during the contact process is completed quickly.

[0263] If the spreading and filling of the curable composition (A) is completed quickly during the contact process, the time required to maintain the mold 106 in contact with the curable composition (A) (the time required for the contact process) can be shortened. Shortening the time required for the contact process leads to a reduction in the time required for pattern formation (film formation), thus improving productivity. The contact process is preferably 0.1 seconds or more and 3 seconds or less, and particularly preferably 0.1 seconds or more and 1 second or less. If the contact process is shorter than 0.1 seconds, the spreading and filling will be insufficient, and defects called unfilled defects tend to occur frequently.

[0264] If the curing process includes a light irradiation process, the mold 106 is made of a light-transmitting material, taking this into consideration. Specifically, preferred materials for the mold 106 include light-transmitting resins such as glass, quartz, 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 contained in the curable composition (A) is selected. Quartz is suitable as a material for the mold 106 because it has a small coefficient of thermal expansion and low pattern distortion.

[0265] The pattern formed on the surface of the mold 106 has a height of, for example, 4 nm to 200 nm. The lower the height of the pattern on the mold 106, the smaller the force required to separate the mold 106 from the cured film of the curable composition during the demolding process, i.e., the demolding force, which reduces the number of demolding defects remaining on the mold 106 due to the pattern of the curable composition being torn off. Also, the impact when separating the mold can cause the pattern of the curable composition to elastically deform, causing adjacent pattern elements to come into contact with each other, resulting in adhesion or damage. However, it is advantageous to have a pattern element height of about 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.

[0266] 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.

[0267] In the contact process, the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the curable composition (A) is not particularly limited, but for example, it may be 0 MPa or more and 100 MPa or less. Preferably, the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the curable composition (A) is 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.

[0268] The contact process can be carried out under any of the following conditions: under an atmospheric atmosphere, under a reduced pressure atmosphere, or under an inert gas atmosphere. However, it is preferable to use a reduced pressure atmosphere or an inert gas atmosphere because it prevents the influence of oxygen and moisture on the curing reaction. Specific examples of inert gases used when carrying out the contact process under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various fluorocarbon gases, or mixtures thereof. A gas containing 10% or more carbon dioxide or helium by molar ratio is preferred, and a gas containing 10% or more carbon dioxide by molar ratio is particularly preferred. Helium gas diffuses easily into the mold, substrate, and curable composition, so atmospheric gas trapped in the mold pattern, etc., disappears quickly. Carbon dioxide dissolves easily in the curable composition and the underlying layer on the substrate, so atmospheric gas trapped in the mold pattern, etc., disappears quickly. The solubility coefficient of carbon dioxide in the curable composition is 0.5 kg / m³. ３ ・ATM or more 10kg / m ３ - Preferably, the pressure is below atm. Details of these are disclosed in Japanese Patent Application Publication No. 2022-99271. When the contact process is performed in a specific gas atmosphere, including an atmospheric atmosphere, the preferred pressure is 0.0001 atmospheres or more and 10 atmospheres or less.

[0269] <Curing Process> In the curing process, as schematically shown in Figure 3F, the curable composition (A) is cured by irradiating it with irradiation light 107 as curing energy to form a cured film. In the curing process, for example, the curable composition (A) is irradiated with irradiation light 107 through the mold 106. More specifically, the curable composition (A) filled in the fine pattern of the mold 106 is irradiated with irradiation light 107 through the mold 106. As a result, the curable composition (A) filled in the fine pattern of the mold 106 hardens to form a cured film 108 having a pattern.

[0270] The irradiation light 107 is selected according to the sensitivity wavelength of the curable composition (A). Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, or electron beams with a wavelength of 150 nm to 400 nm. It is particularly preferable that the irradiation light 107 be ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are compounds that are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, Deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F ２ Lasers are one example of such light sources. However, ultra-high pressure mercury lamps are particularly preferred as light sources that emit ultraviolet light. There may be one or more light sources. Light may be irradiated over the entire surface of the curable composition (A) filled in the fine pattern of the mold, or only over a portion of the surface (limited to a specific area). Light may also be irradiated over the entire surface of the substrate intermittently multiple times, or continuously over the entire surface of the substrate. Furthermore, light may be irradiated over a first surface of the substrate in the first irradiation process, and light may be irradiated over a second surface of the substrate that is different from the first surface in the second irradiation process.

[0271] <Release Process> In the release process, the mold 106 is separated from the cured film 108, as schematically shown in Figure 3G. By separating the patterned cured film 108 from the mold 106, the cured film 108, which has a pattern that is an inversion of the fine pattern of the mold 106, is obtained in an upright state. Here, some of the cured film remains in the recesses of the patterned cured film 108. This film is called residual film.

[0272] 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.

[0273] <Repeat> By a series of steps (manufacturing process) having the above-described arrangement step followed by a demolding step in this order, a cured film having a desired uneven pattern shape (a pattern shape that follows the uneven shape of the mold 106) at the desired position can be obtained.

[0274] In the pattern formation method described herein, the repeating units (shots) from the placement step to the demolding step can be repeated multiple times on the same substrate, making it possible to obtain a cured film 108 having multiple desired patterns at desired positions on the substrate.

[0275] [Method for Manufacturing Articles] The method for manufacturing articles 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 has been 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.

[0276] Furthermore, the cured film 108 having a pattern formed by the pattern forming method of this disclosure 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 this disclosure 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.

[0277] 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, as the source gas, CF ４ , C ２ F ６ , C ３ F ８ , CCl ２ F ２ , CCl ４ , CBrF ３ , BCl ３ , PCL ３ SF ６ , Cl ２ Halogen-based gases such as the following can be used. Also, as a source gas, O ２ CO, CO ２ Gases containing oxygen atoms such as He, N ２ , inert gases such as Ar, H ２ NH ３ Other gases can also be used. Furthermore, these gases can be mixed and used as a source gas. In this case, the photocuring film requires high dry etching resistance in order to process the substrate with good yield.

[0278] 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.

[0279] 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 this disclosure. 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. Furthermore, it is 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.

[0280] [Examples] More specific examples will be described to supplement the embodiments described above, but this disclosure is not limited to the following examples. Unless otherwise specified, "parts" and "%" used below are based on weight.

[0281] <Curable Compositions 1-21> Polymerizable compound (a) (component (a)), photopolymerization initiator (b) (component (b)), solvent (d) (component (d)), and additive (c) (component (c)) were mixed in the weight percentages shown in Table 1 below, and filtered through a polyethylene filter with a pore size of 0.005 μm. Curable compositions 1-21 were prepared in this manner. Table 1

[0282]

[0283] The abbreviations shown in Table 1 are as follows: (Polymerizable compound) a1: DCPDA: Dimethylol-tricyclodecanediaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) (Photopolymerization initiator) b1: Omnirad 819: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM Resin) (Additives) c1: Dynol-604: Acetylene glycol-based surfactant (manufactured by Evonik, HLB value = 8.2) c2: Brownon SA-30 / 70 2000R: Polyoxyethylene polyoxypropylene alkyl ether (manufactured by Aoki Oil Co., Ltd., HLB value = 4.2) c3: Pluronic® 17R2: Polyoxyethylene polyoxypropylene glycol (manufactured by ADEKA, HLB value = 6.1) c4: Pluronic® L81: Polyoxyethylene polyoxypropylene glycol (manufactured by ADEKA, HLB value = 2.0) c5: Pluronic® L101: Polyoxyethylene polyoxypropylene glycol (manufactured by ADEKA, HLB value = 1.0) c6: Ionet MO-200: Polyethylene glycol fatty acid ester (manufactured by Sanyo Chemical Industries, HLB value = 8.4) c7: Pluronic® L-44: Polyoxyethylene polyoxypropylene glycol (manufactured by ADEKA, HLB value = 8.5) c8: Pelletex 4417: Alkylamine alkylene oxide adduct (manufactured by Miyoshi Oil & Fat Co., Ltd., HLB value = 6.3) c9: CH ３ O(C) ２ H ４ O) ２ (C ３ H ６ O) １７ (C ２ H ４ O) CH ３Compound (HLB value = 2.3) (Solvent) d1: PGMEA: Propylene glycol monomethyl ether acetate (boiling point = 146°C) d2: n-propyl acetate (boiling point = 102°C) d3: 1-propanol (boiling point = 97°C) d4: 2-ethyl-1,3-hexanediol (boiling point = 244°C) d5: 1,6-hexanediol (boiling point = 250°C) <Layer-forming composition 1> Compound (a2) and crosslinking agent (e1) were dissolved in volatile solvent (d1) in the following weight %: Compound (a2) 0.2775 Crosslinking agent (e1) 0.0692 Volatile solvent (d1) 99.6533 The mixed solvent thus obtained was filtered through a polyethylene filter with a pore size of 0.005 μm. Layer-forming composition 1 was prepared.

[0284] The abbreviation is as follows: (Compound (a2)) Carboxylic acid anhydride-modified cresol novolac type epoxy acrylate (manufactured by Shin-Nakamura Chemical Industry, trade name: EA-7140) (Formula (1) below)

[0285]

[0286] (Crosslinking agent (e1)) 2,4,6-Tris[bis(methoxymethyl)amino]-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.) (Formula (2) below)

[0287]

[0288] (Volatile solvent (d1)) PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) <Layer-forming composition 2> For layer-forming composition 2, Fujifilm's layer-forming composition FULS-013D was used.

[0289] <Adhesion Layers 1 and 2> Layer-forming compositions 1 and 2 were each applied to a 2-inch silicon wafer using a spin-coating method. Adhesion layers 1 and 2 were formed by baking the silicon wafers coated with layer-forming compositions 1 and 2 at a heating temperature of 220°C for a heating time of 90 seconds.

[0290] <Contact Angle of Curable Composition with Adhesion Layer> An industrial material printer DMP-2850 (manufactured by Fujifilm) was used to measure the contact angle of the curable composition with respect to the adhesion layer. The volume of the curable composition droplet was set to 1 to 2 μL, and the state of the droplet immediately after dropping it onto the adhesion layer was imaged using the top camera of the device. The contact angle was calculated from the droplet diameter obtained from image analysis using the following equations (4) and (5).

[0291] Assuming that droplets of the curable composition expand while maintaining a spherical shape, the relationship between the droplet radius and the droplet height can be expressed by the following equations (4) and (5). The abbreviations shown in equations (4) and (5) are as follows: r: droplet radius V: droplet volume h: droplet height ０ Radius equation when the initial shape of the droplet is a hemisphere (4)

[0292]

[0293] (Formula 5)

[0294]

[0295] <Contact Angle of Curable Composition with Adhesion Layer (Solvent Removed)> For measuring the contact angle, a liquid droplet of 1 μL was used, and an automatic static contact angle measuring device, Dropmaster 300 (manufactured by Kyowa Interfacial Chemical Co., Ltd.), was used. The equilibrium contact angle of the curable composition after the solvent had completely evaporated (for example, the contact angle 15 seconds after dropping the droplet) was measured. The contact angles of the curable composition with respect to the adhesion layer measured in this manner are shown in Table 2 below. Table 2

[0296]

[0297] <Evaluation of Liquid Film Formation> An industrial material printer DMP-2850 (manufactured by Fujifilm) was used to evaluate the liquid film formation properties. The curable compositions of Examples 1 to 15 and Comparative Examples 1 to 8 shown in Table 2 were each filled into cartridges. Droplets of about 2 pl were dropped onto the adhesion layer or silicon substrate in an array of 6 rows x 6 columns at 70 μm intervals. The state of the droplets, i.e., the state of liquid film formation, was observed 5 to 180 seconds after dropping the droplets, and the liquid film formation properties were evaluated according to the following evaluation criteria. (Evaluation Criteria) A: A substantially continuous liquid film was formed within 5 seconds after dropping the droplets. B: A substantially continuous liquid film was formed between 5 and 180 seconds after dropping the droplets. C: A substantially continuous liquid film was not formed even after 180 seconds had elapsed since dropping the droplets. <Evaluation of Liquid Film Stability> An industrial material printer DMP-2850 (manufactured by Fujifilm) was used to evaluate the liquid film stability. In evaluating liquid film formation, the time during which the liquid film remained stable without shrinking or expanding after its formation was measured, and the liquid film stability was evaluated according to the following evaluation criteria. "Shrinking" means that the length of the liquid film becomes smaller than the desired area (design liquid film area), and "expansion" means that the length of the liquid film wets and spreads beyond the desired area. (Evaluation Criteria) A: Liquid film stability of 300 seconds or more. B: Liquid film stability of 80 seconds or more and less than 300 seconds. C: Liquid film stability of less than 80 seconds.

[0298] The evaluation of liquid film stability for Examples 1 to 15 and Comparative Examples 1 to 8 is shown in Table 3 below. Table 3

[0299]

[0300] This disclosure is not limited to the embodiments described above, and various modifications and alterations are possible without departing from the spirit and scope of this disclosure. Accordingly, the claims are attached to make the scope of this disclosure public.

[0301] This application claims priority based on Japanese Patent Application No. 2024-157734, filed on September 11, 2024, and all of its contents are incorporated herein by reference.

Claims

1. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), an additive (c), and a solvent (d), wherein 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 100°C or more and less than 250°C at 1 atmosphere, the additive (c) is a compound consisting of carbon, oxygen and hydrogen, or a compound consisting of carbon, nitrogen, oxygen and hydrogen, and the HLB value of the additive (c) calculated by the Griffin method is 2.0 or more and 8.4 or less.

2. The curable composition according to claim 1, wherein, if the total weight of all components of the composition obtained by removing the solvent (d) from the curable composition is 100 parts by weight, and the amount of additive (c) added is A parts by weight, the HLB value of additive (c) satisfies 0.8 ≤ A × HLB value ≤ 12.

6.

3. The curable composition according to claim 1, characterized in that the additive (c) comprises a polyoxyethylene polyoxypropylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene glycol, an acetylene glycol polyalkylene oxide adduct, or an alkylamine alkylene oxide adduct.

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

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

6. A film-forming method for forming a film of a curable composition on a substrate, comprising: an arrangement step of discretely arranging a plurality of droplets of the curable composition described in claim 1 on the substrate; and a waiting step of waiting until the plurality of droplets combine with adjacent droplets to form a liquid film.

7. The film-forming method according to claim 6, characterized in that the contact angle of the curable composition with respect to the substrate is 1.8 degrees or less.

8. The film formation method according to claim 6, characterized in that the arrangement step involves discretely arranging the plurality of liquid droplets on the substrate using an inkjet method.

9. The film-forming method according to claim 6, characterized in that the waiting step is performed until the solvent contained in the liquid film evaporates and the solvent content is 10% by volume or less relative to the entire liquid film.

10. The film forming method according to claim 6, further comprising a contact step of bringing the liquid film into contact with a mold after the waiting step.

11. The film forming method according to claim 10, characterized in that the mold includes a pattern, the contact step involves bringing the pattern of the mold into contact with the liquid film, and after the contact step, the curing step involves curing the liquid film to form a cured film having a pattern corresponding to the pattern of the mold.

12. The film forming method according to claim 10, characterized in that the mold includes a flat surface, the contact step involves bringing the flat surface of the mold into contact with the liquid film, and after the contact step, the curing step involves curing the liquid film to form a cured film having a surface that conforms to the flat surface of the mold.

13. A method for manufacturing an article, comprising: a forming step of forming a film of a curable composition on a substrate using the film forming method described in claim 6; a processing step of processing the substrate on which the film formed in the forming step is formed; and a manufacturing step of manufacturing an article from the substrate processed in the processing step.

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