Curable composition, film-forming method, and method for manufacturing articles

Abstract

This provides a new technology related to curable compositions. [Solution] A curable composition is provided 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.

Description

[Technical Field]

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

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

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

[0004] Furthermore, in the photolithography process for manufacturing semiconductor devices, it is also necessary to planarize the substrate. For example, in extreme ultraviolet (EUV) lithography, a photolithography technique that has attracted attention in recent years, the depth of focus at which the projected image is formed becomes shallower as miniaturization progresses, so the surface irregularities of the substrate to which the curable composition is supplied must be kept to tens of nanometers or less. In imprint technology, a level of flatness similar to that of EUV is also required 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". [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2022-188736 [Patent Document 2] Special Publication No. 2010-530641 [Overview of the project] [Problems that the invention aims to solve]

[0007] In the technologies disclosed in Patent Documents 1 and 2, by including a solvent in the curable composition to reduce the viscosity of the curable composition, the droplets of the curable composition dropped onto the substrate spread rapidly to such an extent that the droplets bond to each other, thus exhibiting good liquid film formability. However, when a curable composition containing a solvent is used, the liquid film may protrude from the desired region (designed liquid film region). The curable composition (liquid film) protruding from the desired region becomes a factor leading to undesirable states such as eroding the adjacent region and adhering to the side wall of the mold. Also, when the "pinning effect" that appears by adding a specific additive to the curable composition is too strong, the liquid film may shrink. Hereinafter, the performance that can ensure (maintain) a stable state as a liquid film without protrusion and shrinkage of the curable composition (liquid film) in the desired region is referred to as "liquid film stability".

[0008] The present invention has been made in view of such problems of the prior art, and an exemplary object thereof is to provide a new technology regarding a curable composition.

Means for Solving the Problems

[0009] In order to achieve the above object, a curable composition as one aspect of the present invention is a curable composition containing a polymerizable compound (a), a photopolymerization initiator (b), an additive (c), and a solvent (d), wherein the content of the solvent (d) with respect to the whole of the 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 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) calculated by the Griffin method is 2.0 or more and 8.4 or less.

[0010] A further object or other aspect of the present invention will be clarified by the embodiments described below with reference to the accompanying drawings.

Effects of the Invention

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

[0012] [Figure 1] This figure shows the process by which droplets of a curable composition placed on a substrate form a liquid film. [Figure 2] This diagram shows the process by which additive components are adsorbed onto the substrate at the edges of the liquid film of a curable composition. [Figure 3] This figure illustrates a pattern formation method (film formation method) as one aspect of the present invention. [Figure 4] This diagram illustrates the flow behavior of droplets of a curable composition during the waiting process. [Figure 5] This diagram shows a comparison between the conventional technology and the present invention regarding gas containment generated in the contact process. [Modes for carrying out the invention]

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

[0014] In providing a new technology 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.

[0015] [Curable composition (A)] The curable composition (A) in the present invention is, for example, a curable composition for inkjet printing. The curable composition (A) in the present invention is a composition comprising at least a component (a) which is a polymerizable compound, a component (b) which is a photopolymerization initiator, a component (c) which is an additive, and a component (d) which is a solvent.

[0016] In this specification, "cured film" refers to a film obtained by polymerizing and curing a curable composition (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.

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

[0018] Examples of such polymerizable compounds include radical polymerizable compounds. The polymerizable compound that is component (a) may consist of only one type of polymerizable compound, or it may consist of multiple types (one or more types) of polymerizable compounds.

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

[0020] (Meth)acrylic compounds are compounds having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or methacryloyl group include, but are not limited to, the following. Phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO-modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-Tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy(meth)acrylate, PO-modified phenoxy(meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate Acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pliers Isoamyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, undecyl(meth)acrylate, dodecyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, benzyl(meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, 1- or 2-naphthyl(meth)acrylate, 1- or 2-naphthylmethyl(meth)acrylate, 3- or 4-phenoxybenzyl(meth)acrylate, cynoabenzyl(meth)acrylate, naphthalenemethyl(meth)acrylate,

[0021] Examples of commercially available monofunctional (meth)acrylic compounds mentioned above include, but are not limited to, the following: Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (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 Co., Ltd.) Light acrylates BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy esters M-600A, POB-A, OPP-EA (manufactured by Kyoeisha Chemical Co., Ltd.) KAYARAD (registered trademark) TC110S, R-564, R-128H (manufactured by Nippon Kayaku Co., Ltd.) NK Ester AMP-10G, AMP-20G, A-LEN-10 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 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 (made by BASF), ACMO, DMAA, DMAPAA (manufactured by Kojin), HRD-01 (manufactured by Nippon Shokubai)

[0022] Furthermore, examples of polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following. Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, 1,3-Adamantane dimethanol di(meth)acrylate, Tris(2-Hydoxyethyl)isocyanurate tri(meth)acrylate, Tris(Acryloyloxy)isocyanurate, Bis(Hydroxymethyl)tricyclodecane di(meth)acrylate, Dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, o-, m- or p-Benzene di(meth)acrylate, o-, m- or p-Xylylene di(meth)acrylate

[0023] Examples of commercially available polyfunctional (meth)acrylic compounds mentioned above include, but are not limited to, the following: Yupimer (registered trademark) UV SA1002, SA2007 (manufactured by Mitsubishi Chemical Corporation), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 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 Co., Ltd.) KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (manufactured by Nippon Kayaku Co., Ltd.) Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (manufactured by Toagosei), Lipoxy (registered trademark) VR-77, VR-60, VR-90 (manufactured by Showa Polymer Co., Ltd.) Ogusol EA-0200, Ogusol EA-0300 (manufactured by Osaka Gas Chemical), SR295, SR355 (manufactured by Sartmar)

[0024] In the above-mentioned group of compounds, (meth)acrylate means acrylate or methacrylate having an equivalent alcohol residue. (meth)acryloyl group means acryloyl group or methacryloyl group having an equivalent alcohol residue. EO represents ethylene oxide, and EO-modified compound refers to a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are linked via a block structure of ethylene oxide group. Furthermore, PO represents propylene oxide, and PO-modified compound B refers to a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are linked via a block structure of propylene oxide group.

[0025] Specific examples of styrene compounds include, but are not limited to, the following. Alkylstyrenes such as styrene, 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene and iodose Halide styrenes such as ethylene; compounds having a styryl group as a polymerizable functional group, such as nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl.

[0026] Specific examples of vinyl compounds include, but are not limited to, the following. Compounds having a vinyl group as a polymerizable functional group, such as vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate, and acrylonitrile; conjugated diene monomers such as butadiene, isoprene, and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; vinylidenes such as vinylidene chloride; vinyl esters of organic carboxylic acids and their derivatives (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, divinyl adipate, etc., (meth)acrylonitrile, etc.)

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

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

[0029] Examples of fumaric compounds include, but are not limited to, the following: Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, di-sec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, dibenzyl fumarate

[0030] Examples of maleyl compounds include, but are not limited to, the following: Dimethyl maleate, diethyl maleate, diisopropyl maleate, di-sec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, dibenzyl maleate

[0031] Other radical polymerizable compounds include, but are not limited to, the following: Dialkyl esters of itaconic acid and their derivatives (dimethyl itaconic acid, diethyl itaconic acid, diisopropyl itaconic acid, di-sec-butyl itaconic acid, diisobutyl itaconic acid, di-n-butyl itaconic acid, di-2-ethylhexyl itaconic acid, dibenzyl itaconic acid, etc.), N-vinylamide derivatives of organic carboxylic acids (N-methyl-N-vinylacetamide, etc.), maleimides and their derivatives (N-phenylmaleimide, N-cyclohexylmaleimide, etc.)

[0032] When component (a), 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 and polyfunctional polymerizable compounds yields a cured film with an excellent balance of performance, such as high mechanical strength, high dry etching resistance, and high heat resistance.

[0033] In the film formation method of the present invention, since it takes several milliseconds to several hundred seconds for droplets of the curable composition (A) discretely arranged on the substrate to bond together and form a substantially continuous liquid film, 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).

[0034] The boiling point of component (a), which is a polymerizable compound, generally correlates with its molecular weight. Therefore, 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 the present invention. Thus, it is preferable that the boiling point of each of the one or more polymerizable compounds contained in component (a) under normal pressure is 250°C or higher.

[0035] Furthermore, the vapor pressure of the polymerizable compound (component (a)) at 80°C is preferably 0.001 mmHg or less. If 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.

[0036] The boiling points and vapor pressures of various organic compounds under normal pressure can be calculated using methods such as Hansen Solubility Parameters in Practice (HSPiP) 5th Edition, section 5.3.04.

[0037] <Parameters for component (a) of Onishi> V is the dry etching rate of the organic compound, N is the total number of atoms in the organic compound, and N is the total number of carbon atoms in the composition. C , and the total number of oxygen atoms in the composition N O It is known that the following relationship (1) holds true. V∝N / (Nc-No) Equation (1)

[0038] Here, N / (Nc - No) is also called the "Ohnishi parameter" (hereinafter referred to as "OP"). For example, 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 having a small OP.

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

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

[0041]

Number

[0042] Here, OP n is the OP of component a n n and n n is the mole fraction of component a n in the total amount of component (a). n

[0043] 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 include at least one compound (a1-1) as component (a), which has two or more cyclic structures, and at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0044] <Compound (a1-1): Polymerizable compound having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure> The polymerizable compound component (a) in the present invention may include a compound (a1-1) having an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

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

[0046] The aromatic structure preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Specific examples of aromatic rings are as follows: Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indan ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring

[0047] Of the aromatic rings mentioned above, benzene rings or naphthalene rings are preferred, and benzene rings are more preferred. The aromatic rings may have a structure in which multiple rings are linked together, for example, biphenyl rings or bisphenyl rings.

[0048] The aromatic heterocyclic structure preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples of aromatic heterocyclic structures are as follows: Thiofen ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, quinoridine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, sinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxatiin ring, phenoxazine ring

[0049] For alicyclic structures, the number of carbon atoms is preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. Furthermore, for alicyclic structures, the number of carbon atoms is preferably 22 or less, more preferably 18 or less, even more preferably 6 or less, and even more preferably 5 or less. Specific examples include the following. Cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, spirodecane ring, spirononane ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindan ring, bornane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring

[0050] Specific examples of 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℃, vapor pressure 0.0004mmHg at 80℃, molecular weight 254.3),

[0051] [ka]

[0052] 1-Naphthyl acrylate (NaA, OP2.27, boiling point 317°C, vapor pressure 0.0422 mmHg at 80°C, molecular weight 198),

[0053] [ka]

[0054] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2℃, vapor pressure at 80℃ 0.0006 mmHg, molecular weight 268.3),

[0055] [ka]

[0056] 1-Naphthylmethyl acrylate (Na1MA, OP2.33, boiling point 342.1℃, vapor pressure 0.042 mmHg at 80℃, molecular weight 212.2),

[0057] [ka]

[0058] 2-Naphthylmethyl acrylate (Na2MA, OP2.33, boiling point 342.1℃, vapor pressure 0.042 mmHg at 80℃, molecular weight 212.2),

[0059] [ka]

[0060] DPhPA (OP2.38, boiling point 354.5°C, vapor pressure 0.0022 mmHg at 80°C, molecular weight 266.3), as shown in the following formula,

[0061] [ka]

[0062] The following formula shows PhBzA (OP2.29, boiling point 350.4℃, vapor pressure at 80℃ 0.0022mmHg, molecular weight 238.3),

[0063] [ka]

[0064] FLMA (OP2.20, boiling point 349.3°C, vapor pressure 0.0018 mmHg at 80°C, molecular weight 250.3) as shown in the following formula,

[0065] [ka]

[0066] ATMA (OP2.13, boiling point 414.9°C, vapor pressure 0.0001 mmHg at 80°C, molecular weight 262.3), as shown in the following formula,

[0067] [ka]

[0068] The following formula represents DNaMA (OP2.00, boiling point 489.4°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 338.4),

[0069] [ka]

[0070] 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,

[0071] [ka]

[0072] BPh43DA (OP2.63, boiling point 439.5℃, vapor pressure <0.0001mmHg at 80℃, molecular weight 322.3), as shown in the following formula,

[0073] [ka]

[0074] The following formula shows DPhEDA (OP2.63, boiling point 410°C, vapor pressure <0.0001 mmHg at 80°C, molecular weight 322.3),

[0075] [ka]

[0076] The following formula shows BPMDA (OP2.68, boiling point 465.7°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight 364.4),

[0077] [ka]

[0078] 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,

[0079] [ka]

[0080] The following formula (a1-1-1) (OP2.40, boiling point 333.4℃, vapor pressure at 80℃ 0.0181mmHg, molecular weight 199.2),

[0081] [ka]

[0082] The following formula (a1-1-2) (OP2.40, boiling point 333.4℃, vapor pressure at 80℃ 0.0181mmHg, molecular weight 199.2),

[0083] [ka]

[0084] 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),

[0085] [ka]

[0086] The following formula (a1-1-4) (OP2.85, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0087] [ka]

[0088] The following formula (a1-1-5) (OP2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0089] [ka]

[0090] The following formula (a1-1-6) (OP2.87, boiling point 421.0℃, vapor pressure at 80℃ <0.0001 mmHg, molecular weight 338.4),

[0091] [ka]

[0092] The following formula (a1-1-7) (OP2.87, boiling point 465.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 338.4),

[0093] [ka]

[0094] The following formula (a1-1-8) (OP2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4),

[0095] [ka]

[0096] The following formula (a1-1-9) (OP2.50, boiling point 433.1℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 320.3),

[0097] [ka]

[0098] The following formula (a1-1-10) (OP2.64, boiling point 468.1℃, vapor pressure at 80℃ <0.0001 mmHg, molecular weight 326.4),

[0099] [ka]

[0100] The following formula (a1-1-11) (OP3.25, boiling point 553.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 358.4),

[0101] [ka]

[0102] The following formula (a1-1-12) (OP2.63, boiling point 443.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 322.4),

[0103] [ka]

[0104] The following formula (a1-1-13) (OP2.89, boiling point 509.3℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 406.4),

[0105] [ka]

[0106] The following formula (a1-1-14) (OP2.63, boiling point 450.0℃, vapor pressure at 80℃ <0.0001 mmHg, molecular weight 322.4),

[0107] [ka]

[0108] The following formula (a-1-15) (OP3.00, boiling point 476.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 366.4)

[0109] [ka]

[0110] The following formula (a1-1-16) (OP2.68, boiling point 447.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4)

[0111] [ka]

[0112] The following formula (a1-1-17) (OP2.36, boiling point 543.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 398.5),

[0113] [ka]

[0114] The following formula (a1-1-18) (OP3.27, boiling point 526.9℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 396.4),

[0115] [ka]

[0116] The following formula (a1-1-19) (OP2.71, boiling point 333.7℃, vapor pressure at 80℃ 0.0302mmHg, molecular weight 244.3),

[0117] [ka]

[0118] The following formula (a1-1-20) (OP2.73, boiling point 333.7℃, vapor pressure at 80℃ 0.0134mmHg, molecular weight 258.3),

[0119] [ka]

[0120] The following formula (a1-1-21) (OP2.71, boiling point 319.2℃, vapor pressure at 80℃ 0.0566 mmHg, molecular weight 262.3),

[0121] [ka]

[0122] The following formula (a1-1-22) (OP2.71, boiling point 336.9℃, vapor pressure at 80℃ 0.0055mmHg, molecular weight 244.3),

[0123] [ka]

[0124] The following formula (a1-1-23) (OP3.00, boiling point 370.9℃, vapor pressure at 80℃ 0.0021mmHg, molecular weight 274.4),

[0125] [ka]

[0126] The following formula (a1-1-24) (OP3.00, boiling point 376.4℃, vapor pressure at 80℃ 0.0005mmHg, molecular weight 274.4),

[0127] [ka]

[0128] The following formula (a1-1-25) (OP3.00, boiling point 379.4℃, vapor pressure at 80℃ 0.0002mmHg, molecular weight 288.4),

[0129] [ka]

[0130] The following formula (a1-1-26) (OP2.33, boiling point 360.8℃, vapor pressure at 80℃ 0.0006mmHg, molecular weight 252.3),

[0131] [ka]

[0132] The following formula (a1-1-27) (OP2.54, boiling point 371.5℃, vapor pressure at 80℃ 0.0003mmHg, molecular weight 254.3),

[0133] [ka]

[0134] The following formula (a1-1-28) (OP2.57, boiling point 381.2℃, vapor pressure at 80℃ 0.0001mmHg, molecular weight 268.3),

[0135] [ka]

[0136] The following formula (a1-1-29) (OP2.57, boiling point 381.8℃, vapor pressure at 80℃ 0.0004mmHg, molecular weight 268.3),

[0137] [ka]

[0138] The following formula (a1-1-30) (OP2.50, boiling point 487.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 374.4),

[0139] [ka]

[0140] The following formula (a1-1-31) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0141] [ka]

[0142] The following formula (a1-1-32) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0143] [ka]

[0144] The following formula (a1-1-33) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0145] [ka]

[0146] The following formula (a1-1-34) (OP2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3),

[0147] [ka]

[0148] The following formula (a1-1-35) (OP2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3),

[0149] [ka]

[0150] 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 that they contain at least one of the constituent units represented by any of the following structures (1) to (6).

[0151] [ka]

[0152] In structures (1) to (6), each substituent R is a substituent that independently contains a substructure containing an aromatic ring, 1 This is a hydrogen atom or a methyl group. In this specification, the portion of the structural unit represented by structures (1) to (6), excluding R, is used as the main chain of a specific polymer. The formula weight of substituent R is 80 or more, preferably 100 or more, more preferably 130 or more, and even more preferably 150 or more. In practice, the upper limit of the formula weight of substituent R is 500 or less.

[0153] Polymers having polymerizable functional groups are typically compounds with a weight-average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. There is no specific upper limit for the weight-average molecular weight, but for example, 50,000 or less is preferred. By setting the weight-average molecular weight above the lower limit mentioned above, the boiling point can be set to 250°C or higher, and the mechanical properties after curing can be further improved. Furthermore, by setting the weight-average molecular weight below the upper limit mentioned above, solubility in solvents is high, the fluidity of discretely arranged droplets is maintained without excessive viscosity, and the flatness of the liquid film plane can be further improved. In this invention, unless otherwise specified, the weight-average molecular weight (Mw) refers to that measured by gel permeation chromatography (GPC).

[0154] 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.

[0155] 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% to 60% by weight, more preferably 1% to 50% by weight, and even more preferably 10% to 40% by weight, based on the total mass of all components excluding 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.

[0156] <Component (b): Photopolymerization initiator> Component (b) is a photopolymerization initiator. In this specification, a photopolymerization initiator is a compound that senses light of a predetermined wavelength and generates the 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.

[0157] Examples of radical generators include, but are not limited to, the following: 2,4,5-triarylimidazole dimers which may have substituents such as 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazole dimer; benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone Benzophenone derivatives such as 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, and 1,2-benz Quinones such as anthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantaraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone; benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; benzyl Benzyl derivatives such as dimethyl ketal; acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone;Acyl phosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one;

[0158] Examples of commercially available radical generators mentioned above include, but are not limited to, the following: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin (registered trademark) TPO, LR8893, LR8970 (BASF), Yubekrill P36 (manufactured by UCB)

[0159] Of the radical generators mentioned above, component (b) is preferably an acylphosphine oxide polymerization initiator. The acylphosphine oxide polymerization initiators among the radical generators mentioned above are as follows: Acyl phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0160] The proportion of component (b) in the curable composition (A) is preferably 0.1% by weight or more and 50% by weight or less, relative to the total mass of component (a), component (b), and component (c) described later, i.e., the total mass of all components excluding component (d). Furthermore, the proportion of component (b) in the curable composition (A) is more preferably 0.1% by weight or more and 20% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less, relative to the total mass of all components excluding component (d). By increasing the proportion of component (b) to 0.1% by weight or more, the curing rate of the composition can be increased and the reaction efficiency can be improved. Furthermore, by increasing the proportion of component (b) to 50% by weight or less, a cured film with a certain degree of mechanical strength can be obtained.

[0161] <Ingredients (c): Additives> The curable composition (A) in the present invention further comprises an additive as component (c), in addition to component (a), which is a polymerizable compound, and component (b), which is a photopolymerization initiator. 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 between 2.0 and 8.4. The HLB value in the present invention is a value determined 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 determined 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 between 0 and 20. The larger the HLB value, the higher the hydrophilicity, and the higher the overall polarity of the molecule compared to the smaller the HLB value.

[0162] In this invention, 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 below. 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.

[0163] 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 1(a) and 1(b) show the process by which a droplet of curable composition (A) placed on a substrate forms a liquid film. As shown in Figure 1(a), when a droplet of curable composition (A) is placed on a substrate, the droplet wets and spreads. Then, as shown in Figure 1(b), 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.

[0164] 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, the polarity of the curable composition (A) is thought to decrease 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 curable composition (A) can be utilized 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.

[0165] 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).

[0166] 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 2(a) and 2(b) 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 2(a), 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 2(b), with the decrease in polarity at the edges of the liquid film of the curable composition (A), the additive component (c) is induced to be adsorbed onto the substrate, which has higher polarity than the edges of the liquid film. 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).

[0167] 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 invention, 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, making it 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, making it difficult to obtain good liquid film stability.

[0168] From the standpoint 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.

[0169] 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 invention, 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.

[0170] Examples of additive component (c) include the following: These include alkyl alcohol polyalkylene oxide adducts, polyalkylene oxides, acetylene glycol polyalkylene oxide adducts, and alkylamine alkylene oxide adducts, which are formed by adding an alkylene oxide with 2 to 4 carbon atoms to an alkyl alcohol.

[0171] Examples of commercially available polyoxyethylene polyoxypropylene stearyl ether include 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.

[0172] 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.

[0173] 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).

[0174] 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.

[0175] 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.

[0176] From the viewpoint of liquid film stability, it is more preferable that the additive component (c) has the following structure. Structure of polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, acetylene glycol polyalkylene oxide adduct, or alkylamine alkylene oxide adduct

[0177] The optimal blending ratio of component (c), which is an additive in the curable composition (A), varies 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.

[0178] 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.

[0179] <Component (d): Solvent> The curable composition (A) in the present invention contains, as component (d), a solvent having a boiling point of 100°C or higher and less than 250°C under normal pressure. Component (d) can be a solvent in which components (a), (b), 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) under normal pressure is 100°C or higher, preferably 140°C or higher, and particularly preferably 150°C or higher. The boiling point of component (d) under normal pressure is less than 250°C, and 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 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).

[0180] 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-te Monoalcohol solvents such as trandecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; and polyhydric alcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, and diethylene glycol.

[0181] Examples of ketone solvents include the following: Methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone

[0182] Examples of ether-based solvents include the following: 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, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether

[0183] Examples of ester solvents include the following: 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 acetate Polypropylene mono-n-butyl ether, propylene glycol acetate monomethyl ether, propylene glycol acetate monoethyl ether, propylene glycol acetate monopropyl ether, propylene glycol acetate monobutyl ether, dipropylene glycol acetate monomethyl ether, dipropylene glycol acetate monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate

[0184] Examples of nitrogen-containing solvents include the following: N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone

[0185] In the present invention, when the total amount of the curable composition (A) is 100% by volume, the content of the component (d) which is a solvent is 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 amount of the curable composition (A) means the total amount of the component (a) which is a polymerizable compound, the component (b) which is a photopolymerization initiator, the component (c) which is an additive, and the component (d) which is a solvent. For example, the content of the component (d) is 40% by volume or more and 85% by volume or less. When the content of the component (d) is less than 5% by volume, it is difficult to obtain a thin film after the volatilization of the component (d) under the condition that a substantially continuous liquid film can be obtained. Also, when the content of the component (d) is more than 95% by volume, it is difficult to obtain a thick film after the volatilization of the component (d) even when the droplets are dropped most densely by the inkjet method.

[0186] <Temperature at the time of blending the curable composition> When preparing the curable composition (A) in the present invention, at least the component (a) which is a polymerizable compound, the component (b) which is a photopolymerization initiator, the component (c) which is an additive, and the component (d) which is a solvent are mixed and dissolved under predetermined temperature conditions. The predetermined temperature conditions are specifically in the range of 0°C or more and 100°C or less.

[0187] <Viscosity of the curable composition> The curable composition (A) in the present invention is in a liquid state. This is because in the placement step described later, the droplets of the curable composition (A) are discretely dropped onto the substrate by the inkjet method. The viscosity of the curable composition (A) in the present invention is 1.3 mPa·s or more and 60 mPa·s or less 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. When the viscosity of the curable composition (A) is less than 2 mPa·s, the ejection property of the droplets by the inkjet method becomes unstable. Also, when the viscosity of the curable composition (A) is greater than 60 mPa·s, it is difficult to form droplets having a volume of about 1.0 to 3.0 pL which is preferable in the present invention.

[0188] <Contact angle of the 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.

[0189] <Impurities present in the curable composition> In the present invention, the curable composition (A) is preferably free of impurities as much 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 the present invention is preferably obtained through a purification process. Such a purification process can be filtration using a filter.

[0190] 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, 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 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.

[0191] Furthermore, when using the curable composition (A) in the present invention to manufacture semiconductor integrated circuits, it is preferable to avoid, as much as possible, the inclusion of metal atoms (metallic impurities) in the curable composition (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.

[0192] <Glass transition temperature of curable composition> If the glass transition temperature is sufficiently higher than the release temperature, the cured product will be in a strong glassy state at the time of release, i.e., it will exhibit high mechanical strength, making it less likely for the pattern to collapse or break due to the impact of release. Therefore, when the release process is carried out at room temperature, the glass transition temperature of the cured product (after curing of 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.

[0193] Methods for measuring the glass transition temperature of a cured material (photocured material) include differential scanning calorimetry (DSC) and dynamic viscoelasticity measurement. For example, consider measuring the glass transition temperature using DSC. In this case, a straight line is obtained by extending the low-temperature baseline (the portion of the DSC curve in the temperature range where no transition or reaction occurs in the specimen) of the cured material's DSC curve toward the high-temperature side, and a tangent line is drawn at the point where the slope of the curve representing the stepwise change portion of the glass transition is maximum. The extrapolated glass transition onset temperature (Tig) can then be determined from the intersection of this straight line and the tangent line, and this can be considered the glass transition temperature. A major instrument for this method is the STA-6000 (manufactured by Perkin Eimer). On the other hand, when measuring the glass transition temperature using a dynamic viscoelasticity measurement device, the temperature at which the loss sine (tanδ) of the cured material is maximum is defined as the glass transition temperature. A major instrument for measuring dynamic viscoelasticity is the MCR301 (manufactured by Anton Paar).

[0194] <Layer forming composition> The layer-forming composition in the present invention is a composition for forming an adhesion layer between a substrate (base material) and a curable composition (A).

[0195] 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, "adhering the substrate and the curable composition to a tight bond" 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 during the release process. The release process, as described later, is the process of separating the mold from the cured film of the curable composition formed on the substrate during the imprint process.

[0196] The layer-forming composition of the present invention is particularly suitable for forming a cured film (cured product) of a curable composition (A) on a substrate. Furthermore, a laminate comprising an adhesion layer formed by the layer-forming composition of the present invention 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 of the present invention 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, the 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.

[0197] The following describes in detail each component included in the layer-forming composition of the present invention. As described above, the layer-forming composition of the present invention includes a compound (a2), a crosslinking agent (b2), and a solvent (d2).

[0198] <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 mass of the layer-forming composition is 100% by mass. The type of compound (a2) is not particularly limited and broadly includes known compounds.

[0199] 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.

[0200] 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, 2-hydroxyethyl Cetyl (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, 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 Phenoxyethyl (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 monoethyl ether (meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, Di(meth)acrylic 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 bisphenol A di(meth)acrylate, modified bisphenol A di(meth)acrylate, EO-modified bisphenol 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 tri(meth)acrylate Trimethylolpropane 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, pentaerythritol tetra(meth)acrylate, etc.

[0201] Examples of compounds (a2) having an epoxy group include the following: 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, Hydrogenated Bisphenol S diglycidyl ether, 1,4-Butanediol diglycidyl ether, 1,6-Hexanediol diglycidyl ether, Glycerin triglycidyl ether, Trimethylolpropane triglycidyl ether, Poly Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, propylene glycol, and glycerin; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of phenol, cresol, butylphenol, or polyether alcohols obtained by adding alkylene oxides to these; glycidyl esters of higher fatty acids.

[0202] Examples of compounds (a2) having a vinyl ether group include the following: 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, penta Erythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene 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

[0203] As an example, poly(meth)acrylate compounds having an ethylenically unsaturated group (P) and a hydrophilic group (Q) are preferred.

[0204] 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.

[0205] Examples of the hydrophilic group (Q) include the following. An alcoholic hydroxyl group, a carboxyl group, a phenolic hydroxyl group, an ether group (preferably a polyoxyalkylene group), an amino group, an amide group, an imide group, a ureido group, a urethane group, a cyano group, a sulfonamide group, a lactone group, a cyclocarbonate group, etc.

[0206] When the hydrophilic group (Q) is a urethane group, it is preferable that the group adjacent to the urethane group is an oxygen atom, for example, present in the resin as "-O-C(=O)-NH-".

[0207] 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, the poly(meth)acrylate compound (acrylic resin) preferably contains these repeating units in a proportion of 20 to 100 mol%. Further, the poly(meth)acrylate compound (acrylic resin) may contain other repeating units that do not contain both the ethylenically unsaturated group (P) and the hydrophilic group (Q), and the proportion of the other repeating units is preferably 50 mol% or less in the acrylic resin.

[0208] The poly(meth)acrylate compound (acrylic resin) preferably contains repeating units represented by the following general formulas (I) and (II).

[0209] [Chemical formula]

[0210] In the general formulas (I) and (II), R 1 and R 2 each represent a hydrogen atom, a methyl group or a hydroxymethyl group. L 1 represents a trivalent linking group, L 2a represents a single bond or a divalent linking group, L 2brepresents 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.

[0211] 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.

[0212] L 1 As mentioned 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.

[0213] 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.

[0214] 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.

[0215] 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.

[0216] As described above, n is 1 or 2, and is preferably 1.

[0217] Note L 1 , L 2a and L 2b It does not contain ethylenically unsaturated groups or hydrophilic groups.

[0218] Furthermore, the poly(meth)acrylate compound (acrylic resin) may contain repeating units represented by the following general formula (III) and / or general formula (IV).

[0219] [ka]

[0220] 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 with 1 to 12 carbon atoms, an alicyclic group with 3 to 12 carbon atoms, or an aromatic group with 6 to 12 carbon atoms.

[0221] 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.

[0222] 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.

[0223] As mentioned above, Q represents a hydrophilic group. The hydrophilic group represented by Q is the same as the hydrophilic groups exemplified so far, and the preferred hydrophilic group is also the same.

[0224] 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. Note that the aliphatic group, alicyclic group, and aromatic group may have substituents.

[0225] Examples of aliphatic groups having 1 to 12 carbon atoms include the following: Alkyl groups having 1 to 12 carbon atoms (for example, 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.)

[0226] Examples of alicyclic groups having 3 to 12 carbon atoms include the following: Cycloalkyl groups with 3 to 12 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecanyl group), etc.

[0227] Examples of aromatic groups having 6 to 12 carbon atoms include phenyl groups, naphthyl groups, and biphenyl groups, with phenyl and naphthyl groups being preferred.

[0228] Specific examples of acrylic resins that can be used in the present invention 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%.

[0229] [ka]

[0230] Other examples of compounds (a2) that can be used in the present invention 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.

[0231] 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.

[0232] [ka]

[0233] 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.

[0234] 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, more preferably an alkylene group having 1 to 3 carbon atoms, and more preferably "-CH2-". 2 It is preferable that the linking group is a divalent group consisting of "-CH2-", "-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.

[0235] Other examples of compounds (a2) that can be used in the present invention include epoxy poly(meth)acrylate compounds. Other examples of compounds (a2) include those described in paragraphs 0040 to 0056 of Japanese Patent Publication No. 2009-503139, which are incorporated herein by reference.

[0236] Of the compounds (a2) described above, those having functional groups 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.

[0237] 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.

[0238] Compound (a2) may consist of one type of compound or multiple types of compounds.

[0239] <Crosslinking agent (b2)> The crosslinking agent (b2) in the present invention 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.

[0240] The functional group a of the crosslinking agent (b2) in this invention 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.

[0241] In the present invention, the reaction between the functional group a of the crosslinking agent (b2) 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.

[0242] 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.

[0243] 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 in the cured film obtained by curing curable composition (A).

[0244] On the other hand, when using the layer-forming composition of the present invention, 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.

[0245] 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.

[0246] Furthermore, the crosslinking agent (b2) is preferably a compound represented by the following general formula (b2-1).

[0247] [ka]

[0248] In general formula (b2-1), R1 to R6 each independently represent one of the following: a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an alkylol group. However, at least five of R1 to R6 are alkoxyalkyl groups or alkylol groups.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] Furthermore, urea-based compounds may be used as the crosslinking agent (b2), and the following are examples. Methylated urea-based crosslinking agents such as tetrakis(methoxymethyl) glycoluryl, 4,5-dimethoxy-1,3-bis(methoxymethyl)imidazolidined-2-one, tetrakis(butoxymethyl) glycoluryl, tetrakis(ethoxymethyl) glycoluryl, tetrakis(isopropoxymethyl) glycoluryl, tetrakis(amyloxymethyl) glycoluryl, and tetrakis(hexoxymethyl) glycoluryl.

[0253] Examples of commercially available urea-based compounds include the following: Nikalac MX-270, Nikalac MX-280, Nikalac MX-290 (manufactured by Sanwa Chemical Co., Ltd.) Powderlink 1174 (manufactured by American Cyanamid Co.) Cymel 1170 (manufactured by Cytec Industries)

[0254] Furthermore, monomers of the resins mentioned above can also be used, such as the following compounds and dimethoxymethylurea.

[0255] [ka]

[0256] The crosslinking agent (b2) may consist of one type of compound or multiple types of compounds.

[0257] <Mixing ratio of compound (a2) and crosslinking agent (b2)> If the blending 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 blending 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 blending ratio within the range described above.

[0258] 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.

[0259] <Volatile solvent (d2)> The layer-forming composition in the present invention 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.

[0260] 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.

[0261] 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.

[0262] Specific examples of solvents used as the first solvent (d1-1) are listed below, and these solvents may be used individually 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;Acetic acid-based solvents such as 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 monoethyl ether acetate, glycol diacetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, and diethyl malonate; amide-based solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methylpropionamide;

[0263] 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.

[0264] 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.

[0265] Specific examples of solvents used as the second solvent (d2-1) are listed below, and these solvents may be used individually or in combination. 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 Ether-based solvents such as ethylene glycol mono-n-hexyl ether, ethoxytriglycol, 1-phenoxy-2-propanol, dipropylene glycol monopropyl ether, and tripropylene 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.

[0266] As described above, solvent (d2) may contain two types of solvents: 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, then 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 solvent (d2) may contain three or more types of solvents.

[0267] The blending ratio of the volatile solvent (d2) in the layer-forming composition of the present invention 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 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 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 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 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.

[0268] <Other additives (e2)> In addition to the compound (a2), crosslinking agent (b2), and volatile solvent (d2), the layer-forming composition in the present invention may further contain additive components (e2) depending on the purpose, to the extent that they do not impair the effects of the present invention. 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 the present invention 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 process of forming 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.

[0269] <Viscosity of layer-forming composition> The viscosity of the layer-forming composition at 23°C is preferably 0.5 mPa·s to 20 mPa·s, more preferably 1 mPa·s to 10 mPa·s, and even more preferably 1 mPa·s to 5 mPa·s. 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.

[0270] 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 film thickness of the layer-forming composition on the substrate can be easily adjusted.

[0271] <Impurities present in the layer-forming composition> The layer-forming composition in the present invention is preferably free of impurities as much as possible. Impurities refer to substances other than the compound (a2), crosslinking agent (b2), volatile solvent (d2), and other additive components (e2) added as needed. When the layer-forming composition is used in an imprinting process, it is particularly preferable that it is free of particles and solid components. Here, particles are typically gel-like or solid granular substances having a particle size (diameter) of several nanometers to several micrometers. 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. Furthermore, 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 the present invention is preferably obtained through a purification process. Such a purification process may include filtration using a filter.

[0272] 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. More preferably, filtration is performed 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 the inadvertent occurrence of defects in the adhesion layer obtained after coating the layer-forming composition due to impurities mixed into the layer-forming composition.

[0273] Furthermore, when using the layer-forming composition of the present invention 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.

[0274] 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 with ultrapure water, then with alcohol, and finally wash them together with the layer-forming composition.

[0275] <Adhesion layer formation process> In the adhesion layer formation process, an adhesion layer mainly composed of polymer compounds is formed on the substrate using the layer-forming composition described above.

[0276] 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.

[0277] 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.

[0278] Examples of 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, and especially uniformity of film thickness. Inkjet method, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spin coating method, slit scan method, etc. After applying the layer-forming composition to the substrate, 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 compound (a2) or crosslinking agent (b2) while simultaneously evaporating the volatile solvent (d2), and also to react compound (a2) with the crosslinking agent (b2). This forms a bond between the substrate and the adhesion layer, and a bond is formed between compound (a2) and crosslinking agent (b2) in the adhesion layer. It is presumed that a crosslinked structure is formed by the bond between compound (a2) and crosslinking agent (b2).

[0279] 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 heat treatment temperature 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.

[0280] 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.

[0281] 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 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.

[0282] 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 compound (a2).

[0283] [Pattern formation method] The pattern formation method in the present invention will be described with reference to Figures 3(a) to 3(g). The cured film formed by the present invention is preferably a film having a pattern of size 1 nm to 10 mm, and more preferably a film having a pattern of size 10 nm to 100 μm. Generally, a film formation method that uses light to form a film having a nano-sized (1 nm to 100 nm) pattern (uneven structure) is called an optical imprint method. The film formation method in the present invention uses an optical imprint method to form a film of curable composition (A) in the space between the mold and the substrate. However, the curable composition (A) may be cured by other energy (e.g., heat, electromagnetic waves). Furthermore, the film formation method in the present invention may be implemented as a method for forming a film having a pattern, i.e., as a pattern formation method, or as a method for forming a film without a pattern (e.g., a planarized film), i.e., as a planarized film formation method.

[0284] The following describes an example in which the film formation method of the present invention is applied to a pattern formation method. The pattern formation method includes, for example, a formation step, a placement step, a waiting step, a contact step, a curing step, and a release step (separation step). The formation 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 in which the droplets of the curable composition (A) are allowed to bond together and the solvent component (d) is allowed to evaporate. The contact step is a step in which the curable composition (A) is brought into contact with the mold. The curing step is a step in which the curable composition (A) is cured. The release step is a step in which the mold is separated 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 release step is performed after the curing step.

[0285] <Placement process> In the placement process, droplets 102 of the curable composition (A) are discretely placed on the substrate 101, as schematically shown in Figure 1(a). In the placement process, 80 droplets / mm of the curable composition (A) having a volume of 1.0 pL or more are placed. 2 The 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.

[0286] As the silane coupling agent, known silane coupling agents having an acrylic group can be used. Methods for applying the silane coupling agent include the following, but vapor deposition is particularly preferred from the viewpoint of application properties, especially uniformity of film thickness. Inkjet method, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spin coating method, slit scan method, vapor phase evaporation method, etc. Furthermore, an untreated silicon substrate can also be used as the substrate 101.

[0287] 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.

[0288] 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.

[0289] <Standby process> In this invention, a waiting step is provided between the placement step and the contact step. Here, the average initial liquid film thickness is defined as the value obtained by dividing the total volume of droplets of curable composition (A) dropped in one pattern formation by the total area of ​​the region where a pattern is formed in one pattern formation (pattern formation region). During the waiting step, the droplets 102 of curable composition (A) spread out on the substrate 101, as schematically shown in Figure 3(b). As a result, the entire pattern formation region of the substrate 101 is covered with curable composition (A).

[0290] Referring to Figures 4(a) to 4(d), the flow behavior of droplets of the curable composition (A) placed on the substrate during the waiting process will be explained. As shown in Figure 4(a), droplets 102 of the curable composition (A) are discretely arranged on the substrate 101, and as shown in Figure 4(b), each droplet 102 gradually spreads on the substrate. Then, as shown in Figure 4(c), the droplets of the curable composition (A) on the substrate begin to combine to form a liquid film, and as shown in Figure 4(d), it becomes a continuous liquid film (the surface of the substrate 101 is covered with the curable composition (A), and there are no exposed surfaces). The state of the curable composition (A) as shown in Figure 4(d) is referred to as a "substantially continuous liquid film".

[0291] Furthermore, during the waiting process, the solvent 105 (solvent component (d)) contained in the liquid film 104 is evaporated, as schematically shown in Figure 3(d). 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, potentially reducing liquid film formation.

[0292] In the waiting process, a baking process may be carried out to accelerate the volatilization of component (d), which is a solvent, by heating the substrate 101 and the curable composition (A), or by ventilating the atmospheric gas around the substrate 101. The heating is carried out, for example, at a temperature of 30°C to 200°C, preferably 80°C to 150°C, and particularly preferably 90°C to 110°C. The heating time can be 10 seconds to 600 seconds. The baking process can be carried out using a known heating device such as a hot plate or an oven.

[0293] 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.

[0294] 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 the 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 remains covered throughout by a substantially continuous liquid film 104 of the curable composition (A) from which component (d), which is the solvent, has been removed.

[0295] <Contact process> In the contact step, as schematically shown in Figure 3(e), a substantially continuous liquid film 104 of the curable composition (A), from which the solvent component (d) has been removed, is brought into contact with the mold 106. The contact step includes a step of changing the state from one in which the curable composition (A) and the mold 106 are not in contact to a state in which they are in contact, and a step of maintaining the state in which they are in contact. As a result, the liquid of the curable composition (A) fills the recesses of the fine pattern on the surface of the mold 106, and this liquid becomes a liquid film that fills the fine pattern of the mold 106.

[0296] Figure 5 shows a comparison between the prior art (e.g., Japanese Patent Publication No. 6584578) and the present invention regarding the gas trapped between the mold 106 and the substrate 101 during the contact process. In the present invention, 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.

[0297] 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.

[0298] 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.

[0299] The pattern formed on the surface of mold 106 has a height of, for example, 4 nm to 200 nm. The lower the height of the pattern on mold 106, the smaller the force required to separate mold 106 from the cured film of the curable composition during the release process, i.e., the release force, which reduces the number of release defects remaining on mold 106 due to the pattern of the curable composition being torn off. Also, the impact when separating the mold can cause elastic deformation of the pattern of the curable composition, which can cause adjacent pattern elements to come into contact, resulting in adhesion or damage. However, it is advantageous to have a pattern element height of approximately twice the width of the pattern element (aspect ratio of 2 or less) to avoid these problems. On the other hand, if the height of the pattern elements is too low, the processing accuracy of the substrate 101 will be reduced.

[0300] 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.

[0301] In the contact process, the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the curable composition (A) is not particularly limited, but for example, it may be 0 MPa or more and 100 MPa or less. However, the pressure applied to the curable composition (A) when the mold 106 is brought into contact with the curable composition (A) is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and even more preferably 0 MPa or more and 20 MPa or less.

[0302] 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 The pressure is preferably below atm. Further details are disclosed in Japanese Patent Publication No. 2022-99271. When the contact process is performed in a specific gas atmosphere, including an atmospheric atmosphere, the preferred pressure is between 0.0001 atmospheres and 10 atmospheres.

[0303] <Curing process> In the curing process, as schematically shown in Figure 3(f), the curable composition (A) is cured by irradiating it with irradiation light 107 as curing energy to form a cured film. In the curing process, for example, the curable composition (A) is irradiated with irradiation light 107 through the mold 106. More specifically, the curable composition (A) filled in the fine pattern of the mold 106 is irradiated with irradiation light 107 through the mold 106. As a result, the curable composition (A) filled in the fine pattern of the mold 106 is cured to form a cured film 108 having a pattern.

[0304] The irradiation light 107 is selected according to the sensitivity wavelength of the curable composition (A). Specifically, the irradiation light 107 is appropriately selected from ultraviolet light, X-rays, or electron beams with a wavelength of 150 nm to 400 nm. It is particularly preferable that the irradiation light 107 be ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are compounds that are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. However, ultra-high-pressure mercury lamps are particularly preferred as light sources that emit ultraviolet light. There may be one or more light sources. Furthermore, the entire surface of the curable composition (A) filled in the fine pattern of the mold may be irradiated with light, or only a portion of it may be irradiated (limited to a specific area). Additionally, the light irradiation may be performed intermittently over the entire surface of the substrate multiple times, or continuously over the entire surface of the substrate. Moreover, in the first irradiation process, a first region of the substrate may be irradiated with light, and in the second irradiation process, a second region of the substrate different from the first region may be irradiated with light.

[0305] <Mold release process> In the demolding process, the mold 106 is separated from the cured film 108, as schematically shown in Figure 3(g). By separating the patterned cured film 108 from the mold 106, a self-supporting cured film 108 with a pattern that is an inversion of the fine pattern of the mold 106 is obtained. Here, some of the cured film remains in the recesses of the patterned cured film 108. This film is called residual film.

[0306] 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.

[0307] <Repeat> By a series of steps (manufacturing process) including the above-described placement step and demolding step in this order, a cured film having a desired uneven pattern shape (a pattern shape that follows the uneven shape of the mold 106) at a desired position can be obtained.

[0308] In the pattern formation method of the present invention, the repeating units (shots) from the placement step to the demolding step can be repeated multiple times on the same substrate, and a cured film 108 having multiple desired patterns at desired positions on the substrate can be obtained.

[0309] [Method of manufacturing articles] The method for manufacturing an article includes a forming step of forming a film of a curable composition on a substrate using the film forming method described above, a processing step of processing the substrate on which the film of the curable composition was formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. The film forming method is, as described above, a pattern forming method or a planarization film forming method.

[0310] Furthermore, the cured film 108 having a pattern formed by the pattern forming method of the present invention can be used as is as a component of at least a part of various articles. The cured film 108 having a pattern formed by the pattern forming method of the present invention is temporarily used as a mask for etching, ion implantation, etc., on the substrate 101 (or the layer to be processed if the substrate 101 has a layer to be processed). After etching, ion implantation, etc., is performed in the processing process of the substrate 101, the mask is removed. This makes it possible to manufacture various articles.

[0311] When removing hardened material from recesses in the pattern of a hardened material by etching, the specific method is not particularly limited, and known methods, such as dry etching, can be used. Known dry etching apparatus can be used for dry etching. The source gas for dry etching is appropriately selected according to the elemental composition of the hardened material to be etched. Specifically, halogen-based gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2 can be used as source gases. In addition, gases containing oxygen atoms such as O2, CO, and CO2, inert gases such as He, N2, and Ar, and gases such as H2 and NH3 can also be used as source gases. These gases can also be mixed and used as a source gas. In this case, in order to process the substrate with good yield, the photocured film is required to have high dry etching resistance.

[0312] 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.

[0313] Known photolithography processes such as imprint lithography and extreme ultraviolet (EUV) exposure can be performed on the planarized film formed by the planarized film formation method of the present invention. Alternatively, a spin-on-glass (SOG) film and / or a silicon oxide layer can be laminated, and a curable composition can be applied thereon for photolithography. This makes it possible to manufacture devices such as semiconductor devices. Furthermore, it is possible to form electronic devices including such devices, such as displays, cameras, and medical devices. Examples of devices include LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and NAND flash memory.

[0314] [Examples] To supplement the embodiments described above, more specific examples will be explained, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" used below are based on weight.

[0315] <Curable composition 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 to 21 were prepared as a result. Table 1

[0316] [Table 1]

[0317] 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:CH3O(C2H4O)2(C3H6O) 17 (C2H4O)CH3 compound (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)

[0318] <Layer forming composition 1> Compound (a2) and crosslinking agent (e1) were dissolved in volatile solvent (d1) in the following weight percentages. Compound (a2) 0.2775 Crosslinking agent (e1) 0.0692 Volatile solvent (d1) 99.6533

[0319] The mixed solvent obtained in this manner was filtered through a polyethylene filter with a pore size of 0.005 μm. This prepared layer-forming composition 1.

[0320] The abbreviations are as follows: (Compound (a2)) Carboxylic acid anhydride-modified cresol novolac type epoxy acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name: EA-7140) (formula (1) below)

[0321] [ka]

[0322] (Crosslinking agent (e1)) 2,4,6-Tris[bis(methoxymethyl)amino]-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.) (formula (2) below)

[0323] [ka]

[0324] (Volatile solvent (d1)) PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.)

[0325] <Layer forming composition 2> For layer-forming composition 2, we used FULS-013D, a layer-forming composition manufactured by Fujifilm.

[0326] <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. The silicon wafers coated with layer-forming compositions 1 and 2 were baked at a heating temperature of 220°C for 90 seconds to form adhesion layers 1 and 2.

[0327] <Contact angle of curable composition with respect to the 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 1-2 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).

[0328] 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: radius of the droplet V: Volume of the droplet h: droplet height r0: Radius when the initial shape of the droplet is a hemisphere. Formula (4)

[0329]

number

[0330] (Formula 5)

[0331]

number

[0332] <Contact angle of the curable composition (without solvent) with respect to the adhesion layer> For measuring the contact angle, a 1 μL liquid droplet was used, and an automatic static contact angle analyzer, Dropmaster 300 (manufactured by Kyowa Interfacial Chemical Co., Ltd.), was employed. The equilibrium contact angle of the curable composition after the solvent had completely evaporated (for example, the contact angle 15 seconds after the droplet was dropped) 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

[0333] [Table 2]

[0334] <Evaluation of liquid film formation properties> For the evaluation of liquid film formation properties, an industrial material printer DMP-2850 (manufactured by Fujifilm) was used. 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 approximately 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, and the liquid film formation properties were evaluated according to the following evaluation criteria.

[0335] (Evaluation Criteria) A: A substantially continuous liquid film was formed within 5 seconds of the droplet being dropped. B: A substantially continuous liquid film was formed between 5 and 180 seconds after the droplet was dropped. C: Even after 180 seconds had elapsed since the droplet was dropped, a substantially continuous liquid film had not formed.

[0336] <Evaluation of liquid film stability> For evaluating liquid film stability, an industrial material printer DMP-2850 (manufactured by Fujifilm) was used. In the evaluation of 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 criteria. Note that "shrinkage" 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.

[0337] (Evaluation Criteria) A: The liquid film stability was over 300 seconds. B: The liquid film stability was between 80 seconds and less than 300 seconds. C: The liquid film stability was less than 80 seconds.

[0338] The evaluation of liquid film stability for Examples 1-15 and Comparative Examples 1-8 is shown in Table 3 below. Table 3

[0339] [Table 3]

[0340] The disclosures herein include the following curable compositions, film-forming methods, and methods for manufacturing articles.

[0341] (Item 1) A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), an additive (c), and a solvent (d), The content of solvent (d) in the total curable composition is greater than 5% by volume and 95% by volume or less. The boiling point of the solvent (d) is 100°C or higher 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. The HLB value of additive (c) calculated by the Griffin method is between 2.0 and 8.4. A curable composition characterized by the following features.

[0342] (Item 2) If the total weight of all components of the composition obtained by removing 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 the condition 0.8 ≤ A × HLB value ≤ 12.6. A curable composition according to item 1, characterized in that it is a curable composition.

[0343] (Item 3) The curable composition according to item 1 or 2, 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.

[0344] (Item 4) The curable composition according to any one of items 1 to 3, characterized in that the curable composition is a curable composition for inkjet printing.

[0345] (Item 5) The curable composition according to any one of items 1 to 4, characterized in that the curable composition is a curable composition for photoimprinting.

[0346] (Item 6) A method for forming a film of a curable composition on a substrate, A placement step of discretely arranging a plurality of droplets of the curable composition described in any one of items 1 to 5 on the substrate, A waiting step in which the plurality of droplets wait until they combine with adjacent droplets to form a liquid film, A film formation method characterized by having the following:

[0347] (Item 7) The film-forming method according to item 6, characterized in that the contact angle of the curable composition with respect to the substrate is 1.8 degrees or less.

[0348] (Item 8) The film formation method according to item 6 or 7, characterized in that the arrangement step involves discretely arranging the plurality of liquid droplets on the substrate using an inkjet method.

[0349] (Item 9) The film-forming method according to any one of items 6 to 8, characterized in that the waiting step is performed until the solvent contained in the liquid film evaporates and the solvent content is 10% by volume or less relative to the entire liquid film.

[0350] (Item 10) A film forming method according to any one of items 6 to 9, characterized in that, after the waiting step, it further comprises a contact step of bringing the liquid film into contact with a mold.

[0351] (Item 11) The aforementioned type includes a pattern, In the contact step, the pattern of the type and the liquid film are brought into contact. The process further includes a curing step, in which the liquid film is cured after the contact step to form a cured film having a pattern corresponding to the pattern of the mold. A film formation method according to item 10, characterized by the features described above.

[0352] (Item 12) The aforementioned type includes a flat surface, In the contact step, the flat surface of the mold and the liquid film are brought into contact. The process further includes a curing step, in which the liquid film is cured after the contact step to form a cured film having a surface that conforms to the flat surface of the mold. A film formation method according to item 10, characterized by the features described above.

[0353] (Item 13) A forming step of forming a film of a curable composition on a substrate using a film forming method described in any one of items 6 to 12, A processing step for processing the substrate on which the film has been formed in the forming step, A manufacturing process for producing an article from the substrate processed in the above-mentioned processing step, A method for manufacturing an article, characterized by having the following:

[0354] The invention is not limited to the embodiments described above, and various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, claims are attached to disclose the scope of the invention. [Explanation of Symbols]

[0355] 101: Substrate 102: Droplet 103: Liquid film 104: Liquid film 105: Solvent 106: Mold 107: Irradiation light 108: Cured film

Claims

1. A curable composition comprising a polymerizable compound (a), a photopolymerization initiator (b), an additive (c), and a solvent (d), The content of the solvent (d) in the total curable composition is greater than 5% by volume and 95% by volume or less. The boiling point of the solvent (d) is 100°C or higher 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. The HLB value of additive (c) calculated by the Griffin method is between 2.0 and 8.

4. A curable composition characterized by the following features.

2. 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 the additive (c) satisfies the condition 0.8 ≤ A × HLB value ≤ 12.

6. The curable composition according to claim 1.

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

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 aforementioned type includes a pattern, In the contact step, the pattern of the type and the liquid film are brought into contact. The process further includes a curing step, after the contact step, in which the liquid film is cured to form a cured film having a pattern corresponding to the pattern of the mold. The film formation method according to feature 10.

12. The aforementioned type includes a flat surface, In the contact step, the flat surface of the mold and the liquid film are brought into contact. The process further includes a curing step, in which the liquid film is cured after the contact step to form a cured film having a surface that conforms to the flat surface of the mold. The film formation method according to feature 10.

13. 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 for processing the substrate on which the film has been formed in the forming step, A manufacturing process for producing an article from the substrate processed in the above-mentioned processing step, A method for manufacturing an article, characterized by having the following:

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