Film forming method and article manufacturing method

Abstract

To provide a new technique for forming a flattened film on a substrate.SOLUTION: A film formation method for forming a flattened film on a substrate using a super straight having a flat surface includes: a disposing step of disposing a curable composition (A) discretely on the substrate as a plurality of droplets; a waiting step of waiting for the plurality of droplets disposed on the substrate in the disposing step to combine on the substrate to form a liquid film; a contact step of bringing the liquid film on the substrate into contact with the flat surface of the super straight after the waiting step; a curing step of heating and curing the liquid film after the contacting step to form a cured film between the super straight and the substrate; and a separation step of separating the cured film from the super straight after the curing step.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a film forming method and an article manufacturing method. [Background technology]

[0002] Photolithography processes for manufacturing semiconductor devices require planarization of substrates (i.e., forming a planarizing film on a substrate). For example, extreme ultraviolet (EUV) exposure, a photolithography technology that has recently attracted attention, requires that the depth of focus at which a projected image is formed becomes shallower as features become finer. Therefore, the surface irregularities of the substrate onto which the curable composition is applied must be kept to a few tens of nanometers or less. Imprinting technology also requires a level of flatness comparable to that of EUV to improve the filling ability and linewidth accuracy of the curable composition (see Non-Patent Document 1). One known planarization technique involves discretely dispensing droplets of a curable composition onto a substrate with irregularities, in an amount corresponding to the irregularities, and then curing the curable composition while in contact with a mold with a flat surface, thereby obtaining a flat surface (see Patent Documents 1 and 2). The mold with a flat surface is sometimes called a superstrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-140394 [Patent Document 2] US Patent Application Publication No. 2020 / 0286740 [Patent Document 3] Special Publication No. 2009-503139 [Patent Document 4] Japanese Patent Publication No. 2022-27530 [Patent Document 5] U.S. Patent Application Publication No. 2023 / 0203210 [Non-patent literature]

[0004] [Non-Patent Document 1] Proc. SPIE 11324-11 (2020) [Non-patent document 2] A. Oron, SH Davis, SG Bankoff, “Long-scale evolution of thin liquid films”, Review of Modern Physics 69 (1997) 931 Summary of the Invention [Problem to be solved by the invention]

[0005] Planarization films formed by planarization techniques are required not only to be flat, but also to reduce the inclusion of foreign matter. Therefore, planarization techniques must reduce the adhesion of foreign matter on the superstrate (flat surface) to nearly zero. Conventional planarization techniques generally involve curing a photocurable composition by irradiating it with light (e.g., UV light) (see Patent Documents 4 and 5), and have used superstrates made of quartz glass that can transmit light. However, when using superstrates made of quartz glass, there has been a problem in that it is difficult to reduce the adhesion of foreign matter on the superstrate (flat surface) to nearly zero.

[0006] Furthermore, planarization films formed by planarization techniques are sometimes required to have not only flatness but also heat resistance of 450° C. or higher. However, when a photocurable composition is used as in conventional planarization techniques, the heat resistance is limited to 450° C., and it is difficult to form planarization films with higher heat resistance.

[0007] Furthermore, the planarization film formed by the planarization technique is sometimes required to be a permanent insulating film, but it is difficult for the photocurable compositions used in conventional planarization techniques to satisfy the insulating performance, mechanical strength, and durability required for a permanent insulating film, and therefore such a film has not been realized.

[0008] Therefore, an object of the present invention is to provide a new technique for forming a planarizing film on a substrate. [Means for solving the problem]

[0009] In order to achieve the above object, one aspect of the present invention provides a film formation method for forming a planarized film on a substrate using a superstrate having a flat surface, the method comprising: a disposing step of disposing a curable composition (A) discretely on the substrate as a plurality of droplets; a waiting step of waiting for the plurality of droplets disposed on the substrate in the disposing step to combine on the substrate to form a liquid film; a contacting step of bringing the liquid film on the substrate into contact with the flat surface of the superstrate after the waiting step; a curing step of heating and curing the liquid film after the contacting step to form a cured film between the superstrate and the substrate; and and a separating step of separating the cured film from the superstrate, wherein the curable composition (A) disposed on the substrate in the disposing step is thermosetting and has the property of being cured by heating, and contains at least a solvent (d), the viscosity of the curable composition (A) at 23°C is 2 mPa·s or more and 60 mPa·s or less, the content of the solvent (d) in the curable composition (A) is 5 vol% or more and 95 vol% or less, the boiling point of the solvent (d) under normal pressure is less than 250°C, and the mixture of the curable composition (A) other than the solvent (d) has a viscosity of 30 mPa·s or more and 10,000 mPa·s or less at 23°C.

[0010] Further objects and other aspects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings. [Effects of the Invention]

[0011] According to the present invention, a new technique can be provided for forming a planarizing film on a substrate. [Brief explanation of the drawings]

[0012] [Figure 1]FIG. 1 is a diagram illustrating a film forming method according to an embodiment of the present invention. [Figure 2] FIG. 1 is a diagram illustrating the flow behavior of droplets of a curable composition during a waiting step. [Figure 3] FIG. 1 is a diagram showing a comparison between the contacting process in the prior art and the contacting process in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments do not limit the invention according to the claims. Although multiple features are described in the embodiments, not all of these multiple features are necessarily essential to the invention, and multiple features may be combined arbitrarily. Furthermore, in the accompanying drawings, the same reference numerals are used to designate the same or similar components, and redundant explanations will be omitted.

[0014] [Curable composition (A1)] The curable composition (A1) of one embodiment of the present invention is a thermosetting composition that can be cured by heating, and can be used for inkjet printing. The curable composition (A1) of one embodiment is a composition containing at least a polymerizable compound (component (a)), a polymerization initiator (component (b)), and a solvent (component (d)). In one embodiment, the polymerizable compound (component (a)) preferably contains at least a polymerizable compound (a-1) containing one or more aromatic rings or aromatic heterocycles and one or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles. The curable composition (A1) of one embodiment may further contain a non-polymerizable compound (c).

[0015] <Component (a): Polymerizable compound> Component (a) is a polymerizable compound containing one or more aromatic rings or aromatic heterocycles and a vinyl group directly bonded to the aromatic rings or the aromatic heterocycles. In this specification, the polymerizable compound is a compound that reacts with a polymerization factor (radical, cation, etc.) generated from a polymerization initiator (component (b)) to form a film made of a polymer compound through a chain reaction (thermal polymerization reaction).

[0016] Examples of such polymerizable compounds include radically polymerizable compounds and cationically polymerizable compounds. Component (a), which is a polymerizable compound, may be composed of only one type of polymerizable compound, or may be composed of multiple types (two or more) of polymerizable compounds. That is, component (a), which is a polymerizable compound, may contain one or more types of polymerizable compounds. Furthermore, component (a), which is a polymerizable compound, may contain at least a polymer having a polymerizable functional group.

[0017] In one embodiment, the polymerizable compound component (a) preferably includes at least a polymerizable compound (a-1) containing one or more aromatic rings or aromatic heterocycles and one or more vinyl groups directly bonded to the aromatic rings or aromatic heterocycles.

[0018] <Compound (a-1): Polymerizable compound> Specific examples of the compound (a-1) include, but are not limited to, the following: [ka] [ka] [ka]

[0019] Examples of the component (a) that does not fall under the category of compound (a-1) include (meth)acrylic compounds that are radically polymerizable compounds. The (meth)acrylic compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of monofunctional (meth)acrylic compounds having one acryloyl group or one methacryloyl group include, but are not limited to, the following: Phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl (meth)acrylate, EO-modified p-cumylphenol (meth)acrylate, 2-bromophenoxyethyl (meth)acrylate, 2,4-dibromophenoxyethyl (meth)acrylate, 2,4,6-Tribromophenoxyethyl (meth)acrylate, EO-modified phenoxy (meth)acrylate, PO-modified phenoxy (meth)acrylate, polyoxyethylene nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate t)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pliers (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, benzyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, 1- or 2-naphthyl(meth)acrylate, 1- or 2-naphthylmethyl(meth)acrylate, 3- or 4-phenoxybenzyl(meth)acrylate, chinoabenzyl(meth)acrylate,

[0020] Examples of commercially available monofunctional (meth)acrylic compounds include, but are not limited to, the following: Aronix (registered trademark) M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (all manufactured by Toagosei), MEDOL10, M IBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat #150, #155, #158, #19 0, #192, #193, #220, #2000, #2100, #2150 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A, POB-A, OPP-EA (all manufactured by Kyoeisha Chemical Industry Co., Ltd.), KAYARAD (registered trademark) TC110S, R-564, R-128H (all manufactured by Nippon Kayaku), NK Ester AMP-10G, AMP-20G, A-LEN-10 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (all manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (all manufactured by Daiichi Kogyo Seiyaku), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (all manufactured by Kohjin)

[0021] Furthermore, examples of polyfunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, but are not limited to, the following: Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO,PO-modified trimethylolpropane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 9-Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,3-adamantanedimethanol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, EO,PO-modified 2,2-bis(4-((meth)acryloxy)phenyl)propane, o-, m-, or p-benzenedi(meth)acrylate, o-, m-, or p-xylylenedi(meth)acrylate

[0022] Examples of commercially available polyfunctional (meth)acrylic compounds include, but are not limited to, the following: Iupimer (registered trademark) UV SA1002, SA2007 (all manufactured by Mitsubishi Chemical), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA (all manufactured by Osaka Organic Chemical Industry), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical), KAYARAD (registered trademark) PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku), Aronix (registered trademark) M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei), Lipoxy (registered trademark) VR-77, VR-60, VR-90 (all manufactured by Showa Polymer), Oxol EA-0200, Oxol EA-0300 (all manufactured by Osaka Gas Chemicals)

[0023] In the above-mentioned compound group, (meth)acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto. (Meth)acryloyl group means acryloyl group or methacryloyl group having an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound A are bonded via an ethylene oxide group block structure. PO represents propylene oxide, and PO-modified compound B represents a compound in which the (meth)acrylic acid residue and alcohol residue of compound B are bonded via a propylene oxide group block structure.

[0024] In one embodiment of the film-forming method according to the present invention, it takes several milliseconds to several hundred seconds for droplets of the curable composition (A1) dispersed on the substrate to combine and form a substantially continuous liquid film, necessitating a waiting step, as described below. During this waiting step, the solvent (d) is evaporated, but the polymerizable compound (a) must not be evaporated. Therefore, the boiling points of the one or more polymerizable compounds contained in the polymerizable compound (a) under normal pressure are preferably all 250°C or higher, more preferably all 300°C or higher, and even more preferably all 350°C or higher. Furthermore, to achieve high dry etching resistance and high heat resistance in a cured film of the curable composition (A1), the polymerizable compound (a) preferably contains at least a compound having a ring structure, such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0025] The boiling point of the polymerizable compound (a) generally correlates with the molecular weight. Therefore, the one or more polymerizable compounds contained in the polymerizable compound (a) preferably all have a molecular weight of 200 or more, more preferably all have a molecular weight of 240 or more, and even more preferably all have a molecular weight of 250 or more. However, even if the molecular weight is 200 or less, as long as the boiling point is 250°C or more, it can be preferably used as the polymerizable compound (a) of one embodiment according to the present invention.

[0026] Furthermore, the vapor pressure of each of the one or more polymerizable compounds contained in the polymerizable compound (a) is preferably 0.001 mmHg or less at 80° C. This is because heating is preferably performed to accelerate the evaporation of the solvent (d) described below, but the evaporation of the polymerizable compound (a) is suppressed during heating. The boiling points and vapor pressures of various organic compounds under normal pressure can be calculated using Hansen Solubility Parameters in Practice (HSPiP) 5th Edition 5.3.04 or the like.

[0027] <Oonishi parameter (OP) of component (a)> Dry etching rate of organic compound V, total number of atoms in the organic compound N, total number of carbon atoms in the composition N C , and the total number of oxygen atoms in the composition, N O are known to be related by the following formula (1) (Non-Patent Document 2). V ∝ N / (N C -N O ) Formula (1) where N / (N C -N O ) is commonly known as the "Ohnishi parameter" (hereinafter, OP). For example, Patent Document 3 describes a technique for obtaining a curable composition with high dry etching resistance by using a polymerizable compound component with a small OP. According to the above formula (1), it is suggested that the more oxygen atoms there are in the molecule of an organic compound, or the fewer aromatic ring structures or alicyclic structures there are, the larger the OP and the faster the dry etching rate.

[0028] In the curable composition (A1) of one embodiment of the present invention, the OP of the component (a) is preferably 1.80 or more and 2.70 or less, more preferably 2.00 or more and 2.60 or less, and particularly preferably 2.30 or more and 2.60 or less. By making the OP of the component (a) 2.70 or less, the cured film of the curable composition (A1) has high dry etching resistance. By making the OP of the component (a) 1.80 or more, it becomes easy to remove the cured film of the curable composition (A1) after processing the underlayer with the cured film of the curable composition (A1). When the component (a) is composed of multiple types of polymerizable compounds a1, a2, ..., a n When the total amount of the OP is 100% or more, OP can be calculated as a weighted average value based on the molar fraction (molar fraction weighted average value) as shown in the following formula (2). JPEG2025121753000005.jpg18170

[0029] <Compound (a-2): Polymerizable compound having a boiling point of 250°C or higher> The curable composition (A1) according to one embodiment of the present invention may contain, as the polymerizable compound (a), a compound (a-2) having two or more cyclic structures, at least one of which is an aromatic or heteroaromatic cyclic structure. The cyclic structure may be an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0030] 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 the aromatic ring include the following. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenalene ring, fluorene ring, benzocyclooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, chrysene ring, perylene ring, tetrahydronaphthalene ring Among the aromatic rings described above, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The aromatic ring may have a structure in which multiple rings are linked together, such as a biphenyl ring or a bisphenyl ring.

[0031] 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 the aromatic heterocyclic ring include the following. Thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, indole ring, indazole ring, purine ring, quinolizine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring

[0032] The number of carbon atoms in the alicyclic structure is preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. The number of carbon atoms in the alicyclic structure is preferably 22 or less, more preferably 18 or less, even more preferably 6 or less, and even more preferably 5 or less. Specific examples thereof 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, hexahydroindane ring, bornane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring, adamantane ring

[0033] Specific examples of the polymerizable compound (a-2) having a boiling point of 250° C. or higher include, but are not limited to, the following:

[0034] 3-phenoxybenzyl acrylate (mPhOBzA, OP 2.54, boiling point 367.4°C, vapor pressure at 80°C 0.0004mmHg, molecular weight 254.3), [ka]

[0035] 1-naphthyl acrylate (NaA, OP 2.27, boiling point 317°C, vapor pressure at 80°C 0.0422mmHg, molecular weight 198), [ka]

[0036] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP2.57, boiling point 364.2°C, vapor pressure at 80°C 0.0006mmHg, molecular weight 268.3) [ka]

[0037] 1-Naphthylmethyl acrylate (Na1MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2) [ka]

[0038] 2-Naphthylmethyl acrylate (Na2MA, OP 2.33, boiling point 342.1°C, vapor pressure at 80°C 0.042mmHg, molecular weight 212.2) [ka]

[0039] DPhPA (OP 2.38, boiling point 354.5°C, vapor pressure 0.0022mmHg at 80°C, molecular weight 266.3) shown in the formula below [ka]

[0040] PhBzA (OP 2.29, boiling point 350.4°C, vapor pressure at 80°C 0.0022mmHg, molecular weight 238.3) shown in the formula below [ka]

[0041] FLMA (OP 2.20, boiling point 349.3°C, vapor pressure 0.0018mmHg at 80°C, molecular weight 250.3) shown in the formula below [ka]

[0042] ATMA (OP 2.13, boiling point 414.9°C, vapor pressure 0.0001mmHg at 80°C, molecular weight 262.3) shown in the formula below [ka]

[0043] DNaMA (OP 2.00, boiling point 489.4°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 338.4) shown in the formula below [ka]

[0044] BPh44DA (OP 2.63, boiling point 444°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below [ka]

[0045] BPh43DA (OP 2.63, boiling point 439.5°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below [ka]

[0046] DPhEDA (OP 2.63, boiling point 410°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.3) shown in the formula below [ka]

[0047] BPMDA (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4) shown in the formula below [ka]

[0048] Na13MDA (OP 2.71, boiling point 438.8℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 296.3) shown in the formula below [ka]

[0049] Formula (a-2-1) below (OP 2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181mmHg, molecular weight 199.2) [ka]

[0050] Formula (a-2-2) below (OP 2.40, boiling point 333.4°C, vapor pressure at 80°C 0.0181mmHg, molecular weight 199.2) [ka]

[0051] Formula (a-2-3) below (OP 1.86, boiling point 369.5°C, vapor pressure at 80°C 0.0053mmHg, molecular weight 193.3) [ka]

[0052] Formula (a-2-4) below (OP 2.85, boiling point 438.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 296.3) [ka]

[0053] Formula (a-2-5) below (OP 2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 296.3) [ka]

[0054] Formula (a-2-6) below (OP 2.87, boiling point 421.0°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 338.4) [ka]

[0055] Formula (a-2-7) below (OP 2.87, boiling point 465.2°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 338.4) [ka]

[0056] Formula (a-2-8) below (OP 2.68, boiling point 465.7℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4) [ka]

[0057] Formula (a-2-9) below (OP 2.50, boiling point 433.1°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 320.3) [ka]

[0058] Formula (a-2-10) below (OP 2.64, boiling point 468.1°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 326.4) [ka]

[0059] Formula (a-2-11) below (OP 3.25, boiling point 553.4°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 358.4) [ka]

[0060] Formula (a-2-12) below (OP 2.63, boiling point 443.9°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.4) [ka]

[0061] Formula (a-2-13) below (OP 2.89, boiling point 509.3℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 406.4) [ka]

[0062] Formula (a-2-14) below (OP 2.63, boiling point 450.0°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 322.4) [ka]

[0063] Formula (a-2-15) below (OP 3.00, boiling point 476.5℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 366.4) [ka]

[0064] Formula (a-2-16) below (OP 2.68, boiling point 447.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 364.4) [ka]

[0065] Formula (a-2-17) below (OP 2.36, boiling point 543.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 398.5) [ka]

[0066] Formula (a-2-18) below (OP 3.27, boiling point 526.9°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 396.4) [ka]

[0067] Formula (a-2-19) below (OP 2.71, boiling point 333.7°C, vapor pressure at 80°C 0.0302mmHg, molecular weight 244.3) [ka]

[0068] Formula (a-2-20) below (OP 2.73, boiling point 333.7°C, vapor pressure at 80°C 0.0134mmHg, molecular weight 258.3) [ka]

[0069] Formula (a-2-21) below (OP 2.71, boiling point 319.2°C, vapor pressure at 80°C 0.0566mmHg, molecular weight 262.3) [ka]

[0070] Formula (a-2-22) below (OP 2.71, boiling point 336.9°C, vapor pressure at 80°C 0.0055mmHg, molecular weight 244.3) [ka]

[0071] Formula (a-2-23) below (OP 3.00, boiling point 370.9°C, vapor pressure at 80°C 0.0021mmHg, molecular weight 274.4) [ka]

[0072] Formula (a-2-24) below (OP 3.00, boiling point 376.4°C, vapor pressure at 80°C 0.0005mmHg, molecular weight 274.4) [ka]

[0073] Formula (a-2-25) below (OP 3.00, boiling point 379.4°C, vapor pressure at 80°C 0.0002mmHg, molecular weight 288.4) [ka]

[0074] Formula (a-2-26) below (OP 2.33, boiling point 360.8°C, vapor pressure at 80°C 0.0006mmHg, molecular weight 252.3) [ka]

[0075] Formula (a-2-27) below (OP 2.54, boiling point 371.5°C, vapor pressure at 80°C 0.0003mmHg, molecular weight 254.3) [ka]

[0076] Formula (a-2-28) below (OP 2.57, boiling point 381.2°C, vapor pressure at 80°C 0.0001mmHg, molecular weight 268.3) [ka]

[0077] Formula (a-2-29) below (OP 2.57, boiling point 381.8°C, vapor pressure at 80°C 0.0004mmHg, molecular weight 268.3) [ka]

[0078] The following formula (a-2-30) (OP 2.50, boiling point 487.4℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 374.4) [ka]

[0079] The following formula (a-2-31) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3) [ka]

[0080] The following formula (a-2-32) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3) [ka]

[0081] The following formula (a-2-33) (OP 2.67, boiling point 417.2℃, vapor pressure at 80℃ <0.0001mmHg, molecular weight 268.3) [ka]

[0082] The following formula (a-2-34) (OP 2.67, boiling point 417.2°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 268.3) [ka]

[0083] The following formula (a-2-35) (OP 2.71, boiling point 438.8°C, vapor pressure at 80°C <0.0001mmHg, molecular weight 296.3) [ka]

[0084] The blending ratio of component (a) in the curable composition (A1) is preferably 40% by weight or more and 99% by weight or less, based on the combined weight of component (a), component (b) (described below), and component (c) (described below), i.e., the total weight of all components excluding solvent (d). Furthermore, the blending ratio of component (a) in the curable composition (A1) is more preferably 50% by weight or more and 95% by weight or less, and even more preferably 60% by weight or more and 90% by weight or less, based on the total weight of all components excluding solvent (d). By setting the blending ratio of component (a) to 40% by weight or more, the mechanical strength of the cured film of the curable composition (A1) is increased. Furthermore, by setting the blending ratio of component (a) to 99% by weight or less, the blending ratios of components (b) and (c) can be increased, resulting in properties such as a fast thermal polymerization rate. All components in the curable composition (A1) excluding solvent (d) may be understood as a mixture (composition (A1')) of the curable composition (A1) excluding solvent (d).

[0085] <Component (b): Polymerization initiator> The polymerization initiator as component (b) in one embodiment of the present invention means, for example, a thermal radical generator or a thermal acid generator that generates radicals or cations, which are polymerization factors, by heat.

[0086] Examples of thermal radical generators include organic peroxides and azo compounds. Examples of organic peroxides include peroxyesters such as t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-butylperoxyisopropyl carbonate; peroxyketals such as 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane; and diacyl peroxides such as lauroyl peroxide, but are not limited thereto. Examples of azo compounds include azonitriles such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(cyclohexane-1-carbonitrile), but are not limited thereto.

[0087] Examples of the thermal acid generator include onium salt compounds and N-sulfonyloxyimide compounds.

[0088] Examples of the onium salt compound include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, and ammonium salts.

[0089] Examples of sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, and 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate.

[0090] Examples of tetrahydrothiophenium salts include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, and 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

[0091] Examples of iodonium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, and bis(4-t-butylphenyl)iodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

[0092] Examples of the ammonium salt include triethylammonium trifluoromethanesulfonate and triethylammonium nonafluoro-n-butanesulfonate.

[0093] Examples of N-sulfonyloxyimide compounds include N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, and N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide.

[0094] Among these, onium salt compounds are preferred as thermal acid generators, with iodonium salts and ammonium salts being more preferred, and bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate and triethylammonium nonafluoro-n-butanesulfonate being even more preferred as thermal acid generators.

[0095] The blending ratio of component (b) in the curable composition (A1) is preferably 0.1% by weight to 50% by weight, based on the total weight of components (a), (b), and (c) described below, i.e., the total weight of all components excluding solvent (d). Furthermore, the blending ratio of component (b) in the curable composition (A1) is more preferably 0.1% by weight to 20% by weight, and even more preferably 1% by weight to 20% by weight, based on the total weight of all components excluding solvent (d). By incorporating component (b) in a ratio of 0.1% by weight or more, the curing rate of the composition can be increased, improving reaction efficiency. Furthermore, by incorporating component (b) in a ratio of 50% by weight or less, a cured film with a certain level of mechanical strength can be obtained. All components in the curable composition (A1) excluding solvent (d) may be understood as a mixture (composition (A1')) of the curable composition (A1) excluding solvent (d).

[0096] <Component (c): Non-polymerizable compound> In addition to the above-described components (a) and (b), the curable composition (A1) according to one embodiment of the present invention may further contain a non-polymerizable compound as component (c) depending on various purposes, as long as the effects of this embodiment are not impaired. Examples of the non-polymerizable compound include internal mold release agents, antioxidants, polymer components, and other additives. Component (c) may contain multiple types of the above-described compounds.

[0097] An internal mold release agent can be added to the curable composition (A1) to reduce the interfacial bonding strength between the superstrate (mold) and the curable composition (A1), i.e., to reduce the demolding force in the demolding step described below. In one embodiment, "internal mold release" refers to a release agent that is added to the curable composition (A1) before the step of placing the curable composition (A1). Examples of internal mold release agents that can be used include surfactants such as silicon-based surfactants, fluorine-based surfactants, and hydrocarbon-based surfactants. However, in one embodiment, as described below, the amount of fluorine-based surfactants that can be added is limited. In one embodiment, the internal mold release agent is non-polymerizable. One type of internal mold release agent may be used alone, or two or more types may be mixed together.

[0098] Fluorine-based surfactants include the following: Polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols with perfluoroalkyl groups, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyethers The fluorosurfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, etc. in part of its molecular structure (for example, a terminal group). For example, pentadecaethylene glycol mono 1H,1H,2H,2H-perfluorooctyl ether can be mentioned.

[0099] As the fluorine-based surfactant, commercially available products may be used. Examples of commercially available fluorine-based surfactants include the following: Megafac (registered trademark) F-444, TF-2066, TF-2067, TF-2068, abbreviated as DEO-15 (all manufactured by DIC), Fluorad FC-430, FC-431 (all manufactured by Sumitomo 3M), Surflon (registered trademark) S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all manufactured by Tochem Products), PF-636, PF-6320, PF-656, PF-6520 (all manufactured by OMNOVA Solutions), Unidyne (registered trademark) DS-401, DS-403, DS-451 (all manufactured by Daikin Industries), Ftergent (registered trademark) 250, 251, 222F, 208G (all manufactured by Neos)

[0100] The internal release agent may also be a hydrocarbon surfactant. Examples of hydrocarbon surfactants include alkyl alcohol polyalkylene oxide adducts and polyalkylene oxides, which are alkyl alcohols having 1 to 50 carbon atoms and alkylene oxides having 2 to 4 carbon atoms.

[0101] Examples of alkyl alcohol polyalkylene oxide adducts include the following. Methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide / propylene oxide adduct The terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group that can be produced simply by adding a polyalkylene oxide to an alkyl alcohol, and the hydroxyl group may be substituted with other substituents, such as polar functional groups such as a carboxyl group, an amino group, a pyridyl group, a thiol group, or a silanol group, or hydrophobic functional groups such as an alkyl group or an alkoxy group.

[0102] Examples of polyalkylene oxides include the following: Polyethylene glycol, polypropylene glycol, their mono- or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, mono- or didecyl ethers, monoadipate esters, monooleate esters, monostearate esters, monosuccinate esters

[0103] The alkyl alcohol polyalkylene oxide adduct may be a commercially available product. Examples of commercially available alkyl alcohol polyalkylene oxide adducts include the following: Polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305, CH-310) manufactured by Aoki Oil Industry Co., Ltd., polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), randomly polymerized polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R) manufactured by Aoki Oil & Fat Industries, polyoxyethylene methyl ether (Pluriol® A760E) manufactured by BASF, and polyoxyethylene alkyl ether (Emulgen series) manufactured by Kao.

[0104] Alternatively, commercially available polyalkylene oxides may be used, such as BASF's ethylene oxide-propylene oxide copolymer (Pluronic PE6400).

[0105] Fluorine-based surfactants are effective as internal mold release agents because they exhibit an excellent effect of reducing mold release force. The blending ratio of component (c) excluding the fluorine-based surfactant in the curable composition (A1) is preferably 0% by weight or more and 50% by weight or less, based on the total weight of components (a), (b), and (c), i.e., the total weight of all components excluding solvent (d). Furthermore, the blending ratio of component (c) excluding the fluorine-based surfactant in the curable composition (A1) is more preferably 0.1% by weight or more and 50% by weight or less, and even more preferably 0.1% by weight or more and 20% by weight or less, based on the total weight of all components excluding solvent (d). By setting the blending ratio of component (c) excluding the fluorine-based surfactant to 50% by weight or less, a cured film with a certain level of mechanical strength can be obtained.

[0106] <Component (d): Solvent> The curable composition (A1) of the present invention contains, as component (d), a solvent having a boiling point of 80°C or higher but lower than 250°C under normal pressure. Examples of component (d) include solvents in which components (a), (b), and (c) dissolve, such as alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. Component (d) can be used alone or in combination of two or more. The boiling point of component (d) under normal pressure is 80°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 preferably lower than 250°C but lower than 200°C. If the boiling point of component (d) under normal pressure is lower than 80°C, the evaporation rate in the waiting step described below is too fast, which may result in component (d) volatilizing before the droplets of the curable composition (A1) combine together, preventing the droplets of the curable composition (A1) from combining together. Furthermore, if the boiling point of component (d) under normal pressure is 250°C or higher, component (d) may not volatilize sufficiently in the waiting step described below, and component (d) may remain in the cured film of curable composition (A1). Here, when component (d) contains one or more solvents, the boiling point of each of the one or more solvents contained in component (d) under normal pressure is preferably 80°C or higher and lower than 250°C, and more preferably 150°C or higher and lower than 200°C.

[0107] Examples of alcohol-based solvents include the following: Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl Monoalcohol solvents such as alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyalcohol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin.

[0108] Examples of ketone solvents include the following: Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, fenchone

[0109] Examples of ether solvents include the following: Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran

[0110] Examples of the ester solvent include the following: Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate Ether, Diethylene Glycol Mono-n-Butyl Ether Acetate, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl Ether Acetate, Dipropylene Glycol Monomethyl Ether Acetate, Dipropylene Glycol Monoethyl Ether Acetate, Glycol Diacetate, Methoxytriglycol Acetate, Ethyl Propionate, n-Butyl Propionate, Isoamyl Propionate, Diethyl Oxalate, Di-n-Butyl Oxalate, Methyl Lactate, Ethyl Lactate, n-Butyl Lactate, n-Amyl Lactate, Diethyl Malonate, Dimethyl Phthalate, Diethyl Phthalate

[0111] Examples of nitrogen-containing solvents include the following: N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone

[0112] Among the above-mentioned solvents, ether-based solvents and ester-based solvents are preferred, and from the viewpoint of excellent film-forming properties, ether-based solvents and ester-based solvents having a glycol structure are more preferred. Furthermore, the following are more preferred: Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Furthermore, particularly preferred is propylene glycol monomethyl ether acetate. Other examples include ethyl isocyanurate di(meth)acrylate.

[0113] In one embodiment, the preferred solvent is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure, specifically, a solvent selected from propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate, either singly or in combination.

[0114] In one embodiment, component (d) may contain a polymerizable compound having a boiling point under normal pressure of 80° C. or more and less than 250° C. For example, a polymerizable compound having a boiling point under normal pressure of 80° C. or more and less than 250° C. may be used as component (d). Examples of polymerizable compounds having a boiling point under normal pressure of 80° C. or more and less than 250° C. include the following: Cyclohexyl acrylate (198°C), benzyl acrylate (229°C), isobornyl acrylate (245°C), tetrahydrofurfuryl acrylate (202°C), trimethylcyclohexyl acrylate (232°C), isooctyl acrylate (217°C), n-octyl acrylate (228°C), ethoxyethoxyethyl acrylate (boiling point 230°C), divinylbenzene (193°C), 1,3-diisopropenylbenzene (218°C), styrene (145°C), α-methylstyrene (165°C)

[0115] In one embodiment, when the entire curable composition (A1) is taken as 100% by volume, the content of solvent (d) is 5% by volume or more and 95% by volume or less, preferably 5% by volume or more and 85% by volume or less, and more preferably 5% by volume or more and 80% by volume or less. If the content of solvent (d) is less than 5% by volume, a thin film cannot be obtained after evaporation of solvent (d) under conditions that allow for a substantially continuous liquid film to be obtained. On the other hand, if the content of solvent (d) is more than 95% by volume, a thick film cannot be obtained after evaporation of solvent (d) even when droplets are dropped in close-packed fashion by an inkjet method.

[0116] <Glass transition temperature of curable composition after curing> If the glass transition temperature is sufficiently higher than the temperature at the time of demolding, the cured product (cured film) will be in a strong glass state at the time of demolding, i.e., will exhibit high mechanical strength. Therefore, breakage due to the impact of demolding will be unlikely. Therefore, when the demolding step is carried out at room temperature, the glass transition temperature of the cured product is preferably 70°C or higher, more preferably 100°C or higher, and particularly preferably 150°C or higher.

[0117] The glass transition temperature of a cured product can be measured using differential scanning calorimetry (DSC) or a dynamic viscoelasticity analyzer. For example, when measuring using DSC, a straight line is drawn by extending the low-temperature baseline of the DSC curve of the cured product (the portion of the DSC curve in the temperature range where no transition or reaction occurs in the test specimen) toward the high-temperature side, and a tangent is drawn at the point where the gradient of the curve in the stepwise change portion of the glass transition is maximum. The extrapolated glass transition onset temperature (Tig) is then determined from the intersection of the straight line and the tangent, and this can be used as the glass transition temperature. Typical instruments include the STA-6000 (manufactured by PerkinElmer). On the other hand, when measuring using a dynamic viscoelasticity analyzer, the temperature at which the loss tangent (tanδ) of the cured product is maximized is defined as the glass transition temperature. Typical instruments that can measure dynamic viscoelasticity include the MCR301 (manufactured by AntonPaar).

[0118] <Heat resistance of curable composition after curing> The heat resistance of the curable composition (A1) after curing can be measured using thermogravimetric analysis (TGA) or the like. For example, when measuring using TGA, the cured composition is placed in a nitrogen atmosphere with a flow rate of 5 L / hour to 6 L / hour, and the heat resistance of n°C is determined by measuring the thermal weight loss rate when heated to n°C at a heating rate of 20°C / min. Typical instruments include the STA 1000 (manufactured by Linseis). Regarding the heat resistance of the cured product (cured film), the temperature at which the thermal weight loss rate first reaches 2% when heated from 200°C at a heating rate of 20°C / min is preferably 250°C or higher, more preferably 350°C or higher, and particularly preferably 400°C or higher. In other words, the cured film obtained through the curing step should exhibit a weight loss of 2% or less when heated from 200°C to 250°C at a heating rate of 20°C / min.

[0119] When the curable composition (A1) according to one embodiment of the present invention is used to manufacture a semiconductor integrated circuit, it is preferable to minimize the inclusion of impurities containing metal atoms (metal impurities) in the curable composition (A1) so as not to impair the operation of the product. The concentration of metal impurities contained in the curable composition (A1) is preferably 10 ppm or less, more preferably 100 ppb or less.

[0120] [Curable composition (A2)] The curable composition (A2) of one embodiment of the present invention is a thermosetting composition that cures upon heating, and can be used as a curable composition for inkjet printing. The curable composition (A2) of one embodiment is a composition containing at least a main component (p), a thermal acid generator (r), a crosslinking agent (s), and a solvent (d). The curable composition (A2) may also contain an optional component (c) within the scope of the present embodiment, provided that the effects of the present embodiment are not impaired. Each component will be described below. Preferably, the curable composition (A2) has a carbon atom content of 80% by weight or more in the components excluding the solvent (d) (i.e., the mixture other than the solvent (d)).

[0121] <Ingredient (p): Main ingredient> Component (p) is a base compound. Component (p) is a compound containing an aromatic ring such as a benzene ring, a naphthalene ring, or an anthracene ring, preferably with a molecular weight of 300 to 5000, and particularly preferably with a molecular weight of 500 to 2500. A molecular weight of 300 or more is advantageous for obtaining good film-forming properties and can also suppress contamination of manufacturing equipment due to an increase in sublimates during curing. A molecular weight of 5000 or less is advantageous for obtaining good filling / planarization properties.

[0122] Component (p) may contain a branched or cyclic saturated or unsaturated hydrocarbon group, a heteroaromatic group, an ether group, a hydroxyl group, an ester group, a carbonyl group, an amino group, a halogen group, a sulfide group, a carboxyl group, a sulfo group, an amido group, an imido group, a cyano group, an aldehyde group, an imino group, a urea group, a carbamate group, a carbonate group, a nitro group, or a sulfonyl group. Specific examples of component (p) include the following: where R represents an alkyl group. [ka]

[0123] Other specific examples of component (p) include novolak compounds such as phenol novolak, cresol novolak, and naphthol novolak, and substituted polystyrene compounds such as polyhydroxystyrene and polyhydroxyvinylnaphthalene. Component (p) may be used singly or in combination of two or more.

[0124] <Component (d): Solvent> Component (d) is not particularly limited as long as it can dissolve or disperse component (p) and any optional components contained as needed. Examples of component (d) include alcohol solvents, ketone solvents, ether solvents, ester solvents, and nitrogen-containing solvents. Component (d) may be used alone or in combination of two or more.

[0125] Examples of alcohol solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, and sec-tetramethylnonyl alcohol. Examples of suitable solvents include monoalcohol solvents such as ladecyl 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, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin.

[0126] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone.

[0127] Examples of ether solvents include ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, and diethylene glycol diisopropyl ether. glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglyceride, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and the like.

[0128] Examples of ester solvents include diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol mono Examples of the solvent include ethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc. Examples of the nitrogen-containing solvent include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, etc.

[0129] Among these, ether-based solvents and ester-based solvents are preferred, and from the viewpoint of excellent film-forming properties, ether-based solvents and ester-based solvents having a glycol structure are more preferred, with propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate being even more preferred, and propylene glycol monomethyl ether acetate being particularly preferred.

[0130] <Component (r): Thermal acid generator> The curable composition (A2) may contain a thermal acid generator as component (r). Component (r) generates an acid under the action of heat or light and promotes the crosslinking reaction of component (p) with the crosslinking agent (component (s)) described below. When the curable composition (A2) contains component (r), the crosslinking reaction of component (p) is promoted, and the hardness of the formed cured film can be further increased. One type of component (r) may be used alone, or two or more types may be used in combination. Examples of component (r) include onium salt compounds and N-sulfonyloxyimide compounds.

[0131] Examples of the onium salt compound include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, and ammonium salts.

[0132] Examples of sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, and 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate.

[0133] Examples of tetrahydrothiophenium salts include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium nonafluoro-n-butanesulfonate, and 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

[0134] Examples of iodonium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, and bis(4-t-butylphenyl)iodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

[0135] Examples of the ammonium salt include triethylammonium trifluoromethanesulfonate and triethylammonium nonafluoro-n-butanesulfonate.

[0136] Examples of N-sulfonyloxyimide compounds include N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, and N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide.

[0137] Among these, as component (r), onium salt compounds are preferred, with iodonium salts and ammonium salts being more preferred, and bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate and triethylammonium nonafluoro-n-butanesulfonate being even more preferred.

[0138] When the curable composition (A2) contains component (r), the lower limit of the content of component (r) is preferably 0.1 parts by mass, more preferably 1 part by mass, and even more preferably 3 parts by mass, per 100 parts by mass of component (p). The upper limit of the content of component (r) is preferably 15 parts by mass, more preferably 12 parts by mass, and even more preferably 10 parts by mass. By setting the content of component (r) within the above range, the crosslinking reaction of component (p) can be more effectively promoted.

[0139] <Component (s): Crosslinker> The curable composition (A2) may contain a crosslinking agent as component (s). Component (s) is a component that forms crosslinks between compounds contained in component (p) in the curable composition (A2) or forms a crosslinked structure by itself under the action of heat or acid. The inclusion of component (s) in the curable composition (A2) can increase the hardness of the cured film that is formed. One type of component (s) may be used alone, or two or more types may be used in combination.

[0140] Examples of the component (s) include polyfunctional (meth)acrylate compounds, epoxy compounds, hydroxymethyl-substituted phenol compounds, alkoxyalkyl-containing phenol compounds, and compounds having an alkoxyalkylated amino group.

[0141] Examples of polyfunctional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerin tri(meth)acrylate, and tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate. , ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, and the like.

[0142] Examples of the epoxy compound include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

[0143] Examples of hydroxymethyl group-substituted phenol compounds include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis(hydroxymethyl)-p-cresol], and the like.

[0144] Examples of alkoxyalkyl group-containing phenolic compounds include methoxymethyl group-containing phenolic compounds and ethoxymethyl group-containing phenolic compounds.

[0145] Examples of compounds having an alkoxyalkylated amino group include (poly)methylolated melamines such as hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof; (poly)methylolated glycolurils such as tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof; (poly)methylolated benzoguanamines such as tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof; and (poly)methylolated ureas such as dimethoxymethylated dimethoxyethylene urea, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof, which are nitrogen-containing compounds having multiple active methylol groups in one molecule, in which at least one hydrogen atom of the hydroxyl group of the methylol group is substituted with an alkyl group such as a methyl group or a butyl group. The compound having an alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, or may contain an oligomer component formed by partial self-condensation.

[0146] When the curable composition (A2) contains component (s), the lower limit of the content of component (s) is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, even more preferably 1 part by mass, and particularly preferably 3 parts by mass, per 100 parts by mass of component (p). The upper limit of the content of component (s) is preferably 50 parts by mass, more preferably 40 parts by mass, even more preferably 30 parts by mass, and particularly preferably 20 parts by mass. By setting the content of component (s) within the above range, the crosslinking reaction of component (p) can be more effectively induced.

[0147] <Component (c): Other optional components> The curable composition (A2) may contain another optional component (c). Examples of the component (c) include a surfactant. The inclusion of a surfactant in the curable composition (A2) can improve the coatability, thereby improving the uniformity of the coated surface of the formed liquid film and suppressing the occurrence of coating spots. One type of surfactant may be used alone, or two or more types may be used in combination.

[0148] When the curable composition (A2) contains a surfactant, the lower limit of the surfactant content is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, and even more preferably 0.1 parts by mass, relative to 100 parts by mass of the component (p). The upper limit of the surfactant content is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 1 part by mass. By setting the surfactant content within the above range, the coatability of the curable composition can be further improved.

[0149] [Curable composition (A3)] The curable composition (A3) of one embodiment of the present invention is a thermosetting composition that cures upon heating, and can be used as a curable composition for inkjet printing. The curable composition (A3) of one embodiment is a composition containing at least a siloxane component (q) and a solvent component (d). The composition may also contain an optional component (c) within a range that does not impair the effects of this embodiment. Each component will be described below. Preferably, the curable composition (A3) has a silicon atom content of 30% by weight or more in the components excluding the solvent (d) (i.e., the mixture other than the solvent (d)).

[0150] Siloxane component (q) is a general term for polymer compounds with Si-O bonds (siloxane bonds), and is a chain siloxane H3SiO(H2SiO) n -SiH3, cyclic siloxane (-H2SiO-) n The compounds include compounds represented by the following general formulas:

[0151] Specific examples of component (q) include, but are not limited to, the following: where R represents an alkyl group or a hydroxy group. [ka] [ka] [ka]

[0152] <Component (d): Solvent> Component (d) is not particularly limited as long as it can dissolve or disperse component (q) and any optional components contained as needed. Examples of component (d) include alcohol solvents, ketone solvents, ether solvents, ester solvents, and nitrogen-containing solvents. Component (d) may be used alone or in combination of two or more.

[0153] Examples of alcohol solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, and sec-tetramethylnonyl alcohol. Examples of suitable solvents include monoalcohol solvents such as ladecyl 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, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin.

[0154] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone.

[0155] Examples of ether solvents include ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexoxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, and diethylene glycol diisopropyl ether. glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglyceride, tetraethylene glycol di-n-butyl ether, 1-n-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and the like.

[0156] Examples of ester solvents include diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol mono Examples of the solvent include ethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc. Examples of the nitrogen-containing solvent include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, etc.

[0157] Among these, ether-based solvents and ester-based solvents are preferred, and from the viewpoint of excellent film-forming properties, ether-based solvents and ester-based solvents having a glycol structure are more preferred, with propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate being even more preferred, and propylene glycol monomethyl ether acetate being particularly preferred.

[0158] <Component (c): Other optional components> The curable composition (A3) may contain another optional component (c). Examples of the component (c) include a surfactant. The inclusion of a surfactant in the curable composition (A3) can improve the coatability, thereby improving the uniformity of the coated surface of the formed liquid film and suppressing the occurrence of coating irregularities. One type of surfactant may be used alone, or two or more types may be used in combination.

[0159] When the curable composition (A3) contains a surfactant, the lower limit of the surfactant content is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, and even more preferably 0.1 parts by mass, relative to 100 parts by mass of component (q). The upper limit of the surfactant content is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 1 part by mass. By setting the surfactant content within the above range, the coatability of the curable composition can be further improved.

[0160] [Curable composition (A)] Hereinafter, the common characteristics of the above curable compositions (A1), (A2), and (A3) will be described collectively as the curable composition (A).

[0161] <Temperature when compounding the curable composition> When preparing the curable composition (A) of one embodiment of the present invention, the components are mixed and dissolved under a predetermined temperature condition, specifically, in the range of 0°C or higher and 100°C or lower.

[0162] <Viscosity of Curable Composition> The curable composition (A) according to one embodiment of the present invention is liquid. This is because, in the disposing step described below, the curable composition (A) is discretely dropped (disposed) on a substrate as multiple droplets by an inkjet method. The viscosity of the curable composition (A) according to one embodiment of the present invention at 23°C is 2 mPa·s or more and 60 mPa·s or less, preferably 5 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 15 mPa·s or less. If the viscosity of the curable composition (A) is less than 2 mPa·s, the ejection of droplets by the inkjet method becomes unstable. Furthermore, if the viscosity of the curable composition (A) is greater than 60 mPa·s, it is not possible to form droplets with a volume of approximately 1.0 to 3.0 pL, which is preferred in one embodiment.

[0163] The viscosity of the components of the curable composition (A) excluding the solvent (d), i.e., the mixture of the curable composition (A) excluding the solvent (d), at 23°C is 30 mPa·s or more and 10,000 mPa·s or less. The viscosity of the mixture at 23°C is preferably 90 mPa·s or more and 2,000 mPa·s or less, for example, 120 mPa·s or more and 1,000 mPa·s or less, and more preferably 150 mPa·s or more and 500 mPa·s or less. By making the viscosity of the mixture at 23°C 1,000 mPa·s or less, spreading and filling are completed quickly when the curable composition (A) is brought into contact with the superstrate. Therefore, by using the curable composition (A) of one embodiment according to the present invention, imprint processing can be performed with high throughput and defects due to insufficient filling can be suppressed. Furthermore, by making the viscosity of the mixture at 23°C 1 mPa·s or more, unwanted flow of droplets of the curable composition after the solvent (d) has evaporated can be prevented. Furthermore, when the curable composition (A) is brought into contact with the superstrate, the curable composition (A) is less likely to flow out from the edge of the superstrate. Note that the components of the curable composition (A) other than the solvent (d) may be understood as the components (mixture, composition) remaining after all of the solvent (d) has evaporated from the curable composition (A).

[0164] <Surface tension of curable composition> Regarding the surface tension of the curable composition (A) according to one embodiment of the present invention, the surface tension of the mixture of the curable composition (A) excluding the solvent (d) at 23°C is preferably 5 mN / m or more and 70 mN / m or less. The surface tension of the mixture at 23°C is more preferably 7 mN / m or more and 50 mN / m or less, and even more preferably 10 mN / m or more and 40 mN / m or less. The higher the surface tension of the mixture at 23°C, for example, 5 mN / m or more, the stronger the capillary force, and therefore the faster the spreading (spreading and filling) when the curable composition (A) is brought into contact with a superstrate. Furthermore, by setting the surface tension to 70 mN / m or less, the cured film obtained by curing the curable composition (A) has a smooth surface.

[0165] <Contact angle of curable composition> Regarding the contact angle of the curable composition (A) according to one embodiment of the present invention, the contact angle of the mixture of the curable composition (A) other than the solvent (d) with both the substrate surface and the superstrate surface is preferably 0° or more and 90° or less. The contact angle of the mixture is particularly preferably 0° or more and 10° or less. If the contact angle of the mixture is greater than 90°, the capillary force in the gap between the substrate and the superstrate acts in the negative direction (in a direction that shrinks the contact interface between the superstrate and the curable composition (A)), which may result in failure to fill the gap. Furthermore, the smaller the contact angle of the mixture, the stronger the capillary force, resulting in a faster filling rate.

[0166] <Impurities contained in the curable composition> The curable composition (A) according to one embodiment of the present invention preferably contains as few impurities as possible. The impurities in the curable composition (A1) refer to components other than the above-described components (a), (b), (c), and (d). The impurities in the curable composition (A2) refer to components other than the above-described components (p), (S), (r), (d), and (c). The impurities in the curable composition (A3) refer to components other than the above-described components (q), (d), and (c). Therefore, the curable composition (A) according to one embodiment of the present invention is preferably obtained through a purification step. Such a purification step is preferably filtration using a filter.

[0167] Regarding filtration using a filter, it is preferable to mix all of the above-mentioned components except for component (d), which corresponds to the solvent, and then filter the mixture using a filter with a pore size of 0.001 μm to 5.0 μm. When performing filtration using a filter, it is more preferable to perform the filtration in multiple stages or repeatedly (circulating filtration). Furthermore, the liquid filtered through the filter may be filtered again, or it may be filtered using multiple filters with different pore sizes. Examples of filters used for filtration include, but are not limited to, filters made of polyethylene resin, polypropylene resin, fluororesin, and nylon resin. By undergoing such a purification step, impurities such as particles mixed in the curable composition (A) can be removed. This prevents impurities mixed in the curable composition (A) from accidentally causing irregularities and defects in the cured film obtained after curing the curable composition (A).

[0168] [substrate] In this specification, the member onto which the droplets of the curable composition (A) are discretely dispensed is referred to as a substrate.

[0169] The substrate is a substrate to be processed, and is typically a silicon wafer. The substrate may have a processable layer on its surface. The substrate may have another layer formed below the processable layer. However, the substrate is not limited to a silicon wafer or a quartz substrate. The substrate can be selected from any substrate known as a substrate for semiconductor devices, such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, or silicon nitride. The surface of the substrate or the processable layer may be subjected to a surface treatment such as silane coupling treatment, silazane treatment, or formation of an organic thin film to improve adhesion to the curable composition (A).

[0170] [Membrane formation method] A film forming method according to one embodiment of the present invention will be described below. The film forming method is a method for forming a planarizing film on a substrate using a mold, and includes, for example, a disposing step, a waiting step, a contacting step, a curing step, and a demolding step. The disposing step is a step of disposing a plurality of droplets of the curable composition (A) on the substrate. The waiting step is a step of waiting until the plurality of droplets of the curable composition (A) disposed on the substrate in the disposing step combine to form a liquid film. The contacting step is a step of bringing the liquid film of the curable composition (A) on the substrate into contact with the mold. The curing step is a step of heating and curing the curable composition (A) while the liquid film of the curable composition (A) on the substrate is in contact with the mold, thereby forming a cured film of the curable composition (A) between the mold and the substrate. The demolding step is a step (separation step) of separating the cured film of the curable composition (A) from the mold. The waiting step is performed after the placing step, the contacting step is performed after the waiting step, the curing step is performed after the contacting step, and the demolding step is performed after the curing step.

[0171] In one embodiment of the film-forming method according to the present invention, a substrate having irregularities with a height difference of about 10 to 1,000 nm is used as the substrate, and a mold having a flat surface (hereinafter, sometimes referred to as a superstrate) is used as the mold. A superstrate can be defined as having a contact surface that comes into contact with the curable composition (A) on the substrate, and 90% or more (preferably 95% or more) of that contact surface being a flat surface. In one embodiment of the film-forming method, a cured film having a surface conforming to the flat surface of the superstrate is formed on the substrate through the above-mentioned disposing step, waiting step, contacting step, curing step, and demolding step. Here, in the disposing step, droplets of the curable composition (A) are densely disposed in the recessed portions of the substrate, and the curable composition (A) is sparsely disposed in the protruding portions of the substrate.

[0172] <Placement process> In the disposing step, as shown in Fig. 1[1], the curable composition (A) is discretely disposed as a plurality of droplets on a substrate. The substrate may be a substrate having a base layer laminated thereon. The surface of the substrate may be subjected to a surface treatment such as a silane coupling treatment, a silazane treatment, or the formation of an organic thin film to improve adhesion to the curable composition (A).

[0173] The inkjet method is particularly preferred as a disposition method for disposing multiple droplets of the curable composition (A) on a substrate. To determine the volume of the curable composition (A) to be disposed on the substrate, an index called the average remaining liquid film thickness is defined. The average remaining liquid film thickness is the value obtained by dividing the volume of the curable composition (A) (specifically, the mixture other than the solvent (d)) disposed on the substrate in the disposition step by the area of the film-forming region (contact surface, flat surface) of the superstrate. The volume of the curable composition (A) (specifically, the mixture other than the solvent (d)) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (d) has evaporated. According to this definition, even if the substrate surface is uneven, the average remaining liquid film thickness can be determined regardless of the unevenness of the surface.

[0174] <Standby process> In the waiting step, the droplets of the curable composition (A) spread on the substrate as shown in Fig. 1 [2], so that the entire area of the substrate where the planarizing film is to be formed (film formation area) is covered with the curable composition (A).

[0175] Referring to Figures 2[1] to [4], the flow behavior of droplets of the curable composition (A) placed on a substrate during the waiting process will be described. As shown in Figure 2[1], droplets of the curable composition (A) are discretely placed on the substrate, and as shown in Figure 2[2], each droplet gradually spreads on the substrate. Then, as shown in Figure 2[3], the droplets of the curable composition (A) on the substrate begin to combine with each other to form a liquid film, which then becomes a continuous liquid film as shown in Figure 2[4] (the surface of the substrate is covered with the curable composition (A), with no exposed surface). Hereinafter, the state of the curable composition (A) as shown in Figure 2[4] may be referred to as a "substantially continuous liquid film."

[0176] Furthermore, in the waiting step, as shown schematically in Figure 1 [4], the solvent (d) contained in the liquid film is volatilized. The remaining amount (content) of the solvent (d) in the liquid film after the waiting step is preferably 10% by volume or less, assuming that the total weight of the components (mixture) other than the solvent (d) in the curable composition (A) constituting the liquid film is 100% by volume. That is, in the waiting step, waiting is continued until the remaining amount (content) of the solvent (d) in the curable composition (A) constituting the liquid film becomes 10% by volume or less relative to the components (mixture) other than the solvent (d). If the remaining amount of solvent (d) is more than 10% by volume, the mechanical properties of the cured film may be reduced.

[0177] During the waiting step, a baking step may be performed to heat the substrate and curable composition (A) or to ventilate the ambient gas surrounding the substrate in order to accelerate the evaporation of the solvent (d). Heating is performed, 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 may be 10 seconds to 600 seconds. The baking step may be performed using a known heater such as a hot plate or oven.

[0178] The waiting step is, for example, 0.1 to 600 seconds, preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 second, the droplets of the curable composition (A) will not bond sufficiently, and a substantially continuous liquid film will not be formed. If the waiting step exceeds 600 seconds, productivity will decrease. Therefore, to prevent a decrease in productivity, substrates that have completed the placement step may be sequentially transferred to the waiting step, and the waiting step may be performed on multiple substrates in parallel, and the substrates that have completed the waiting step may be sequentially transferred to the contacting step. Note that in conventional technology, it theoretically takes several thousand to tens of thousands of seconds for a substantially continuous liquid film to be formed, but in reality, the spreading of the droplets of the curable composition stagnates due to volatilization, making it impossible to form a continuous liquid film.

[0179] In the waiting step, when the solvent (d) evaporates, a substantially continuous liquid film consisting of components (mixture) other than the solvent (d) remains. The average remaining liquid film thickness of the substantially continuous liquid film after the solvent (d) has volatilized (removed) is thinner than the liquid film by the amount of solvent (d) that has volatilized. The entire film formation region of the substrate remains covered with a substantially continuous liquid film of the curable composition (A) from which the solvent (d) has been removed.

[0180] <Contact process> In the contacting step, as shown in Figure 1 [5], a substantially continuous liquid film of the curable composition (A) from which the solvent (d) has been removed is brought into contact with the superstrate. The contacting step includes a step of changing the state in which the curable composition (A) and the superstrate are not in contact with each other to a state in which they are in contact with each other, and a step of maintaining the state in which they are in contact with each other. This allows the liquid film of the curable composition (A) to be flattened in accordance with the flatness of the contact surface (flat surface) of the superstrate.

[0181] In one embodiment of the present invention, in the waiting step, the curable composition (A) becomes a substantially continuous liquid film from which the solvent (d) has been removed, thereby reducing the volume of gas trapped between the superstrate and the substrate. Therefore, the spreading of the curable composition (A) in the contacting step is completed quickly. A comparison (difference) between the contacting step in the prior art disclosed in Patent Document 1 and the contacting step in one embodiment of the present invention is shown in Figure 3.

[0182] If the spreading and filling of the curable composition (A) is completed quickly in the contacting step, the time required to keep the superstrate in contact with the curable composition (A) (the time required for the contacting step) can be shortened. Furthermore, shortening the time required for the contacting step leads to a shortening of the time required for forming the planarizing film, thereby improving productivity. The contacting step is preferably from 0.1 to 3 seconds, and particularly preferably from 0.1 to 1 second. If the contacting step is shorter than 0.1 seconds, spreading and filling are insufficient, and defects known as unfilled defects tend to occur frequently.

[0183] In one embodiment of the present invention, the superstrate is preferably a silicon wafer or a quartz wafer, with a silicon wafer being particularly preferred. Commercially available silicon wafers, such as those with diameters of 450 mm, 300 mm, 200 mm, 150 mm, 100 mm, and 50 mm, can be used as the silicon wafer. Prior to the contact step, it is preferable to clean the contact surface of the superstrate and confirm using an existing defect inspection device that there are no more than 10 particles of 50 nm or larger on the contact surface. When the superstrate is used continuously through repeated contact steps, the above-described method for cleaning and checking for foreign particles is first performed prior to the first contact step. Furthermore, it is preferable to perform the above-described method for cleaning and checking for foreign particles prior to the contact step every time the superstrate is used continuously a predetermined number of times (e.g., 1,000 times).

[0184] If the difference in the thermal expansion coefficient between the superstrate and the substrate is small, the distortion of the cured film formed on the substrate can be reduced. When a silicon wafer is used as the substrate, the thermal expansion coefficient of the superstrate at 290K to 310K is 1×10 -6 K -1 7x10 or more -6 K -1 The thermal expansion coefficient is preferably 2×10 or less. -6 K -1 6×10 or more -6 K -1 More preferably, it is 3×10 or less. -6 K -1 5x10 or more -6 K -1 It is more preferable that:

[0185] Furthermore, by reducing the difference in thickness between the superstrate and the substrate, distortion of the cured film formed on the substrate can be reduced. When a 300 mm diameter silicon wafer is used as the substrate, the thickness of the superstrate is preferably 550 μm to 1000 μm, more preferably 650 μm to 900 μm, and even more preferably 750 μm to 800 μm. When a 200 mm diameter silicon wafer is used as the substrate, the thickness of the superstrate is preferably 500 μm to 950 μm, more preferably 600 μm to 850 μm, and even more preferably 700 μm to 750 μm.

[0186] The superstraight may be surface-treated before the contact step to improve the releasability of the superstraight from the curable composition (A). Examples of surface treatments include applying a release agent to the surface of the superstraight to form a release agent layer. Examples of release agents that can be applied to the surface of the superstraight include silicone-based release agents, fluorine-based release agents, hydrocarbon-based release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin-based release agents, montan-based release agents, and carnauba-based release agents. Commercially available coating-type release agents, such as Optool (registered trademark) DSX manufactured by Daikin Industries, Ltd., can also be used. One type of release agent may be used alone, or two or more types may be used in combination. Of the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly preferred.

[0187] In the contacting step, the pressure applied to the curable composition (A) when the superstrate is brought into contact with the curable composition (A) is not particularly limited, but is, for example, 0 MPa or more and 100 MPa or less, 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.

[0188] The contacting step can be carried out under any of the conditions of air, reduced pressure, and inert gas atmosphere, but a reduced pressure or inert gas atmosphere is preferred because it can prevent the influence of oxygen and moisture on the curing reaction. Specific examples of the inert gas used when the contacting step is carried out under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbon gases, and mixtures of these. When the contacting step is carried out under a specific gas atmosphere, including air, the preferred pressure is 0.0001 atmospheres or more and 10 atmospheres or less.

[0189] <Curing process> A curing step is provided to cure the curable composition (A) to such an extent that peeling or deformation does not occur in the demolding step described below. In the curing step, as schematically shown in Figure 1 [6], the curable composition (A) is heated to cure the curable composition (A) and form a cured film. As a result, the liquid film of the curable composition (A) filled between the superstrate and the substrate is cured to form a cured film. The heating temperature of the curable composition (A) in the curing step is preferably 100°C or higher and 400°C or lower.

[0190] <Mold release process> In the demolding step, as shown in Figure 1 [7], the superstrate is detached from the cured film of the curable composition (A) formed on the substrate in the curing step. By detaching the cured film from the superstrate, a cured film with a flat surface is formed on the substrate. In the following, a cured film with a flat surface may be referred to as a "flat cured film."

[0191] The method for separating the superstrate from the cured film on the substrate is not particularly limited as long as a portion of the flat cured film is not physically damaged during the separation. For example, the superstrate may be separated from the cured film on the substrate by moving the superstrate away from the substrate while the substrate is fixed. Alternatively, the superstrate may be separated from the cured film on the substrate by moving the substrate away from the superstrate while the superstrate is fixed. The superstrate may also be separated from the cured film on the substrate by moving both the superstrate and the substrate in opposite directions.

[0192] <Hard bake process> In one embodiment of the film-forming method according to the present invention, a hard bake step may be performed after the demolding step to reheat the cured film formed on the substrate after the demolding step in order to obtain desired film properties. For example, when curable composition (A2) is used as curable composition (A), the hard bake step promotes the volatilization of residual solvent and carbonization of the remaining curable composition, resulting in a flat cured film with etching resistance. When curable composition (A3) is used as curable composition (A), the hard bake step promotes the volatilization of residual solvent and the formation of a three-dimensional crosslinked structure through dehydration condensation, resulting in a flat cured film with etching resistance, heat resistance, transparency, insulating properties, and the like. The upper limit of the heating temperature in the hard bake step is preferably the heat resistance temperature. When measuring the heat resistance temperature using TGA, the heat resistance temperature is determined by placing the cured curable composition (A) in a nitrogen atmosphere with a flow rate of 5 L / hour to 6 L / hour and measuring the thermal weight loss rate when the temperature is raised to n°C at a heating rate of 20°C / min. The temperature at which the thermal weight loss rate first reaches 2% is defined as the heat resistance temperature. The main equipment used is the STA 1000 (manufactured by Linseis).

[0193] [Product manufacturing method] An article manufacturing method according to one embodiment of the present invention includes a forming step of forming a planarizing film of a curable composition on a substrate using the above-described film forming method, a processing step of processing the substrate on which the planarizing film has been formed in the forming step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. As described above, the film forming method is a method of forming a planarizing film on a substrate using a superstrate, and may include, for example, a positioning step, a waiting step, a contact step, a curing step, and a demolding step.

[0194] Known photolithography processes, such as imprint lithography and extreme ultraviolet (EUV) exposure, can be performed on a planarization film formed on a substrate by the film formation method of one embodiment of the present invention. Alternatively, a spin-on-glass (SOG) film and / or a silicon oxide layer can be laminated, and a curable composition can be applied thereon to perform a photolithography process. This allows devices such as semiconductor devices to be manufactured. Furthermore, electronic devices including such devices, such as displays, cameras, and medical devices, can also be formed. Examples of such devices include LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and NAND flash memory.

[0195] Here, the term "article" refers to an electric circuit element, an optical element, a MEMS, a recording element, a sensor, or a mold. Examples of electric circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensor, and FPGA. Examples of optical elements include microlenses, light guides, waveguides, anti-reflection films, diffraction gratings, polarizing elements, color filters, light-emitting elements, displays, and solar cells. Examples of MEMS include DMDs, microchannels, and electromechanical conversion elements. Examples of recording elements include optical disks such as CDs and DVDs, magnetic disks, magneto-optical disks, and magnetic heads. Examples of sensors include magnetic sensors, optical sensors, and gyro sensors. Examples of molds include imprint molds.

[0196] To supplement the above-described embodiment, more specific examples will be described. Below, Example 1, in which a silicon wafer is used as the superstrate, and Comparative Example 1, in which a quartz wafer is used as the superstrate, will be described. Note that a silicon wafer is used as the substrate.

[0197] [Example 1] A silicon wafer can be prepared as a superstrate that satisfies the above-described conditions of one embodiment of the present invention. Therefore, in Example 1, a 300 mm diameter silicon wafer with fewer than 10 foreign particles of 50 nm or larger is used as the superstrate. The silicon wafer as the superstrate may be cleaned using a commercially available cleaning device, if necessary.

[0198] [Comparative Example 1] It is difficult to prepare a quartz wafer as a superstrate that satisfies the above-described conditions of one embodiment of the present invention. Specifically, it is difficult to obtain a 300 mm diameter quartz wafer with fewer than 100 foreign particles of 50 nm or larger. Therefore, in Comparative Example 1, a 300 mm diameter quartz wafer with 100 or more foreign particles of 50 nm or larger is used as the superstrate.

[0199] The thermal expansion coefficients of silicon wafers and quartz wafers at 290K to 310K are shown in the table below. When a silicon wafer is used as the substrate and a quartz wafer is used as the superstrate (Comparative Example 1), the thermal expansion coefficient of the substrate is 4×10 -6 K -1 whereas the thermal expansion coefficient of the superstrate is 6×10 -7 K -1 That is, in Comparative Example 1, the ratio of the thermal expansion coefficients of the substrate and the superstrate is 6 times or more. On the other hand, when a silicon wafer is used as both the substrate and the superstrate (Example 1), the thermal expansion coefficients of both the substrate and the superstrate are 4×10 -6 K -1 Therefore, when a silicon wafer is used as the superstrate (Example 1), the difference in thermal expansion coefficient between the substrate and the superstrate is smaller than when a quartz wafer is used as the superstrate (Comparative Example 1). In other words, the distortion of the cured film formed on the substrate by the film formation method according to one embodiment of the present invention can be reduced. [Table 1]

[0200] <Summary of the embodiment> The disclosure of the present specification includes at least the following film forming method and article manufacturing method. (Item 1) A film forming method for forming a planarized film on a substrate using a superstrate having a flat surface, comprising: a disposing step of disposing the curable composition (A) discretely as a plurality of droplets on the substrate; a waiting step of waiting for the plurality of droplets disposed on the substrate in the disposing step to combine with each other to form a liquid film on the substrate; a contacting step of contacting the liquid film on the substrate with the flat surface of the superstrate after the waiting step; a curing step of heating and curing the liquid film after the contacting step to form a cured film between the superstrate and the substrate; a separation step of separating the cured film from the superstrate after the curing step; Including, the curable composition (A) disposed on the substrate in the disposing step is thermosetting and has the property of being cured by heating, and contains at least a solvent (d); The viscosity of the curable composition (A) at 23°C is 2 mPa s or more and 60 mPa s or less, the content of the solvent (d) in the curable composition (A) is 5% by volume or more and 95% by volume or less; The boiling point of the solvent (d) under normal pressure is less than 250°C, A film-forming method, wherein the mixture of the curable composition (A) other than the solvent (d) has a viscosity of 30 mPa·s or more and 10,000 mPa·s or less at 23°C. (Item 2) 2. The film forming method according to item 1, wherein the superstrate is a silicon wafer. (Item 3) The thermal expansion coefficient of the superstrate at 290K to 310K is 1×10 -6 K -1 7x10 or more-6 K -1 3. The film forming method according to item 1 or 2, wherein: (Item 4) 4. The film forming method according to any one of items 1 to 3, wherein in the disposing step, the curable composition (A) is discretely disposed on the substrate as the plurality of droplets by using an inkjet method. (Item 5) 5. The film forming method according to any one of items 1 to 4, wherein the cured film obtained through the curing step exhibits a weight loss of 2% or less when heated from 200°C to 250°C at a heating rate of 20°C / min. (Item 6) The curable composition (A) contains at least a polymerizable compound (a) and a radical generator (b), 6. The film forming method according to any one of items 1 to 5, wherein the polymerizable compound (a) includes at least a polymerizable compound (a-1) containing one or more aromatic rings or aromatic heterocycles and a vinyl group directly bonded to the aromatic rings or aromatic heterocycles. (Item 7) The polymerizable compound (a) contains one or more polymerizable compounds, 7. The film forming method according to item 6, wherein the boiling point of each of the one or more polymerizable compounds under normal pressure is 250° C. or higher. (Item 8) The polymerizable compound (a) contains one or more polymerizable compounds, 8. The film forming method according to item 6 or 7, wherein the molecular weight of each of the one or more polymerizable compounds is 200 or more. (Item 9) The polymerizable compound (a) contains one or more polymerizable compounds, 9. The film forming method according to any one of items 6 to 8, wherein the vapor pressure of each of the one or more polymerizable compounds at 80° C. is 0.001 mmHg or less. (Item 10) 10. The film forming method according to any one of items 6 to 9, wherein the polymerizable compound (a) contains at least a polymer having a polymerizable functional group. (Item 11) The curable composition (A) contains a compound (p) having a molecular weight of 300 to 5000 and containing a benzene ring, a thermal acid generator (r), and a crosslinking agent (s), 11. The method for forming a film according to any one of items 1 to 10, wherein the carbon atom content of the mixture of the curable composition (A) other than the solvent (d) is 80% by weight or more. (Item 12) The curable composition (A) contains a siloxane component (q), 12. The film forming method according to any one of items 1 to 11, wherein the silicon atom content of the mixture of the curable composition (A) other than the solvent (d) is 30% by weight or more. (Item 13) 13. The film forming method according to any one of items 1 to 12, wherein the curable composition (A) contains a surfactant. (Item 14) The solvent (d) includes one or more solvents, 14. The film forming method according to any one of items 1 to 13, wherein the boiling point of each of the one or more solvents under normal pressure is 80°C or higher and lower than 250°C. (Item 15) The solvent (d) includes one or more solvents, 15. The film forming method according to any one of items 1 to 14, wherein the boiling point of each of the one or more solvents under normal pressure is 150°C or higher and lower than 200°C. (Item 16) 16. The film forming method according to any one of items 1 to 15, wherein the solvent (d) contains a polymerizable compound having a boiling point of 80° C. or higher and lower than 250° C. under normal pressure. (Item 17) 17. The film forming method according to any one of items 1 to 16, wherein the content of the solvent (d) in the curable composition (A) is 5% by volume or more and 85% by volume or less. (Item 18) 18. The film forming method according to any one of items 1 to 17, wherein the curable composition (A) is a curable composition for inkjet printing. (Item 19) 19. The film forming method according to any one of items 1 to 18, wherein in the waiting step, waiting is performed until the content of the solvent (d) in the liquid film becomes 10% by volume or less with respect to the mixture. (Item 20) 20. The film forming method according to any one of items 1 to 19, wherein in the waiting step, the substrate is heated at a temperature of 30° C. or higher and 200° C. or lower for 10 seconds or higher and 600 seconds or lower. (Item 21) 21. The film forming method according to any one of items 1 to 20, further comprising a hard baking step of heating the cured film on the substrate after the separating step. (Item 22) A forming step of forming a planarizing film on a substrate using the film forming method according to any one of items 1 to 21; a processing step of processing the substrate on which the planarization film has been formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising:

[0201] The invention is not limited to the above-described embodiments, and various changes and modifications can be made without departing from the spirit and scope of the invention. Accordingly, the following claims are appended to apprise the public of the scope of the invention.

Claims

1. A film forming method for forming a planarized film on a substrate using a superstrate having a flat surface, comprising: a disposing step of disposing the curable composition (A) discretely as a plurality of droplets on the substrate; a waiting step of waiting for the plurality of droplets disposed on the substrate in the disposing step to combine with each other to form a liquid film on the substrate; a contacting step of contacting the liquid film on the substrate with the flat surface of the superstrate after the waiting step; a curing step of heating and curing the liquid film after the contacting step to form a cured film between the superstrate and the substrate; a separation step of separating the cured film from the superstrate after the curing step; Including, the curable composition (A) disposed on the substrate in the disposing step is thermosetting and has the property of being cured by heating, and contains at least a solvent (d); The viscosity of the curable composition (A) at 23°C is 2 mPa·s or more and 60 mPa·s or less, the content of the solvent (d) in the curable composition (A) is 5% by volume or more and 95% by volume or less, The boiling point of the solvent (d) under normal pressure is less than 250°C, a mixture of the curable composition (A) other than the solvent (d) having a viscosity of 30 mPa·s or more and 10,000 mPa·s or less at 23°C;

2. 2. The film forming method according to claim 1, wherein the superstrate is a silicon wafer.

3. The thermal expansion coefficient of the superstrate at 290K to 310K is 1×10 －６ K －１ 7 x 10 or more －６ K －１ 2. The film forming method according to claim 1, wherein:

4. 2. The film forming method according to claim 1, wherein in the disposing step, the curable composition (A) is discretely disposed on the substrate as the plurality of droplets using an inkjet method.

5. 2. The film forming method according to claim 1, wherein the cured film obtained through the curing step loses a weight of 2% or less when heated from 200°C to 250°C at a heating rate of 20°C / min.

6. The curable composition (A) contains at least a polymerizable compound (a) and a radical generator (b), 2. The film forming method according to claim 1, wherein the polymerizable compound (a) includes at least a polymerizable compound (a-1) containing one or more aromatic rings or aromatic heterocycles and a vinyl group directly bonded to the aromatic rings or aromatic heterocycles.

7. The polymerizable compound (a) contains one or more polymerizable compounds, 7. The film forming method according to claim 6, wherein the boiling point of each of the one or more polymerizable compounds under normal pressure is 250[deg.] C. or higher.

8. The polymerizable compound (a) contains one or more polymerizable compounds, 7. The film forming method according to claim 6, wherein each of the one or more polymerizable compounds has a molecular weight of 200 or more.

9. The polymerizable compound (a) contains one or more polymerizable compounds, 7. The film forming method according to claim 6, wherein the vapor pressure of each of the one or more polymerizable compounds at 80°C is 0.001 mmHg or less.

10. 7. The film forming method according to claim 6, wherein the polymerizable compound (a) contains at least a polymer having a polymerizable functional group.

11. The curable composition (A) contains a compound (p) having a molecular weight of 300 to 5000 and containing a benzene ring, a thermal acid generator (r), and a crosslinking agent (s), 2. The film forming method according to claim 1, wherein the carbon atom content of the mixture of the curable composition (A) other than the solvent (d) is 80% by weight or more.

12. The curable composition (A) contains a siloxane component (q), 2. The film forming method according to claim 1, wherein the silicon atom content of the mixture of the curable composition (A) other than the solvent (d) is 30% by weight or more.

13. The film forming method according to claim 1 , wherein the curable composition (A) contains a surfactant.

14. The solvent (d) includes one or more solvents, 2. The film forming method according to claim 1, wherein the boiling point of each of the one or more solvents under normal pressure is 80° C. or higher and lower than 250° C.

15. The solvent (d) includes one or more solvents, 2. The film forming method according to claim 1, wherein the boiling point of each of the one or more solvents under normal pressure is 150° C. or higher and lower than 200° C.

16. 2. The film forming method according to claim 1, wherein the solvent (d) contains a polymerizable compound having a boiling point of 80° C. or higher and lower than 250° C. under normal pressure.

17. 2. The film forming method according to claim 1, wherein the content of the solvent (d) in the curable composition (A) is 5% by volume or more and 85% by volume or less.

18. 2. The film forming method according to claim 1, wherein the curable composition (A) is a curable composition for inkjet printing.

19. 2. The film forming method according to claim 1, wherein the waiting step waits until the content of the solvent (d) in the liquid film becomes 10% by volume or less with respect to the mixture.

20. 2. The film forming method according to claim 1, wherein the substrate is heated at a temperature of 30° C. to 200° C. for 10 seconds to 600 seconds in the waiting step.

21. 2. The film forming method according to claim 1, further comprising a hard-baking step of heating the cured film on the substrate after the separating step.

22. A forming step of forming a planarizing film on a substrate by using the film forming method according to any one of claims 1 to 21; a processing step of processing the substrate on which the planarization film has been formed in the forming step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising:

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