Film forming method and article manufacturing method

Abstract

The invention relates to a film forming method and an article manufacturing method. The present invention provides a film forming method for forming a planarized film on a substrate using a cover plate having a flat surface, comprising: discretely arranging a curable composition (A) in the form of a plurality of droplets on the substrate; waiting until the plurality of droplets arranged on the substrate in the arrangement combine with each other on the substrate to form a liquid film; bringing the liquid film on the substrate and the flat surface of the cover plate into contact with each other after the waiting; heating and curing the liquid film after bringing them into contact with each other, thereby forming a cured film between the cover plate and the substrate; and detaching the cover plate from the cured film after curing.

Description

Technical Field

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

[0002] The photolithography step for manufacturing semiconductor devices requires flattening of the substrate (i.e., forming a flattening film on the substrate). For example, in the extreme ultraviolet exposure technology (EUV) that has attracted much attention as a photolithography technology in recent years, as miniaturization advances, the depth of focus for forming a projected image decreases, and therefore the concavity and convexity on the surface of the substrate to which the curable composition is supplied must be reduced to less than tens of nm. In imprint technology, a flatness comparable to that of EUV is also required in order to improve the filling performance and line width accuracy of the curable composition (see non-patent document 1). As a flattening technology, it is known that a technology for obtaining a flat surface is provided by discretely dripping a drop of a curable composition corresponding to the concavity and convexity on a substrate having concavities and convexities, and curing the curable composition in a state where a mold with a flat surface is in contact with the curable composition (see patent documents 1 and 2). Note that a mold with a flat surface is sometimes referred to as a superstrate.

[0003] The flattening film formed by the flattening technology needs not only to be flat, but also to reduce the mixing of foreign matter. Therefore, in the flattening technology, the adhesion of foreign matter on the cover plate (flat surface) needs to be close to zero. In conventional flattening technology, the photocurable composition is usually cured by irradiating light (e.g., ultraviolet light) (see Patent Documents 4 and 5), and a cover plate made of quartz glass that can transmit light is used. However, when a cover plate made of quartz glass is used, it is difficult to make the foreign matter on the cover plate (flat surface) close to zero.

[0004] In addition, a planarization film formed by a planarization technique is sometimes required to have not only flatness but also heat resistance of approximately 450° C. or higher. However, if a photocurable composition is used, as in conventional planarization techniques, the heat resistance limit is 450° C., and it is difficult to form a planarization film with higher heat resistance.

[0005] Furthermore, a planarization film formed by a planarization technique is sometimes required to be a permanent insulating film. However, the photocurable compositions used in conventional planarization techniques have difficulty satisfying and cannot achieve the required insulating properties, mechanical strength, and durability of a permanent insulating film.

[0006] Citation List Patent Literature Patent Document 1: Japanese Patent Publication No. 2019-140394 Patent Document 2: US-2020-0286740 Patent Document 3: Japanese Patent Publication No. 2009-503139 Patent Document 4: Japanese Patent Publication No. 2022-27530 Patent Document 5: US-2023-0203210 Non-patent literature 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

[0007] The present invention provides, for example, a new technology regarding a method for forming a planarization film on a substrate.

[0008] According to one aspect of the present invention, there is provided a film forming method for forming a planarized film on a substrate using a cover plate having a flat surface, comprising: discretely arranging a curable composition (A) in the form of a plurality of droplets on the substrate; waiting until the plurality of droplets arranged on the substrate in the arrangement are combined with each other on the substrate to form a liquid film; after the waiting, bringing the liquid film on the substrate and the flat surface of the cover plate into contact with each other; heating and curing the liquid film after bringing them into contact with each other, thereby forming a cured film between the cover plate and the substrate; and detaching the cover plate from the cured film after curing, wherein the plurality of droplets arranged on the substrate in the arrangement are combined with each other to form a liquid film. The curable composition (A) on the plate is a thermosetting curable composition having a property of being cured by heating, and contains at least a solvent (d), wherein the viscosity of the curable composition (A) at 23°C is 2 mPa·s or more and 60 mPa·s or less, wherein the content of the solvent (d) in the curable composition (A) is 5% by volume or more and 95% by volume or less, wherein the boiling point of the solvent (d) at normal pressure is less than 250°C, and wherein the viscosity of the mixture other than the solvent (d) in the curable composition (A) at 23°C is 30 mPa·s or more and 10,000 mPa·s or less.

[0009] Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 is a view for explaining a film forming method according to an embodiment of the present invention;

[0011] Figure 2 is a diagram for explaining the flow behavior of droplets of the curable composition during the waiting step; and

[0012] Figure 3 is a view showing a comparison between a contact step in conventional technology and a contact step in the present invention. DETAILED DESCRIPTION

[0013] Hereinafter, the embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments are not intended to limit the scope of the claimed invention. Although a plurality of features are described in the embodiments, the invention is not limited to all of these features, but rather a plurality of these features may be appropriately combined. In addition, in the accompanying drawings, the same reference numerals are given to the same or similar structures, and redundant descriptions thereof are omitted.

[0014] [Curable composition (A1)] The curable composition (A1) of the present invention is a thermosetting curable composition having the property of being cured by heating, and can be a curable composition for inkjet. The curable composition (A1) according to one embodiment is a composition containing at least component (a) as a polymerizable compound, component (b) as a photopolymerization initiator, and component (d) as a solvent. In this embodiment, component (a) as a polymerizable compound 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 this 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 heterocyclic rings and a vinyl group directly bonded to the aromatic rings or aromatic heterocyclic rings. In this specification, a polymerizable compound is a compound that reacts with a polymerization factor (e.g., a radical or a cation) generated by a photopolymerization initiator (component (b)) to form a film made of a polymer compound through a chain reaction (thermal polymerization reaction).

[0016] Examples of the polymerizable compound include free radical polymerizable compounds and cationic polymerizable compounds. Component (a) as a polymerizable compound may be formed from only one type of polymerizable compound or from multiple types (two or more) of polymerizable compounds. That is, component (a) as a polymerizable compound may contain one or more types of polymerizable compounds. Furthermore, component (a) as a polymerizable compound may contain at least a polymer having a polymerizable functional group.

[0017] In this 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.

[0018] <Compound (a-1): Polymerizable compound> Actual examples of the compound (a-1) are as follows. However, the compound (a-1) is not limited to these examples.

[0019] An example of the component (a) which does not correspond to the compound (a-1) is a (meth)acrylic acid compound which is a radical polymerizable compound.

[0020] The (meth)acrylic compound is a compound having one or more acryloyl groups or methacryloyl groups. Examples of the monofunctional (meth)acrylic compound having one acryloyl group or methacryloyl group are as follows, but the compound is not limited to these examples. 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, polyethylene oxide 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, tricyclodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)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, tert-butyl (meth)acrylate, amyl (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 acrylate, ethoxydiglycol (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, tert-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, and cyanobenzyl (meth)acrylate.

[0021] Examples of commercially available products of the above-mentioned monofunctional (meth)acrylic compound are as follows, but the products are not limited to these examples. M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150 and M156 (manufactured by East Asia Synthetics); MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA and Viscoat#150, #155, #1 58, #190, #192, #193, #220, #2000, #2100 and #2150 (manufactured by Osaka Organic Chemical Industry); light acrylates BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, epoxy ester M-600A, POB-A and OPP-EA (manufactured by Kyoeisha Chemical); TC110S, R-564 and R-128H (manufactured by Nippon Kayaku); NK Ester AMP-10G, AMP-20G and A-LEN-10 (manufactured by Shin-Nakamura Chemical); FA-511A, 512A and 513A (manufactured by Hitachi Chemical); PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M and BR-32 (manufactured by DKS); VP (manufactured by BASF); and ACMO, DMAA and DMAPAA (manufactured by Kohjin).

[0022] Examples of the polyfunctional (meth)acrylic compound having two or more acryloyl groups or methacryloyl groups are as follows, but the compound is not limited to these examples. Trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO- and 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)acryloyloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, EO- and PO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, o-phthalic di(meth)acrylate, isophthalic di(meth)acrylate or terephthalic di(meth)acrylate, and o-phthalic di(meth)acrylate, isophthalic di(meth)acrylate or terephthalic di(meth)acrylate.

[0023] Examples of commercially available products of the above-mentioned polyfunctional (meth)acrylic compound are as follows, but the products are not limited to these examples. UV SA1002 and SA2007 (manufactured by Mitsubishi Chemical); Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, and 3PA (manufactured by Osaka Organic Chemical Industry); Light acrylates 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, and DPE-6A (manufactured by Kyoeisha Chemical); PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60 and -120, HX-620, D-310 and D-330 (manufactured by Nippon Kayaku); M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, and M400 (manufactured by Toa Gosei); VR-77, VR-60, and VR-90 (manufactured by Showa Highpolymer); and OGSOL EA-0200 and OGSOL EA-0300 (manufactured by Osaka Gas Chemical).

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

[0025] The film forming method according to an embodiment of the present invention takes several milliseconds to several hundred seconds until the droplets of the curable composition (A1) discretely arranged on the substrate combine with each other and form a substantially continuous liquid film, so a waiting step (described later) is necessary. In this waiting step, the solvent (d) volatilizes, but the polymerizable compound (a) should not volatilize. Therefore, the boiling point of one or more types of polymerizable compounds contained in the polymerizable compound (a) at normal pressure is preferably 250°C or more, more preferably 300°C or more, and further preferably 350°C or more. In addition, in order to obtain high dry etching resistance and high heat resistance in the cured film of the curable composition (A1), the polymerizable compound (a) preferably contains at least a compound having a cyclic structure, such as an aromatic structure, an aromatic heterocyclic structure or an alicyclic structure.

[0026] The boiling point of the polymerizable compound (a) is generally correlated with the molecular weight. Therefore, the molecular weight of the one or more types of polymerizable compounds contained in the polymerizable compound (a) is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more. However, even when the molecular weight is 200 or less, if the boiling point is 250° C. or more, the compound can be preferably used as the polymerizable compound (a) according to an embodiment of the present invention.

[0027] In addition, the vapor pressure of each of the one or more polymerizable compounds contained in the polymerizable compound (a) at 80° C. is preferably 0.001 mmHg or less. This is because, although it is advantageous to heat to accelerate the volatilization of the solvent (d) (described later), it is necessary to suppress the volatilization of the polymerizable compound (a) during heating.

[0028] Note that the boiling point and vapor pressure of each organic compound at normal pressure can be calculated by, for example, Hansen Solubility Parameters in Practice (HSPiP) 5th edition 5.3.04.

[0029] <Ohnishi Parameter (OP) of Component (a)> Given the dry etching rate V of the organic compound, the number of all atoms in the organic compound N, and the number of all carbon atoms in the composition N C and the number of all oxygen atoms in the composition N O There is a relationship as shown in the following equation (1) (see Non-Patent Document 2). V∝N / (N C -N o )...(1) where N / (N C -N o ) is also called "Oasi parameter" (hereinafter referred to as "OP"). For example, Patent Document 3 describes a technique for obtaining a curable composition having high dry etching resistance by using a polymerizable compound component having a small OP.

[0030] Equation (1) shows that an organic compound having many oxygen atoms or having few aromatic ring structures or alicyclic structures in a molecule has a large OP and a high dry etching rate.

[0031] In the curable composition (A1) according to an embodiment of the present invention, the OP of 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. When the OP of component (a) is 2.70 or less, the cured film of the curable composition (A1) has high dry etching resistance. In addition, when the OP of component (a) is 1.80 or more, when the bottom layer is processed by using the cured film of the curable composition (A1), the cured film of the curable composition (A1) can be easily removed. When component (a) is composed of multiple types of polymerizable compounds a1, a2, ..., a n When formed, OP can be calculated as a weighted average (mole fraction weighted average) based on the mole fraction shown in the following equation (2):

[0032] <Compound (a-2): Polymerizable compound having a boiling point of 250°C or higher> The curable composition (A1) according to an embodiment of the present invention, which is a polymerizable compound (a), may include a compound (a-2) having two or more cyclic structures, at least one of which is an aromatic structure or an aromatic heterocyclic structure.

[0033] Examples of the cyclic structure are an aromatic structure, an aromatic heterocyclic structure, and an alicyclic structure.

[0034] The carbon number of the aromatic structure is preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 10. Actual examples of the aromatic ring are as follows. Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, phenanthren ring, fluorene ring, benzooctene ring, acenaphthylene ring, biphenylene ring, indene ring, indane ring, triphenylene ring, pyrene ring, ring, perylene ring and tetralin ring.

[0035] Among the above aromatic rings, 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 connected, such as a biphenyl ring and a diphenyl ring.

[0036] The carbon number of the aromatic heterocyclic structure is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 5. Actual examples of the aromatic heterocyclic ring are as follows. 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, quinolinazine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenoxathiazole ring and phenoxazine ring.

[0037] The carbon number of the alicyclic structure is preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. Furthermore, the carbon number of 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. Actual examples are as follows. 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, camphane ring, norbornane ring, norbornene ring, isobornane ring, tricyclodecane ring, tetracyclododecane ring and adamantane ring.

[0038] Actual examples of the compound (a-2) having a boiling point of 250° C. or higher are shown below, but the compound is not limited to these examples.

[0039] 3-Phenoxybenzyl acrylate (mPhOBzA, OP = 2.54, boiling point = 367.4°C, vapor pressure at 80°C = 0.0004 mmHg, molecular weight = 254.3)

[0040] 1-Naphthyl acrylate (NaA, OP = 2.27, boiling point = 317°C, vapor pressure at 80°C = 0.0422 mmHg, molecular weight = 198)

[0041] 2-Phenylphenoxyethyl acrylate (PhPhOEA, OP = 2.57, boiling point = 364.2°C, vapor pressure at 80°C = 0.0006 mmHg, molecular weight = 268.3)

[0042] 1-Naphthylmethyl acrylate (Na1MA, OP = 2.33, boiling point = 342.1°C, vapor pressure at 80°C = 0.042 mmHg, molecular weight = 212.2)

[0043] 2-Naphthylmethyl acrylate (Na2MA, OP = 2.33, boiling point = 342.1°C, vapor pressure at 80°C = 0.042 mmHg, molecular weight = 212.2)

[0044] DPhPA represented by the following formula (OP = 2.38, boiling point = 354.5°C, vapor pressure at 80°C = 0.0022 mmHg, molecular weight = 266.3)

[0045] PhBzA represented by the following formula (OP = 2.29, boiling point = 350.4°C, vapor pressure at 80°C = 0.0022 mmHg, molecular weight = 238.3)

[0046] FLMA represented by the following formula (OP = 2.20, boiling point = 349.3°C, vapor pressure at 80°C = 0.0018 mmHg, molecular weight = 250.3)

[0047] ATMA represented by the following formula (OP = 2.13, boiling point = 414.9°C, vapor pressure at 80°C = 0.0001 mmHg, molecular weight = 262.3)

[0048] DNaMA represented by the following formula (OP = 2.00, boiling point = 489.4°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 338.4)

[0049] BPh44DA represented by the following formula (OP = 2.63, boiling point = 444 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 322.3)

[0050] BPh43DA represented by the following formula (OP = 2.63, boiling point = 439.5 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 322.3)

[0051] DPhEDA represented by the following formula (OP = 2.63, boiling point = 410°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 322.3)

[0052] BPMDA represented by the following formula (OP = 2.68, boiling point = 465.7°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 364.4)

[0053] Na13MDA represented by the following formula (OP=2.71, boiling point=438.8°C, vapor pressure at 80°C <0.0001 mmHg, molecular weight=296.3)

[0054] The following formula (a-2-1) (OP = 2.40, boiling point = 333.4°C, vapor pressure at 80°C = 0.0181 mmHg, molecular weight = 199.2)

[0055] The following formula (a-2-2) (OP = 2.40, boiling point = 333.4°C, vapor pressure at 80°C = 0.0181 mmHg, molecular weight = 199.2)

[0056] The following formula (a-2-3) (OP = 1.86, boiling point = 369.5°C, vapor pressure at 80°C = 0.0053 mmHg, molecular weight = 193.3)

[0057] The following formula (a-2-4) (OP = 2.85, boiling point = 438.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 296.3)

[0058] The following formula (a-2-5) (OP = 2.71, boiling point = 438.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 296.3)

[0059] The following formula (a-2-6) (OP = 2.87, boiling point = 421.0°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 338.4)

[0060] The following formula (a-2-7) (OP = 2.87, boiling point = 465.2°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 338.4)

[0061] The following formula (a-2-8) (OP = 2.68, boiling point = 465.7°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 364.4)

[0062] The following formula (a-2-9) (OP = 2.50, boiling point = 433.1 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 320.3)

[0063] The following formula (a-2-10) (OP = 2.64, boiling point = 468.1°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 326.4)

[0064] The following formula (a-2-11) (OP = 3.25, boiling point = 553.4 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 358.4)

[0065] The following formula (a-2-12) (OP = 2.63, boiling point = 443.9 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 322.4)

[0066] The following formula (a-2-13) (OP = 2.89, boiling point = 509.3 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 406.4)

[0067] The following formula (a-2-14) (OP = 2.63, boiling point = 450.0°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 322.4)

[0068] The following formula (a-2-15) (OP = 3.00, boiling point = 476.5 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 366.4)

[0069] The following formula (a-2-16) (OP = 2.68, boiling point = 447.4 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 364.4)

[0070] The following formula (a-2-17) (OP = 2.36, boiling point = 543.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 398.5)

[0071] The following formula (a-2-18) (OP = 3.27, boiling point = 526.9°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 396.4)

[0072] The following formula (a-2-19) (OP = 2.71, boiling point = 333.7°C, vapor pressure at 80°C = 0.0302 mmHg, molecular weight = 244.3)

[0073] The following formula (a-2-20) (OP = 2.73, boiling point = 333.7°C, vapor pressure at 80°C = 0.0134 mmHg, molecular weight = 258.3)

[0074] The following formula (a-2-21) (OP = 2.71, boiling point = 319.2°C, vapor pressure at 80°C = 0.0566 mmHg, molecular weight = 262.3)

[0075] The following formula (a-2-22) (OP = 2.71, boiling point = 336.9°C, vapor pressure at 80°C = 0.0055 mmHg, molecular weight = 244.3)

[0076] The following formula (a-2-23) (OP = 3.00, boiling point = 370.9°C, vapor pressure at 80°C = 0.0021 mmHg, molecular weight = 274.4)

[0077] The following formula (a-2-24) (OP = 3.00, boiling point = 376.4°C, vapor pressure at 80°C = 0.0005 mmHg, molecular weight = 274.4)

[0078] The following formula (a-2-25) (OP = 3.00, boiling point = 379.4°C, vapor pressure at 80°C = 0.0002 mmHg, molecular weight = 288.4)

[0079] The following formula (a-2-26) (OP = 2.33, boiling point = 360.8°C, vapor pressure at 80°C = 0.0006 mmHg, molecular weight = 252.3)

[0080] The following formula (a-2-27) (OP = 2.54, boiling point = 371.5°C, vapor pressure at 80°C = 0.0003 mmHg, molecular weight = 254.3)

[0081] The following formula (a-2-28) (OP = 2.57, boiling point = 381.2°C, vapor pressure at 80°C = 0.0001 mmHg, molecular weight = 268.3)

[0082] The following formula (a-2-29) (OP = 2.57, boiling point = 381.8°C, vapor pressure at 80°C = 0.0004 mmHg, molecular weight = 268.3)

[0083] The following formula (a-2-30) (OP = 2.50, boiling point = 487.4 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 374.4)

[0084] The following formula (a-2-31) (OP = 2.67, boiling point = 417.2°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 268.3)

[0085] The following formula (a-2-32) (OP = 2.67, boiling point = 417.2°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 268.3)

[0086] The following formula (a-2-33) (OP = 2.67, boiling point = 417.2°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 268.3)

[0087] The following formula (a-2-34) (OP = 2.67, boiling point = 417.2°C, vapor pressure at 80°C < 0.0001 mmHg, molecular weight = 268.3)

[0088] The following formula (a-2-35) (OP = 2.71, boiling point = 438.8 ° C, vapor pressure at 80 ° C < 0.0001 mmHg, molecular weight = 296.3)

[0089] Relative to the synthesis of component (b) (described later) and component (c) (described later), that is, the total mass of all components except solvent (d), the mixing ratio of component (a) in curable composition (A1) is preferably 40% by weight or more and 99% by weight or less. Relative to the total mass of all components except solvent (d), the mixing ratio of component (a) in curable composition (A1) is more preferably 50% by weight or more and 95% by weight or less, further preferably 60% by weight or more and 90% by weight or less. When the mixing ratio of component (a) is 40% by weight or more, the mechanical strength of the cured film of curable composition (A1) increases. In addition, when the mixing ratio of component (a) is 99% by weight or less, the mixing ratio of components (b) and (c) can be increased, and properties such as a high thermal polymerization rate are obtained. Note that all components except solvent (d) in curable composition (A1) can be understood as a mixture (composition (A1')) except solvent (d) of curable composition (A1).

[0090] <Component (b): Polymerization Initiator> The polymerization initiator as the component (b) according to an embodiment of the present invention refers to, for example, a thermal radical generator or a thermal acid generator that generates radicals or cations as polymerization factors by heating.

[0091] Examples of thermal free radical generators are organic peroxides and azo compounds. Examples of organic peroxides are peroxyesters such as tert-hexyl peroxyisopropyl monocarbonate, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, and tert-butyl peroxyisopropyl carbonate; peroxyketals such as 1,1-bis(tert-hexyl peroxy)-3,3,5-trimethylcyclohexane; and diacyl peroxides such as lauroyl peroxide, but organic peroxides are not limited to these. Examples of azo compounds are azonitrile such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(cyclohexane-1-carbonitrile), but azo compounds are not limited to these.

[0092] Examples of the thermal acid generator are onium salt compounds and N-sulfonyloxyimide compounds.

[0093] Examples of the onium salt compound are sulfonium salts, tetrahydrothiophenium salts, iodonium salts and ammonium salts.

[0094] Examples of sulfonium salts are triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate.

[0095] Examples of tetrahydrothiophenium salts are 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.

[0096] Examples of iodonium salts are diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, bis(4-tert-butylphenyl)iodonium nonafluoro-n-butanesulfonate, and bis(4-tert-butylphenyl)iodonium 2-bicyclo[2,2,1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

[0097] Examples of ammonium salts are triethylammonium trifluoromethanesulfonate and triethylammonium nonafluoro-n-butanesulfonate.

[0098] Examples of the N-sulfonyloxyimide compound are 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.

[0099] Among these, onium salt compounds are favorable as thermal acid generators, and iodonium salts and ammonium salts are more favorable. As thermal acid generators, bis(4-tert-butylphenyl)iodonium nonafluoro-n-butanesulfonate and triethylammonium nonafluoro-n-butanesulfonate are more favorable.

[0100] Relative to the sum of component (a), component (b) and component (c) (described later), that is, the total mass of all ingredients except solvent (d), the mixing ratio of component (b) in curable composition (A1) is preferably 0.1 weight % or more and 50 weight % or less. In addition, relative to the total mass of all ingredients except solvent (d), the mixing ratio of component (b) in curable composition (A1) is more preferably 0.1 weight % or more and 20 weight % or less, further preferably 1 weight % or more and 20 weight % or less. When the mixing ratio of component (b) is set to 0.1 weight % or more, the curing rate of the composition increases, and therefore the reaction efficiency can be improved. In addition, when the mixing ratio of component (b) is set to 50 weight % or less, a cured film with certain mechanical strength can be obtained. Note that all ingredients except solvent (d) in curable composition (A1) can be understood as a mixture (composition (A1 ')) except the solvent (d) of curable composition (A1).

[0101] <Component (c): Non-polymerizable compound> In addition to the above components (a) and (b), the curable composition (A1) according to an embodiment of the present invention may further contain a non-polymerizable compound as component (c) within a range that does not impair the effects of the embodiment. Examples of non-polymerizable compounds are internal mold release agents, antioxidants, polymer components, and other additives. Component (c) may contain various types of the above compounds.

[0102] In order to reduce the interfacial bonding force between the cover plate (form) and the curable composition (A1), i.e., to reduce the demoulding force in the demoulding step (described later), an internal release agent can be added to the curable composition (A1). In this embodiment, "inside" means that before the arrangement step of the curable composition (A1), a release agent is pre-added to the curable composition (A1). As an internal release agent, a surfactant such as a silicon-based surfactant, a fluorine-based surfactant or a hydrocarbon-based surfactant can be used. However, in this embodiment, the addition amount of the fluorine-based surfactant is limited, as described later. Note that the internal release agent according to this embodiment is non-polymerizable. One type of internal release agent can be used alone, or two or more types of internal release agents can be used in combination.

[0103] Fluorine-based surfactants include the following. Polyalkylene oxide (eg polyethylene oxide or polypropylene oxide) adducts of alcohols having a perfluoroalkyl group, and polyalkylene oxide (eg polyethylene oxide or polypropylene oxide) adducts of perfluoropolyethers.

[0104] Note that the fluorine-based surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, or a thiol group in a portion of the molecular structure (e.g., a terminal group). An example is pentaethylene glycol mono-1H,1H,2H,2H-perfluorooctyl ether.

[0105] Commercially available products may also be used as the fluorine-based surfactant. Examples of commercially available fluorine-based surfactants are as follows. F-444, TF-2066, TF-2067 and TF-2068, and DEO-15 (abbreviation) (manufactured by DIC); Fluorad FC-430 and FC-431 (manufactured by Sumitomo 3M); S-382 (manufactured by AGC); EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, and MF-100 (manufactured by Tochem Products); PF-636, PF-6320, PF-656, and PF-6520 (manufactured by OMNOVA Solutions); DS-401, DS-403 and DS-451 (manufactured by Daikin); and 250, 251, 222F and 208G (manufactured by NEOS).

[0106] The internal mold release agent may also be a hydrocarbon surfactant. Hydrocarbon surfactants include alkyl alcohol-polyalkylene oxide adducts obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms, and polyalkylene oxides.

[0107] Examples of the alkyl alcohol-polyalkylene oxide adducts are as follows. Methanol-ethylene oxide adduct, decanol-ethylene oxide adduct, lauryl alcohol-ethylene oxide adduct, cetyl alcohol-ethylene oxide adduct, stearyl alcohol-ethylene oxide adduct, and stearyl alcohol-ethylene oxide / propylene oxide adduct.

[0108] Note that the terminal group of the alkyl alcohol-polyalkylene oxide adduct is not limited to a hydroxyl group, which can be produced by simply adding polyalkylene oxide to an alkyl alcohol. The hydroxyl group may also be substituted with a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group, or a silanol group, or with a hydrophobic group such as an alkyl group or an alkoxy group.

[0109] Examples of the polyalkylene oxides are as follows. Polyethylene glycol, polypropylene glycol, their mono- or dimethyl ethers, mono- or dioctyl ethers, mono- or dinonyl ethers, mono- or didecyl ethers, monoadipates, monooleates, monostearates and monosuccinates.

[0110] Commercially available products may also be used as the alkyl alcohol-polyalkylene oxide adduct. Examples of commercially available products of the alkyl alcohol-polyalkylene oxide adduct are as follows. Polyoxyethylene methyl ether (methanol ethylene oxide adduct) (BLAUNON MP-400, MP-550 and MP-1000) manufactured by Aoki Oil and Fat Industries, polyoxyethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307 and D-1310) manufactured by Aoki Oil and Fat Industries, polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by Aoki Oil and Fat Industries, polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305 and CH-310) manufactured by Aoki Oil and Fat Industries, polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730 and SR-750), randomly polymerized polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 501000R and SA-30 / 70 2000R) manufactured by Aoki Oil and Fat Industry, polyoxyethylene methyl ether ( A760E), and polyoxyethylene alkyl ethers (EMULGEN series) manufactured by Kao.

[0111] Commercially available products can also be used as polyalkylene oxides. One example is an ethylene oxide / propylene oxide copolymer (Pluronic PE6400) manufactured by BASF.

[0112] Fluorine-based surfactants show excellent demoulding force reduction effects and are therefore effective as internal release agents. Relative to the sum of components (a), (b) and (c), that is, the total mass of all components except the solvent (d), the mixing ratio of component (c) other than the fluorine-based surfactant in the curable composition (A1) is preferably 0% by weight or more and 50% by weight or less. Relative to the total mass of all components except the solvent (d), the mixing ratio of component (c) other than 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 further preferably 0.1% by weight or more and 20% by weight or less. When the mixing ratio of component (c) other than the fluorine-based surfactant is set to 50% by weight or less, a cured film with certain mechanical strength can be obtained.

[0113] <Component (d): Solvent> The curable composition (A1) of the present invention contains a solvent having a boiling point of 80°C or more and less than 250°C at normal pressure as component (d). Component (d) is a solvent that dissolves components (a), (b) and (c). Examples are alcoholic solvents, ketone solvents, etheric solvents and nitrogen-containing solvents. As component (d), one type of component can be used alone, or two or more types of components can be used by combining them. The boiling point of component (d) at normal pressure is 80°C or more, preferably 140°C or more, particularly preferably 150°C or more. The boiling point of component (d) at normal pressure is lower than 250°C, preferably 200°C or less. If the boiling point of component (d) at normal pressure is lower than 80°C, the volatilization rate in the waiting step (described later) is too high, so component (d) may volatilize before the droplets of the curable composition (A1) combine with each other, so that the droplets of the curable composition (A1) cannot combine. Furthermore, if the boiling point of component (d) at normal pressure is 250°C or higher, the volatilization of component (d) in the waiting step (described later) may be insufficient, and thus component (d) may remain in the cured film of curable composition (A1). Here, if component (d) contains one or more types of solvents, the boiling point of each of the one or more types of solvents contained in component (d) at normal pressure is preferably 80°C or higher and lower than 250°C, preferably 150°C or higher and lower than 200°C.

[0114] Examples of the alcoholic solvents are as follows. Monohydric alcohol solvents, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 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-nonanol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, Secondary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzylmethanol, diacetone alcohol and cresol; and polyol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 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 glycerol.

[0115] Examples of ketone-based solvents are as follows. Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl-n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone and fenthion.

[0116] Examples of the ether-based solvents are as follows. Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyl dioxane, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol diethyl ether, 2-n-butoxyethanol, 2-n-hexyloxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether alcohol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, 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 and 2-methyltetrahydrofuran.

[0117] Examples of the ester-based solvents are as follows. 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-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, 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, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isopentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0118] Examples of nitrogen-containing solvents are as follows. N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide and N-methylpyrrolidone.

[0119] Among the above solvents, ether solvents and ester solvents are favorable. Note that, from the viewpoint of good film-forming properties, ether solvents and ester solvents each having a diol structure are more favorable.

[0120] Other advantageous examples are as follows. 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.

[0121] A particularly advantageous example is propylene glycol monomethyl ether acetate. Note that (ethyl)isocyanurate di(meth)acrylate is also advantageous.

[0122] In an embodiment, a favorable solvent is a solvent having at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure. More specifically, a favorable solvent is a solvent or a solvent mixture selected from propylene glycol monomethyl ether acetate (boiling point = 146° C.), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate.

[0123] In an embodiment, component (d) may contain a polymerizable compound having a boiling point of 80° C. or higher and lower than 250° C. at normal pressure. For example, a polymerizable compound having a boiling point of 80° C. or higher and lower than 250° C. at normal pressure may also be used as component (d). Examples of polymerizable compounds having a boiling point of 80° C. or higher and lower than 250° C. at normal pressure are as follows. 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) and α-methylstyrene (165°C).

[0124] In an embodiment, when the total volume of the curable composition (A1) is 100%, the content of the solvent (d) is 5% to 95% by volume, preferably 5% to 85% by volume, and more preferably 5% to 80% by volume. If the content of the solvent (d) is less than 5% by volume, even under conditions that allow a substantially continuous liquid film to be obtained, a thin film cannot be obtained after the solvent (d) evaporates. On the other hand, if the content of the solvent (d) exceeds 95% by volume, even if the droplets are densely deposited by an inkjet method, a thick film cannot be obtained after the solvent (d) evaporates.

[0125] <Glass Transition Temperature of Cured Curable Composition> When the glass transition temperature is sufficiently higher than the demolding temperature, the cured product (cured film) exhibits a strong glassy state during demolding, i.e., high mechanical strength. Therefore, damage caused by the impact of demolding is unlikely to occur. Therefore, when the demolding step is performed 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.

[0126] As a method for measuring the glass transition temperature of a cured product, differential scanning calorimetry (DSC) or a dynamic viscoelasticity device can be used for measurement. For example, when using DSC for measurement, the following line and tangent are obtained: a line obtained by extending the baseline of the DSC curve of the cured product at the low temperature side (the DSC curve portion in the temperature region where neither transformation nor reaction occurs in the test piece) to the high temperature side, and a tangent drawn at a point where the gradient of the curve of the gradually changing portion of the glass transition is the largest. By the intersection of the line and the tangent, an extrapolated glass transition onset temperature (Tig) is obtained, which can be used as the glass transition temperature. The example of a main device is STA-6000 (manufactured by Perkin Eimer). On the other hand, when using a dynamic viscoelasticity device for measurement, the temperature at which the loss sine (tan δ) of the cured product is the largest is defined as the glass transition temperature. The example of a main device for measuring dynamic viscoelasticity is MCR301 (manufactured by Anton Paar).

[0127] <Heat Resistance of Cured Curable Composition> As a method for measuring the heat resistance of the cured curable composition (A1), it can be measured by using thermogravimetric analysis (TGA) or the like. For example, when measuring using TGA, the cured curable composition is placed in a nitrogen atmosphere with a flow rate of 5 L / hr to 6 L / hr, and the thermogravimetric reduction rate is measured when the temperature is raised to n°C at a heating rate of 20°C / min. This indicates whether the product has heat resistance to n°C. An example of a main device is STA 1000 (manufactured by Linseis). Regarding the heat resistance of the cured product (cured film), when the temperature is raised from 200°C at a heating rate of 20°C / min, the temperature at which the thermogravimetric reduction rate first reaches 2% is preferably 250°C or higher, more preferably 350°C or higher, and particularly preferably 400°C or higher. That is, in the cured film obtained by the curing step, when the temperature is raised from 200°C to 250°C at a heating rate of 20°C / min, the weight reduction is preferably 2% or less.

[0128] When using the curable composition (A1) according to the present invention to manufacture semiconductor integrated circuits, it is advantageous to minimize the incorporation of impurities containing metal atoms (metal impurities) into the curable composition (A1) to prevent them from hindering the operation of the product. The concentration of metal impurities in the curable composition (A1) is preferably 10 ppm or less, more preferably 100 ppb or less.

[0129] [Curable composition (A2)] According to the curable composition (A2) of the embodiment of the present invention, it can be a thermosetting curable composition with the characteristic of being cured by heating, and can be a curable composition for inkjet. According to the curable composition (A2) of the present embodiment, it is a composition containing at least the following components: as the component (p) of the main agent, as the component (r) of the thermal acid generator, as the component (s) of the cross-linking agent and as the component (d) of the solvent. Curable composition (A2) can also contain other arbitrary components (c) in the range of not damaging the effect of the embodiment. These components will be described below. Here, in curable composition (A2), the content of carbon atoms in the component (that is, the mixture of the component other than the solvent (d)) is preferably 80 weight % or more.

[0130] <Ingredient (p): Main agent> Component (p) is a main agent. Component (p) is a compound containing an aromatic ring (such as a benzene ring, naphthalene ring, or anthracene ring) with a molecular weight preferably between 300 and 5000, particularly preferably between 500 and 2500. A molecular weight of 300 or greater facilitates good deposition performance and suppresses contamination of manufacturing equipment caused by increased sublimation during curing. A molecular weight of 5000 or less facilitates good embedding and planarization properties.

[0131] Component (p) may contain branched or cyclic, saturated or unsaturated hydrocarbon or heteroaromatic groups. Component (p) may contain ether, hydroxyl, ester, carbonyl, amino, halide, thioether, carboxyl, sulfo, amide, imide, cyano, aldehyde, imino, urea, carbamate, carbonate, nitro or sulfonyl groups.

[0132] Actual examples of component (p) are as follows: Here, R represents an alkyl group.

[0133] Other practical examples of component (p) are novolac-based compounds such as phenol novolac, cresol novolac, and naphthol novolac, and substituted polystyrene compounds such as polyhydroxystyrene and polyhydroxyvinylnaphthalene. However, component (p) is not limited to these. As component (P), one type of compound may be used alone, or two or more types of compounds may be used by mixing.

[0134] <Component (d): Solvent> Component (d) is not particularly limited as long as it can dissolve or disperse component (p) and any other components to be included as needed. Examples of component (d) are alcohol solvents, ketone solvents, ether solvents, ester solvents, and nitrogen-containing solvents. As component (d), one type of solvent may be used alone, or two or more types of solvents may be used in combination.

[0135] Examples of alcohol solvents are as follows. Monohydric alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 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-nonanol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, Secondary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzylmethanol, diacetone alcohol and cresol; and polyol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 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 glycerol.

[0136] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenthion.

[0137] Examples of ether solvents are as follows. 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-hexyloxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, alcohol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, 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 and 2-methyltetrahydrofuran.

[0138] Examples of ester solvents are as follows. 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-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl 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, Examples of the nitrogen-containing solvent include diethylene glycol monoethyl ether acetate, 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, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isopentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate. Examples of the nitrogen-containing solvent include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone.

[0139] Among the above solvents, ether solvents and ester solvents are advantageous. From the viewpoint of good film-forming properties, ether solvents and ester solvents each having a diol structure are more advantageous, 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 are further advantageous, and propylene glycol monomethyl ether acetate is particularly advantageous.

[0140] <Ingredient (r): Thermal Acid Generator> Curable composition (A2) may contain a thermal acid generator as component (r). Component (r) is a component that generates acid by the action of heat or light and promotes the crosslinking reaction of component (p) by a crosslinking agent (component (s)) described later. When curable composition (A2) contains component (r), the crosslinking reaction of component (p) is promoted, and the hardness of the cured film to be formed can be further improved. As component (r), one type of component can be used alone, or two or more types of components can be used in combination. Examples of component (r) are onium salt compounds and N-sulfonyloxyimide compounds.

[0141] Examples of the onium salt compound are tetrahydrothiophenium salt, iodonium salt and ammonium salt.

[0142] Examples of the sulfonium salt are triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, and 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate.

[0143] Examples of tetrahydrothiophenium salts are 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.

[0144] Examples of iodonium salts are diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, bis(4-tert-butylphenyl)iodonium nonafluoro-n-butanesulfonate, and bis(4-tert-butylphenyl)iodonium 2-bicyclo[2,2,1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

[0145] Examples of ammonium salts are triethylammonium trifluoromethanesulfonate and triethylammonium nonafluoro-n-butanesulfonate.

[0146] Examples of the N-sulfonyloxyimide compound are 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.

[0147] Among these examples of component (r), onium salt compounds are favorable, iodonium salts and ammonium salts are more favorable, and bis(4-tert-butylphenyl)iodonium nonafluoro-n-butanesulfonate and triethylammonium nonafluoro-n-butanesulfonate are more favorable.

[0148] 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 relative to 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. When the content of component (r) is within the above range, the crosslinking reaction of component (p) can be more effectively promoted.

[0149] <Ingredient(s): Cross-linking agent> Curable composition (A2) can also contain a cross-linking agent as component (s). Component (s) is a component that forms a cross-linked bond between the compounds contained in the component (p) of the curable composition (A2), or a component that forms a cross-linked structure by the action of heat or acid itself. When curable composition (A2) contains component (s), the hardness of the cured film to be formed can be improved. As component (s), one type of component can be used alone, or two or more types of components can be used in combination.

[0150] Examples of the component (s) are polyfunctional (meth)acrylate compounds, epoxy compounds, hydroxymethyl-substituted phenol compounds, alkoxyalkyl group-containing phenol compounds, and compounds having an alkoxyalkylated amino group.

[0151] Examples of the multifunctional (meth)acrylate compound are trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, glycerol tri(meth)acrylate, 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, and bis(2-hydroxyethyl)isocyanate di(meth)acrylate.

[0152] Examples of the epoxy compound are novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins and aliphatic epoxy resins.

[0153] Examples of hydroxymethyl-substituted phenolic compounds are 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trimethylolbenzene and 3,5-dihydroxymethyl-4-methoxytoluene [2,6-bis(hydroxymethyl)-p-cresol].

[0154] Examples of the alkoxyalkyl group-containing phenol compound are a methoxymethyl group-containing phenol compound and an ethoxymethyl group-containing phenol compound.

[0155] Examples of compounds having an alkoxyalkylated amino group are nitrogen-containing compounds having multiple active hydroxymethyl groups in one molecule and in which at least one hydrogen atom of the hydroxyl group in the hydroxymethyl group is substituted by an alkyl group (such as a methyl or butyl group). Examples include (poly)hydroxymethylated melamines such as hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxyl substituents, and their partial self-condensates; (poly)hydroxymethylated glycolurils such as tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxyl substituents, and their partial self-condensates; (poly)hydroxymethylated benzoguanamines such as tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxyl substituents, and their partial self-condensates; and (poly)hydroxymethylated ureas such as dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxyl substituents, and their partial self-condensates. Note that the compound having an alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, or may be a compound containing an oligomer component obtained by partial self-condensation.

[0156] 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, further preferably 1 part by mass, and particularly preferably 3 parts by mass relative to 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, further preferably 30 parts by mass, and particularly preferably 20 parts by mass. When the content of component (s) is within the above range, the crosslinking reaction of component (p) can be more effectively induced.

[0157] <Component (c): Other optional components> Curable composition (A2) can contain other arbitrary components (c).An example of component (c) is surfactant.When curable composition (A2) contains surfactant, coating performance can be improved.Therefore, the coating surface uniformity of the underlying film to be formed is improved, and the occurrence of uneven coating can be suppressed.Can use one type of surfactant alone, also can use two or more types of surfactants in combination.

[0158] 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 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. When the surfactant content is within the above range, the coating performance of the curable composition can be further improved.

[0159] [Curable composition (A3)] According to the curable composition (A3) of the embodiment of the present invention, it can be a thermosetting curable composition with the characteristic of being cured by heating, and can be a curable composition for inkjet. According to the curable composition (A3) of this embodiment, it is a composition containing at least a siloxane component (q) and a component (d) as a solvent. Curable composition (A3) can also contain other arbitrary components (c) in the range of not damaging the effect of this embodiment. These components will be described below. Here, in curable composition (A3), the silicon atom content in the component (that is, the mixture of the component other than the solvent (d)) other than the solvent (d) is preferably more than 30 weight %.

[0160] "Siloxane component (q)" is a general term for polymer compounds having Si-O bonds (siloxane bonds), including those composed of H3SiO (H2SiO) n -SiH3 chain siloxane compounds, and cyclic siloxane (-H2SiO-) n .

[0161] Actual examples of the component (q) are as follows, but the component (q) is not limited thereto: Here, R represents an alkyl group or a hydroxyl group.

[0162] <Component (d): Solvent> Component (d) is not particularly limited as long as it can dissolve or disperse component (q) and any other components to be included as needed. Examples of component (d) are alcohol solvents, ketone solvents, ether solvents, ester solvents, and nitrogen-containing solvents. As component (d), one type of solvent may be used alone, or two or more types of solvents may be used in combination.

[0163] Examples of alcohol solvents are as follows. Monohydric alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 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-nonanol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecanol, Secondary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, benzylmethanol, diacetone alcohol and cresol; and polyol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 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 glycerol.

[0164] Examples of ketone-based solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenthion.

[0165] Examples of ether solvents are as follows. 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-hexyloxyethanol, 2-phenoxyethanol, 2-(2-ethylbutoxy)ethanol, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, alcohol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, 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 and 2-methyltetrahydrofuran.

[0166] Examples of ester solvents are as follows. 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-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl 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, Examples of the nitrogen-containing solvent include diethylene glycol monoethyl ether acetate, 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, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isopentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate. Examples of the nitrogen-containing solvent include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone.

[0167] Among the above solvents, ether solvents and ester solvents are advantageous. From the viewpoint of good film-forming properties, ether solvents and ester solvents each having a diol structure are more advantageous, 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 are further advantageous, and propylene glycol monomethyl ether acetate is particularly advantageous.

[0168] <Component (c): Other optional components> Curable composition (A3) can contain other arbitrary components (c).An example of component (c) is surfactant.When curable composition (A3) contains surfactant, coating performance can be improved.Therefore, the coating surface uniformity of the underlying film to be formed is improved, and the occurrence of uneven coating can be suppressed.Can use one type of surfactant alone, also can use two or more types of surfactants in combination.

[0169] When the curable composition (A3) contains a surfactant, the lower limit of the content of the surfactant 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 content of the surfactant is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 1 part by mass. When the content of the surfactant is within the above range, the coating performance of the curable composition can be further improved.

[0170] [Curable composition (A)] Hereinafter, with respect to the common features of the above-mentioned curable compositions (A1), (A2), and (A3), these features will be collectively described as curable composition (A).

[0171] <Temperature when mixing the curable composition> When preparing the curable composition (A) according to an embodiment of the present invention, the components are mixed and dissolved under a predetermined temperature condition. More specifically, the predetermined temperature condition is 0° C. or higher and 100° C. or lower.

[0172] <Viscosity of Curable Component> The curable composition (A) according to an embodiment of the present invention is a liquid. This is because, in the arrangement step (described later), a plurality of droplets of the curable composition (A) are discretely dripped (arranged) on the substrate by an inkjet method. At 23 ° C., the viscosity of the curable composition (A) according to an embodiment of the present invention is 2 mPa s or more and 60 mPa s or less, preferably 5 mPa s or more and 30 mPa s or less, 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 discharge characteristics of the droplets by the inkjet method become unstable. In addition, if the viscosity of the curable composition (A) is greater than 60 mPa s, it is impossible to form droplets with a volume of about 1.0 to 3.0 pL, which is advantageous in this embodiment.

[0173] The viscosity of the component obtained by removing the solvent (d) (i.e., the mixture of the components 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. When the viscosity of the mixture at 23°C is set to 1,000 mPa·s or less, when the curable composition (A) is brought into contact with the cover plate, spreading and filling are completed quickly. Therefore, using the curable composition (A) according to an embodiment of the present invention enables high-throughput imprinting processes and suppresses defects caused by insufficient filling. In addition, when the viscosity of the mixture at 23°C is set to 1 mPa·s or more, unnecessary flow of droplets of the curable composition (A) after the solvent (d) has evaporated can be prevented. Furthermore, when the curable composition (A) is brought into contact with the cover sheet, the curable composition (A) is less likely to flow out from the end of the cover sheet. Note that the mixture of components other than the solvent (d) of the curable composition (A) can be understood as the components (mixture or composition) remaining after the solvent (d) has completely volatilized from the curable composition (A).

[0174] <Surface Tension of Curable Composition> Regarding the surface tension of the curable composition (A) of the embodiment of the present invention, the surface tension of the mixture of the components other than the solvent (d) in the curable composition (A) 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 further preferably 10 mN / m or more and 40 mN / m or less. Note that when the surface tension of the mixture at 23°C is high, for example, 5 mN / m or more, the capillary action is strong, so when the curable composition (A) and the cover plate are brought into contact with each other, filling (expansion and filling) is completed in a short period of time. In addition, when the surface tension is 70 mN / m or less, the cured film obtained by curing the curable composition (A) has a surface smoothness.

[0175] <Contact Angle of Curable Composition> Regarding the contact angle of the curable composition (A) according to an embodiment of the present invention, the contact angle of the mixture of the components other than the solvent (d) in the curable composition (A) relative to both the substrate surface and the cover plate 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 acts in the negative direction (the direction in which the contact interface between the cover plate and the curable composition (A) contracts) in the gap between the substrate and the cover plate, which may make filling impossible. When the contact angle of the mixture is small, the capillary action is strong and the filling speed increases.

[0176] <Impurities Mixed in the Curable Composition> The curable composition (A) according to an embodiment of the present invention preferably contains as little impurities as possible. Note that the impurities in the curable composition (A1) refer to the components other than the above-mentioned components (a), (b), (c) and (d). The impurities in the curable composition (A2) refer to the components other than the above-mentioned components (p), (s), (r), (d) and (c). The impurities in the curable composition (A3) refer to the components other than the above-mentioned components (q), (d) and (c). Therefore, the curable composition (A) according to an embodiment of the present invention is advantageously a composition obtained by a purification step. Such a purification step is preferably filtered using a filter.

[0177] As this filtration using a filter, it is advantageous that the above-mentioned components (except the components (d) as a solvent) are mixed, and the mixture is filtered by using, for example, a filter having a pore size of 0.001 μm or more and 5.0 μm or less. When filtering using a filter, it is further advantageous to filter in multiple stages, or to repeat filtering multiple times (circulation filtration). The liquid can also be filtered again after filtering through a filter, or to filter using a filter with different pore sizes. The example of the filter for filtering is a filter made of, for example, polyethylene resin, polypropylene resin, fluororesin and nylon resin, but the filter is not particularly limited. Impurities (such as particles) mixed into the curable composition (A) can be removed by the above-mentioned refining step. Therefore, it is possible to prevent the impurities mixed into the curable composition (A) from causing pattern defects by forming unexpected concave-convex objects on the cured film obtained after the curable composition (A) is cured.

[0178] [Substrate] In this specification, a member on which droplets of the curable composition (A) are discretely dropped is described as a substrate.

[0179] The substrate is a substrate to be processed, generally using a silicon wafer. The substrate may have a layer to be processed on the surface. On the substrate, another layer may also be formed below the layer to be processed. However, the substrate is not limited to a silicon wafer or a quartz substrate. The substrate may be freely selected from those substrates known as semiconductor device substrates, such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, and silicon nitride. Note that it is preferred that the surface of the substrate or the layer to be processed be processed by surface treatments such as silane coupling treatment, silazane treatment, or organic thin film deposition to improve the adhesion to the curable composition (A).

[0180] [Film Formation Method] The film forming method according to an embodiment of the present invention will be described below. The film forming method is a method for forming a planarized film on a substrate using a mold, and includes, for example, an arrangement step, a waiting step, a contacting step, a curing step, and a demoulding step. The arrangement step is a step in which curable composition (A) is arranged on a substrate in the form of a plurality of droplets. The waiting step is a step in which a plurality of droplets of the curable composition (A) arranged on the substrate in the arrangement step are combined with each other to form a liquid film. The contacting step is a step in which the liquid film of the curable composition (A) on the substrate is contacted with the mold. The curing step is a step in which the curable composition (A) is heated and cured under the condition that 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 demoulding step is a step (separation step) in which the mold is separated from the cured film of the curable composition (A). After the arrangement step, a waiting step is performed, after the waiting step, a contacting step is performed, after the contacting step, a curing step is performed, and after the curing step, a demoulding step is performed.

[0181] In the film forming method according to an embodiment of the present invention, as a substrate, a substrate with a concave-convex height difference of about 10 to 1000 nm is used, and as a mold, a mold with a flat surface (hereinafter sometimes referred to as a cover plate) is used. The cover plate can be defined as a mold having a contact surface in contact with the curable composition (A) on the substrate, wherein more than 90% (preferably more than 95%) of the contact surface is a flat surface. In the film forming method according to this embodiment, a cured film having a surface consistent with the flat surface of the cover plate is formed on the substrate by the above-mentioned arrangement step, waiting step, contact step, curing step and demoulding step. Here, in the arrangement step, the droplets of the curable composition (A) are densely arranged in the concave portion of the substrate, and the droplets of the curable composition (A) are sparsely arranged in the convex portion of the substrate.

[0182] <Layout Steps> In the layout step, if Figure 1Step 1 in the diagram schematically shows that multiple droplets of the curable composition (A) are discretely arranged on a substrate. A substrate stacked with a bottom layer can be used as a substrate. In addition, the adhesion of the substrate surface to the curable composition (A) can be improved by surface treatment such as silane coupling treatment, silazane treatment or deposition of an organic film.

[0183] The inkjet method is particularly advantageous as a method for arranging a curable composition (A) in the form of multiple droplets on a substrate. An index called the average residual liquid film thickness is defined to specify the volume of the curable composition (A) to be arranged on the substrate. The average residual liquid film thickness is a value obtained by dividing the volume of the curable composition (A) (more specifically, a mixture of components other than the solvent (d)) to be arranged on the substrate in the arrangement step by the area of the film forming region (contact surface or flat surface) of the cover plate. The volume of the curable composition (A) (more specifically, a mixture of components other than the solvent (d)) is the sum of the volumes of the individual droplets of the curable composition (A) after the solvent (d) evaporates. According to this definition, even when the substrate surface is uneven, the average residual liquid film thickness can be specified regardless of the uneven state.

[0184] <Waiting Step> In the waiting step, if Figure 1 Step 2 in the diagram shows that the droplets of the curable composition (A) spread on the substrate. Therefore, the entire area of the substrate where the planarized film is to be formed (film formation area) is covered with the curable composition (A), as shown in FIG. Figure 1 Step 3 in the diagram is shown.

[0185] Will refer to Figure 2 The flow behavior of the droplets of the curable composition (A) arranged on the substrate during the waiting step is explained by referring to states 1 to 4 in FIG. The droplets of the curable composition (A) are discretely arranged on the substrate, as shown in FIG. Figure 2 As shown in step 1 in , each droplet gradually expands on the substrate, as Figure 2 Then, the droplets of the curable composition (A) on the substrate begin to combine with each other to form a liquid film, as shown in step 2. Figure 2 As shown in State 3 in FIG, a continuous liquid film is formed (the surface of the substrate is covered with the curable composition (A) and there is no longer an exposed surface), as shown in FIG. Figure 2 As shown in state 4. In the following, as Figure 2 The state of the curable composition (A) shown in State 4 in is sometimes referred to as a "substantially continuous liquid film."

[0186] In addition, if Figure 1Step 4 in the diagram shows that the solvent (d) contained in the liquid film evaporates in the waiting step. Assuming that the total weight of the components (mixture) other than the solvent (d) in the curable composition (A) forming the liquid film is 100 volume %, the residual amount (content) of the solvent (d) in the liquid film after the waiting step is preferably 10 volume % or less. That is, in the waiting step, the process is waited until the residual amount (content) of the solvent (d) in the curable composition (A) forming the liquid film becomes less than 10 volume % relative to the components (mixture) other than the solvent (d). If the residual amount of solvent (d) is greater than 10 volume %, the mechanical properties of the cured film will deteriorate.

[0187] During the waiting step, a baking step of heating the substrate and the curable composition (A) or ventilating the atmosphere around the substrate may be performed to accelerate the volatilization of the solvent (d). Heating is performed at a temperature of, for example, 30°C to 200°C, preferably 80°C to 150°C, 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 (e.g., a hot plate or oven).

[0188] The waiting step is, for example, 0.1 to 600 seconds (sec), preferably 10 to 300 seconds. If the waiting step is shorter than 0.1 second, the combination of the droplet of curable composition (A) becomes insufficient, and therefore a substantial continuous liquid film cannot be formed. If the waiting step exceeds 600 seconds, productivity decreases. Therefore, in order to suppress the reduction in productivity, the substrate processed completely in the arrangement step can also be moved to the waiting step in sequence, multiple substrates are implemented in parallel to the waiting step, and the substrate processed completely in the waiting step is moved to the contact step in sequence. Note that in the prior art, several thousand seconds to tens of thousands of seconds are theoretically required before forming a substantial continuous liquid film. However, in practice, due to the influence of volatilization, the droplet expansion of the curable composition stagnates, and therefore a continuous liquid film cannot be formed.

[0189] When the solvent (d) evaporates in the waiting step, a substantially continuous liquid film containing components (a mixture) other than the solvent (d) remains. Due to the amount of solvent (d) evaporated, the average remaining liquid film thickness of the substantially continuous liquid film after the solvent (d) evaporates (is removed) becomes smaller than the liquid film. A state in which the film-forming region of the substrate is covered with a substantially continuous liquid film of the curable composition (A) from which the solvent (d) has been removed is maintained throughout the entire region.

[0190] <Contact Steps> In the contacting step, as Figure 1Step 5 in the diagram schematically illustrates contacting the superstrate with a substantially continuous liquid film of the curable composition (A) from which the solvent (d) has been removed. The contact 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. Thus, the liquid film of the curable composition (A) is flattened depending on the flatness of the contact surface (flat surface) of the superstrate.

[0191] In an embodiment of the present invention, during the waiting step, the curable composition (A) forms a substantially continuous liquid film from which the solvent (d) is removed, thereby reducing the volume of gas trapped between the cover plate and the substrate. Consequently, the curable composition (A) rapidly expands during the contact step. Figure 3 A comparison (difference) between the contact step in the related art disclosed in Patent Document 1 and the like and the contact step according to an embodiment of the present invention is shown.

[0192] When the expansion and filling of the curable composition (A) are completed quickly in the contact step, the time for maintaining the state in which the cover plate is in contact with the curable composition (A) (the time required for the contact step) can be shortened. Since the time required for the contact step is shortened, the time required for the flattening film to be formed is shortened, and thus productivity is improved. The contact step is preferably 0.1 seconds or more and 3 seconds or less, particularly preferably 0.1 seconds or more and 1 second or less. If the contact step is shorter than 0.1 seconds, expansion and filling become insufficient, and therefore many defects referred to as incomplete filling defects tend to occur.

[0193] The cover plate according to an embodiment of the present invention is preferably a silicon wafer or a quartz wafer, and a silicon wafer is particularly preferred. As the silicon wafer, a commercially available silicon wafer with a size of 450 mm Φ, 300 mm Φ, 200 mm Φ, 150 mm Φ, 100 mm Φ or 50 mm Φ can be used. Before the contact step, it is advantageous to clean the foreign matter present on the contact surface of the cover plate, and use existing defect inspection equipment, etc. to confirm that the number of foreign matter present on the contact surface and with a size of 50 nm or more is 10 or less. When the cover plate is used continuously by repeating the contact step, first, before the first contact step, foreign matter cleaning and foreign matter confirmation are performed by the above method. Each time the cover plate is used continuously for a predetermined number of times (for example, 1000 times), it is preferred to perform foreign matter cleaning and foreign matter confirmation by the above method before the contact step.

[0194] If the difference in thermal expansion coefficient between the superstrate and the substrate is small, the strain of the cured film formed on the substrate can be reduced. If a silicon wafer is used as the substrate, the thermal expansion coefficient of the substrate at 290K to 310K is preferably 1×10 -6 K -1 Above and 7×10 -6 K -1The thermal expansion coefficient is more preferably 2×10 -6 K -1 Above and 6×10 -6 K -1 Below, more preferably 3×10 -6 K -1 Above and 5×10 -6 K -1 the following.

[0195] When the difference in thickness between the cover plate and the substrate is small, the cured film formed on the substrate can have less strain. If a 300 mm Φ silicon wafer is used as the substrate, the thickness of the cover plate is preferably 550 μm to 1000 μm, more preferably 650 μm to 900 μm, and even more preferably 750 μm to 800 μm. If a 200 mm Φ silicon wafer is used as the substrate, the thickness of the cover plate is preferably 500 μm to 950 μm, more preferably 600 μm to 850 μm, and even more preferably 700 μm to 750 μm.

[0196] In order to improve the peelability of the cover plate relative to the curable composition (A), the cover plate may also be subjected to a surface treatment before the contacting step. An example of such a surface treatment is to form a release agent layer by coating the surface of the cover plate with a release agent. Examples of release agents applied to the surface of the cover plate are silicone release agents, fluorine release agents, hydrocarbon release agents, polyethylene release agents, polypropylene release agents, paraffin release agents, montane release agents, and palm wax release agents. Commercially available coating-type release agents, such as those manufactured by Daikin, may also be appropriately used. DSX. Note that one type of release agent may be used alone, or two or more types of release agents may be used together. Among the above-mentioned release agents, fluorine-based and hydrocarbon-based release agents are particularly advantageous.

[0197] In the contacting step, when the cover sheet is brought into contact with the curable composition (A), the pressure applied to the curable composition (A) is not particularly limited and can be, for example, 0 MPa to 100 MPa. The pressure is preferably 0 MPa to 50 MPa, more preferably 0 MPa to 30 MPa, and even more preferably 0 MPa to 20 MPa.

[0198] The contacting step can be carried out in any of a normal air atmosphere, a reduced pressure atmosphere, and an inert gas atmosphere. However, a reduced pressure atmosphere or an inert gas atmosphere is advantageous because it can prevent the effects of oxygen or water on the curing reaction. Practical examples of inert gases used when carrying out the contacting step in an inert gas atmosphere are nitrogen, carbon dioxide, helium, argon, various freon gases, and gaseous mixtures thereof. When the contacting step is carried out in a specific gas atmosphere including a normal air atmosphere, a favorable pressure is 0.0001 atm or more and 10 atm or less.

[0199] <Curing Step> The curing step is provided in order to cure the curable composition (A) to such an extent that it does not cause separation or deformation in the demolding step described later. Figure 1 Step 6 schematically illustrates heating the curable composition (A) to cure it and form a cured film. Consequently, the liquid film of the curable composition (A) filling the gap between the cover plate and the substrate solidifies to form a cured film. The heating temperature of the curable composition (A) in the curing step is preferably 100°C to 400°C.

[0200] <Demolding Step> In the demoulding step, as Figure 1 Step 7 in the figure schematically shows that the cover plate is detached (separated) from the cured film of the curable composition (A) formed on the substrate in the curing step. When the cover plate is detached from the cured film, a cured film having a flat surface is formed on the substrate. Note that hereinafter, the cured film having a flat surface may sometimes be referred to as a "flat cured film").

[0201] As a method for detaching the cover plate from the cured film on the substrate, any method that prevents a portion of the flat cured film from being physically damaged during detachment is sufficient, and various conditions and the like are not particularly limited. For example, the cover plate can be detached from the cured film on the substrate by moving the cover plate away from the substrate while the substrate is fixed. Alternatively, the cover plate can be detached from the cured film on the substrate by moving the cover plate away from the substrate while the cover plate is fixed. The cover plate can be detached from the cured film on the substrate by moving both the cover plate and the substrate in opposite directions.

[0202] <Hard baking step> In the film forming method according to an embodiment of the present invention, in order to obtain the desired film properties in the cured film formed on the substrate by the demolding step, a hard baking step of heating the cured film on the substrate again after the demolding step can be performed. For example, in the case of using a curable composition (A2) as the curable composition (A), when a hard baking step is provided, the volatilization of the residual solvent and the carbonization of the residual curable composition can be promoted, and a flat cured film with etching resistance can be obtained. In the case of using a curable composition (A3) as the curable composition (A), when a hard baking step is provided, the volatilization of the residual solvent and the formation of a three-dimensional cross-linked structure by dehydration condensation can be promoted, and a flat cured film with etching resistance, heat resistance, transparency and insulation can be obtained. The upper limit of the heating temperature in the hard baking step is preferably a heat-resistant temperature. When TGA is used for measurement, the heat-resistant temperature can be obtained as follows: the cured curable composition (A) is placed in a nitrogen atmosphere with a flow rate of 5L / hrs to 6L / hrs, and the thermogravimetric reduction rate is measured when the temperature is raised to n°C at a heating rate of 20°C / min. The temperature at which the thermogravimetric reduction rate first reaches 2% is defined as the heat-resistant temperature. An example of a main apparatus is STA1000 (manufactured by Linseis).

[0203] [Item Manufacturing Method] The article manufacturing method according to an embodiment of the present invention includes: forming a planarized film of a curable composition on a substrate using the above-described film-forming method; processing the substrate having the planarized film formed in the forming step; and manufacturing an article from the substrate processed in the processing step. As described above, the film-forming method is a method for forming a planarized film on a substrate using a cover plate, and may include, for example, an arrangement step, a waiting step, a contact step, a curing step, and a demolding step.

[0204] Well-known photolithography steps, such as imprint lithography or extreme ultraviolet exposure technology (EUV), can be carried out on the planarized film formed on the substrate by the film-forming method according to an embodiment of the present invention. Spin-on-glass (SOG) film and / or silicon oxide layer can also be stacked, and photolithography steps are carried out by applying curable composition thereon. Therefore, devices such as semiconductor devices can be manufactured. Equipment including the device can also be formed, such as electronic equipment, such as display, camera or medical equipment. The example of the device is LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM and NAND flash memory.

[0205] Here, the article is, for example, a circuit element, an optical element, a MEMS, a recording element, a sensor, or a mold. Examples of circuit elements are 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 are microlenses, light guides, waveguides, anti-reflection films, diffraction gratings, polarizers, color filters, light-emitting elements, displays, and solar cells. Examples of MEMS are DMDs, microchannels, and electromechanical transducers. Examples of recording elements are optical discs (such as CDs and DVDs), magnetic disks, magneto-optical discs, and magnetic heads. Examples of sensors are magnetic sensors, optical sensors, and gyro sensors. Examples of molds are molds for imprinting.

[0206] More practical examples will be described below to supplement the above embodiments. Example 1 in which a silicon wafer was used as a superstrate and Comparative Example 1 in which a quartz wafer was used as a superstrate will be described below. Note that as a substrate, a silicon wafer was used.

[0207] [Example 1] A silicon wafer can be prepared as a superstrate that meets the above-described conditions of the present embodiment. Therefore, in Example 1, a silicon wafer having a size of 300 mφ and having less than 10 foreign particles having a size of 50 nm or greater was used as the superstrate. Commercially available cleaning equipment can be used to clean the silicon wafer used as the superstrate.

[0208] [Comparative Example 1] It is difficult to prepare a quartz wafer as a cover plate that meets the above-mentioned conditions of the embodiments of the present invention. More specifically, it is difficult to obtain a quartz wafer having a size of 300 mφ and a number of less than 100 foreign particles having a size of 50 nm or larger. Therefore, in Comparative Example 1, a quartz wafer having a size of 300 mφ and a number of 100 or more foreign particles having a size of 50 nm or larger was used as the cover plate.

[0209] The thermal expansion coefficients of silicon wafers and quartz wafers at 290K to 310K are shown in the table below. In the case of using a silicon wafer as a substrate and a quartz wafer as a cover plate (Comparative Example 1), the thermal expansion coefficient of the substrate is 4×10 -6 K -1 The thermal expansion coefficient of the cover plate 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 six times or more. On the other hand, in the case where a silicon wafer is used as the substrate and also as the superstrate (Example 1), the thermal expansion coefficients of the substrate and the superstrate are 4×10 -6 K -1and are equal. Therefore, in the case of using a silicon wafer as the superstrate (Example 1), the difference in thermal expansion coefficient between the substrate and the superstrate is smaller than in the case of using a quartz wafer as the superstrate (Comparative Example 1). In other words, the strain of the cured film formed on the substrate using the film-forming method according to an embodiment of the present invention can be reduced.

[0210] [Table 1]

[0211] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims

1. A film forming method for forming a planarization film on a substrate using a cover plate having a flat surface, comprising: discretely disposing the curable composition (A) in the form of a plurality of droplets on a substrate; Waiting until a plurality of liquid droplets arranged on the substrate in the arrangement are combined with each other on the substrate to form a liquid film; After the waiting, the liquid film on the substrate and the flat surface of the cover plate are brought into contact with each other; heating and solidifying the liquid film after bringing them into contact with each other, thereby forming a solidified film between the superstrate and the substrate; as well as After curing, the cover sheet is separated from the cured film. wherein the curable composition (A) disposed on the substrate in the arrangement is a thermosetting curable composition having a property of being cured by heating and contains at least a solvent (d), wherein the viscosity of the curable composition (A) at 23° C. is 2 mPa·s or more and 60 mPa·s or less, wherein the content of the solvent (d) in the curable composition (A) is 5% by volume or more and 95% by volume or less, wherein the boiling point of the solvent (d) at normal pressure is less than 250°C, and The viscosity of the mixture excluding the solvent (d) in the curable composition (A) at 23° C. is 30 mPa·s or more and 10,000 mPa·s or less. The method of claim 1 , wherein the superstrate is a silicon wafer.

3. The method according to claim 1, wherein the thermal expansion coefficient of the superstrate at 290K to 310K is 1×10 - 6 K -1 Above and 7×10 -6 K -1 the following. 4 . The method according to claim 1 , wherein in the disposing, the curable composition (A) is discretely disposed on the substrate in the form of a plurality of droplets using an inkjet method.

5. The method according to claim 1, wherein when the temperature is increased from 200°C to 250°C at a heating rate of 20°C / min, the weight reduction of the cured film obtained in the curing is 2% or less.

6. The method according to claim 1, wherein The curable composition (A) contains at least a polymerizable compound (a) and a radical generator (b), and 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 method according to claim 6, wherein The polymerizable compound (a) contains one or more types of polymerizable compounds, and Each of the one or more types of polymerizable compounds has a boiling point of 250° C. or higher at normal pressure.

8. The method according to claim 6, wherein The polymerizable compound (a) contains one or more types of polymerizable compounds, and The molecular weight of each of the one or more types of polymerizable compounds is 200 or more.

9. The method according to claim 6, wherein The polymerizable compound (a) contains one or more types of polymerizable compounds, and Each of the one or more types of polymerizable compounds has a vapor pressure of 0.001 mmHg or less at 80°C. 10 . The method according to claim 6 , wherein the polymerizable compound (a) contains at least a polymer having a polymerizable functional group.

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

12. The method according to claim 1, wherein The curable composition (A) comprises a silicone component (q), and The silicon atom content in the mixture excluding the solvent (d) in the curable composition (A) is 30% by weight or more.

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

14. The method according to claim 1, wherein The solvent (d) contains more than one type of solvent, and Each of the one or more types of solvents has a boiling point of 80° C. or higher and less than 250° C. at normal pressure.

15. The method according to claim 1, wherein The solvent (d) contains more than one type of solvent, and Each of the one or more types of solvents has a boiling point of 150° C. or higher and less than 200° C. at normal pressure. 16 . The method according to claim 1 , wherein the solvent (d) comprises a polymerizable compound having a boiling point of 80° C. or higher and less than 250° C. at normal pressure. 17 . The 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. The method according to claim 1, wherein the curable composition (A) is a curable composition for inkjet.

19. The method according to claim 1, wherein in the waiting, the process is waited until the content of the solvent (d) in the liquid film becomes 10% by volume or less relative to the mixture. 20 . The method according to claim 1 , wherein in the waiting, the substrate is heated under the conditions of a temperature of 30° C. to 200° C. both inclusive and a heating time of 10 seconds to 600 seconds both inclusive.

21. The method of claim 1, further comprising heating the cured film on the substrate after the detaching.

22. A method for manufacturing an article, comprising: forming a planarization film on a substrate using the film forming method defined in any one of claims 1 to 21; processing the substrate using the planarization film formed in the forming; as well as An article is manufactured from the substrate processed in the process.

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