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

Abstract

The invention relates to a curable composition, a film forming method and a manufacturing method of an article. The curable composition includes a polymerizable compound (a), a photopolymerization initiator (b), and a solvent (d). The curable composition has a viscosity of 1.3 mPa * s to 60 mPa * s at 23 DEG C and 1 atm. The amount of the solvent (d) is greater than 5 vol% to 95 vol% with respect to the entire curable composition. The boiling point of the solvent (d) is less than 250 DEG C. The viscosity of the curable composition in a state where the curable composition does not include the solvent (d) at 23 DEG C and 1 atm is from 8 mPa.s to 30 mPa.s.

Description

Technical Field

[0001] This disclosure relates to curable compositions, methods of film formation, and methods of manufacturing articles. Background Technology

[0002] In the fields of semiconductor devices, microelectromechanical systems (MEMS), and similar technologies, miniaturization is increasingly needed, and imprinting technology (optical imprinting) is gaining attention as a microfabrication technique. In imprinting, a curable composition is supplied (applied) to a substrate, and a mold with a finely patterned relief on its contact surface is cured while in contact with the composition. Thus, the relief pattern of the mold is transferred to a cured film of the curable composition, thereby forming a pattern on the substrate. Imprinting technology enables the formation of micropatterns (structures) with dimensions of several nanometers on a substrate.

[0003] An example of pattern formation using an imprinting technique will be described. First, a liquid curable composition is discretely dropped (applied) onto a pattern formation area on a substrate. The droplets of the curable composition in the pattern formation area spread across the substrate surface. This phenomenon is called pre-spreading. Next, the curable composition on the substrate is brought into contact with (pressed onto) the contact surface of a mold. As a result, droplets of the curable composition spread across the gap between the substrate and the mold due to capillary action. This phenomenon is called spreading. Furthermore, the curable composition fills the recesses of the mold pattern due to capillary action. This phenomenon is called filling. The duration required to complete this spreading and filling is called the filling time. After filling is complete, the curable composition is irradiated with light to cure it. Then, the cured composition on the substrate is separated from the mold. Thus, a cured pattern of the curable composition is formed by transferring the pattern of the mold onto the curable composition on the substrate using these steps. At this point, the cured pattern of the curable composition formed on the substrate has a residual film. The residual film is the cured film retained between the recesses (protrusions of the mold pattern) of the cured film of the curable composition and the substrate.

[0004] Furthermore, photolithography used in the manufacture of semiconductor devices requires the substrate to be planarized. For example, in extreme ultraviolet (EUV) lithography, a technique that has attracted attention in recent years, the depth of focus for forming the projected image decreases with miniaturization, so the uneven pattern on the substrate surface to which the curable composition is supplied must be limited to tens of nanometers or smaller. Imprint lithography also requires planarization to the same degree as EUV to improve the fill power and linewidth accuracy of the curable composition. In planarization technology (Japanese Patent Publication No. 2019-140394), a flat surface is formed by discretely dropping the curable composition onto a substrate with an uneven structure in amounts corresponding to the unevenness and then curing the composition while it is in contact with a mold having a flat surface.

[0005] In pattern forming methods and planarization techniques using embossing, a curable composition on a substrate is brought into contact with a mold while the droplets of the curable composition are not in contact with each other. This process inevitably results in air bubbles being trapped between the mold, the substrate, and the composition. Therefore, it takes a long time for the air bubbles to diffuse through the mold and the substrate and disappear, which is one of the factors that reduces productivity (yield). Therefore, a technique has been developed to merge the droplets of the curable composition on the substrate before the curable composition comes into contact with the mold (see Japanese Patent Publication No. 2022-188736).

[0006] The technology disclosed in Japanese Patent Publication No. 2022-188736 describes a curable composition that fills the contact area (patterning area) between a mold and a substrate by bringing a mold into contact with a liquid film of the curable composition formed by spreading droplets (pressing the mold against the liquid film), reaching the end (edge). This phenomenon is called edge filling. The speed at which edge filling occurs is called the edge filling speed. In patterning methods and planarization techniques using embossing, it takes a certain amount of time to bring droplets of the curable composition on the substrate into contact with the mold and fill the desired area (patterning area) until the end (edge). This is one of the factors that reduce productivity (yield). Summary of the Invention

[0007] Therefore, this disclosure provides a new technique for curable compositions.

[0008] According to one aspect of this disclosure, a curable composition is provided, the curable composition comprising:

[0009] The polymerizable compound (a); a photopolymerization initiator (b); and a solvent with a boiling point less than 250°C (d), wherein the amount of the solvent is greater than 5% to 95% by volume relative to the entire curable composition.

[0010] The curable composition has a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm.

[0011] The composition formed by removing the solvent (d) from the curable composition has a viscosity of 8 mPa·s to 30 mPa·s at 23°C and 1 atm.

[0012] Another aspect of this disclosure relates to a curable composition comprising:

[0013] The composition comprises: (a) a polymerizable compound; (b) a photopolymerization initiator; (c) a surfactant having a viscosity of 500 mPa·s or less at 23°C and 1 atm; and (d) a solvent with a boiling point less than 250°C, wherein the amount of the solvent is greater than 5% to 95% by volume relative to the entire curable composition. The curable composition has a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm.

[0014] The features of this disclosure will become clear from the following description of the embodiments with reference to the accompanying drawings. The following description of the embodiments is illustrated by way of example. Attached Figure Description

[0015] Figures 1A to 1G This is a schematic diagram illustrating a method (film forming method) for forming a pattern according to one aspect of this disclosure.

[0016] Figures 2A to 2D This is a schematic diagram illustrating the flow behavior of droplets of the curable composition during the waiting step.

[0017] Figure 3 This is a schematic diagram illustrating surfactant segregation during the contact step.

[0018] Figure 4 This is a schematic diagram illustrating the contact steps.

[0019] Figure 5 It is a curve showing how the edge filling speed changes as the viscosity coefficient of the liquid film is altered.

[0020] Figure 6 It comes from and Figure 5 A coordinate graph of the same calculation results, where the horizontal axis is plotted as time / viscosity coefficient.

[0021] Figure 7 It is a coordinate graph showing how the edge filling speed changes as the average liquid film thickness is altered.

[0022] Figure 8 It is a coordinate graph showing the relationship between the average liquid film thickness and the edge filling speed. Detailed Implementation

[0023] Embodiments of the present disclosure will now be described with reference to the accompanying drawings. However, it should be understood that the embodiments described below are not intended to limit the scope of the appended claims. Although the embodiments include several features, not all of these features are necessary and can be combined as needed. In the drawings, identical or similar parts are indicated by the same reference numerals, and therefore their description is omitted.

[0024] Curing composition

[0025] The curable composition (A) disclosed herein is used in an inkjet process. The curable composition (A) disclosed herein comprises a component (a) as a polymerizable compound and a component (b) as a photopolymerization initiator, and a solvent as component (d), and may also comprise a component (c) as a surfactant and other components (e). In the description given herein, the non-volatile component composition (A') is defined as the portion of the curable composition (A) excluding component (d).

[0026] As used herein, the term "cured film" refers to a film formed by polymerizing a curable composition to cure the composition on a substrate. The shape of the cured film is not particularly limited, and it may have patterns on its surface. Furthermore, the cured film remaining between the recesses (protrusions of the patterned shape) of the cured film in the curable composition and the substrate is referred to as a residual film.

[0027] Component (a): Polymer compound

[0028] Component (a) consists of one or more polymerizable compounds. The term “polymerizable compound” as used herein refers to a compound that reacts with polymerization factors (such as free radicals) generated by a photopolymerization initiator (component (b)) and forms a polymer film through a chain reaction (polymerization reaction).

[0029] Examples of such polymerizable compounds include free radical polymerizable compounds. Component (a) may be a single polymerizable compound or a combination of multiple (two or more) polymerizable compounds.

[0030] Free radical polymerizable compounds include (meth)acrylic acid compounds, styrene compounds, vinyl compounds, allyl compounds, fumaric acid compounds, and maleic acid compounds.

[0031] (Meth)acrylic acid compounds have one or more acryloyl or methacryloyl groups. Examples of monofunctional (meth)acrylic acid compounds containing one acryloyl or methacryloyl group include, but are not limited to:

[0032] Phenoxyethyl methacrylate, phenoxy-2-methylethyl methacrylate, phenoxyethoxyethyl methacrylate, 3-phenoxy-2-hydroxypropyl methacrylate, 2-phenylphenoxyethyl methacrylate, 4-phenylphenoxyethyl methacrylate, 3-(2-phenylphenyl)-2-hydroxypropyl methacrylate, EO-modified p-cumylphenol methacrylate, 2-bromophenoxyethyl methacrylate, 2,4-dibromophenoxyethyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, EO-modified phenoxy(meth)acrylate, PO-modified phenoxy(meth)acrylate, polyoxyethylene Nonylphenyl ether (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, borneol (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acrylmorpholine, 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 methacrylate, Amyl methacrylate, Isobutyl methacrylate, Tert-butyl methacrylate, Amyl methacrylate, Isoamyl methacrylate, Hexyl methacrylate, Heptyl methacrylate, Octyl methacrylate, Isoooctyl methacrylate, 2-Ethylhexyl methacrylate, Nonyl methacrylate, Decyl methacrylate, Isodecyl methacrylate, Undecyl methacrylate, Dodecyl methacrylate, Lauryl methacrylate, Stearyl methacrylate, Isostearyl methacrylate, Benzyl methacrylate, Tetrahydrofurfuryl methacrylate, (methyl) Butoxyethyl acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxy polyethylene 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, cyanobenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate.

[0033] Examples of commercially available products of this type of monofunctional (meth)acrylic acid compound include, but are not limited to:

[0034] Aronix (registered trademark) series M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150 and M156 (all manufactured by Toagosei); MEDOL 10, MIBDOL 10, CHDOL 10, MMDOL 30, MEDOL 30, MIBDOL 30, CHDOL 30, LA, IBXA, 2-MTA, HPA and Biscoat series #150, #155, #158, #190, #192, #193, #220, #2000, #2100 and #2150 (all manufactured by Osaka Organic Chemicals) (Manufactured by Industry); Light acrylates BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, and NP-8EA; and epoxy esters M-600A, POB-A, and OPP-EA (all manufactured by Kyoeisha Chemical); KAYARAD (registered trademark) series TC110S, R-564, and R-128H (all manufactured by Nippon Kayaku); NK Esters AMP-10G, AMP-20G, and A-LEN-10 (all manufactured by Shin-Nakamura Chemical); FA-511A, FA-512A, and FA-513A (all manufactured by Resonac Corporation); PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, and BR-32 (all manufactured by Dai-ichi Kogyo) Manufactured by Seiyaku); VP (manufactured by BASF), ACMO, DMAA and DMAPAA (all manufactured by Kohjin); and HRD-01 (manufactured by Nippon Shokubai).

[0035] Examples of polyfunctional (meth)acrylic acid compounds containing two or more acryloyl or methacryloyl groups include, but are not limited to:

[0036] Trimethylolpropane di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, EO-modified Trimethylolpropane tri(meth)acrylate, PO-modified Trimethylolpropane tri(meth)acrylate, EO-modified Trimethylolpropane tri(meth)acrylate, 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-Nonadiol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, 1,3- Adamantane dimethyl di(meth)acrylate, tri(2-hydroxyethyl) isocyanurate tri(meth)acrylate, tri(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, pentaerythritol penta(meth)acrylate, pentaerythritol hexa(meth)acrylate, EO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, EO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, PO-modified 2,2-bis(4-((meth)acryloyloxy)phenyl)propane, phthalic acid di(meth)acrylate, isophthalic acid di(meth)acrylate or terephthalic acid di(meth)acrylate, and o-xylene di(meth)acrylate, m-xylene di(meth)acrylate or p-xylene di(meth)acrylate.

[0037] Examples of commercially available products containing such multifunctional (meth)acrylic acid compounds include, but are not limited to:

[0038] Yupimer (registered trademark) UV series SA1002 and SA2007 (both manufactured by Mitsubishi Chemical); Biscoat series #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT and 3PA (all 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); KAYARAD (Registered trademark) series PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60 and -120, HX-620, D-310 and D-330 (all manufactured by Nippon Kayaku); Aronix (Registered trademark) series M208, M210, M215, M220, M240, M305, M309, M310, M315, M325 and M400 (all manufactured by Toagosei); Ripoxy (Registered trademarks) VR-77, VR-60 and VR-90 (all manufactured by Resonac Corporation); OGSOL EA-0200 and OGSOL EA-0300 (all manufactured by Osaka Gas Chemicals); and SR295 and SR355 (all manufactured by Sartomer).

[0039] In the compounds given above, (meth)acrylate refers to acrylate or methacrylate having an equivalent number of alcohol residues. Furthermore, (meth)acryloyl is a general term for acryloyl or methacryloyl groups. EO represents ethylene oxide, and EO-modified compound A is a compound in which (meth)acrylate residues and alcohol residues are bonded together and have an ethylene oxide block structure. PO represents propylene oxide, and PO-modified compound B is a compound in which (meth)acrylate residues and alcohol residues are bonded together and have a propylene oxide block structure.

[0040] Specific examples of styrene compounds include, but are not limited to:

[0041] Styrene; alkyl styrene, such as 2,4-dimethyl-α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,6-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, 2,4,5-trimethylstyrene, pentamethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, 2,4-diisopropylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrene, such as fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromobenzene Ethylene, dibromostyrene, and iodostyrene; and other compounds having a styrene group as a polymerizable functional group, such as nitrostyrene, acetylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-vinyl-p-terphenyl, 1-vinylanthracene, α-methylstyrene, o-isopropenyltoluene, m-isopropenyltoluene, p-isopropenyltoluene, 2,3-dimethyl-α-methylstyrene, 3,5-dimethyl-α-methylstyrene, p-isopropyl-α-methylstyrene, α-ethylstyrene, α-chlorostyrene, divinylbenzene, diisopropylbenzene, and divinylbiphenyl.

[0042] Specific examples of vinyl compounds include, but are not limited to:

[0043] Vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate, and acrylonitrile; conjugated diene monomers, such as butadiene, isoprene, and chloroprene; halogenated vinyl compounds, such as vinyl chloride and vinyl bromide; halogenated vinylidene compounds, such as vinylidene chloride, vinyl esters of organic carboxylic acids, and their derivatives, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and divinyl adipate; and (meth)acrylonitrile and other compounds having vinyl groups as polymerizable functional groups.

[0044] The (meth)acrylonitrile mentioned in this article is a collective term for acrylonitrile and methacrylonitrile.

[0045] Examples of acrylic acid compounds include, but are not limited to:

[0046] Allyl acetate, allyl benzoate, diallyl adipate, diallyl terephthalate, diallyl isophthalate, and diallyl phthalate.

[0047] Examples of fumaric acid compounds include, but are not limited to:

[0048] Dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, disec-butyl fumarate, diisobutyl fumarate, di-n-butyl fumarate, di-2-ethylhexyl fumarate, and dibenzyl fumarate.

[0049] Examples of maleic acid compounds include, but are not limited to:

[0050] Dimethyl maleate, diethyl maleate, diisopropyl maleate, disec-butyl maleate, diisobutyl maleate, di-n-butyl maleate, di-2-ethylhexyl maleate, and dibenzyl maleate.

[0051] Examples of other free radical polymerizable compounds include, but are not limited to:

[0052] Dialkyl esters of itaconic acid and their derivatives, such as dimethyl itaconic acid, diethyl itaconic acid, diisopropyl itaconic acid, disec-butyl itaconic acid, diisobutyl itaconic acid, di-n-butyl itaconic acid, di-2-ethylhexyl itaconic acid, and dibenzyl itaconic acid; N-vinylamide derivatives of organic carboxylic acids, such as N-methyl-N-vinylacetamide; and maleimides and their derivatives, such as N-phenylmaleimide and N-cyclohexylmaleimide.

[0053] When component (a) consists of multiple compounds having one or more polymerizable functional groups, component (a) preferably includes both monofunctional and polyfunctional polymerizable compounds. The proportion of polyfunctional polymerizable compounds in component (a) is preferably 20% by mass or more, more preferably 25% by mass or more, and particularly 40% by mass or more. This is because combining monofunctional and polyfunctional polymerizable compounds results in a cured film exhibiting an excellent balance of properties, including high mechanical strength, high dry etching resistance, and high heat resistance.

[0054] In the film formation method disclosed herein, a few milliseconds to several hundred seconds are taken before the droplets of the curable composition (A) discretely applied to the substrate coalesce to form a substantially continuous liquid film. Therefore, a waiting step is required. This waiting step allows the solvent (component (d)) to evaporate, but not component (a). Therefore, the boiling points of one or more polymeric compounds in component (a) are preferably 250°C or higher at atmospheric pressure, more preferably 300°C or higher, and even more preferably 350°C or higher. To impart high dry etching resistance and high heat resistance to the cured film of the curable composition (A), component (a) preferably includes at least compounds having aromatic structures, aromatic heterocyclic structures, alicyclic structures, etc. Note that atmospheric pressure is defined as 1 atm (atmospheric pressure).

[0055] The boiling point of the polymeric compound (component (a)) is generally related to its molecular weight. The molecular weight of each of the one or more polymeric compounds in component (a) is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more. Even when the molecular weight of the polymeric compound is 200 or less, the polymeric compound can still be advantageously used as component (a), provided that its boiling point is 250°C or more. Therefore, the boiling point of each of the one or more polymeric compounds in component (a) is preferably 250°C or more at atmospheric pressure.

[0056] Furthermore, the vapor pressure of the polymerizable compound (component (a)) at 80°C is preferably 0.001 mmHg or lower. When component (a) comprises one or more polymerizable compounds, the vapor pressure of each polymerizable compound is desirablely 0.001 mmHg or lower at 80°C. This is because while heating the polymerizable compound is preferred to accelerate the evaporation of the solvent (component (d)) described later, the evaporation of component (a) should be suppressed.

[0057] The boiling point and vapor pressure of organic compounds can be calculated from, for example, the following literature: Hansen Solubility Parameters in Practice (HSPiP) 5th Edition, Ver. 5.3.04.

[0058] Ohnishi parameter of component (a)

[0059] Dry etching rate V, total number of atoms N, and total number of carbon atoms N for organic compounds C The total number of oxygen atoms N O It has the following relation (1):

[0060]

[0061] In this relationship, N / (Nc-No) is referred to as the "Atlantic parameter" (abbreviated as "OP" below). For example, U.S. Patent Application Publication No. 2020 / 0286740 discloses a technique for producing photocurable compositions that are highly resistant to dry etching using polymerizable compounds with low OP.

[0062] Equation (1) shows that organic compounds containing a large number of oxygen atoms or a small number of aromatic or alicyclic structures exhibit higher OP and correspondingly higher dry etching rates.

[0063] In the curable composition (A) disclosed herein, component (a) has an OP of 1.80 to 4.00. Preferably, the OP of component (a) is 2.00 to 3.50, particularly 2.40 to 3.00. When the OP of component (a) is below 4.00, the cured film of the curable composition (A) exhibits high dry etching resistance. Furthermore, when the OP of component (a) is above 1.80, the cured film of the curable composition (A) can be easily removed after processing the underlying layer using the cured film. For a variety of polymeric compounds a1, a2, ... and a n The composition of component (a) is used to calculate OP using a weighted average based on mole fraction (mole fraction weighted average), as expressed in the following equation (2):

[0064] (2)

[0065] OP n Indicates component a n The OP, and n n Indicates component a n Mole fraction in the total of component (a).

[0066] Therefore, based on the N / (N) of their respective polymerizable compounds C - N O The OP of component (a) consisting of two or more polymeric compounds is calculated by weighting the mole fraction of the values.

[0067] In order to control the OP of component (a) in the range of 1.80 to 2.70, preferably, component (a) includes at least a compound (a-1) having two or more cyclic structures, at least one of which is an aromatic or aromatic heterocyclic structure.

[0068] Compound (a-1): Polymerizable compounds having aromatic, aromatic heterocyclic, or alicyclic structures.

[0069] Component (a) may include a polymeric compound (a-1) having an aromatic, aromatic heterocyclic, or alicyclic structure. Preferably, the polymeric compound (a-1) accounts for 65% by mass or more in component (a). When the proportion of the polymeric compound (a-1) is 65% by mass or more, the OP can be reduced to 2.70 or less.

[0070] The ring structure can be an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0071] Aromatic structures preferably have 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples of aromatic structures include:

[0072] Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, finaene ring, fluorene ring, benzo[a]octene ring, acenaphthene ring, biphenylene ring, indene ring, indene ring, benzo[a]phenanthrene ring, pyrene ring, β-ring, perylene ring, and tetrahydronaphthalene ring.

[0073] Among these aromatic rings, benzene rings or naphthalene rings are preferred, with benzene rings being more preferred. The aromatic structure may have a combination of multiple aromatic rings, and examples include biphenyl rings and diphenyl rings.

[0074] The aromatic heterocyclic structure preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specific examples of aromatic heterocyclic structures include:

[0075] Thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetraazole 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, quinolineazine ring, isoquinoline ring, quinoline ring, naphthidine ring including phthalazine ring, quinoxaline ring, quinazoline ring, and cyclophosphine ring, carbazole ring, acridine ring, phenazine ring, phenothiazine ring, phenothiazine ring, and phenothiazine ring.

[0076] The alicyclic structure preferably has 3 or more carbon atoms, more preferably 4 or more carbon atoms, and even more preferably 6 or more carbon atoms. The alicyclic structure preferably has 22 or fewer carbon atoms, more preferably 18 or fewer carbon atoms, even more preferably 6 or fewer carbon atoms, and even more preferably 5 or fewer carbon atoms. Specific examples of the alicyclic structure include:

[0077] Cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, bicyclopentadiene ring, spirodecane ring, spirononane ring, tetrahydrobicyclopentadiene ring, octahydronaphthalene ring, decahydronaphthalene ring, hexahydroindene ring, camphene ring, norcamphene ring, norcamphene ring, isocamphene ring, tricyclodecane ring, tetracyclododecane ring, and adamantane ring.

[0078] Specific examples of polymeric compounds (a-1) with boiling points above 250°C include, but are not limited to:

[0079] 3-Phenoxybenzyl acrylate (mPhOBzA, OP: 2.54, boiling point: 367.4℃, vapor pressure at 80℃: 0.0004 mmHg, molecular weight: 254.3):

[0080]

[0081] 1-Naphthyl acrylate (NaA, OP: 2.27, boiling point: 317℃, vapor pressure at 80℃: 0.0422 mmHg, molecular weight: 198):

[0082]

[0083] 2-Phenylenoxyethyl acrylate (PhPhOEA, OP: 2.57, boiling point: 364.2℃, vapor pressure at 80℃: 0.0006mmHg, molecular weight: 268.3):

[0084]

[0085] 1-Naphthylmethyl acrylate (Na1MA, OP: 2.33, boiling point: 342.1℃, vapor pressure at 80℃: 0.042 mmHg, molecular weight: 212.2):

[0086]

[0087] 2-Naphthylmethyl acrylate (Na2MA, OP: 2.33, boiling point: 342.1℃, vapor pressure at 80℃: 0.042 mmHg, molecular weight = 212.2):

[0088]

[0089] DPhPA (OP: 2.38, boiling point: 354.5℃, vapor pressure at 80℃: 0.0022 mmHg, molecular weight = 266.3) is represented by the following formula:

[0090]

[0091] PhBzA (OP: 2.29, boiling point: 350.4℃, vapor pressure at 80℃: 0.0022 mmHg, molecular weight: 238.3) is represented by the following formula:

[0092]

[0093] FLMA (OP: 2.20, boiling point: 349.3℃, vapor pressure at 80℃: 0.0018 mmHg, molecular weight: 250.3) is represented by the following formula:

[0094]

[0095] ATMA (OP: 2.13, boiling point: 414.9℃, vapor pressure at 80℃: 0.0001 mmHg, molecular weight: 262.3) is represented by the following formula:

[0096]

[0097] DNaMA (OP: 2.00, boiling point: 489.4℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 338.4) is represented by the following formula:

[0098]

[0099] BPh44DA (OP: 2.63, boiling point: 444℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 322.3) is represented by the following formula:

[0100]

[0101] BPh43DA (OP: 2.63, boiling point: 439.5℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 322.3) is represented by the following formula:

[0102]

[0103] DPhEDA (OP: 2.63, boiling point: 410℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 322.3) is represented by the following formula:

[0104]

[0105] BPMDA (OP: 2.68, boiling point: 465.7℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 364.4) is represented by the following formula:

[0106]

[0107] Na13MDA (OP: 2.71, boiling point: 438.8℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 296.3) is represented by the following formula:

[0108]

[0109] The polymerizable compound (a-1-1) (OP: 2.40, boiling point: 333.4℃, vapor pressure at 80℃: 0.0181 mmHg, molecular weight: 199.2) is represented by the following formula:

[0110]

[0111] The polymerizable compound (a-1-2) (OP: 2.40, boiling point: 333.4℃, vapor pressure at 80℃: 0.0181 mmHg, molecular weight: 199.2) is represented by the following formula:

[0112]

[0113] The polymerizable compound (a-1-3) (OP: 1.86, boiling point: 369.5℃, vapor pressure at 80℃: 0.0053 mmHg, molecular weight: 193.3) is represented by the following formula:

[0114]

[0115] The polymerizable compound (a-1-4) (OP: 2.85, boiling point: 438.8℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 296.3) is represented by the following formula:

[0116]

[0117] The polymerizable compound (a-1-5) (OP=2.71, boiling point: 438.8℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 296.3) is represented by the following formula:

[0118]

[0119] The polymerizable compound (a-1-6) (OP: 2.87, boiling point: 421.0℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 338.4) is represented by the following formula:

[0120]

[0121] The polymerizable compound (a-1-7) (OP: 2.87, boiling point: 465.2℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 338.4) is represented by the following formula:

[0122]

[0123] The polymerizable compound (a-1-8) (OP: 2.68, boiling point: 465.7℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 364.4) is represented by the following formula:

[0124]

[0125] The polymerizable compound (a-1-9) (OP: 2.50, boiling point: 433.1℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 320.3) is represented by the following formula:

[0126]

[0127] The polymerizable compound (a-1-10) (OP: 2.64, boiling point: 468.1℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 326.4) is represented by the following formula:

[0128]

[0129] The polymerizable compound (a-1-11) (OP: 3.25, boiling point: 553.4℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 358.4) is represented by the following formula:

[0130]

[0131] The polymerizable compound (a-1-12) (OP: 2.63, boiling point: 443.9℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 322.4) is represented by the following formula:

[0132]

[0133] The polymerizable compound (a-1-13) (OP: 2.89, boiling point: 509.3℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 406.4) is represented by the following formula:

[0134]

[0135] The polymerizable compound (a-1-14) (OP: 2.63, boiling point: 450.0℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 322.4) is represented by the following formula:

[0136]

[0137] The polymerizable compound (a-1-15) (OP: 3.00, boiling point: 476.5℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 366.4) is represented by the following formula:

[0138]

[0139] The polymerizable compound (a-1-16) (OP: 2.68, boiling point: 447.4℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 364.4) is represented by the following formula:

[0140]

[0141] The polymerizable compound (a-1-17) (OP: 2.36, boiling point: 543.8℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 398.5) is represented by the following formula:

[0142]

[0143] The polymerizable compound (a-1-18) (OP: 3.27, boiling point: 526.9℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 396.4) is represented by the following formula:

[0144]

[0145] The polymerizable compound (a-1-19) (OP: 2.71, boiling point: 333.7℃, vapor pressure at 80℃: 0.0302 mmHg, molecular weight: 244.3) is represented by the following formula:

[0146]

[0147] The polymerizable compound (a-1-20) (OP: 2.73, boiling point: 333.7℃, vapor pressure at 80℃: 0.0134 mmHg, molecular weight: 258.3) is represented by the following formula:

[0148]

[0149] The polymerizable compound (a-1-21) (OP: 2.71, boiling point: 319.2℃, vapor pressure at 80℃: 0.0566 mmHg, molecular weight: 262.3) is represented by the following formula:

[0150]

[0151] The polymerizable compound (a-1-22) (OP: 2.71, boiling point: 336.9℃, vapor pressure at 80℃: 0.0055 mmHg, molecular weight: 244.3) is represented by the following formula:

[0152]

[0153] The polymerizable compound (a-1-23) (OP: 3.00, boiling point: 370.9℃, vapor pressure at 80℃: 0.0021 mmHg, molecular weight: 274.4) is represented by the following formula:

[0154]

[0155] The polymerizable compound (a-1-24) (OP: 3.00, boiling point: 376.4℃, vapor pressure at 80℃: 0.0005 mmHg, molecular weight: 274.4) is represented by the following formula:

[0156]

[0157] The polymerizable compound (a-1-25) (OP: 3.00, boiling point: 379.4℃, vapor pressure at 80℃: 0.0002 mmHg, molecular weight: 288.4) is represented by the following formula:

[0158]

[0159] The polymerizable compound (a-1-26) (OP: 2.33, boiling point: 360.8℃, vapor pressure at 80℃: 0.0006 mmHg, molecular weight: 252.3) is represented by the following formula:

[0160]

[0161] The polymerizable compound (a-1-27) (OP: 2.54, boiling point: 371.5℃, vapor pressure at 80℃: 0.0003 mmHg, molecular weight: 254.3) is represented by the following formula:

[0162]

[0163] The polymerizable compound (a-1-28) (OP: 2.57, boiling point: 381.2℃, vapor pressure at 80℃: 0.0001 mmHg, molecular weight: 268.3) is represented by the following formula:

[0164]

[0165] The polymerizable compound (a-1-29) (OP: 2.57, boiling point: 381.8℃, vapor pressure at 80℃: 0.0004 mmHg, molecular weight: 268.3) is represented by the following formula:

[0166]

[0167] The polymerizable compound (a-1-30) (OP: 2.50, boiling point: 487.4℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 374.4) is represented by the following formula:

[0168]

[0169] The polymerizable compound (a-1-31) (OP: 2.67, boiling point: 417.2℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 268.3) is represented by the following formula:

[0170]

[0171] The polymerizable compound (a-1-32) (OP: 2.67, boiling point: 417.2℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 268.3) is represented by the following formula:

[0172]

[0173] The polymerizable compound (a-1-33) (OP: 2.67, boiling point: 417.2℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 268.3) is represented by the following formula:

[0174]

[0175] The polymerizable compound (a-1-34) (OP: 2.67, boiling point: 417.2℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 268.3) is represented by the following formula:

[0176]

[0177] The polymerizable compound (a-1-35) (OP: 2.71, boiling point: 438.8℃, vapor pressure at 80℃: <0.0001 mmHg, molecular weight: 296.3) is represented by the following formula:

[0178]

[0179] mXDA (OP: 3.20, boiling point: 335.9℃, vapor pressure at 80℃: 0.0043 mmHg, molecular weight: 246.26, viscosity at 23℃: 13 mPa·s) is expressed by the following formula:

[0180]

[0181] PhEDA (OP: 3.20, boiling point: 327.8℃, vapor pressure at 80℃: 0.0057 mmHg, molecular weight: 246.26, viscosity at 23℃: 23 mPa·s) is expressed by the following formula:

[0182]

[0183] PhPDA (OP: 3.18, boiling point: 339.7℃, vapor pressure at 80℃: 0.0017 mmHg, molecular weight: 260.29, viscosity at 23℃: 38 mPa·s) is represented by the following formula:

[0184]

[0185] Na26MDA (OP: 2.71, boiling point: *℃, vapor pressure at 80℃: * mmHg, molecular weight: 296.32, viscosity at 23℃: 117 mPa·s) is represented by the following formula:

[0186]

[0187] TMD47 DA (OP: 3.38, boiling point: 365.4℃, vapor pressure at 80℃: 0.0035 mmHg, molecular weight: 334.4, viscosity at 23℃: 20 mPa·s) is expressed by the following formula:

[0188]

[0189] NDODA (OP: 3.91, boiling point: 322.2℃, vapor pressure at 80℃: 0.0174 mmHg, molecular weight: 268.35, viscosity at 23℃: 8 mPa·s) is represented by the following formula:

[0190]

[0191] DDODA (OP: 3.83, boiling point: 338.5℃, vapor pressure at 80℃: 0.00067 mmHg, molecular weight: 282.38, viscosity at 23℃: 9 mPa·s) is expressed by the following formula:

[0192]

[0193] DA1 (molecular weight: 258.27) is represented by the following formula:

[0194]

[0195] DA2 (molecular weight: 268.35) is expressed by the following formula:

[0196]

[0197] DA3 (molecular weight: 252.31) is expressed by the following formula:

[0198]

[0199] DA4 (molecular weight: 250.29) is represented by the following formula:

[0200]

[0201] DA5 (molecular weight: 262.31) is expressed by the following formula:

[0202]

[0203] DA6 (molecular weight: 252.31) is expressed by the following formula:

[0204]

[0205] DA7 (molecular weight: 252.31) is expressed by the following formula:

[0206]

[0207] DA8 (molecular weight: 252.31) is expressed by the following formula:

[0208]

[0209] DA9 (molecular weight: 304.39) is represented by the following formula:

[0210]

[0211] MA1 (molecular weight: 236.27) is expressed by the following formula:

[0212]

[0213] MA2 (molecular weight: 238.29) is expressed by the following formula:

[0214]

[0215] Compound (a-2): A polymeric compound containing Si atoms.

[0216] Component (a) may include a polymeric compound (a-2) containing at least one Si atom. When component (a) includes polymeric compound (a-2), the curable composition (A) preferably contains more than 10% by mass of Si atoms relative to the total mass of the curable composition (A) after removing the solvent (d).

[0217] Polymerizable compounds containing at least one Si atom (a-2) can be linear or branched. Examples include cyclic siloxane compounds represented by the following structures, wherein group Q has a polymerizable functional group, such as a free radical polymerizable functional group. Specific examples of free radical polymerizable functional groups include (meth)acryloyl, (meth)acrylamide, vinylbenzene, propylene ether, vinyl ether, and maleimide. Group Q having a polymerizable functional group can be any group having such a polymerizable functional group.

[0218]

[0219] Other examples of polymerizable compounds (a-2) include those having a silsesquioxane skeleton represented by the following chemical formula (I) or a silicone skeleton represented by the following chemical formula (II). In chemical formula (I), m+n=8 (8≥m≥1) holds true, and R1 is a divalent organic group. In chemical formula (II), A, B, R2, and R3 are each independently an alkyl, cycloalkyl, alkoxy, phenyl, and hydroxyl group having 1 to 6 carbon atoms, and t represents an integer from 1 to 3, and at least one of A and B is a polymerizable functional group.

[0220]

[0221]

[0222] The group Q having a polymerizable functional group, as well as the polymerizable functional groups represented by A and B, can be a free radical polymerizable functional group. Specific examples of such free radical polymerizable functional groups include: (meth)acryloyl, (meth)acrylamide, vinylbenzene, propylene ether, vinyl ether compounds, and maleimide. The group Q having a polymerizable functional group can be any group having such a polymerizable functional group.

[0223] Silicon-containing (meth)acrylic acid compounds contain at least one acryloyl group or methacryloyl group. Examples of silicon-containing monofunctional (meth)acrylic acid compounds having one acryloyl group or methacryloyl group include, but are not limited to, the following:

[0224] (2-Acryloylethoxy)trimethylsilane,

[0225] N-(3-Acryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane,

[0226] Acryloyloxymethyltrimethoxysilane,

[0227] (Acryloyloxymethyl)phenylethyltrimethylsilane,

[0228] Acryloyloxymethyltrimethylsilane,

[0229] (3-Acryloyloxypropyl)dimethylmethoxysilane,

[0230] (3-Acryloyloxypropyl)methylbis(trimethylsiloxy)silane,

[0231] (3-Acryloyloxypropyl)methyldichlorosilane,

[0232] (3-Acryloyloxypropyl)methyldiethoxysilane,

[0233] (3-Acryloyloxypropyl)methyldimethoxysilane,

[0234] (3-Acryloyloxypropyl)trichlorosilane,

[0235] (3-Acryloyloxypropyl)trimethoxysilane,

[0236] (3-Acryloyloxypropyl)tris(trimethylsiloxy)silane,

[0237] Acryloyloxytriisopropylsilane,

[0238] Acryloyloxytrimethylsilane,

[0239] Methacryloxymethyltrimethoxysilane,

[0240] o-(methacryloyloxyethoxy)carbamoylpropylmethyldimethoxysilane,

[0241] (methacryloyloxymethyl)bis(trimethylsiloxy)methylsilane,

[0242] N-(3-methacryloyl-2-hydroxypropyl)-3-aminopropyltriethoxysilane,

[0243] (methacryloyloxymethyl)methyldimethoxysilane,

[0244] (methacryloyloxymethyl)methyldiethoxysilane,

[0245] Methacryloxymethyltriethoxysilane,

[0246] Methacryloxypropyltrimethoxysilane,

[0247] Methacrylpropyltriisopropoxysilane,

[0248] o-(methacryloyloxyethyl)-N-(triethoxysilylpropyl)carbamate,

[0249] Methacryloxypropylmethyldimethoxysilane,

[0250] Methacryloxypropylmethyldiethoxysilane,

[0251] Methacryloxypropyl dimethylmethoxysilane,

[0252] Methacryloxypropyl dimethylethoxysilane,

[0253] (methacryloyloxymethyl)dimethylethoxysilane,

[0254] Methacryloxypropyltriethoxysilane,

[0255] Methacryloxypropyltriazine tricyclic methacryloyloxypropyltriazine

[0256] Methacryloxypentamethyldisiloxane,

[0257] (methacryloyloxymethyl)phenyldimethylsilane,

[0258] Methacryloxytrimethylsilane,

[0259] Methacryloxymethyltrimethylsilane,

[0260] (3-Methacryloxy-2-hydroxypropoxypropyl)methylbis(trimethylsiloxy)silane

[0261] Methacryloxypropylpentamethyldisiloxane,

[0262] o-(methacryloyloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propylcarbamate,

[0263] Methacryloxymethyltris(trimethylsiloxy)silane,

[0264] Methacryloxyethoxytrimethylsilane,

[0265] Methacryloxypropyltris(vinyldimethylsiloxy)silane,

[0266] Methacryloxypropyltris(trimethylsiloxy)silane,

[0267] 3-Methacryloxypropyltriacetoxysilane,

[0268] Methacryloxypropylmethyldichlorosilane,

[0269] Methacryloxypropyltrichlorosilane,

[0270] 3-Methacryloxypropylbis(trimethylsiloxy)methylsilane,

[0271] 3-Methacryloxypropyldimethylchlorosilane,

[0272] o-Methacryloyloxy (polyvinyloxy)trimethylsilane,

[0273] Poly(methacryloyloxypropyl)silsesquioxane, and

[0274] Methacryloxypropyl heptaisobutyl-T8-sesquioxane.

[0275] Examples of commercially available products containing such silicon-containing monofunctional (meth)acrylic acid compounds include, but are not limited to:

[0276] SIA0160.0, SIA0180.0, SIA0182.0, SIA0184.0, SIA0186.0, SIA0190.0, SIA0194.0, SIA0196.0, SIA0197.0, SIA0198.0, SIA0199.0, SIA0200.0, SIA0200.A1, SIA0210.0, SIA0315.0, SIA0320.0, SIM6483.0, SIM6487.5, SIM6480.76, SIM6481.2, SIM6486.1, SIM6481.1, SIM6481.46, SIM6481. 43. SIM6482.0, SIM6487.4, SIM6487.35, SIM6480.8, SIM6486.9, SIM6486.8, SIM6486.5, SIM6486 .4. SIM6481.3, SIM6487.3, SIM6487.1, SIM6487.6, SIM6486.14, SIM6481.48, SIM6481.5, SIM64 91.0, SIM6485.6, SIM6481.15, SIM6487.0, SIM6481.05, SIM6485.8, SIM6481.0, SIM6487.4LI, SI M6481.16, SIM6487.8, SIM6487.6HP, SIM6487.17, SIM6486.7, SIM6487.2, SIM6486.0, SIM6486.2, SIM6487.6-06, SIM6487.6-20, SIM6485.9, SST-R8C42, SLT-3R01, and SIM6486.65 (all manufactured by GELEST), and

[0277] TM-0701T, FM-0711, FM-0721 and FM-0725 (all manufactured by JNC).

[0278] Silicon-containing (meth)acrylamide compounds contain at least one acrylamide group or a methacrylamide group. Silicon-containing monofunctional (meth)acrylamide compounds having one acrylamide group or a methacrylamide group include, but are not limited to:

[0279] 3-Acrylamidopropyltrimethoxysilane and 3-Acrylamidopropyltris(trimethylsiloxy)silane.

[0280] Examples of commercially available products containing such silicon-containing monofunctional (meth)acrylamide compounds include, but are not limited to:

[0281] SIA0146.0 and SIA0150.0 (both manufactured by GELEST).

[0282] Examples of polyfunctional (meth)acrylic acid compounds having two or more acryloyl or methacryloyl groups include, but are not limited to:

[0283] A linear polydimethylsiloxane with both ends modified with acryloyloxypropyl groups.

[0284] A linear polydimethylsiloxane with both ends modified with methacryloxypropyl groups.

[0285] Cyclic siloxanes modified with multiple acryloyloxypropyl groups

[0286] Cyclic siloxanes modified with multiple methacryloyloxypropyl groups

[0287] Silsesquioxanes modified with multiple acryloyloxypropyl groups, and

[0288] Silsesquioxanes modified with multiple methacryloyloxypropyl groups.

[0289] Examples of commercially available products containing such silicon-containing polyfunctional (meth)acrylic acid compounds include, but are not limited to:

[0290] SIA0200.2, SIA0200.3, SIM6487.42, DMS-R11, DMS-R05, DMS-R22, DMS-R18 and DMS-R31 (all manufactured by GELEST);

[0291] FM-7711, FM-7721 and FM-7725 (all manufactured by JNC).

[0292] X-22-2445 (manufactured by Shin-Etsu Chemical), and

[0293] AC-SQ TA-100, MAC-SQ TM-100, AC-SQSI-20 and MAC-SQ SI-20 (all manufactured by Toagosei)

[0294] Furthermore, according to known literature, Ogawa et al.'s "Ultraviolet curable branched siloxanes as low-k dielectrics for imprint lithography", J. Vac. Sci. Technol. B 31(1), 011601, the following compounds can be synthesized or obtained:

[0295] A linear modified polydimethylsiloxane (MA-Si-12) with both ends modified with methacryloxypropyl groups.

[0296] An 8-membered siloxane (8-ring) modified with four methacryloyloxypropyl groups, and

[0297] A 10-membered siloxane (10-cyclo) modified with five methacryloyloxypropyl groups.

[0298] The proportion of component (a) in the curable composition (A) is preferably 40% to 99% by mass relative to the mass of the non-volatile component composition (A'). More preferably, the proportion of component (a) in the curable composition (A) is 50% to 95% by mass relative to the mass of the non-volatile component composition (A'), and even more preferably 60% to 90% by mass. When the proportion of component (a) is 40% by mass or more, the curable composition produces a cured film with high mechanical strength. Moreover, a proportion of component (a) of 99% by mass or less results in a high proportion of components (b), (c), and (e), thereby leading to a good high photopolymerization rate, etc. At least a portion of component (a) comprising one or more polymerizable compounds may be a polymer containing polymerizable functional groups. Preferably, the polymer contains at least a cyclic structure, such as an aromatic structure, an aromatic heterocyclic structure, or an alicyclic structure.

[0299] For example, the polymer preferably contains at least one of the structural units represented by the following structures (1) to (6):

[0300]

[0301] In structures (1) to (6), each R independently represents a substituent containing a local structure having an aromatic ring, and R 1 Represents a hydrogen atom or a methyl group. In the structural units represented by structures (1) to (6) used herein, the portion excluding R is the main chain of the specific polymer.

[0302] The chemical formula weight of the substituent R is preferably 80 or more, more preferably 100 or more, even more preferably 130 or more, and even more preferably 150 or more. The upper limit of the chemical formula weight of the substituent R is actually 500 or less.

[0303] Polymers containing polymerizable functional groups are typically compounds with a weight-average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. There is no upper limit for the weight-average molecular weight, but it is preferably, for example, 50,000 or less. When the weight-average molecular weight is at or above the lower limit mentioned above, the polymer has a boiling point of 250°C or higher, thereby improving the mechanical strength of the cured film. Furthermore, when the weight-average molecular weight is at or below the upper limit mentioned above, the polymer is very soluble in solvents and can maintain the fluidity of the droplets to be discretely applied, and the viscosity is not very high, thereby improving the surface flatness of the resulting liquid film. The weight-average molecular weight (Mw) mentioned herein is a value measured by gel permeation chromatography (GPC), unless otherwise specified.

[0304] Specific examples of polymerizable functional groups in polymers include (meth)acryloyl, epoxy, oxetane, hydroxymethyl, hydroxymethyl ether, and vinyl ether. From the viewpoint of ease of polymerization, (meth)acryloyl is particularly preferred.

[0305] When a polymer containing polymeric functional groups is added as at least a portion of component (a), the polymer can be added in any proportion in which the viscosity of the curable composition is within the range subsequently specified. For example, the amount of the polymer is preferably from 0.1% by mass to 60% by mass, more preferably from 1% by mass to 50% by mass, and even more preferably from 10% by mass to 40% by mass relative to the total mass of all components other than component (d). When the proportion of the polymer containing polymeric functional groups is 0.1% by mass or more, the curable composition can exhibit enhanced heat resistance, dry etching resistance, and mechanical strength, as well as reduced volatility. When the proportion of the polymer containing polymeric functional groups is 60% by mass or less, the curable composition can exhibit a viscosity within the range subsequently specified.

[0306] Component (b): Photopolymerization initiator

[0307] Component (b) is a photopolymerization initiator. As used herein, "photopolymerization initiator" is a compound that senses light of a specific wavelength and generates polymerization factors (free radicals). Specifically, a photopolymerization initiator is a polymerization initiator (free radical generator) that generates free radicals using light (infrared, visible, ultraviolet, far-ultraviolet, X-rays), charged particle radiation such as electron beams, or other radiation. Component (b) may be a single photopolymerization initiator or a combination of multiple photopolymerization initiators.

[0308] Examples of free radical generating agents include, but are not limited to, the following:

[0309] Substituted or unsubstituted 2,4,5-triarylimidazolium dimers, such as 2-(o-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, and 2-(o- or p-methoxyphenyl)-4,5-diphenylimidazolium dimer; benzophenone and benzophenone derivatives, such as N,N'-tetramethyl-4,4'-diaminobenzophenone (benzophenone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, etc. Benzene and 4,4'-diaminobenzophenone; α-amino aromatic ketone derivatives, such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)but-1-one and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylprop-1-one; quinones, such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone and 2,3-dimethylanthraquinone; benzoin ether derivatives, such as benzoin methyl ether and benzoin Diethyl ether and benzoin phenyl ether; benzoin and benzoin derivatives, such as methyl benzoin, ethyl benzoin and propyl benzoin; benzyl derivatives, such as benzyl dimethyl ketal; acridine derivatives, such as 9-phenyl acridine and 1,7-bis(9,9'-acridyl)heptane; N-phenylglycine and N-phenylglycine derivatives; acetophenone and acetophenone derivatives, such as 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl ketone and 2,2-dimethoxy-2-phenylacetophenone; thioxanthone and thioxanthone derivatives, such as diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; acylphosphine oxide derivatives, such as 2,4,6-trimethylbenzyl benzoin Acyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; oxime ester derivatives, such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(ortho-benzoyl oxime)], and acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(ortho-acetyl oxime); and xanthonesone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1-(4-isopropylphenyl)-2-hydroxy-2-methylprop-1-one and 2-hydroxy-2-methyl-1-phenylprop-1-one.

[0310] Examples of commercially available products of this type of free radical generating agent include, but are not limited to:

[0311] Irgacure series 184, 369, 651, 500, 819, 907, 784 and 2959, CGI-1700, -1750 and -1850, CG24-61, Darocur series l116 and 1173, and Lucirin (registered trademark) series TPO, LR 8893 and LR 8970 (all manufactured by BASF); and Ubecryl P36 (manufactured by UCB).

[0312] Among these free radical generating agents, component (b) is preferably an acylphosphine oxide-based photopolymerization initiator. The acylphosphine oxide-based photopolymerization initiators among the above free radical generating agents include:

[0313] 2,4,6-Trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0314] The proportion of component (b) in the curable composition (A) relative to the non-volatile component composition (A') is preferably from 0.1% to 50% by mass. More preferably, the proportion of component (b) in the curable composition (A) relative to the non-volatile component composition (A') is from 0.1% to 20% by mass, and even more preferably from 1% to 20% by mass. When the proportion of component (b) is 0.1% by mass or more, the curable composition can cure at high speed, thus improving the reaction efficiency. When the proportion of component (b) is 50% by mass or less, the curable composition can form a cured film with a certain mechanical strength.

[0315] Component (c): Surfactant

[0316] Component (c) is a surfactant. As used herein, the term "surfactant" refers to a compound that reduces the interfacial bond strength between the mold and the curable composition, i.e., reduces the release force during the release step described subsequently. Suitable surfactants include silicone surfactants, fluorinated surfactants, and hydrocarbon surfactants. Component (c) may be a single surfactant or a mixture of two or more surfactants.

[0317] Examples of fluorinated surfactants include:

[0318] Polyalkylene oxide adducts of alcohols having perfluoroalkyl groups (such as ethylene oxide or propylene oxide) and polyalkylene oxide adducts of perfluoropolyethers (such as ethylene oxide or propylene oxide).

[0319] Fluorinated surfactants can have hydroxyl, alkoxy, alkyl, amino, or thiol groups in a portion of their molecular structure (e.g., as end groups). One example is pentadecyl glycol mono-1H,1H,2H,2H-perfluorooctyl ether.

[0320] Fluorinated surfactants can be commercially available products. Examples of commercially available fluorinated surfactants include:

[0321] Megafac (registered trademark) series F-444, TF-2066, TF-2067, TF-2068, and DEO-15 (abbreviation) (all manufactured by DIC); Fluorad series FC-430 and FC-431 (all manufactured by Sumitomo 3M); Surflon (registered trademark) S-382 (manufactured by AGC); EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, and MF-100 (all manufactured by Tochem Products); PF-636, PF-6320, PF-656, and PF-6520 (all manufactured by OMNOVA Solutions); Unidyne (registered trademark) series DS-401, DS-403, and DS-451 (all manufactured by Daikin). (Manufactured by Industries); and Ftergent (registered trademark) series 250, 251, 222F and 208G (all manufactured by Neos).

[0322] Component (c) may be a hydrocarbon surfactant. The hydrocarbon surfactant may be an alkyl alcohol-polyalkylene oxide adduct produced by adding an alkyl alcohol having 1 to 50 carbon atoms.

[0323] Examples of alkyl alcohol-polyepoxyalkane adducts include:

[0324] 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.

[0325] The terminal groups of alkyl alcohol-polyepoxyalkane adducts are not limited to simple hydroxyl groups produced by adding polyepoxyalkane to alkyl alcohols. The terminal hydroxyl groups can also be substituted with polar functional groups, such as carboxyl, amino, pyridyl, thiol, or silanol groups, or with hydrophobic functional groups such as alkyl or alkoxy groups.

[0326] Examples of polyepoxides include:

[0327] Polyethylene glycol and polypropylene glycol; their monomethyl ethers or dimethyl ethers, monooctyl ethers or dioctyl ethers, monononyl ethers or dinonyl ethers, monodecyl ethers or didecyl ethers; monoadipate esters, monooleate esters, monostearate esters and monosuccinate esters.

[0328] Commercially available alkyl alcohol polyepoxyalkane adducts can be used. Examples of commercially available alkyl alcohol polyepoxyalkane adducts include:

[0329] Polyoxyethylene methyl ether (methanol ethylene oxide adduct) BLAUNON series MP-400, MP-550 and MP-1000, manufactured by Aoki Oil Industrial; polyoxyethylene decyl ether (decanol ethylene oxide adduct) FINESURF series D-1303, D-1305, D-1307 and D-1310, manufactured by Aoki Oil Industrial; polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) BLAUNON EL-1505, manufactured by Aoki Oil Industrial; polyoxyethylene hexadecyl ether (cetyl alcohol ethylene oxide adduct) BLAUNON series CH-305 and CH-310, manufactured by Aoki Oil Industrial. Industrial manufactured; BLAUNON series polyoxyethylene stearyl ethers (stearyl ethylene oxide adducts) SR-705, SR-707, SR-715, SR-720, SR-730 and SR-750, manufactured by Aoki Oil Industrial; BLAUNON series random copolymer polyoxyethylene polyoxypropylene alkyl ethers SA-50 / 50 1000R and SA-30 / 70 2000R, WONDERSURF 140 and FINESURF TDP-0633K, manufactured by Aoki Oil Industrial. Industrial manufactured; Pluriol (registered trademark) A760E, manufactured by BASF; EMULGEN series of polyoxyethylene alkyl ethers, manufactured by Kao; PLURONIC (registered trademark) series of polyoxyethylene-polyoxypropylene block polymers L-44, L-43, L-42, L-31, 17R2 and 25R1, manufactured by ADEKA; Briji S10, manufactured by DOW; BLAUNON series of polyoxyethylene alkyl ethers EN-1504, EL-1502.2P and EN-902 are manufactured by Aoki Oil Industrial; TERGITOL series EH-9, EH-6, and EH-3 of polyoxypropylene polyoxyethylene 2-ethylhexyl ether are manufactured by DOW; BLAUNON series of polyoxyethylene 2-ethylhexyl ether EH-2 and EH-4 are manufactured by Aoki Oil Industrial; TERGITOL series HW-1000 and TMN-3 of polyethylene glycol trimethyl nonyl ether are manufactured by DOW; TRITON (registered trademark) series of polyoxyethylene tert-octylphenyl ether X-15 and X-45 are manufactured by DOW; Dynol-604 of ethoxylated acetylenol is manufactured by Evonik; E100 and E13T of the Acetylenol series are manufactured by Kawaken Fine Chemical; and SE and 420 of the Surfynol series are manufactured by Nissin Chemical Industry.

[0330] Commercially available polyalkylene oxides can be used, and for example, ethylene oxide-propylene oxide copolymer Pluronic PE 6400 manufactured by BASF can be used.

[0331] Examples of silicone surfactants include: SI-10 series (trade name, manufactured by Takemoto Oil & Fat), Megafac Paintad 31 (manufactured by DIC), and KP-341 (manufactured by Shin-Etsu Chemical).

[0332] Surfactants can contain fluorine and silicon atoms. Examples of surfactants containing fluorine and silicon atoms include:

[0333] X-70-090, X-70-091, X-70-092 and X-70-093 (all trade names, manufactured by Shin-Etsu Chemical); and Megafac series (trade names) R-08 and XRB-4 (both manufactured by DIC).

[0334] Through their in-depth research, the inventors discovered that, as described later, the segregation of component (c) at the edges of the liquid film of the curable composition (A) increases the liquid film viscosity, particularly at the edges, thereby reducing the edge-filling rate. Therefore, in this disclosure, the viscosity of component (c) or the surfactant at 23°C and 1 atm is preferably 500 mPa·s or less, more preferably 400 mPa·s or less, and even more preferably 300 mPa·s or less. Reference Figure 3At the interface 111 between the liquid film and the atmospheric gas, the surfactant increases the viscosity, and the surfactant or component (c) is segregated. If the viscosity of the surfactant or component (c) is higher than 500 mPa·s, the fluidity of the liquid at interface 111 is relatively reduced. Therefore, when the non-volatile component composition (A') after the solvent or component (d) has evaporated comes into contact with the mold, the edge filling speed is low. Therefore, high-volume embossing processes can be achieved using the curable composition (A) disclosed herein containing a surfactant or component (c) with a viscosity of less than 500 mPa·s.

[0335] Examples of surfactants that can be used as component (c) with a viscosity of 500 mPa·s or less at 23°C and 1 atm include PLURONIC L-44 (435.4 mPa·s) and PLURONIC 17R2 (407.1 mPa·s), both manufactured by ADEKA; WONDERSURF 140 (146.6 mPa·s), BLAUNON SA-50 / 50 1000R (114.6 mPa·s) and BLAUNON SA-30 / 70 2000R (217.0 mPa·s), both manufactured by Aoki Oil Industrial; TERGITOL EH-9 (101.8 mPa·s), TERGITOL HW-1000 (41.2 mPa·s), TERGITOL TMN-3 (22.4 mPa·s), and TRITON (registered trademark) X-45 (374.0 mPa·s). The following are the main components of the drug: Dynol-604 (340.45 mPa·s), manufactured by Dow; Acetylenol E100 (171.3 mPa·s), manufactured by Kawaken Fine Chemical; Surfynol 420 (295.6 mPa·s), manufactured by Nissin Chemical Industry; and Acetylenol E13T (295.6 mPa·s), manufactured by Kawaken Fine Chemical.

[0336] The proportion of component (c) in the curable composition (A) is preferably from 0.01% to 10% by mass relative to the mass of the non-volatile component composition (A'). More preferably, the proportion of component (c) in the curable composition (A) is from 0.1% to 5% by mass relative to the mass of the non-volatile component composition (A'), and even more preferably from 0.5% to 3% by mass. Component (c) in a proportion of 0.01% by mass or more reduces the interfacial bonding strength between the curable composition and the mold, thus reducing the release force in the demolding step described later. Furthermore, when the proportion of component (c) is 10% by mass or less, the curable composition can form a cured film with a certain degree of mechanical strength.

[0337] Component (e): Non-polymeric compound

[0338] In addition to components (a), (b), and (c), the curable composition (A) disclosed herein may, depending on the purpose, contain a non-polymerizable compound as component (e) to the extent that the beneficial effects contemplated in this disclosure are not impaired. Such component (e) may be a compound that does not have a polymerizable functional group such as (meth)acryloyl and cannot sense light of a specific wavelength to generate the aforementioned polymerization factor (free radical). Examples of non-polymerizable compounds include sensitizers, hydrogen donors, antioxidants, polymer components, and other additives. Component (e) may include a variety of such compounds.

[0339] Sensitizers are compounds that are optionally added to promote polymerization or improve reaction conversion. These sensitizers can be single compounds or mixtures of two or more compounds.

[0340] Sensitizers can be sensitizing dyes, etc. Sensitizing dyes are compounds that absorb light of a specific wavelength, are excited, and interact with a photopolymerization initiator as component (b).

[0341] This interaction involves energy or electron transfer from the excited sensitized dye to the photopolymerization initiator, which is component (b). Specific examples of the sensitized dye include, but are not limited to:

[0342] Anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanone derivatives, xanthonone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiaranonium salt dyes, cyanine dyes, quinoline dyes, styrylquinoline dyes, ketocumarin dyes, thioxanone dyes, xanthonone dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyranonium salt dyes.

[0343] The hydrogen donor is a compound that can react with the initiator radical or chain-terminal radical generated by the photopolymerization initiator as component (b) to produce a more reactive radical. When the photopolymerization initiator serving as component (b) is a photoradical generator, the addition of a hydrogen donor is preferred.

[0344] Specific examples of hydrogen donors include, but are not limited to:

[0345] Amine compounds, such as n-butylamine, di-n-butylamine, tri-n-butylphosphine, allyl thiourea, s-benzyl isothiourea-p-toluenesulfonate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis(dialkylamino)benzophenone, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl 4-(dimethylamino)benzoate, triethanolamine, and N-phenylglycine; and thiol compounds, such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

[0346] The hydrogen donor to be used can be a single compound or a mixture of two or more compounds.

[0347] Hydrogen donors can function as sensitizers.

[0348] The proportion of component (e) in the curable composition (A) is preferably from 0.01% by weight to 50% by weight relative to the mass of the non-volatile component composition (A'). More preferably, the proportion of component (e) in the curable composition (A) is from 0.01% by weight to 20% by weight relative to the mass of the non-volatile component composition (A'). When the proportion of component (e) is less than 50% by weight, the curable composition can form a cured film with a certain degree of mechanical strength.

[0349] Component (d): Solvent

[0350] The curable composition (A) disclosed herein may contain a solvent as component (d) having a boiling point of 100°C to less than 250°C at atmospheric pressure. Component (d) may be a solvent capable of dissolving components (a), (b), (c), and (e), and examples include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. Such solvents as component (d) may be used alone or in combination. The boiling point of component (d) at atmospheric pressure is preferably 100°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher. The boiling point of component (d) at atmospheric pressure is 250°C or lower, preferably less than 200°C. When the boiling point of component (d) at atmospheric pressure is less than 100°C, the evaporation rate in the waiting step described later may be so high that component (d) evaporates before the droplets of the curable composition (A) coalesce. Therefore, the droplets of the curable composition (A) cannot coalesce. Furthermore, when component (d) has a boiling point above 250°C at atmospheric pressure, the solvent (component (d)) may not evaporate sufficiently and thus remain in the cured product of the curable composition (A). In the case where component (d) consists of two or more solvents, the boiling point of each solvent at atmospheric pressure is preferably from 100°C to less than 250°C (e.g., from 100°C to less than 200°C).

[0351] Examples of alcohol-based solvents include:

[0352] 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-dimethylhept-4-ol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanool. Heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, and cresol; and polyol solvents such as ethylene glycol, 1,2-propanediol, 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.

[0353] Examples of ketone solvents include:

[0354] Acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2,4-pentanedione, acetone-acetone, diacetone alcohol, acetophenone, and finchone.

[0355] Examples of ether-based solvents include:

[0356] Diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, 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... 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.

[0357] Examples of ester-based solvents include:

[0358] Diethyl carbonate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate Diethylene glycol monoethyl 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, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0359] Examples of nitrogen-containing solvents include:

[0360] N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone.

[0361] Among the solvents mentioned above, ether-based or ester-based solvents are preferred. From the viewpoint of easy film formation, ether-based and ester-based solvents having a diol structure are more preferred.

[0362] Examples of such preferred solvents include:

[0363] 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.

[0364] A particularly preferred option is propylene glycol monomethyl ether acetate. (Ethyl)isocyanurate di(meth)acrylate may also be used.

[0365] Preferably, the solvent used herein has at least one of an ester structure, a ketone structure, a hydroxyl group, and an ether structure. More specifically, the solvent is one or a mixture selected from propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether, cyclohexanone, 2-heptanone, γ-butyrolactone, and ethyl lactate.

[0366] In one embodiment, the solvent or component (d) may be a polymeric compound with a boiling point of 80°C to less than 250°C at atmospheric pressure. Examples of polymeric compounds with a boiling point of 80°C to less than 250°C at atmospheric pressure include:

[0367] Cyclohexyl acrylate (boiling point 198℃), benzyl acrylate (boiling point 229℃), isobornyl acrylate (boiling point 245℃), tetrahydrofurfuryl acrylate (boiling point 202℃), trimethylcyclohexyl acrylate (boiling point 232℃), isooctyl acrylate (boiling point 217℃), n-octyl acrylate (boiling point 228℃), ethoxyethoxyethyl acrylate (boiling point 230℃), divinylbenzene (boiling point 193℃), 1,3-diisopropenylbenzene (boiling point 218℃), styrene (boiling point 145℃), and α-methylstyrene (boiling point 165℃).

[0368] In embodiments of this disclosure, the amount of component (d) or solvent is greater than 5% by volume and less than 95% by volume relative to 100% volume of the curable composition (A), preferably from 15% to 85% by volume, more preferably from 40% to 80% by volume. For example, the amount of solvent (component (d)) is from 40% to 85% by volume. If the amount of solvent (component (d)) is less than 5% by volume, a thin film cannot be obtained after solvent evaporation, even if a substantially continuous liquid film of the curable composition is formed. If the amount of solvent (component (d)) is greater than 95% by volume, even the most densely dripped droplets by inkjet printing cannot form a thick film after solvent evaporation.

[0369] Temperature used to prepare the curable composition

[0370] To prepare the curable composition (A) disclosed herein, at least components (a), (b), (c), and (d) are mixed and dissolved at a specific temperature. Specifically, the specific temperature is from 0°C to 100°C. This also applies when the curable composition (A) contains component (e).

[0371] Viscosity of curable composition

[0372] The curable composition (A) disclosed herein is a liquid. This is because, in the application step described later, the curable composition (A) is discretely dripped onto the substrate in droplet form by an inkjet method. The curable composition (A) disclosed herein has a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm, preferably 2 mPa·s to 30 mPa·s, and more preferably 5 mPa·s to 15 mPa·s. If the viscosity of the curable composition (A) is less than 2 mPa·s, it is unstable to spray droplets by inkjet method. Furthermore, curable compositions (A) with a viscosity of 60 mPa·s or higher cannot form droplets with a volume of about 1.0 pL to 3.0 pL, which is desirable in the embodiments of this disclosure.

[0373] Through their in-depth research, the inventors have discovered that the viscosity of the non-volatile component composition (A') dominates the edge-filling speed. In embodiments of this disclosure, the viscosity of the non-volatile component composition (A') at 23°C and 1 atm is preferably from 8 mPa·s to 70 mPa·s. More preferably, the viscosity of the non-volatile component composition (A') at 23°C and 1 atm is preferably from 8 mPa·s to 30 mPa·s, and even more preferably from 8 mPa·s to 20 mPa·s. If the viscosity is greater than 70 mPa·s, the edge-filling speed is lower when the non-volatile component composition (A') comes into contact with the mold. Therefore, high-volume stamping processes can be achieved using the curable composition (A) disclosed herein, in which the viscosity of the non-volatile component composition (A') is controlled to be below 70 mPa·s.

[0374] Surface tension of curing compositions

[0375] In embodiments of this disclosure, the surface tension of the non-volatile component composition (A') at 23°C and 1 atm is preferably from 5 mN / m to 70 mN / m. The non-volatile component composition (A') is a curable composition that does not contain a solvent (component (d)) and preferably has a surface tension of 7 mN / m to 50 mN / m, more preferably from 10 mN / m to 40 mN / m, at 23°C and 1 atm. Higher surface tensions, such as 5 mN / m or greater, result in stronger capillary forces. Therefore, when the non-volatile component composition (A') comes into contact with the mold, the filling step of the composition (which includes spreading and filling) is completed in a short time. Furthermore, a surface tension below 70 mN / m allows the curable composition to form a cured film with a smooth surface through curing.

[0376] Contact angle of the curable composition

[0377] In embodiments of this disclosure, the contact angle of the curable composition (A) on the substrate surface is preferably 0° to 90°. If the contact angle is greater than 90°, the droplets on the substrate cannot contact each other to form a continuous liquid film.

[0378] In embodiments of this disclosure, the contact angle of the non-volatile component composition (A') on the substrate surface and the mold surface (contact surfaces) is preferably 0° to 90°. When the contact angle exceeds 90°, capillary forces act in the negative direction within the mold pattern and in the gap between the substrate and the mold (i.e., the direction that causes shrinkage at the interface between the mold and the curable composition). This may hinder the filling of the mold by the non-volatile component composition (A'). The smaller the contact angle, the stronger the capillary force, which increases the filling speed.

[0379] Impurities in curable compositions

[0380] Ideally, impurities in the cured composition (A) disclosed herein should be minimized. Impurities, as referred to herein, are components other than (a), (b), (c), (d), and (e). Therefore, the cured composition (A) disclosed herein is obtained through a purification step. The purification step is preferably performed by filtration or the like.

[0381] Preferably, filtration is performed by passing a mixture of components (a), (b), (c), and (e) through a filter with a pore size of, for example, 0.001 μm to 5.0 μm. Preferably, filtration using the filter is performed in multiple steps or repeated multiple times (circular filtration). The filtrate can be filtered again using the same filter or several filters with different pore sizes. The filter can be made of polyethylene, polypropylene, fluoropolymer, or nylon, but is not limited to these materials. Such a purification step removes impurities, such as particulate matter, from the curable composition. Therefore, unintended defects caused by unevenness in the cured film due to impurities in the curable composition can be prevented.

[0382] When the curable compositions disclosed herein are used in the manufacture of semiconductor integrated circuits, it is desirable to minimize contamination of the curable compositions by impurities containing metal atoms (metal impurities) to prevent interference with product operation. The concentration of metal impurities in the curable compositions is preferably below 10 ppm, and more preferably below 100 ppb.

[0383] Glass transition temperature of curable compositions

[0384] When the curable composition has a glass transition temperature much higher than the demolding temperature, the cured product is in a tough glassy state upon release from the mold, and therefore exhibits high mechanical strength, making it less prone to pattern collapse or breakage due to demolding. Therefore, for a demolding step at room temperature, the glass transition temperature of the cured product of the non-volatile component composition (A') is preferably 70°C or higher, more preferably 100°C or higher, and even more preferably 150°C or higher.

[0385] The glass transition temperature of cured products (photocured products) can be measured using differential scanning calorimetry (DSC) or a dynamic viscoelasticity meter. For example, the case of measuring the glass transition temperature by DSC will be described. In this case, a tangent is drawn at the point where the slope of the curve reaches its maximum during the stepwise change in the glass transition region, obtained by extending the baseline of the DSC curve of the cured product on the low-temperature side (the portion of the DSC curve where no phase transition or reaction has occurred in the sample) towards the high-temperature side. The intersection of the straight line and the tangent is then used to obtain the extrapolated glass transition onset temperature (Tig), which is defined as the glass transition temperature. For example, the STA-6000 (manufactured by Perkin Eimer) is one of the main measuring devices. In another case, when measuring the glass transition temperature using a dynamic viscoelasticity meter, the temperature at which the loss tangent (tanδ) of the cured product reaches its maximum value is defined as the glass transition temperature. The device used to measure dynamic viscoelasticity can be, for example, the MCR301 (manufactured by Anton Paar).

[0386] substrate

[0387] In the description of this disclosure, the part on which droplets of the curable composition (A) are discretely dropped is referred to as a substrate.

[0388] The substrate is the substrate to be processed, and is typically a silicon wafer. The substrate may have a layer to be processed on its surface. The substrate may include other layers beneath the layer to be processed. Using quartz as a substrate makes it possible to manufacture a replica of the embossing mold (replica mold). However, the substrate is not limited to silicon wafers or quartz substrates. The substrate can be arbitrarily selected from materials known as substrates for semiconductor devices, such as aluminum, titanium-tungsten alloys, aluminum-silicon alloys, aluminum-copper-silicon alloys, silicon oxide, and silicon nitride. Preferably, the surface of the substrate or the layer to be processed is surface-processed by silane coupling treatment, silazane treatment, or deposition of an organic thin film to increase adhesion to the curable composition (A). For example, the adhesive layer disclosed in PCT Japanese Patent Publication No. 2009-503139 is an example of an organic thin film deposited as a surface treatment.

[0389] Pattern Formation Method

[0390] Now refer to the appendix Figures 1A to 1G The present disclosure describes a method for forming patterns. The cured film formed in this disclosure preferably has a pattern with a size of 1 nm to 10 mm, more preferably a pattern with a size of 10 nm to 100 μm. The technique of using light to form nanoscale (1 nm to 100 nm) patterns (undulating structures) is commonly referred to as nanoimprinting. The film formation method used herein utilizes photoimprinting to form a film of a curable composition in the gap between a mold and a substrate. Alternatively, the curable composition can be cured using other energies, such as heat or electromagnetic waves. The film formation method described herein can be used as a pattern forming method for forming patterned films or as a planarization film forming method for forming films without patterns (e.g., planarization films).

[0391] An example of applying the film formation method described herein to a pattern formation method will now be described. The pattern formation method includes, for example, a formation step, an application step, a waiting step, a contact step, a curing step, and a demolding step. In the formation step, a priming layer is formed. In the application step, droplets of a curable composition (A) are discretely applied onto the priming layer. The waiting step is a sustained period during which the droplets of the curable composition (A) coalesce and the solvent (component (d)) evaporates. In the contact step, the curable composition (A) is brought into contact with a mold. In the curing step, the curable composition (A) is cured. In the demolding step, the cured film of the curable composition (A) is separated from the mold. The application step is performed after the formation step. The waiting step follows the application step. The contact step is performed after the waiting step. The curing step is performed after the contact step. The demolding step is performed after the curing step.

[0392] Application Steps

[0393] In the application step, droplets 102 of the curable composition (A) are discretely applied onto the substrate 101, such as... Figure 1A Schematic illustration. In this step, at a rate of 80 droplets / mm. 2 The above-mentioned density of droplets 102 of the curable composition (A) each has a volume of 1.0 pL or more. A base coating can be deposited on the substrate 101. The substrate 101 can be surface-treated by silane coupling treatment, silazane treatment, or deposition of an organic thin film to increase adhesion to the curable composition (A).

[0394] For applying droplets 102 of the curable composition (A) onto the substrate, an inkjet method is particularly preferred. Preferably, droplets 102 of the curable composition (A) are densely applied over a region of the substrate 101 opposite to the region of the dies 106 with densely arranged patterned recesses. Conversely, droplets 102 are sparsely applied over a region of the substrate 101 opposite to the region of the dies 106 with sparsely arranged patterned recesses. As a result, the film (residual film) of the curable composition (A), described later, formed on the substrate 101 is controlled to have a uniform thickness, regardless of the pattern density of the dies 106.

[0395] To specify the volume of the non-volatile component composition (A') to be applied, an indicator and an average liquid film thickness are defined. The average liquid film thickness is a quotient obtained by dividing the volume of the non-volatile component composition (A') applied in the application step by the area of ​​the film-forming region of the mold. The volume of the non-volatile component composition (A') is the sum of the droplet volumes of the cured composition (A) after the solvent (component (d)) has evaporated. This definition allows for the specification of the average liquid film thickness regardless of any unevenness on the substrate surface. The average liquid film thickness can be interpreted as a quotient obtained by dividing the volume of the remaining non-volatile component composition (A') after the waiting step by the area of ​​the film-forming region, and is preferably from 5 nm to 170 nm.

[0396] Waiting steps

[0397] In this disclosure, the waiting step occurs after the application step and before the contact step. The average initial liquid film thickness is then defined as a quotient obtained by dividing the total volume of droplets of the curable composition (A) dropped in a single patterning operation by the total area of ​​the region patterned (patterning region) formed by the single patterning operation. During the waiting step, droplets 102 of the curable composition (A) spread over the substrate 101, as... Figure 1B As shown schematically, the curable composition (A) covers the entire patterned area of ​​the substrate 101.

[0398] Now refer to Figures 2A to 2D This describes the behavior of droplets of curable composition (A) applied to a substrate during a waiting step. Droplets 102 of curable composition (A) are discretely applied to substrate 101, as follows: Figure 2A As shown, and gradually spread on the substrate, as Figure 2B As shown. Then, droplets of the curable composition (A) on the substrate begin to coalesce to form as shown. Figure 2C The liquid film shown forms a continuous liquid film (covering the surface of substrate 101 without leaving any exposed surface), such as... Figure 2D As shown. Figure 2D The state of the curable composition (A) described herein is referred to as a “substantially continuous liquid film”.

[0399] Furthermore, during the waiting step, the solvent 105 (component (d)) in the liquid film 104 evaporates, such as Figure 1D As illustrated schematically. When the total volume of the components excluding solvent (component (d)) is considered 100% by volume, the amount of solvent (component (d)) remaining in the liquid film 103 after the waiting step is preferably controlled to be less than 10% by volume. If more than 10% by volume of solvent (component (d)) remains, the mechanical properties of the resulting cured film will decrease.

[0400] During the waiting step, to accelerate the evaporation of the solvent (component (d)), a baking step can be performed by heating the substrate 101 and the curable composition (A), or the atmosphere around the substrate 101 can be ventilated. This heating can be performed, for example, at temperatures ranging from 30°C to 200°C, preferably from 80°C to 150°C, and particularly from 90°C to 110°C. The heating time can be from 10 seconds to 600 seconds. The baking step can be performed using a heating device, such as a hot plate or an oven.

[0401] The duration of the waiting step is, for example, from 0.1 seconds to 600 seconds, preferably from 10 seconds to 300 seconds. If the duration of the waiting step is less than 0.1 seconds, the droplets of the curable composition (A) cannot coalesce sufficiently, and a substantially continuous liquid film cannot be formed. Conversely, a waiting step duration exceeding 600 seconds reduces productivity. Therefore, to reduce the reduction in productivity, substrates can be sequentially transferred to the waiting step after the application step is completed, allowing multiple substrates to undergo the waiting step in parallel, and then sequentially transferred to the contact step after the waiting step is completed. In the known art, theoretically, thousands to tens of thousands of seconds are required to form a substantially continuous liquid film. However, in practice, evaporation affects the spread of droplets in the curable composition, thus preventing the formation of a continuous liquid film.

[0402] During the waiting step, as the solvent (component (d)) evaporates, a substantially continuous liquid film 104 of the non-volatile component composition (A') consisting of components (a), (b), (c), and (e) remains. The average thickness of the substantially continuous liquid film 104 after the solvent (component (d)) has evaporated (removed) is less than the average thickness of the liquid film 103 by the amount of evaporated solvent (component (d)). The patterned area of ​​the substrate 101 remains completely coated by the substantially continuous liquid film 104 of the curable composition (A), from which the solvent (component (d)) is removed.

[0403] Contact Steps

[0404] In the curing step, a substantially continuous liquid film 104 (i.e., the non-volatile component composition (A') from which the solvent (component (d)) has been removed) of the curable composition (A) is brought into contact with the mold 106, such as... Figure 1E As schematically shown. The contact step includes the following sub-steps: a sub-step of changing the state of the non-volatile component composition (A') and the mold 106 from a state of non-contact to a state of contact, and a sub-step of maintaining their contact state. Through these sub-steps, the liquid of the non-volatile component composition (A') fills the recesses of the fine patterns in the surface of the mold 106, thereby forming a liquid film that fills the fine patterns of the mold 106.

[0405] In this disclosure, during the waiting step, the curable composition (A) forms a substantially continuous liquid film 104 of the non-volatile component composition (A'), from which the solvent (component (d)) has been removed, thus reducing the volume of gas trapped between the mold 106 and the substrate 101. Therefore, the spreading of the non-volatile component composition (A') is rapidly completed during the contact step.

[0406] Rapidly completing the spreading and filling of the non-volatile component composition (A') in the contact step reduces the duration for which the mold 106 remains in contact with the non-volatile component composition (A') (the time required for the contact step). Reducing the time required for the contact step results in a reduction in the time required for pattern formation (film formation), thereby increasing productivity. Preferably, the duration of the contact step is from 0.1 seconds to 3 seconds, particularly from 0.1 seconds to 1 second. Contact steps shorter than 0.1 seconds result in insufficient spreading and filling, leading to a tendency for defects known as incomplete filling to frequently occur.

[0407] According to this disclosure, the duration (time required for the contact step) during which the mold 106 remains in contact with the non-volatile component composition (A') can be reduced. Reducing the time required for the contact step results in a reduction in the time required for pattern formation (film formation), thereby increasing productivity (yield). Preferably, the duration of the contact step is from 0.1 seconds to 3 seconds, particularly from 0.1 seconds to 1 second. Contact steps shorter than 0.1 seconds result in insufficient edge filling, leading to a tendency for defects known as incomplete edge filling to frequently occur. Therefore, high-productivity (high-yield) embossing processes can be achieved using the non-volatile component composition (A) disclosed herein.

[0408] When the curing step includes a sub-step of light irradiation, the mold 106 is made of an optically transparent material, taking into account this irradiation sub-step. Examples of materials for the mold 106 include glass, quartz, optically transparent resins (such as polymethyl methacrylate (PMMA) and polycarbonate), transparent metal films formed by vapor deposition, soft films such as polydimethylsiloxane, photocurable films, and metal films. When an optically transparent resin is used as the material for the mold 106, a resin that is insoluble in any component of the curable composition (A) is selected. Quartz is suitable as a material for the mold 106 because it has a small coefficient of thermal expansion, thereby minimizing pattern distortion.

[0409] The pattern formed in the surface of mold 106 has a height of, for example, 4 nm to 200 nm. The smaller the height of the pattern in mold 106, the less force is required to separate mold 106 from the cured film of the curable composition during the demolding step, i.e., the smaller the demolding force. This reduces the number of demolding defects where the pattern of the curable composition is torn off and left in mold 106. Furthermore, the effect of separating the mold can cause elastic deformation of the pattern of the curable composition, which may cause adjacent pattern elements to come into contact with each other, resulting in adhesion or damage. However, to avoid these problems, it is advantageous that the height of the pattern elements is less than twice the width of the pattern elements (an aspect ratio of less than 2). In addition, excessively small pattern element heights lead to a reduction in the processing accuracy of substrate 101.

[0410] The mold 106 may undergo a surface treatment prior to the contact step to improve its release from the curable composition (A). For the surface treatment, a release agent may be applied to the surface of the mold 106 to form a release agent layer. Examples of release agents to be applied to the surface of the mold 106 include: silicone-based release agents, fluorinated release agents, hydrocarbon release agents, polyethylene-based release agents, polypropylene-based release agents, paraffin release agents, montan wax release agents, and carnauba wax release agents. Commercially available coating release agents, such as Optool (registered trademark) DSX manufactured by Daikin Industries, may be suitable. A single release agent may be used, or two or more release agents may be used in combination. Fluorinated release agents and hydrocarbon release agents are particularly preferred.

[0411] During the contact step, when the mold 106 comes into contact with the non-volatile component composition (A'), the pressure applied to the curable composition (A) is, for example, but not limited to, 0 MPa to 100 MPa. Preferably, the pressure applied to the curable composition (A) to contact the mold 106 with the non-volatile component composition (A') is 0 MPa to 50 MPa, more preferably 0 MPa to 30 MPa, and particularly 0 MPa to 20 MPa.

[0412] While the contact step can be performed in any atmosphere, including air, reduced pressure, and inert gas, a reduced pressure or inert gas atmosphere is preferred. Such an atmosphere prevents oxygen or moisture from affecting the curing reaction. Examples of inert gases that can be used in the contact step include nitrogen, carbon dioxide, helium, argon, chlorofluorocarbons (CFCs), and mixtures of these gases. Gases containing 10 mol% carbon dioxide or helium are preferred, particularly those containing 10 wt% carbon dioxide. Helium readily diffuses into the mold, substrate, curable composition, etc., thereby dissipating atmospheric gases trapped in the mold pattern, etc. Carbon dioxide readily dissolves in the undercoat of the curable composition or substrate, thereby dissipating atmospheric gases trapped in the mold pattern, etc. (see Japanese Patent Publication No. 2022-99271). In this case, the curable composition preferably exhibits a carbon dioxide concentration of 0.5 kg / m³. 3 • atm to 10 kg / m 3 • Solubility coefficient atm. When the contact step is carried out in an atmosphere of a specific gas (including atmospheric air), the gas pressure is preferably from 0.0001 to 10 atmospheres.

[0413] Curing steps

[0414] In the curing step, the non-volatile component composition (A') is cured by irradiation with irradiation light 107, which serves as the curing energy. Figure 1F As schematically shown, a cured film is thus formed. In the curing step, irradiation light 107 is applied to the non-volatile component composition (A') through the mold 106. More specifically, irradiation light 107 is applied to the non-volatile component composition (A') that fills the fine pattern of the mold 106 through the mold 106. Thus, the non-volatile component composition (A') that fills the fine pattern of the mold 106 is cured into a patterned cured film 108.

[0415] The irradiation light 107 is selected based on the wavelength sensed by the non-volatile component composition (A'). Specifically, the irradiation light 107 is selected from irradiation light with wavelengths from 150 nm to 400 nm, such as ultraviolet light, X-ray radiation, and electron beams. Ultraviolet light is particularly preferred as the irradiation light 107. This is because many commercially available curing aids (photopolymerization initiators) are sensitive to ultraviolet light. Examples of light sources emitting ultraviolet light include high-pressure mercury vapor lamps, ultra-high-pressure mercury vapor lamps, low-pressure mercury vapor lamps, Deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F2 lasers. Ultra-high-pressure mercury vapor lamps are particularly preferred as the light source emitting ultraviolet light. The number of light sources can be one or more. The entire non-volatile component composition (A') or a portion (limited to a specific area) of the non-volatile component composition filling the fine pattern of the mold can be irradiated with light. Irradiation can be performed intermittently multiple times or continuously over the entire area of ​​the substrate.

[0416] Alternatively, for example, a first region can be irradiated in a first irradiation phase, and a second region different from the first region can be irradiated in a second irradiation phase.

[0417] Demolding steps

[0418] In the demolding step, the mold 106 is separated from the cured film 108, such as... Figure 1G As illustrated schematically, the separation of the mold 106 from the patterned cured film 108 provides a patterned, independent cured film 108, the pattern being a reversal of the fine pattern of the mold 106.

[0419] In this state, the patterned curing film 108 retains the cured product of the curable composition in the recesses of the curing film. This cured product is referred to as a residual film.

[0420] To separate the mold 106 from the patterned cured film 108, the separation conditions are not limited, as long as the patterned portion of the cured film 108 is not physically damaged. For example, the substrate 101 is fixed, and the mold 106 moves away from the fixed substrate 101. Alternatively, the mold 106 can be fixed, and the substrate 101 can move away from the fixed mold 106. The mold 106 can be separated from the patterned cured film 108 by moving both the mold 106 and the substrate 101 in opposite directions.

[0421] repeat

[0422] The series of steps from the application step to the demolding step are performed in this order (manufacturing process) to form a cured film with the desired raised and recessed pattern structure (the pattern structure of the raised and recessed pattern structure according to the mold 106) at the desired location.

[0423] The patterning method disclosed herein allows the series of (shot) steps, from the application step to the demolding step, to be repeated several times on the same substrate, thereby providing a cured film 108 with multiple desired patterns.

[0424] Planarization film formation method

[0425] An example of applying the film formation method described herein to a planarization film formation method will now be described. The planarization film formation method includes, for example, an application step, a waiting step, a contact step, a curing step, and a demolding step. In the application step, droplets of a curable composition (A) are applied onto a substrate. The waiting step is a period during which the droplets of the curable composition (A) coalesce and the solvent (component (d)) evaporates. In the contact step, a non-volatile component composition (A') is brought into contact with a mold. In the curing step, the non-volatile component composition (A') is cured. In the demolding step, the cured film of the non-volatile component composition (A') is separated from the mold. In the planarization film formation method, a cured film having a flat surface conforming to the mold is formed using a substrate with an uneven surface having a height difference of about 10 nm to 1,000 nm and a mold having a flat surface, through the contact step, curing step, and demolding step. In the application step, droplets of the curable composition (A) are densely applied to the recesses of the substrate, and the curable composition (A) is sparsely applied to the protrusions of the substrate. A waiting step follows the application step. A contact step is performed after the waiting step. A curing step is performed after the contact step. A demolding step is performed after the curing step.

[0426] Manufacturing method of the product

[0427] The method for manufacturing the article includes: a film forming step of forming a film of a curable composition on a substrate using the film forming method described above; a processing step of processing the substrate having the film of the curable composition formed in the film forming step; and a manufacturing step of manufacturing the article using the substrate processed in the processing step. This film forming method can be implemented using either the pattern forming method or the planarization film forming method described above.

[0428] The cured film 108 having a pattern formed by the patterning method described herein can be used as at least one component of various articles. Alternatively, the cured film 108 having a pattern formed by the patterning method described herein can be temporarily used as a mask for etching or ion implanting onto the substrate 101 (or, when the substrate 101 has a layer to be processed). The mask is removed after etching or ion implantation in the step of processing the substrate 101. Thus, various articles are manufactured.

[0429] To remove cured products (residual film) from the recesses of a patterned cured film by etching, known techniques (e.g., dry etching) can be used, but not limited to any particular technique. For dry etching, known dry etching equipment can be used. The dry etching source gas is appropriately selected based on the elemental composition of the cured product to be etched. Specifically, examples of source gases include halogen gases such as CF4, C2F6, C3F8, CCl2F2, CCl4, CBrF3, BCl3, PCl3, SF6, and Cl2. Other examples of source gases include oxygen-containing gases such as O2, CO, and CO2; and inert gases such as He, N2, and Ar. H2 or NH3 can also be used. The source gas can be a mixture of these gases. In this operation, the cured film needs to have high dry etching resistance to achieve high yields when processing the underlying substrate.

[0430] The articles of manufacture mentioned herein include circuit elements, optical devices, microelectromechanical systems (MEMS), recording devices, sensors, and molds. Examples of circuit elements include volatile or non-volatile semiconductor memories, such as dynamic random access memory (DRAM), static random access memory (SRAM), flash memory, or magnetoresistive random access memory (MRAM); and semiconductor devices, such as large-scale integrated circuits (LSI), charge-coupled devices (CCD), image sensors, and field-programmable gate arrays (FPGAs). Exemplary optical devices include microlenses, light guides, waveguides, antireflective coatings, diffraction gratings, polarizers, color filters, light-emitting devices, displays, and solar cells. Examples of MEMS devices include digital micromirror devices (DMDs), microfluidic channels, and electromechanical switching elements. Examples of recording devices include optical discs (such as CDs and DVDs), magnetic disks, magneto-optical discs, and magnetic heads. Examples of sensors include magnetic sensors, optical sensors, and gyroscope sensors. Examples of molds include those used for imprinting.

[0431] Known photolithography processes, such as imprint lithography and extreme ultraviolet (EUV) lithography, can be performed on the planarization film formed by the planarization film formation method described herein. Furthermore, the curable compositions disclosed herein can be applied to a stack comprising a spin-coated glass (SOG) film and / or a silicon oxide layer for photolithography processes. Therefore, devices such as semiconductor devices can be manufactured. Additionally, electronic devices incorporating such devices, such as displays, cameras, and medical devices, can be manufactured. Examples of such devices include LSIs, system LSIs, DRAMs, synchronous dynamic random access memory (SDRAM), Rambus DRAM (RDRAM), direct Rambus DRAM (D-RDRAM), and NAND flash memory.

[0432] Example

[0433] Specific embodiments will be described to supplement the above implementation scheme.

[0434] Example 1

[0435] When a mixture of a curable composition and a surfactant comes into contact with an ambient gas, if the surfactant is highly hydrophobic and has a low sp. value (SP), it segregates within a few nanometers of the ambient gas interface. The degree of segregation can be determined by applying the Flory-Huggins theory to a system containing a mixture of the curable composition, surfactant, and air, and calculating the material distribution at which the system's free energy is minimized. The material distribution is determined by the relationship between the SP values ​​of the curable composition, surfactant, and air. For example, air has an SP value of 10, while the hydrophobic portion of the surfactant Surfynol has an SP value of 13.8, and the polymeric compound tricyclodecanediethanol diacrylate has an SP value of 15.8. Therefore, surfactants with SP values ​​closer to each other tend to segregate at the air interface.

[0436] Example 2

[0437] Example 2 aims to demonstrate that the edge filling speed v is given by Equation 1 using the viscosity μ (mPa·s) of the non-volatile component composition and the average liquid film thickness h (m) of the curable composition.

[0438]

[0439] Where, C = 9.75 e -2 α = 0.489, and μ0 = 50 (mPa·s)

[0440] Assuming a contact process, this embodiment uses a set of simultaneous equations combining the Navier-Stokes equations (approximately for a thin film confined between walls) and the elastic deformation equations of the mold to determine the edge filling speed. Figure 4 The state of the computational region is shown. Reference numeral 106 indicates the mold; 102 indicates the liquid film; 101 indicates the substrate; 109 indicates the edge of the patterning region; and 110 indicates the initial position of the end of the liquid film. Figure 4 The x-axis and y-axis are shown. This calculation is approximated as a two-dimensional problem, where the negative end of the x-axis is treated as a symmetric boundary and assumed to be perpendicular to... Figure 4 The plane is symmetrical in direction.

[0441] The model is constructed as a linear elastic body with a Young's modulus of 72 GPa and a Poisson's ratio of 0.17. The surface tension coefficient of the liquid film is set to 30 mN / m. Figure 4As shown, a fixed average initial liquid film thickness is maintained, and the distance between 110 and 109 is set to 100 μm. On the negative x-axis side relative to A05, it is assumed that the gap between the mold and the substrate is filled by the liquid film, and there is no gap between the liquid film and the mold. The liquid film contacts the substrate at A05 with a contact angle of 0°. The simulation begins in a static state. The numerical calculation method used in this embodiment is merely an example, and other calculation methods can be used.

[0442] Figure 5 The change in edge-filling rate is shown as the viscosity coefficient of a liquid film with an average film thickness of 40 nm varies. Figure 5 In the diagram, the horizontal axis represents time, and the vertical axis represents the distance between the end of the liquid film and the edge of the pattern-forming area. Note that the vertical axis is oriented downwards as positive. B01, B02, and B03 correspond to the results for liquid films with viscosities of 50 mPa·s, 150 mPa·s, and 300 mPa·s, respectively. These results indicate that the lower the viscosity, the faster the edge-filling speed. Figure 6 Results from the same calculations are shown, with the horizontal axis plotted as time / viscosity coefficient. As shown in C01, the results form the same curve. These results indicate that the edge-filling rate is inversely proportional to the viscosity coefficient. Therefore, it has been demonstrated that the flow rate of the liquid film is inversely proportional to the viscosity coefficient.

[0443] Figure 7 This is a graph showing the change in edge filling velocity as the average thickness of a liquid film with a viscosity coefficient of 50 mPa·s changes. Figure 7 In the diagram, the horizontal axis represents time, and the vertical axis represents the distance between the end of the liquid film and the edge of the pattern-forming area. Note that the vertical axis is oriented downwards as positive. D01, D02, D03, D04, and D05 correspond to the results for liquid films with average film thicknesses of 1000 nm, 200 nm, 100 nm, 80 nm, and 40 nm, respectively. These results indicate that a larger average liquid film thickness corresponds to a faster edge-filling rate.

[0444] Figure 8 A graph showing the average liquid film thickness on the horizontal axis and the edge-filling rate on the vertical axis is presented. The plotted points represent the calculation results, and the curve represents Equation 1. Therefore, Equation 1 can be used to represent the dependence of the edge-filling rate on the average liquid film thickness. As mentioned above, the edge-filling rate is inversely proportional to the viscosity coefficient, thus showing that the viscosity coefficient dependence can also be represented by Equation 1.

[0445] Therefore, it has been proven that the edge filling speed can be expressed as a function of μ and h (Equation 1).

[0446] Table 1 shows the viscosity measurements of the surfactant (component (c)) at 23 °C and 1 atm.

[0447] Table 1

[0448]

[0449] Table 2 presents the viscosity at 23 °C and 1 atm, and the edge-filling rate of the non-volatile component (A') obtained by mixing components (a), (b), (e), and (d) in total at 100% by mass to prepare a curable composition (A) and removing component (d) from the curable composition (A). In Table 2, the first component DCPDA in component (a) refers to tricyclodecanediethanol diacrylate, and the second component DDODA refers to 1,10-decanediol diacrylate. PGMEA in component (d) represents propylene glycol monomethyl ether. The edge-filling rate was evaluated using Equation 2 and was assessed using an average liquid film thickness of 300 nm according to the following criteria:

[0450] A: Fill the edges with a speed of 100 μm / s or higher.

[0451] B: Fill the edges with a speed of less than 100 μm / s.

[0452] Table 2

[0453]

[0454] As described above, when used for embossing, the curable compositions disclosed herein exhibit high edge-filling speeds and achieve high productivity.

[0455] The concept of this disclosure is not limited to the above-described embodiments, and various modifications and changes can be made without departing from the spirit and scope of the invention. Therefore, claims are appended below to disclose the scope of this disclosure.

[0456] Therefore, this disclosure provides a new technique for curable compositions.

[0457] While this disclosure has been described with reference to exemplary embodiments, it should be understood that this disclosure is not limited to the disclosed embodiments. The scope of the following claims should be given the broadest interpretation to cover all such modifications and equivalent structures and functions.

Claims

1. A curable composition, said curable composition comprising: Polymer compound (a); Photopolymerization initiator (b); and A solvent with a boiling point less than 250°C (d), wherein the amount of said solvent is greater than 5% to 95% by volume relative to the entire curable composition. in, The curable composition has a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm, and The composition formed by removing the solvent (d) from the curable composition has a viscosity of 8 mPa·s to 30 mPa·s at 23°C and 1 atm.

2. A curable composition, said curable composition comprising: Polymer compound (a); Photopolymerization initiator (b); Surfactant (c), said surfactant having a viscosity of 500 mPa·s or less at 23°C and 1 atm; and A solvent with a boiling point less than 250°C (d), wherein the amount of said solvent is greater than 5% to 95% by volume relative to the entire curable composition. in, The curable composition has a viscosity of 1.3 mPa·s to 60 mPa·s at 23°C and 1 atm.

3. The curable composition according to claim 1, wherein, The composition formed by removing the solvent (d) from the curable composition has a viscosity of 8 mPa·s to 20 mPa·s at 23°C and 1 atm.

4. The curable composition according to claim 2, wherein, The surfactant (c) has a viscosity of 400 mPa·s or less at 23°C and 1 atm.

5. The curable composition according to claim 1, wherein, The solvent (d) includes one or more solvents, and each of the one or more solvents has a boiling point of 100°C to less than 250°C at 1 atm.

6. The curable composition according to claim 1, wherein, The polymeric compound (a) includes one or more polymeric compounds, each of which has a boiling point of 250°C or higher at 1 atm.

7. The curable composition according to claim 1, wherein, The polymerizable compound (a) includes monofunctional polymerizable compounds and polyfunctional polymerizable compounds, and The multifunctional polymeric compound accounts for more than 20% by mass of the polymeric compound (a).

8. The curable composition according to claim 1, wherein, The polymeric compound (a) includes one or more polymeric compounds, and each of the one or more polymeric compounds has a molecular weight of 200 or more.

9. The curable composition according to claim 1, wherein, The polymeric compound (a) includes polymers having polymeric functional groups.

10. The curable composition according to claim 1, wherein, The curable composition exhibits a glass transition temperature of over 70°C after curing.

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

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

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

14. The curable composition according to claim 1, wherein, The composition obtained by removing the solvent (d) contains more than 10% by mass of silicon atoms.

15. The curable composition according to claim 1, wherein, The curable composition has a strength of 0.5 kg / m³. 3 •atm to 10kg / m 3 • atm, the carbon dioxide solubility coefficient.

16. The curable composition according to claim 1, wherein, The curable composition is used in inkjet printing.

17. A film forming method for forming a film of a curable composition on a substrate using a mold, the method comprising: A plurality of droplets of the curable composition according to any one of claims 1 to 16 are discretely applied to the substrate; After the application of the droplets, the plurality of droplets on the substrate are brought into contact with the mold to form a liquid film between the substrate and the mold; After the droplet comes into contact with the mold, the liquid film is solidified into a cured film; and After curing, the cured film is detached from the mold.

18. The film formation method of claim 17, further comprising waiting until the droplets of the curable composition merge on the substrate to form a substantially continuous liquid film between the application and the contact, and until the solvent in the liquid film evaporates.

19. The membrane formation method according to claim 18, wherein, The waiting continues until the solvent in the liquid film evaporates to less than 10% by volume relative to the entire liquid film.

20. The membrane formation method according to claim 18, wherein, During the waiting step, the substrate is heated at a temperature of 30°C to 200°C for 10 to 600 seconds.

21. The membrane formation method according to claim 17, wherein, The application is performed at a rate of 80 droplets / mm. 2 The above density is achieved by applying droplets of the curable composition onto the substrate, each droplet having a volume of 1.0 pL or more.

22. The membrane formation method according to claim 17, wherein, The mold has a contact surface with a raised or recessed pattern, and the contact is achieved by bringing the liquid film into contact with the pattern of the mold. The film forming method further includes additionally curing the cured film formed by the curing of the contact and the liquid film, thereby forming a cured film having a pattern corresponding to the pattern of the mold.

23. The membrane formation method according to claim 17, wherein, The mold has a contact surface, the contact surface being flat, and the contact is achieved by bringing the liquid film into contact with the flat surface of the mold. The film forming method further includes additionally curing the cured film formed by the curing of the contact and the liquid film, thereby forming a cured film with a flat surface conforming to the mold.

24. A method of manufacturing an article, comprising: A film of a curable composition is formed on a substrate using the film formation method according to claim 17; The substrate having the film formed in the film formation is processed; and Articles are manufactured using a substrate that has been processed in the aforementioned processing of the substrate.

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