Polysiloxane composition

Abstract

Polysiloxane composition having a specific structure for improving the exposure sensitivity of metal oxide resists How to use things.

Description

[Technical Field]

[0001] The present invention relates to the use of a polysiloxane composition. The present invention also relates to a metal oxide resist underlayer film composition, a method for producing a film using the same, a film using the same, and a method for producing an electronic device including the film. [Background technology]

[0002] In the manufacturing process of semiconductor devices, etc., microfabrication using lithography technology with photoresist is commonly performed. The wavelength used for exposure is becoming shorter, and lithography technology using extreme ultraviolet (EUV) light with a wavelength of 13.5 nm is being investigated. Under conventional exposure conditions using wavelengths of 248 nm or 193 nm, chemically amplified resist compositions are used as resist materials. When EUV is used, various resist materials are being considered, one of which is metal oxide resist (MOR). A composition containing a silane having a specific structure has been proposed as a composition for forming an underlayer film of an EUV resist (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication 2013 / 051558 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have recognized that there are one or more problems that still require improvement, including, for example: Metal oxide resists have low exposure sensitivity; poor adhesion between metal oxide resists and underlying films; low etching selectivity of underlying films for metal oxide resists; many defects occur in processes using metal oxide resists; and the process window for processes using metal oxide resists is narrow. [Means for solving the problem]

[0005] The present invention relates to a method for improving the exposure sensitivity of a metal oxide resist by using a composition comprising a polysiloxane comprising a repeating unit represented by the following formula (Ia):

[0006] [ka] (where, R Ia is unsubstituted or C 1-5 alkyl-substituted phenyl, naphthyl, phenalenyl, phenanthrenyl, or anthracenyl)

[0007] The present invention relates to a metal oxide resist underlayer film composition comprising a polysiloxane comprising a repeating unit represented by formula (Ia) and a solvent.

[0008] [ka] (where, R Ia is unsubstituted or C 1-5 alkyl-substituted phenyl, naphthyl, phenalenyl, phenanthrenyl, or anthracenyl)

[0009] The present invention relates to a method for producing a metal oxide resist film, comprising the following steps: (a) applying the composition onto a substrate to form a metal oxide resist underlayer film; (b) irradiating the metal oxide resist underlayer film with energy rays; and (c) forming a metal oxide resist film on the metal oxide resist underlayer film irradiated with energy rays;

[0010] The present invention also relates to a method for producing an electronic device according to the present invention, which comprises the above-mentioned method for producing a resist film. [Effects of the Invention]

[0011] According to the present invention, one or more of the following effects can be expected. The metal oxide resist has sufficient exposure sensitivity; the metal oxide resist has sufficient adhesion to the underlayer; the metal oxide resist has sufficient etching selectivity for the underlayer; defects that occur in processes using the metal oxide resist are suppressed; and the process window of processes using the metal oxide resist is sufficient. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Definition] In this specification, unless otherwise specified, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "one" and "the" mean "at least one." An element of a concept can be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of elements as well as any single element. When a numerical range is indicated using "~" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less. "C x-y "," "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to alkyl chains having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. This copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are represented by structural formulas, the n or m in parentheses indicates the repeating number. The temperature unit is Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to the compound itself that has that function (for example, in the case of a base generator, it refers to the compound itself that generates a base). The compound may be dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition of the present invention as a solvent or other component.

[0013] Hereinafter, embodiments of the present invention will be described in detail.

[0014] <Method of using a composition containing polysiloxane> The present invention provides a method for improving the exposure sensitivity of a metal oxide resist by using a composition comprising a polysiloxane comprising a repeating unit represented by the following formula (Ia): The metal oxide resist is more preferably an organic metal oxide hydroxide-containing resist, and the resist described in JP-A-2021-73367 can be used. The metal oxide resist is preferably an EUV resist, and in one preferred embodiment, is a negative resist. The composition containing polysiloxane is used, for example, to form a film under a metal oxide resist, and is preferably applied to an organic film such as SOC (Spin on Carbon) formed on a substrate to form a film. In a preferred embodiment, a film is formed directly on the SOC film using the composition containing polysiloxane, and a metal oxide resist film is formed directly on the film. The composition comprising polysiloxane preferably further comprises a solvent. The content of the solvent is preferably 90.0 to 99.9 mass % based on the total mass of the composition. The composition comprising polysiloxane may contain components other than the solvent. The solvent and other components that can be used are the same as those described in the metal oxide resist underlayer film composition below.

[0015] <Polysiloxane> The polysiloxane used in the present invention comprises a repeating unit represented by formula (Ia). It is believed that the exposure sensitivity of the metal oxide resist is improved when the polysiloxane contains a repeating unit represented by formula (Ia). Without being bound by theory, this is because, for example, after a composition containing polysiloxane is formed into a film, the R Ia Because the group has a specific structure containing an aromatic ring, it is prone to elimination by light irradiation, etc. This elimination generates hydroxyl groups on the film surface, which improves adhesion between the films, especially when a metal oxide resist film is placed directly above it. This improved adhesion is thought to improve exposure sensitivity. Also, R Ia Since the group is a bulky group having an aromatic ring, the elastic modulus of the film formed using the polysiloxane is suppressed, which also has the effect of suppressing peeling from the metal oxide resist film.

[0016] [ka] where: R Ia is unsubstituted or C 1-5 It is phenyl, naphthyl, phenalenyl, phenanthrenyl, or anthracenyl substituted with alkyl, preferably unsubstituted phenyl, naphthyl, phenalenyl, phenanthrenyl, or anthracenyl, more preferably phenyl or naphthyl. R Ia More preferably, it is phenyl.

[0017] The number of repeating units represented by formula (Ia) is preferably 5 to 100%, more preferably 10 to 100%, even more preferably 15 to 90%, and still more preferably 30 to 700%, based on the total number of repeating units contained in the polysiloxane molecule.

[0018] Preferably, the polysiloxane used in the present invention further comprises a repeating unit represented by formula (Ib).

[0019] [ka] where: R Ib is C 1-6 alkyl, preferably linear or branched C 1-5 R is alkyl, and more preferably methyl, ethyl, propyl, or butyl. In order to increase the hardness of the film after curing and to increase chemical resistance, 1 More preferably, is methyl.

[0020] The number of repeating units represented by formula (Ib) is preferably 5 to 90%, more preferably 20 to 80%, and even more preferably 30 to 70%, based on the total number of repeating units contained in the polysiloxane molecule.

[0021] The polysiloxane used in the present invention may further contain a repeating unit represented by formula (Ic).

[0022] [ka]

[0023] The number of repeating units represented by formula (Ic) is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 1%, based on the total number of repeating units contained in the polysiloxane molecule. In one preferred embodiment, the polysiloxane used in the present invention does not contain any repeating units represented by formula (Ic) (0%). The repeating unit represented by formula (Ic) does not undergo elimination of the substituent upon irradiation with light after film formation, and therefore does not generate a hydroxy group, and is therefore not thought to contribute to improving exposure sensitivity as occurs when the repeating unit represented by formula (Ia) is included. Furthermore, when the repeating unit represented by formula (Ic) is contained, the elastic modulus is high and the film is rigid, so it is thought that peeling tends to occur easily between the film containing this and other films (e.g., metal oxide resist films).

[0024] The polysiloxane used in the present invention may contain repeating units other than those described above, but the number of repeating units other than those described above is preferably 20% or less, and more preferably 10% or less, based on the total number of repeating units contained in the polysiloxane molecule. A preferred embodiment of the present invention is one in which no repeating units other than those described above are contained. Examples of repeating units other than those mentioned above include R Ib The group corresponding to the formula (I) can be a monovalent group such as hydrogen, a fluoroalkyl, a fluoroaryl, a nitrogen-containing group, or an oxygen-containing group. This group may be divalent or trivalent, and in this case, this group connects Si atoms contained in multiple repeating units together.

[0025] The polysiloxane used in the present invention preferably has a silanol group at the terminal. Here, silanol refers to a group in which an OH group is directly bonded to the Si skeleton of the polysiloxane, and is a group in which a hydroxy group is directly bonded to a silicon atom in a polysiloxane containing the above-mentioned repeating units, etc. That is, -O in the above formula 0.5 -O 0.5Silanol is formed by bonding H. The silanol content in polysiloxane varies depending on the synthesis conditions of polysiloxane, such as the monomer ratio and the type of reaction catalyst.

[0026] The mass average molecular weight of the polysiloxane used in the present invention is preferably 500 to 20,000, more preferably 800 to 15,000, and even more preferably 1,000 to 10,000. Here, the mass average molecular weight is the mass average molecular weight in terms of polystyrene, and can be measured by gel permeation chromatography using polystyrene as the standard.

[0027] <Metal oxide resist underlayer film composition> The metal oxide resist underlayer film composition according to the present invention (hereinafter, sometimes referred to as the underlayer film composition) comprises: The underlayer film composition comprises a polysiloxane containing a repeating unit represented by formula (Ia) and a solvent. Each component contained in the underlayer film composition will be described in detail below.

[0028] <Polysiloxane> The polysiloxane used in the underlayer film composition of the present invention is as described above. The content of polysiloxane is preferably 0.10 to 10.0 mass %, more preferably 0.10 to 5.0 mass %, and even more preferably 0.10 to 3.0 mass %, based on the total mass of the composition.

[0029] <Solvent> The solvent is not particularly limited as long as it can uniformly dissolve or disperse the polysiloxane and additives added as needed. Examples of solvents that can be used in the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether. Examples of suitable solvents include propylene glycol alkyl ether acetates such as acetate, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-methoxybutanol, and 1,3-butanediol, esters such as ethyl lactate, butyl acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone. The solvents may be used alone or in combination of two or more.

[0030] The content of the solvent is preferably 90.0 to 99.9 mass %, more preferably 95.0 to 99.9 mass %, and even more preferably 97.0 to 99.9 mass %, based on the total mass of the composition according to the present invention.

[0031] <Ionic liquid> The underlayer film composition according to the present invention can include an ionic liquid. An ionic liquid is a salt that exists as a liquid over a wide temperature range and is a liquid consisting only of ions. Generally, a salt having a melting point of 100°C or less is defined as an ionic liquid. The ionic liquid used in the present invention has a melting point of 100°C or less, preferably 80°C or less, more preferably 60°C or less, and even more preferably 30°C or less. The ionic liquid used in the present invention is preferably a basic ionic liquid, and is preferably a combination of a strong base and a weak acid.

[0032] The cation of the ionic liquid is preferably at least one cation selected from the group consisting of imidazolium-based ions, pyrrolidinium-based ions, piperidinium-based ions, pyridinium-based ions, and ammonium-based ions, and more preferably an imidazolium-based ion.

[0033] The imidazolium-based ion is preferably represented by the following formula (A):

[0034] [ka] where: R 11 , R 12 , R 13 , R 14 and R 15 are each independently hydrogen, straight-chain or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl, or C 6-14 It is aryl.

[0035] Specific examples of imidazolium ions include 1-methylimidazolium, 1-methyl-2-ethylimidazolium, 1-methyl-3-octylimidazolium, 1,2-dimethylimidazolium, 1,3-dimethylimidazolium, 2,3-dimethylimidazolium, 3,4-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1,3,4-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1-ethylimidazolium, 1-ethyl-2-methylimidazolium, 1-ethyl-3-methylimidazolium, 1 -Ethyl-2,3-dimethylimidazolium, 2-ethyl-3,4-dimethylimidazolium, 1-propylimidazolium, 1-propyl-2-methylimidazolium, 1-propyl-3-methylimidazolium, 1-propyl-2,3-dimethylimidazolium, 1,3-dipropylimidazolium, 1-butylimidazolium, 1-butyl-2-methylimidazolium, 1-butyl-3-methylimidazolium, 1-butyl-4-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1-butyl-3,4-dimethylimidazolium 1-butyl-3,4,5-trimethylimidazolium, 1-butyl-2-ethylimidazolium, 1-butyl-3-ethylimidazolium, 1-butyl-2-ethyl-5-methylimidazolium, 1,3-dibutylimidazolium, 1,3-dibutyl-2-methylimidazolium, 1-pentylimidazolium, 1-pentyl-2-methylimidazolium, 1-pentyl-3-methylimidazolium, 1-pentyl-2,3-dimethylimidazolium, 1-hexylimidazolium, 1-hexyl-2-methylimidazolium, 1-hexyl-3-methylimidazolium Examples of the imidazolium include 1-ethyl-3-methylimidazolium, 1-hexyl-2,3-dimethylimidazolium, 1-octyl-2-methylimidazolium, 1-octyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, 1-dodecyl-3-methylimidazolium, 1-tetradecyl-3-methylimidazolium, 1-hexadecyl-3-methylimidazolium and 1-benzyl-3-methylimidazolium, and preferred are 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-propyl-3-methylimidazolium, 1-propyl-2,3-dimethylimidazolium, 1-butyl-3-methylimidazolium, 1-butyl-2,3-dimethylimidazolium, and 1-octyl-3-methylimidazolium.

[0036] The pyrrolidinium-based ion is preferably represented by the following formula (B):

[0037] [ka] where: R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are each independently hydrogen, straight-chain or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl, or C 6-14 It is aryl.

[0038] Specific examples of pyrrolidinium ions include 1-methyl-1-ethylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, 1-methyl-1-butylpyrrolidinium, 1-methyl-1-pentylpyrrolidinium, 1-methyl-1-hexylpyrrolidinium, and 1-methyl-1-octylpyrrolidinium, with 1-methyl-1-propylpyrrolidinium being preferred.

[0039] The piperidinium-based ion is preferably represented by the following formula (C):

[0040] [ka] where: R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R37 are each independently hydrogen, straight-chain or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl, or C 6-14 It is aryl.

[0041] Specific examples of piperidinium ions include 1-methyl-1-ethylpiperidinium, 1-methyl-1-propylpiperidinium, 1-methyl-1-butylpiperidinium, 1-methyl-1-pentylpiperidinium, 1-methyl-1-hexylpiperidinium, and 1-methyl-1-octylpiperidinium, with 1-methyl-1-butylpiperidinium being preferred.

[0042] The pyridinium-based ion is preferably represented by the following formula (D):

[0043] [ka] where: R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are each independently hydrogen, straight-chain or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl, or C 6-14 It is aryl.

[0044] Specific examples of pyridinium ions include 1-methylpyridinium, 1-ethylpyridinium, 1-propylpyridinium, 1-butylpyridinium, 1-pentylpyridinium, 1-hexylpyridinium, 1-octylpyridinium, 1-methyl-3-ethylpyridinium, 1-methyl-4-ethylpyridinium, 1-methyl-3-butylpyridinium, 1-methyl-4-butylpyridinium, 1-ethyl-3-methylpyridinium, 1-ethyl-4-methylpyridinium, 1-propyl-3-methylpyridinium, 1-propyl-4-methylpyridinium, 1-butyl-3-methylpyridinium, 1-butyl-4-methylpyridinium, 1-hexyl-4-methylpyridinium, and 1-octyl-4-methylpyridinium, with 1-butylpyridinium and 1-ethyl-4-methylpyridinium being preferred.

[0045] The ammonium-based ion is preferably represented by the following formula (E):

[0046] [ka] where: R 51 , R 52 , R 53 and R 54 are each independently a linear or branched C 1-18 Alkyl, linear or branched C 1-18 Hydroxyalkyl, cyclic C 5-12 Alkyl, or C 6-14 It is aryl.

[0047] Specific examples of ammonium ions include trimethylethylammonium, trimethylbutylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trihexylmethylammonium, trioctylmethylammonium, tetrabutylammonium, 2-hydroxyethyltrimethylammonium, and tris(2-hydroxyethyl)methylammonium, and preferred are tetrabutylammonium, tributylmethylammonium, and 2-hydroxyethyltrimethylammonium.

[0048] The anion of the ionic liquid is preferably at least one anion selected from the group consisting of formate ion, acetate ion, propionate ion, lactate ion, oleate ion, salicylate ion, dicyanamide ion, cyanamide ion, thiocyanate ion, methyl sulfate ion, ethyl sulfate ion, hydrogen sulfate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, bis(trifluoromethylsulfonyl)imide ion, bis(fluorosulfonyl)imide ion, methyl carbonate ion, hydrogen carbonate ion, diethyl phosphate ion, dibutyl phosphate ion, hexafluorophosphate ion, tetrafluoroborate ion, chloride ion, and bromide ion, and more preferably acetate ion, dicyanamide ion, cyanamide ion, chloride ion, and bromide ion.

[0049] In a preferred embodiment, specific examples of the ionic liquid include trimethylbutylammonium bis(trifluoromethylsulfonyl)imide, tributylmethylammonium dicyanamide, tributylmethylammonium bis(trifluoromethylsulfonyl)imide, tris(2-hydroxyethyl)methylammonium methylsulfate, 2-hydroxyethyltrimethylammonium acetate, 2-hydroxyethyltrimethylammonium lactate, 2-hydroxyethyltrimethylammonium salicylate, tetrabutylammonium chloride, 1,3-dimethylimidazolium methylsulfate, 1,2,3-trimethylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium dicyanamide, and 1-ethyl-3-methylimidazolium methylsulfate. Imidazolium methyl sulfate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, 1-propyl-3-methylimidazolium acetate, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-propyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium thiocyanate, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-2,Examples include 3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, 1-octyl-3-methylimidazolium acetate, 1-octyl-3-methylimidazolium bromide, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-methyl-1-butylpyrrolidinium dicyanamide, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide, and 1-butylpyridinium tetrafluoroborate. In a more preferred embodiment, the ionic liquid has an imidazolium ion as the cation and an acetate as the anion, and specific examples include 1-ethyl-3-methylimidazolium acetate, 1-propyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, and 1-octyl-3-methylimidazolium acetate.

[0050] Ionic liquids have a catalytic effect that accelerates the curing of polysiloxane, and it is believed that curing can be completed even at relatively low temperatures. The blending ratio of ionic liquid to polysiloxane (ionic liquid / polysiloxane) is preferably 0.000030 to 0.10, more preferably 0.000050 to 0.10, and even more preferably 0.00010 to 0.10, by mass ratio. This range tends to enhance the low-temperature curing effect and increase the density of the cured film. Furthermore, compared to commonly used curing accelerators (e.g., thermal base generators), ionic liquids can be present more uniformly in the composition, which is thought to be effective in suppressing voids.

[0051] The ionic liquid may be used alone or in combination of two or more kinds. The content of the ionic liquid is preferably 0.00020 to 4.0 mass %, more preferably 0.00020 to 3.2 mass %, based on the total mass of the composition according to the present invention.

[0052] <Acid> The underlayer film composition according to the present invention may include an acid. The acid may be an inorganic acid or an organic acid, but is preferably an organic acid, more preferably a carboxylic acid, even more preferably a monocarboxylic acid or dicarboxylic acid, and even more preferably a dicarboxylic acid.

[0053] Examples of the monocarboxylic acid include acetic acid, formic acid, propionic acid, butyric acid, valeric acid, and acrylic acid, with acetic acid being preferred. Examples of dicarboxylic acids include oxalic acid, maleic acid, fumaric acid, phthalic acid, succinic acid, glutaconic acid, aspartic acid, glutamic acid, malic acid, citraconic acid, acetylenedicarboxylic acid, itaconic acid, mesaconic acid, 3-aminohexanedioic acid, and malonic acid. Preferred are oxalic acid, maleic acid, fumaric acid, phthalic acid, succinic acid, malic acid, citraconic acid, acetylenedicarboxylic acid, and malonic acid. More preferred are oxalic acid, maleic acid, fumaric acid, phthalic acid, citraconic acid, and acetylenedicarboxylic acid.

[0054] The acid preferably has high sublimability, so that it sublimates when heated for curing. Specifically, the sublimation temperature is preferably 90 to 300° C., more preferably 90 to 250° C. This is because, when the coating film is cured, the acid sublimes, reducing the amount of the remaining cured film.

[0055] Without being bound by theory, as described above, the ionic liquid functions as a catalyst that accelerates the curing of polysiloxane at low temperatures. Compositions containing an ionic liquid, a polysiloxane, and a solvent may continue to cure even during long-term storage at room temperature, resulting in gelation and other problems. In contrast, combining an acid is believed to suppress the catalytic activity of the ionic liquid and provide sufficient storage stability. It is believed that the acid sublimes during heating for curing, thereby enabling the catalytic activity of the ionic liquid to be expressed and allowing the composition to cure at low temperatures. To achieve better storage stability and low-temperature curing properties, the present invention preferably includes a combination of an ionic liquid and a carboxylic acid, more preferably a combination of an ionic liquid and oxalic acid, maleic acid, fumaric acid, phthalic acid, citraconic acid, or acetylenedicarboxylic acid, and even more preferably a combination of an ionic liquid whose cation is an imidazolium ion and whose anion is an acetate ion with maleic acid.

[0056] In a preferred embodiment, specific examples of the combination of an ionic liquid and an acid (ionic liquid / acid) include tributylmethylammonium dicyanamide / acetic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / acetic acid, 2-hydroxyethyltrimethylammonium acetate / acetic acid, 2-hydroxyethyltrimethylammonium lactate / acetic acid, 2-hydroxyethyltrimethylammonium salicylate / acetic acid, tetrabutylammonium chloride / acetic acid, 1-ethyl-3-methylimidazolium acetate / acetic acid, 1-ethyl-3-methylimidazolium acetate / acetic acid, and 1-ethyl-3-methylimidazolium acetate / acetic acid. 1-ethyl-3-methylimidazolium dicyanamide / acetic acid, 1-ethyl-3-methylimidazolium methyl sulfate / acetic acid, 1-ethyl-3-methylimidazolium thiocyanate / acetic acid, 1-propyl-3-methylimidazolium acetate / acetic acid, 1-butyl-3-methylimidazolium acetate / acetic acid, 1-butyl-3-methylimidazolium dicyanamide / acetic acid, 1-butyl-3-methylimidazolium thiocyanate / acetic acid, 1-butyl-3-methylimidazolium bromide / acetic acid, 1-octyl-3-methylimidazolium acetate acetate / acetic acid, 1-octyl-3-methylimidazolium bromide / acetic acid, tributylmethylammonium dicyanamide / succinic acid, tris(2-hydroxyethyl)methylammonium methyl sulfate / succinic acid, 2-hydroxyethyltrimethylammonium acetate / succinic acid, 2-hydroxyethyltrimethylammonium lactate / succinic acid, 2-hydroxyethyltrimethylammonium salicylate / succinic acid, tetrabutylammonium chloride / succinic acid, 1-ethyl-3-methylimidazolium acetate / succinic acid acid, 1-ethyl-3-methylimidazolium dicyanamide / succinic acid, 1-ethyl-3-methylimidazolium methyl sulfate / succinic acid, 1-ethyl-3-methylimidazolium thiocyanate / succinic acid, 1-propyl-3-methylimidazolium acetate / succinic acid, 1-butyl-3-methylimidazolium acetate / succinic acid, 1-butyl-3-methylimidazolium dicyanamide / succinic acid, 1-butyl-3-methylimidazolium thiocyanate / succinic acid, 1-butyl-3-methylimidazolium bromide / succinic acid,1-Octyl-3-methylimidazolium acetate / succinic acid, 1-Octyl-3-methylimidazolium bromide / succinic acid, 1-Methyl-1-butylpyrrolidinium dicyanamide / succinic acid, Tributylmethylammonium dicyanamide / glutaconic acid, Tris(2-hydroxyethyl)methylammonium methylsulfate / glutaconic acid, 2-Hydroxyethyltrimethylammonium acetate / glutaconic acid, 2-Hydroxyethyltrimethylammonium lactate / glutaconic acid, 2-Hydroxyethyltrimethylammonium Musalicylate / glutaconic acid, tetrabutylammonium chloride / glutaconic acid, 1-ethyl-3-methylimidazolium acetate / glutaconic acid, 1-ethyl-3-methylimidazolium dicyanamide / glutaconic acid, 1-ethyl-3-methylimidazolium methylsulfate / glutaconic acid, 1-ethyl-3-methylimidazolium thiocyanate / glutaconic acid, 1-propyl-3-methylimidazolium acetate / glutaconic acid, 1-butyl-3-methylimidazolium acetate / glutaconic acid, 1-butyl-3-methylimidazolium 1-Butyl-3-methylimidazolium dicyanamide / glutaconic acid, 1-butyl-3-methylimidazolium thiocyanate / glutaconic acid, 1-butyl-3-methylimidazolium bromide / glutaconic acid, 1-octyl-3-methylimidazolium acetate / glutaconic acid, 1-octyl-3-methylimidazolium bromide / glutaconic acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / citraconic acid, tributylmethylammonium dicyanamide / citraconic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide )imide / citraconic acid, tris(2-hydroxyethyl)methylammonium methyl sulfate / citraconic acid, 2-hydroxyethyltrimethylammonium acetate / citraconic acid, 2-hydroxyethyltrimethylammonium lactate / citraconic acid, 2-hydroxyethyltrimethylammonium salicylate / citraconic acid, tetrabutylammonium chloride / citraconic acid, 1,3-dimethylimidazolium methyl sulfate / citraconic acid, 1,2,3-trimethylimidazolium methyl sulfate / citraconic acid,1-Ethyl-3-methylimidazolium acetate / citraconic acid, 1-ethyl-3-methylimidazolium dicyanamide / citraconic acid, 1-ethyl-3-methylimidazolium methylsulfate / citraconic acid, 1-ethyl-3-methylimidazolium thiocyanate / citraconic acid, 1-propyl-3-methylimidazolium acetate / citraconic acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / citraconic acid, 1-butyl-3-methylimidazolium acetate / citraconic acid , 1-butyl-3-methylimidazolium dicyanamide / citraconate, 1-butyl-3-methylimidazolium thiocyanate / citraconate, 1-butyl-3-methylimidazolium bromide / citraconate, 1-butyl-3-methylimidazolium hexafluorophosphate / citraconate, 1-butyl-3-methylimidazolium tetrafluoroborate / citraconate, 1-octyl-3-methylimidazolium acetate / citraconate, 1-octyl-3-methylimidazolium bromide / citraconate, 1-octyl 1-methyl-3-methylimidazolium tetrafluoroborate / citraconic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / citraconic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / citraconic acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / citraconic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / citraconic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / citraconic acid, 1- Butylpyridinium tetrafluoroborate / citraconate, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, tributylmethylammonium dicyanamide / acetylenedicarboxylic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / acetylenedicarboxylic acid, 2-hydroxyethyltrimethylammonium acetate / acetylenedicarboxylic acid,2-Hydroxyethyltrimethylammonium lactate / acetylenedicarboxylic acid, 2-Hydroxyethyltrimethylammonium salicylate / acetylenedicarboxylic acid, Tetrabutylammonium chloride / acetylenedicarboxylic acid, 1,3-dimethylimidazolium methyl sulfate / acetylenedicarboxylic acid, 1,2,3-trimethylimidazolium methyl sulfate / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium Mudicyanamide / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium methylsulfate / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium thiocyanate / acetylenedicarboxylic acid, 1-propyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium Umdicyanamide / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium thiocyanate / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium bromide / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium hexafluorophosphate / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / acetylenedicarboxylic acid, 1-octyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-octyl-3-methylimidazolium bromide amide / acetylene dicarboxylic acid, 1-octyl-3-methylimidazolium tetrafluoroborate / acetylene dicarboxylic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / acetylene dicarboxylic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / acetylene dicarboxylic acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / acetylene dicarboxylic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / acetylene dicarboxylic acid,1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, 1-butylpyridinium tetrafluoroborate / acetylenedicarboxylic acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / oxalic acid, tributylmethylammonium dicyanamide / oxalic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / oxalic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / oxalic acid, 2-hydroxyethyl Trimethylammonium acetate / oxalic acid, 2-hydroxyethyltrimethylammonium lactate / oxalic acid, 2-hydroxyethyltrimethylammonium salicylate / oxalic acid, tetrabutylammonium chloride / oxalic acid, 1,3-dimethylimidazolium methyl sulfate / oxalic acid, 1,2,3-trimethylimidazolium methyl sulfate / oxalic acid, 1-ethyl-3-methylimidazolium acetate / oxalic acid, 1-ethyl-3-methylimidazolium dicyanamide / oxalic acid, 1-ethyl-3-methylimidazolium Zolium methyl sulfate / oxalic acid, 1-ethyl-3-methylimidazolium thiocyanate / oxalic acid, 1-propyl-3-methylimidazolium acetate / oxalic acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / oxalic acid, 1-butyl-3-methylimidazolium acetate / oxalic acid, 1-butyl-3-methylimidazolium dicyanamide / oxalic acid, 1-butyl-3-methylimidazolium thiocyanate / oxalic acid, 1-butyl-3-methylimidazolium bromide / oxalic acid , 1-butyl-3-methylimidazolium hexafluorophosphate / oxalic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / oxalic acid, 1-octyl-3-methylimidazolium acetate / oxalic acid, 1-octyl-3-methylimidazolium bromide / oxalic acid, 1-octyl-3-methylimidazolium tetrafluoroborate / oxalic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / oxalic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / oxalic acid,1-Methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / oxalic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / oxalic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / oxalic acid, 1-butylpyridinium tetrafluoroborate / oxalic acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / maleic acid, tributylmethylammonium dicyanamide / maleic acid, tributylmethylammonium bis(trifluoromethyl, Sulfonyl)imide / maleic acid, tris(2-hydroxyethyl)methylammonium methyl sulfate / maleic acid, 2-hydroxyethyltrimethylammonium acetate / maleic acid, 2-hydroxyethyltrimethylammonium lactate / maleic acid, 2-hydroxyethyltrimethylammonium salicylate / maleic acid, tetrabutylammonium chloride / maleic acid, 1,3-dimethylimidazolium methyl sulfate / maleic acid, 1,2,3-trimethylimidazolium methyl sulfate / maleic acid , 1-ethyl-3-methylimidazolium acetate / maleic acid, 1-ethyl-3-methylimidazolium dicyanamide / maleic acid, 1-ethyl-3-methylimidazolium methylsulfate / maleic acid, 1-ethyl-3-methylimidazolium thiocyanate / maleic acid, 1-propyl-3-methylimidazolium acetate / maleic acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-butyl-3-methylimidazolium acetate / maleic acid, 1-butyl-3- Methylimidazolium dicyanamide / maleic acid, 1-butyl-3-methylimidazolium thiocyanate / maleic acid, 1-butyl-3-methylimidazolium bromide / maleic acid, 1-butyl-3-methylimidazolium hexafluorophosphate / maleic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / maleic acid, 1-octyl-3-methylimidazolium acetate / maleic acid, 1-octyl-3-methylimidazolium bromide / maleic acid, 1-octyl-3-methylimidazolium tetrafluoroborate fluoroborate / maleic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / maleic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / maleic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-butylpyridinium tetrafluoroborate / maleic acid,Trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / fumaric acid, tributylmethylammonium dicyanamide / fumaric acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / fumaric acid, tris(2-hydroxyethyl)methylammonium methylsulfate / fumaric acid, 2-hydroxyethyltrimethylammonium acetate / fumaric acid, 2-hydroxyethyltrimethylammonium lactate / fumaric acid, 2-hydroxyethyltrimethylammonium salicylate / fumaric acid Acid, tetrabutylammonium chloride / fumaric acid, 1,3-dimethylimidazolium methyl sulfate / fumaric acid, 1,2,3-trimethylimidazolium methyl sulfate / fumaric acid, 1-ethyl-3-methylimidazolium acetate / fumaric acid, 1-ethyl-3-methylimidazolium dicyanamide / fumaric acid, 1-ethyl-3-methylimidazolium methyl sulfate / fumaric acid, 1-ethyl-3-methylimidazolium thiocyanate / fumaric acid, 1-propyl-3-methylimidazolium acetate / fumaric acid, 1 -Propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-butyl-3-methylimidazolium acetate / fumaric acid, 1-butyl-3-methylimidazolium dicyanamide / fumaric acid, 1-butyl-3-methylimidazolium thiocyanate / fumaric acid, 1-butyl-3-methylimidazolium bromide / fumaric acid, 1-butyl-3-methylimidazolium hexafluorophosphate / fumaric acid, 1-butyl-3-methylimidazolium tetrafluoroborate / fumaric acid, 1-octyl 1-Methylimidazolium acetate / fumaric acid, 1-octyl-3-methylimidazolium bromide / fumaric acid, 1-octyl-3-methylimidazolium tetrafluoroborate / fumaric acid, 1-methyl-1-butylpyrrolidinium dicyanamide / fumaric acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-ethyl-3-methylpyridinium ethyl sulfate / fumaric acid,1-Butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-butylpyridinium tetrafluoroborate / fumaric acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / phthalic acid, tributylmethylammonium dicyanamide / phthalic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / phthalic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / phthalic acid, 2-hydroxyethyltrimethylammonium ammonium Acetate / Phthalic Acid, 2-Hydroxyethyltrimethylammonium Lactate / Phthalic Acid, 2-Hydroxyethyltrimethylammonium Salicylate / Phthalic Acid, Tetrabutylammonium Chloride / Phthalic Acid, 1,3-Dimethylimidazolium Methyl Sulfate / Phthalic Acid, 1,2,3-Trimethylimidazolium Methyl Sulfate / Phthalic Acid, 1-Ethyl-3-Methylimidazolium Acetate / Phthalic Acid, 1-Ethyl-3-Methylimidazolium Dicyanamide / Phthalic Acid, 1-Ethyl-3-Methylimidazolium Methyl Sulfate / phthalic acid, 1-ethyl-3-methylimidazolium thiocyanate / phthalic acid, 1-propyl-3-methylimidazolium acetate / phthalic acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / phthalic acid, 1-butyl-3-methylimidazolium acetate / phthalic acid, 1-butyl-3-methylimidazolium dicyanamide / phthalic acid, 1-butyl-3-methylimidazolium thiocyanate / phthalic acid, 1-butyl-3-methylimidazolium bromide / phthalic acid, 1-butyl 1-butyl-3-methylimidazolium hexafluorophosphate / phthalic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / phthalic acid, 1-octyl-3-methylimidazolium acetate / phthalic acid, 1-octyl-3-methylimidazolium bromide / phthalic acid, 1-octyl-3-methylimidazolium tetrafluoroborate / phthalic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / phthalic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / phthalic acid,Examples include 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / phthalic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / phthalic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / phthalic acid, and 1-butylpyridinium tetrafluoroborate / phthalic acid.

[0057] In a more preferred embodiment, specific examples of the combination of an ionic liquid and an acid (ionic liquid / acid) include trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / citraconic acid, tributylmethylammonium dicyanamide / citraconic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / citraconic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / citraconic acid, 2-hydroxyethyltrimethylammonium acetate / citraconic acid, and 2-hydroxyethyltrimethylammonium methylsulfate. ammonium lactate / citraconate, 2-hydroxyethyltrimethylammonium salicylate / citraconate, tetrabutylammonium chloride / citraconate, 1,3-dimethylimidazolium methyl sulfate / citraconate, 1,2,3-trimethylimidazolium methyl sulfate / citraconate, 1-ethyl-3-methylimidazolium acetate / citraconate, 1-ethyl-3-methylimidazolium dicyanamide / citraconate, 1-ethyl-3-methylimidazolium methyl sulfate / citraconate, 1-ethyl 1-butyl-3-methylimidazolium thiocyanate / citraconic acid, 1-propyl-3-methylimidazolium acetate / citraconic acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / citraconic acid, 1-butyl-3-methylimidazolium acetate / citraconic acid, 1-butyl-3-methylimidazolium dicyanamide / citraconic acid, 1-butyl-3-methylimidazolium thiocyanate / citraconic acid, 1-butyl-3-methylimidazolium bromide / citraconic acid, 1-butyl-3-methylimidazolium Imidazolium hexafluorophosphate / citraconic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / citraconic acid, 1-octyl-3-methylimidazolium acetate / citraconic acid, 1-octyl-3-methylimidazolium bromide / citraconic acid, 1-octyl-3-methylimidazolium tetrafluoroborate / citraconic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / citraconic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / citraconic acid,1-Methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / citraconic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / citraconic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / citraconic acid, 1-butylpyridinium tetrafluoroborate / citraconic acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / acetylene dicarboxylic acid, tributylmethylammonium dicyanamide / acetylene dicarboxylic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / acetylene dicarboxylic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / acetylene dicarboxylic acid, 2-hydroxyethyltrimethylammonium acetate / acetylene dicarboxylic acid, 2-hydroxyethyltrimethylammonium lactate / acetylene dicarboxylic acid, 2-hydroxyethyltrimethylammonium salicylate / acetylene dicarboxylic acid, tetrabutylammonium chloride / acetylene dicarboxylic acid, 1,3-dimethylimidazoline 1-Ethyl-3-methylimidazolium methyl sulfate / acetylenedicarboxylic acid, 1,2,3-trimethylimidazolium methyl sulfate / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium dicyanamide / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium methyl sulfate / citraconic acid, 1-ethyl-3-methylimidazolium thiocyanate / acetylenedicarboxylic acid, 1-propyl-3-methylimidazolium acetate / acetylenedicarboxylic acid Acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / acetylene dicarboxylic acid, 1-butyl-3-methylimidazolium acetate / acetylene dicarboxylic acid, 1-butyl-3-methylimidazolium dicyanamide / acetylene dicarboxylic acid, 1-butyl-3-methylimidazolium thiocyanate / acetylene dicarboxylic acid, 1-butyl-3-methylimidazolium bromide / acetylene dicarboxylic acid, 1-butyl-3-methylimidazolium hexafluorophosphate / acetylene dicarboxylic acid,1-Butyl-3-methylimidazolium tetrafluoroborate / acetylenedicarboxylic acid, 1-octyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-octyl-3-methylimidazolium bromide / acetylenedicarboxylic acid, 1-octyl-3-methylimidazolium tetrafluoroborate / acetylenedicarboxylic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / acetylenedicarboxylic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid Phosphoric acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / acetylene dicarboxylic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / acetylene dicarboxylic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / acetylene dicarboxylic acid, 1-butylpyridinium tetrafluoroborate / acetylene dicarboxylic acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / oxalic acid, tributylmethylammonium dicyanamide / oxalic acid , tributylmethylammonium bis(trifluoromethylsulfonyl)imide / oxalic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / oxalic acid, 2-hydroxyethyltrimethylammonium acetate / oxalic acid, 2-hydroxyethyltrimethylammonium lactate / oxalic acid, 2-hydroxyethyltrimethylammonium salicylate / oxalic acid, tetrabutylammonium chloride / oxalic acid, 1,3-dimethylimidazolium methylsulfate / oxalic acid, 1,2,3-trimethylimidazo 1-ethyl-3-methylimidazolium methyl sulfate / oxalic acid, 1-ethyl-3-methylimidazolium acetate / oxalic acid, 1-ethyl-3-methylimidazolium dicyanamide / oxalic acid, 1-ethyl-3-methylimidazolium methyl sulfate / oxalic acid, 1-ethyl-3-methylimidazolium thiocyanate / oxalic acid, 1-propyl-3-methylimidazolium acetate / oxalic acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / oxalic acid, 1-butyl-3-methylimidazolium acetate / oxalic acid1-Butyl-3-methylimidazolium dicyanamide / oxalic acid, 1-butyl-3-methylimidazolium thiocyanate / oxalic acid, 1-butyl-3-methylimidazolium bromide / oxalic acid, 1-butyl-3-methylimidazolium hexafluorophosphate / oxalic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / oxalic acid, 1-octyl-3-methylimidazolium acetate / oxalic acid, 1-octyl-3-methylimidazolium bromide / oxalic acid, 1-octyl-3-methylimidazolium tetrafluoroborate Fluoroborate / oxalic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / oxalic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / oxalic acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / oxalic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / oxalic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / oxalic acid, 1-butylpyridinium tetrafluoroborate / oxalic acid, trimethylbutyl ammonium bis(trifluoromethylsulfonyl)imide / maleic acid, tributylmethylammonium dicyanamide / maleic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / maleic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / maleic acid, 2-hydroxyethyltrimethylammonium acetate / maleic acid, 2-hydroxyethyltrimethylammonium lactate / maleic acid, 2-hydroxyethyltrimethylammonium salicylate / maleic acid, tetrahydrofuran Tributylammonium chloride / maleic acid, 1,3-dimethylimidazolium methyl sulfate / maleic acid, 1,2,3-trimethylimidazolium methyl sulfate / maleic acid, 1-ethyl-3-methylimidazolium acetate / maleic acid, 1-ethyl-3-methylimidazolium dicyanamide / maleic acid, 1-ethyl-3-methylimidazolium methyl sulfate / maleic acid, 1-ethyl-3-methylimidazolium thiocyanate / maleic acid, 1-propyl-3-methylimidazolium acetate / maleic acid,1-Propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-butyl-3-methylimidazolium acetate / maleic acid, 1-butyl-3-methylimidazolium dicyanamide / maleic acid, 1-butyl-3-methylimidazolium thiocyanate / maleic acid, 1-butyl-3-methylimidazolium bromide / maleic acid, 1-butyl-3-methylimidazolium hexafluorophosphate / maleic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / maleic acid, 1-octyl 1-octyl-3-methylimidazolium acetate / maleic acid, 1-octyl-3-methylimidazolium bromide / maleic acid, 1-octyl-3-methylimidazolium tetrafluoroborate / maleic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / maleic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / maleic acid Acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / maleic acid, 1-butylpyridinium tetrafluoroborate / maleic acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / fumaric acid, tributylmethylammonium dicyanamide / fumaric acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / fumaric acid, tris(2-hydroxyethyl)methylammonium methylsulfate / fumaric acid, 2-hydroxyethyltrimethylammonium acetate / fumaric acid, 2-hydroxyethyltrimethylammonium lactate / fumaric acid, 2-hydroxyethyltrimethylammonium salicylate / fumaric acid, tetrabutylammonium chloride / fumaric acid, 1,3-dimethylimidazolium methyl sulfate / fumaric acid, 1,2,3-trimethylimidazolium methyl sulfate / fumaric acid, 1-ethyl-3-methylimidazolium acetate / fumaric acid, 1-ethyl-3-methylimidazolium dicyanamide / fumaric acid, 1-ethyl-3-methylimidazolium methyl sulfate / fumaric acid,1-Ethyl-3-methylimidazolium thiocyanate / fumaric acid, 1-propyl-3-methylimidazolium acetate / fumaric acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-butyl-3-methylimidazolium acetate / fumaric acid, 1-butyl-3-methylimidazolium dicyanamide / fumaric acid, 1-butyl-3-methylimidazolium thiocyanate, ocyanate / fumaric acid, 1-butyl-3-methylimidazolium bromide / fumaric acid, 1-butyl-3-methylimidazolium hexafluorophosphate / fumaric acid, 1-butyl-3-methylimidazolium tetrafluoroborate / fumaric acid, 1-octyl-3-methylimidazolium acetate / fumaric acid, 1-octyl-3-methylimidazolium bromide / fumaric acid, 1-octyl-3-methylimidazolium tetrafluoroborate / fumaric acid, 1-methyl-1-butylpyrrolidinium dicyanamide / fumaric acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-ethyl-3-methylpyridinium ethyl sulfate / fumaric acid, 1-butyl 4-Methylpyridinium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-butylpyridinium tetrafluoroborate / fumaric acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / phthalic acid, tributylmethylammonium dicyanamide / phthalic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / phthalic acid, tris(2-hydroxyethyl)methylammonium methylsulfate / phthalic acid, 2-hydroxyethyltrimethylammonium acetate / phthalic acid, 2-hydroxyethyltrimethylammonium lactate / phthalic acid, 2-hydroxyethyltrimethylammonium salicylate / phthalic acid, tetrabutylammonium chloride / phthalic acid, 1,3-dimethylimidazolium methylsulfate / phthalic acid, 1,2,3-Trimethylimidazolium methyl sulfate / phthalic acid, 1-ethyl-3-methylimidazolium acetate / phthalic acid, 1-ethyl-3-methylimidazolium dicyanamide / phthalic acid, 1-ethyl-3-methylimidazolium methyl sulfate / phthalic acid, 1-ethyl-3-methylimidazolium thiocyanate / phthalic acid, 1-propyl-3-methylimidazolium acetate / phthalic acid, 1-propyl 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / phthalic acid, 1-butyl-3-methylimidazolium acetate / phthalic acid, 1-butyl-3-methylimidazolium dicyanamide / phthalic acid, 1-butyl-3-methylimidazolium thiocyanate / phthalic acid, 1-butyl-3-methylimidazolium bromide / phthalic acid, 1-butyl-3-methylimidazolium hexafluorophosphate phosphate / phthalic acid, 1-butyl-3-methylimidazolium tetrafluoroborate / phthalic acid, 1-octyl-3-methylimidazolium acetate / phthalic acid, 1-octyl-3-methylimidazolium bromide / phthalic acid, 1-octyl-3-methylimidazolium tetrafluoroborate / phthalic acid, 1-methyl-1-butylpyrrolidinium dicyanamide / phthalic acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / phthalic acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / phthalic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / phthalic acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / phthalic acid, and 1-butylpyridinium tetrafluoroborate / phthalic acid.

[0058] In an even more preferred embodiment, specific examples of the combination of an ionic liquid and an acid (ionic liquid / acid) include 1-ethyl-3-methylimidazolium acetate / maleic acid, 1-propyl-3-methylimidazolium acetate / maleic acid, 1-butyl-3-methylimidazolium acetate / maleic acid, and 1-octyl-3-methylimidazolium acetate / maleic acid.

[0059] The compounding ratio of the ionic liquid to the acid (ionic liquid / acid) is preferably an equivalent ratio of 0.10 to 1.0, more preferably 0.20 to 1.0. If the equivalent ratio is less than 0.10, the density of the cured film tends to decrease, and if it exceeds 1.0, the storage stability tends to decrease.

[0060] The acid may be used alone or in combination of two or more kinds. The content of the acid is preferably 0.00020 to 10.0 mass%, more preferably 0.020 to 10.0 mass%, and even more preferably 0.020 to 8.0 mass%, based on the total mass of the composition according to the present invention.

[0061] The underlayer film composition of the present invention can be combined with additional compounds as needed. The materials that can be combined are described below. The total amount of components other than those described above in the entire composition is preferably 10% or less, more preferably 5% or less, based on the total mass of the composition. A preferred embodiment of the present invention is one in which no components other than those described above are included.

[0062] Examples of other additives include surfactants, adhesion promoters, antifoaming agents, and heat curing accelerators.

[0063] <Metal Oxide Resist Film Manufacturing Method> The method for producing a metal oxide resist film according to the present invention comprises the following steps: (a) applying an underlayer film composition according to the present invention onto a substrate to form a metal oxide resist underlayer film; (b) irradiating the metal oxide resist underlayer film with energy rays; and (c) forming a metal oxide resist film on the metal oxide resist underlayer film irradiated with energy rays;

[0064] Process (a) Examples of the substrate include a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate, and an ITO substrate, and the above-described underlayer film composition is applied onto the substrate by an appropriate method to form a metal oxide resist underlayer film. In the present invention, the term "on a substrate" includes cases where the organic film is formed directly on the substrate and cases where the organic film is formed via another layer. For example, an organic film may be formed directly on the substrate, and the underlayer film composition of the present invention may be applied directly on the SOC film. In a preferred embodiment, the organic film is formed below the metal oxide resist underlayer film (including cases where the organic film is formed directly below the substrate and via another layer), and more preferably, the organic film (more preferably the SOC film) is formed directly below the metal oxide resist underlayer film. The application method is not particularly limited, but examples include coating using a spinner or coater. After coating, the underlayer film is formed by heating (pre-baking). Pre-baking is performed, for example, using a hot plate. The heating temperature is preferably 80 to 200°C (more preferably 100 to 180°C; even more preferably 120 to 180°C). The heating time is preferably 30 to 300 seconds.

[0065] Process (b) The energy rays irradiated onto the metal oxide resist underlayer film are preferably ultraviolet rays having a peak wavelength of 200 nm or less, more preferably a peak wavelength of 150 to 200 nm. The irradiation dose of the energy rays is preferably 150 to 500 mJ / cm. 2 and more preferably 200 to 450 mJ / cm 2 is.

[0066] After the irradiation of energy rays in step (b), the method preferably further comprises a step of heating the metal oxide resist underlayer film at 200 to 500°C (preferably 200 to 450°C). This heating cures the polysiloxane. In a preferred embodiment, the heating for curing is carried out at 200 to 250°C. The heating time is preferably 30 seconds to 30 minutes, more preferably 30 seconds to 15 minutes. The film thickness of the metal oxide resist underlayer film is preferably 0.5 to 50 nm, more preferably 1 to 30 nm, and even more preferably 3 to 15 nm.

[0067] Process (c) After step (b), if necessary, a heating step for curing is performed, and then a metal oxide resist film is formed on the metal oxide resist underlayer film. Preferably, the metal oxide resist film is formed directly on the metal oxide resist underlayer film. The method for applying the resist composition is not particularly limited, but may be the same as the application described above, and vapor phase deposition methods are also possible. A more preferred method is a coating method. After application, the metal oxide resist composition is preferably prebaked. The prebaking temperature is preferably 75 to 200°C (more preferably 80 to 180°C). The heating time is preferably 30 to 240 seconds (more preferably 90 to 180 seconds). Heating is preferably carried out in air or a nitrogen gas atmosphere. The thickness of the resist film is preferably 10 to 70 nm (more preferably 10 to 50 nm, and even more preferably 20 to 30 nm).

[0068] The method for producing a resist pattern according to the present invention comprises the following steps. forming a metal oxide resist film by the above method; exposing the metal oxide resist film to light; and developing the metal oxide resist film;

[0069] Exposure process The resist film is then exposed through a predetermined mask. The wavelength of the light used for exposure is not particularly limited, but exposure with light having a wavelength of 13.5 to 248 nm is preferred. Specifically, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), extreme ultraviolet light (wavelength 13.5 nm), etc. can be used, with extreme ultraviolet light being preferred.

[0070] After exposure, post-exposure baking (PEB) can be performed as needed. The PEB temperature is preferably 100 to 200°C (more preferably 150 to 190°C), and the heating time is preferably 30 to 240 seconds (more preferably 90 to 180 seconds).

[0071] Development process The exposed resist film is developed using a developer to form a resist pattern. Examples of development methods include alkaline development and organic solvent development, with organic solvent development being preferred. The developer contains an organic solvent, more preferably an organic solvent. In the case of organic solvent development, examples of the developer include hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, and alcohol solvents, with ester solvents or ketone solvents being preferred. Specific examples of the developer include 2-heptanone, butyl acetate, and PGMEA.

[0072] Thereafter, the substrate is further processed as necessary to produce an electronic device. These further processing steps can be performed using known methods. The method for producing an electronic device according to the present invention comprises the method for producing a resist film described above.

[0073] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

[0074] Gel permeation chromatography (GPC) is performed using an alliance™ e2695 high-speed GPC system (Nihon Waters, Inc.) and a Super Multipore HZ-N GPC column (Tosoh Corporation). Measurements are performed using monodisperse polystyrene as a standard sample and tetrahydrofuran as a developing solvent under measurement conditions of a flow rate of 0.6 ml / min and a column temperature of 40°C, and the mass-average molecular weight (hereinafter sometimes referred to as Mw) is calculated as the molecular weight relative to the standard sample.

[0075] <Polysiloxanes A to F> Polysiloxanes A to F are obtained by synthesizing the monomers shown in Table 1 in the molar ratios shown in Table 1. Mw of each is shown in Table 1.

[0076] [Table 1]

[0077] Preparation of Polysiloxane Composition The polysiloxane compositions of Examples 1 to 7 and Comparative Example 2 were prepared by mixing 0.5 parts by mass of the polysiloxane shown in Table 2 and 99.5 parts by mass of the solvent PGMEA. The polysiloxane composition of Example 8 is prepared by mixing 1.0 part by mass of polysiloxane A, 0.010 parts by mass of 1-ethyl-3-methylimidazolium acetate (EMIMAc) as an ionic liquid, 0.050 parts by mass of maleic acid, and 98.94 parts by mass of the solvent PGMEA.

[0078] <Examples 1 to 8 and Comparative Example 2> The SOC-forming composition is spin-coated onto a silicon wafer, pre-baked at 180° C., and then heated at 400° C. for curing, to obtain an SOC layer with a thickness of 55 nm. The composition prepared above was spin-coated onto the SOC layer, pre-baked at 150°C, then heated for curing at the temperature shown in Table 2, and then irradiated with 172 nm UV at 250 mJ / cm. 2The thickness of the polysiloxane underlayer film is shown in Table 2. An organometallic tin oxyhydroxide resist composition is spin-coated onto the polysiloxane underlayer film and pre-baked at 150° C. to obtain a metal oxide resist layer with a thickness of 22 nm. Using the EUV exposure machine NXE3400NA0.33 (ASML), 59 to 101 mJ / cm 2 Then, post-exposure baking (PEB) is performed at 180° C. Thereafter, development is performed using 2-heptanone as a developer to form a resist pattern. Table 2 shows the exposure dose when a resist pattern with a 1:1 line and space ratio is formed using a 32 nm pitch line and space mask. <Comparative Example 1> In Comparative Example 1, a resist pattern is formed in the same manner as above, except that a metal oxide resist layer is formed directly on the SOC layer. Pattern peeling and pattern collapse are observed in the formed pattern, but the exposure dose is determined in areas where these do not occur.

[0079] [Table 2]

Claims

1. A method for improving the exposure sensitivity of a metal oxide resist, using a composition comprising a polysiloxane comprising a repeating unit represented by the following formula (Ia): 【Chemistry 1】 (where, R Ｉａ is unsubstituted or C １－５ alkyl-substituted phenyl, naphthyl, phenalenyl, phenanthrenyl, or anthracenyl)

2. 2. The method of claim 1, wherein the polysiloxane further comprises a repeating unit represented by formula (Ib): 【Chemistry 2】 (where, R Ｉｂ is C １－６ alkyl)

3. 3. The method of claim 1, wherein the polysiloxane further comprises a repeating unit represented by formula (Ic): 【Transformation 3】

4. The method according to any one of claims 1 to 3, wherein the composition is applied onto an organic film formed on a substrate and used to form a film: Preferably, the film is a metal oxide resist underlayer film.

5. The method according to any one of claims 1 to 4, wherein the composition further comprises a solvent; preferably, the content of the solvent is 90.0 to 99.9% by weight, based on the total weight of the composition.

6. A metal oxide resist underlayer film composition comprising a polysiloxane comprising a repeating unit represented by formula (Ia) and a solvent. 【Chemistry 4】 (where, R Ｉａ is unsubstituted or C １－５ alkyl-substituted phenyl, naphthyl, phenalenyl, phenanthrenyl, or anthracenyl)

7. 7. The composition of claim 6, wherein the polysiloxane further comprises a repeating unit represented by formula (Ib): 【Transformation 5】 (where, R Ｉｂ is C １－６ alkyl)

8. 8. The composition of claim 6 or 7, wherein the polysiloxane further comprises a repeating unit represented by formula (Ic): 【Transformation 6】

9. The composition according to any one of claims 6 to 8, wherein the polysiloxane has a weight average molecular weight of 500 to 20,000.

10. The composition according to any one of claims 6 to 9, wherein the solvent is at least one selected from the group consisting of propylene glycol monomethyl ether, 3-methoxybutanol, 1,3-butanediol, propylene glycol monomethyl ether acetate, ethyl lactate, butyl acetate, and 3-methoxybutyl acetate.

11. The composition according to any one of claims 6 to 10, wherein the content of the solvent is 90.0 to 99.9 mass% based on the total mass of the composition.

12. The composition according to any one of claims 6 to 11, further comprising an ionic liquid.

13. A method for producing a metal oxide resist film, comprising the steps of: (a) applying the composition according to any one of claims 6 to 12 onto a substrate to form a metal oxide resist underlayer film; (b) irradiating the metal oxide resist underlayer film with energy rays; and (c) forming a metal oxide resist film on the metal oxide resist underlayer film irradiated with energy rays;

14. The method according to claim 13 , wherein an organic film is formed below the resist underlayer film.

15. The method according to claim 13 or 14, wherein the energy ray is ultraviolet light having a peak wavelength of 200 nm or less.

16. The irradiation dose of the energy beam is 150 to 500 mJ / cm ２ The method according to any one of claims 13 to 15, wherein

17. The method according to any one of claims 13 to 16, further comprising the step of further heating the resist underlayer film at 200 to 500°C after forming the resist underlayer film irradiated with the energy rays.

18. A method for producing a resist pattern, comprising the following steps: A step of forming a metal oxide resist film by the method according to any one of claims 13 to 17; exposing the metal oxide resist film to light; and developing the metal oxide resist film;

19. A method for producing an electronic device, comprising the method according to any one of claims 13 to 18.

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