Polysiloxane composition

Abstract

Provided is a polysiloxane composition capable of low-temperature curing and having excellent storage stability. 【Solution means】The polysiloxane composition according to the present invention comprises (I) a polysiloxane having a specific structure, (II) an ionic liquid, (III) an acid, and (IV) a solvent.

Description

Technical Field

[0001] The present invention relates to a polysiloxane composition. The present invention also relates to 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 Art

[0002] Polysiloxane is known for its high temperature resistance. When forming a cured film from a composition containing polysiloxane, the coating film is heated at a high temperature to rapidly progress the condensation reaction of silanol groups in the polysiloxane and the reaction of a polymer having an unsaturated bond, thereby curing. If unreacted reactive groups remain, they may react with the chemicals used in the device manufacturing process. Due to the influence on other materials in the substrate and the equipment conditions, there is a demand for the development of a polysiloxane-containing composition that can be cured at a lower temperature. The development of a composition containing polysiloxane is desired.

[0003] For the purpose of curing an epoxy resin at a low temperature, it has been proposed to combine an epoxy resin, an anionic polymerizable curing agent, and an ionic liquid (for example, Patent Document 1). In a comparative example that does not contain an anionic polymerizable curing agent, curing does not occur.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made based on the above circumstances, and an object thereof is to provide a polysiloxane composition that can be cured at a low temperature and has excellent storage stability. Another object is to provide a method for producing a cured film and an electronic device using the same.

Means for Solving the Problems

[0006] The polysiloxane composition according to the present invention is (I) a polysiloxane containing a repeating unit represented by formula (Ia) and having silanol at a terminal or side chain, [Chemical formula] (where R 1 is hydrogen, a linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group having 1 to 3 valences, or an aromatic hydrocarbon group having 1 to 3 valences of C 1-30 , and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or C 6-30 alkoxy, in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or one or more methylenes are replaced with oxy, imide or carbonyl, provided that R 1-8 is not hydroxy or alkoxy, when R 1 is divalent or trivalent, R R 1 connects Si's contained in a plurality of repeating units) 1 when the polysiloxane is measured and analyzed by the FT-IR method, the ratio S2 / S1 of the area intensity S1 of the absorption band attributed to Si-O in the range of 1100 ± 100 cm -1 and the area intensity S2 of the absorption band attributed to SiOH in the range of 900 ± 100 cm -1 is 0.010 to 0.10, (II) an ionic liquid, (III) an acid, and (IV) a solvent and comprises the same.

[0007] Further, the method for producing a cured film according to the present invention comprises applying the above composition to a substrate to form a coating film, and heating the coating film.

[0008] Further, the method for manufacturing an electronic device according to the present invention includes the above-described method for manufacturing a cured film.

Advantages of the Invention

[0009] The polysiloxane composition according to the present invention can be cured at a temperature lower than the temperature range employed in general thermosettable compositions. The polysiloxane composition according to the present invention has excellent storage stability. The resulting cured film has little film peeling amount, excellent film thickness uniformity, and a small elastic modulus, so that it can follow substrate deformation. Further, when applied to a substrate with a high aspect ratio, it has excellent embedding properties. Since the resulting cured film has excellent flatness and electrical insulation properties, it can be suitably used for optical devices such as an interlayer insulating film of a semiconductor device, a passivation film, a substrate planarization film, an antireflection film, an optical filter, a high-brightness light-emitting diode, a touch panel, a solar cell, and an optical waveguide.

Embodiments for Carrying Out the Invention

[0010] [Definitions] In this specification, unless otherwise particularly limited, the definitions and examples described in this paragraph shall apply. The singular form includes the plural form, and "one" and "the" mean "at least one". The elements of a certain concept can be expressed by multiple types, and when the amount thereof (for example, mass% or mol%) is described, the amount means the sum of those multiple types. "And / or" includes all combinations of elements and also includes use alone. When a numerical range is indicated using "~" or "-", these include both endpoints and the units are common. For example, 5~25 mol% means 5 mol% or more and 25 mol% or less. "C x-y ", "C x ~C y " and "C x " and the like denote the number of carbons in a molecule or a substituent. For example, C 1-6Alkyl means an alkyl chain having 1 to 6 carbons (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When the polymer has multiple types of repeating units, these repeating units copolymerize. These copolymerizations can be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or any mixture thereof. When indicating a polymer or resin by a structural formula, n, m, etc. written in parentheses indicate the number of repetitions. The unit of temperature uses Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to the compound itself having that function (for example, if it is a base generator, it is the compound itself that generates a base). There may also be a form in which the compound is dissolved or dispersed in a solvent and added to the composition. As one form of the present invention, such a solvent is preferably contained in the composition according to the present invention as solvent (IV) or as other components.

[0011] Hereinafter, embodiments of the present invention will be described in detail.

[0012] Polysiloxane composition The polysiloxane composition according to the present invention (hereinafter sometimes simply referred to as the composition) comprises (I) a polysiloxane having a specific structure, (II) an ionic liquid, (III) an acid, and (IV) a solvent. Hereinafter, each component contained in the composition according to the present invention will be described in detail.

[0013] (I) Polysiloxane The polysiloxane used in the present invention comprises a repeating unit represented by the following formula (Ia) and has silanol at the terminal or side chain. Here, silanol refers to a compound in which an OH group is directly bonded to the Si skeleton of the polysiloxane, and in the polysiloxane containing a repeating unit such as the repeating unit of formula (Ia), it is a compound in which hydroxy is directly bonded to a silicon atom. That is, for the -O 0.5 - against, -O 0.5Silanol is formed by the bonding of H. The silanol content in polysiloxane varies depending on the synthesis conditions of the polysiloxane, such as the blending ratio of monomers and the type of reaction catalyst. This silanol content can be evaluated by quantitative infrared absorption spectrum measurement. The absorption band attributed to silanol (SiOH) appears as an absorption band having a peak in the range of 900 ± 100 cm -1 in the infrared absorption spectrum. When the silanol content is high, the intensity of this absorption band increases.

[0014] When the polysiloxane used in the present invention is measured and analyzed by the FT-IR method, the ratio S2 / S1 of the area intensity S1 of the absorption band attributed to Si-O in the range of 1100 ± 100 cm -1 to the area intensity S2 of the absorption band attributed to SiOH in the range of 900 ± 100 cm -1 is 0.010 to 0.10, preferably 0.015 to 0.090, and more preferably 0.020 to 0.080. The area intensity of the absorption band is determined in consideration of the noise of the infrared absorption spectrum, etc. In the typical infrared absorption spectrum of polysiloxane, an absorption band attributed to Si-OH having a peak in the range of 900 ± 100 cm -1 and an absorption band attributed to Si-O having a peak in the range of 1100 ± 100 cm -1 are confirmed. The area intensities of these absorption bands can be measured as the area considering the baseline considering noise, etc. The tails of the absorption band attributed to Si-OH and the tail of the absorption band attributed to Si-O may overlap. In that case, the wavenumber corresponding to the minimum point between the two absorption bands in the spectrum is taken as the boundary. The same applies when the tails of other absorption bands overlap with the tails of the absorption bands attributed to Si-OH or Si-O.

[0015] Formula (Ia) is as follows.

Chemical formula

[0016] In formula (Ia), when R 1 is a monovalent group, R 1Examples include, in addition to hydrogen, (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryl groups such as phenyl, tolyl, and benzyl; (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryl groups; (v) cycloalkyl groups such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amino; (vii) oxygen-containing groups having an epoxy structure such as glycidyl, or an acryloyl structure or a methacryloyl structure. Preferably, they are methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, and isocyanate. As the fluoroalkyl group, perfluoroalkyl, particularly trifluoromethyl and pentafluoroethyl, is preferred. Since the raw materials are easily available, the film hardness after curing is high, and it has high chemical resistance, R 1 is preferably methyl. Also, to increase the solubility of the polysiloxane in the solvent and make the cured film less likely to crack, R 1 is preferably phenyl.

[0017] R 1 When R is a divalent or trivalent group, R 1 is, for example, (i) a group obtained by removing two or three hydrogens from alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, and decane; (ii) a group obtained by removing two or three hydrogens from cycloalkanes such as cycloheptane, cyclohexane, and cyclooctane; (iii) a group obtained by removing two or three hydrogens from aromatic compounds composed only of hydrocarbons such as benzene and naphthalene; and (iv) a group obtained by removing two or three hydrogens from nitrogen- and / or oxygen-containing cycloaliphatic hydrocarbon compounds containing amino groups, imino groups, and / or carbonyl groups such as piperidine, pyrrolidine, and isocyanurate. It is more preferably (iv) because it improves the pattern collapse and the adhesion to the substrate is enhanced.

[0018] The number of repeating units represented by formula (Ia) is preferably 80% or more, more preferably 90% or more, based on the total number of repeating units contained in the polysiloxane molecule. In one embodiment of the present invention, the polysiloxane preferably consists essentially of repeating units represented by formula (Ia), and more preferably consists of repeating units represented by formula (Ia).

[0019] The polysiloxane used in the present invention may further contain repeating units represented by the following formula (Ib).

Chemical formula

[0020] The polysiloxane used in the present invention may further contain a repeating unit represented by the following formula (Ic). However, the repeating unit represented by formula (Ic) is preferably small from the viewpoints of compatibility with the solvent, suppression of crack generation, and low elastic modulus. Specifically, it is preferably 10% or less, more preferably 5% or less, based on the total number of repeating units contained in the polysiloxane molecule. In a preferred embodiment, the polysiloxane used in the present invention substantially does not contain the repeating unit represented by formula (Ic), and more preferably does not contain the repeating unit represented by formula (Ic), that is, 0%.

Chemical formula

[0021] The polysiloxane used in the present invention may also contain repeating units other than the repeating units represented by (Ia), (Ib), and (Ic). However, the number of repeating units other than the above is preferably 20% or less, more preferably 10% or less, based on the total number of repeating units contained in the polysiloxane molecule. Not containing repeating units other than the above is also a preferred embodiment of the present invention.

[0022] The mass average molecular weight of the polysiloxane used in the present invention is preferably 500 to 10,000, more preferably 500 to 4,000, and even more preferably 1,000 to 3,000, from the viewpoints of solubility in organic solvents, coatability on substrates, and solubility in alkaline developers. Here, the mass average molecular weight is the polystyrene-converted mass average molecular weight, which can be measured by gel permeation chromatography using polystyrene as a reference.

[0023] The polysiloxane can be used alone or in combination of two or more. The content of the polysiloxane is preferably 0.5 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the polysiloxane composition.

[0024] Such a polysiloxane is, for example, of the formula (ia): R 1’ [Si(OR a )3] p (ia) (where p is an integer from 1 to 3, R 1’ is hydrogen, a linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group having 1 to 3 valences, or an aromatic hydrocarbon group having 1 to 3 valences, 1-30 wherein the aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or C 6-30 alkoxy, in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or one or more methylenes are replaced with oxy, imide or carbonyl, provided that R 1-8 is not hydroxy or alkoxy, R 1’ is C a alkyl, preferably methyl, ethyl, n-propyl, isopropyl, and n-butyl) 1-10 is a silicon compound represented by 11 and can be obtained by hydrolysis and condensation, if necessary, in the presence of an acidic catalyst or a basic catalyst.

[0025] ​​​Specific examples of the silicon compound represented by the general formula (ia) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, tris-(3-trimethoxysilylpropyl)isocyanurate, tris-(3-triethoxysilylpropyl)isocyanurate, tris-(3-trimethoxysilylethyl)isocyanurate, etc. Among them, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and phenyltrimethoxysilane are preferred.

[0026] Here, two or more kinds of silicon compounds can also be used in combination.

[0027] (II) Ionic liquid The composition according to the present invention comprises an ionic liquid. An ionic liquid is a salt that exists as a liquid in a wide temperature range and is a liquid composed only of ions. Generally, a salt having a melting point of 100°C or lower is defined as an ionic liquid. The ionic liquid used in the present invention has a melting point of 100°C or lower, preferably 80°C or lower, more preferably 60°C or lower, and even more preferably 30°C or lower. The ionic liquid used in the present invention is preferably a basic ionic liquid, and those composed of a combination of a strong base and a weak acid are preferred.

[0028] 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.

[0029] The imidazolium-based ion is preferably represented by the following formula (A). [Chemical formula] Here, R 11 、R 12 、R 13 、R 14 and R 15 are each independently hydrogen, linear or branched C 1-18 alkyl, cyclic C 5-12 alkyl, or C 6-14 aryl.

[0030] Specific examples of imidazolium-based 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, 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. Preferably, 1-ethyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,3-dimethylimidazolium, 1,2,They are 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.,

[0031] The pyrrolidinium-based ion is preferably represented by the following formula (B).

Chemical formula

[0032] Specific examples of the pyrrolidinium-based ion 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, and preferably 1-methyl-1-propylpyrrolidinium.

[0033] The piperidinium-based ion is preferably represented by the following formula (C).

Chemical formula

[0034] 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, preferably 1-methyl-1-butylpiperidinium.

[0035] Pyridinium ions are preferably represented by the following formula (D). [Chemical formula] Here, R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are each independently hydrogen, linear or branched C 1-18 alkyl, cyclic C 5-12 alkyl, or C 6-14 aryl.

[0036] 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, preferably 1-butylpyridinium and 1-ethyl-4-methylpyridinium.

[0037] The ammonium-based ion is preferably represented by the following formula (E).

Chemical formula

[0038] Specific examples of the ammonium-based ion include trimethylethylammonium, trimethylbutylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trihexylmethylammonium, trioctylmethylammonium, tetrabutylammonium, 2-hydroxyethyltrimethylammonium, and tris(2-hydroxyethyl)methylammonium. Preferably, they are tetrabutylammonium, tributylmethylammonium, and 2-hydroxyethyltrimethylammonium.

[0039] 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, more preferably acetate ion, dicyanamide ion, cyanamide ion, chloride ion, and bromide ion.

[0040] 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 methyl sulfate, 2-hydroxyethyltrimethylammonium acetate, 2-hydroxyethyltrimethylammonium lactate, 2-hydroxyethyltrimethylammonium salicylate, tetrabutylammonium chloride, 1,3-dimethylimidazolium methyl sulfate, 1,2,3-trimethylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium 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-2,3-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 form, the ionic liquid has an imidazolium-based ion as the cation and acetate as the anion. Specific examples include 1-ethyl-3-methylimidazolium acetate, 1-propyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, and 1-octyl-3-methylimidazolium acetate.,

[0041] The ionic liquid has a catalytic action to promote the curing of polysiloxane and is considered to be able to complete the curing even at a relatively low temperature. The mixing ratio of the ionic liquid to polysiloxane (ionic liquid / polysiloxane) is preferably 0.000010 to 0.10, more preferably 0.000020 to 0.10, by mass ratio. This is because being within such a range can more effectively exhibit the effect of low-temperature curing and the density of the cured film tends to increase. The ionic liquid can be uniformly present in the composition compared to commonly used curing accelerators (e.g., thermal base generators), so it is considered to be effective in suppressing voids. The inclusion of the ionic liquid in the composition can also be expected to improve the adhesion to the substrate.

[0042] The ionic liquid can be used alone or in combination of two or more. The content of the ionic liquid is preferably 0.00010 to 4.0% by mass, more preferably 0.00020 to 3.2% by mass, based on the total mass of the composition according to the present invention.

[0043] (III) Acid The composition according to the present invention contains an acid. The acid may be an inorganic acid or an organic acid, preferably an organic acid, more preferably a carboxylic acid, still more preferably a monocarboxylic acid or a dicarboxylic acid, and even more preferably a dicarboxylic acid.

[0044] Examples of the monocarboxylic acid include acetic acid, formic acid, propionic acid, butyric acid, valeric acid, and acrylic acid, preferably acetic acid. Examples of the dicarboxylic acid 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. Preferably, oxalic acid, maleic acid, fumaric acid, phthalic acid, succinic acid, malic acid, citraconic acid, acetylenedicarboxylic acid, or malonic acid, and more preferably oxalic acid, maleic acid, fumaric acid, phthalic acid, citraconic acid, or acetylenedicarboxylic acid.

[0045] The acid preferably has high sublimability and sublimes during heating 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 remaining amount of the acid decreases due to sublimation.

[0046] Although not restricted by theory, as described above, the ionic liquid functions as a catalyst that promotes the curing of polysiloxane at low temperatures. A composition containing an ionic liquid, polysiloxane, and a solvent may undergo curing and gelation during long-term storage at room temperature. In contrast, it is thought that by combining an acid, the catalytic action of the ionic liquid can be suppressed, and good storage stability can be exhibited. It is thought that when the acid sublimes during heating for curing, the catalytic action of the ionic liquid is expressed, and curing can occur at a low temperature. In order to exhibit better storage stability and low-temperature curability, in the present invention, it preferably contains 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 in which the cation is an imidazolium-based ion and the anion is an acetate ion, and maleic acid.

[0047] 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 methyl sulfate / 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 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 / 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, 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 / glutaric acid, tris(2-hydroxyethyl)methylammonium methyl sulfate / glutaric acid, 2-hydroxyethyltrimethylammonium acetate / glutaric acid, 2-hydroxyethyltrimethylammonium lactate / glutaric acid, 2-hydroxyethyltrimethylammonium salicylate / glutaric acid, tetrabutylammonium chloride / glutaric acid, 1-ethyl-3-methylimidazolium acetate / glutaric acid, 1-ethyl-3-methylimidazolium dicyanamide / glutaric acid, 1-ethyl-3-methylimidazolium methyl sulfate / glutaric acid, 1-ethyl-3-methylimidazolium thiocyanate / glutaric acid, 1-propyl-3-methylimidazolium acetate / glutaric acid, 1-butyl-3-methylimidazolium acetate / glutaric acid, 1-butyl-3-methylimidazolium dicyanamide / glutaric acid, 1-butyl-3-methylimidazolium thiocyanate / glutaric acid, 1-butyl-3-methylimidazolium bromide / glutaric acid, 1-octyl-3-methylimidazolium acetate / glutaric acid, 1-octyl-3-methylimidazolium bromide / glutaric acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / citric acid, tributylmethylammonium dicyanamide / citric acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / citric acid, tris(2-hydroxyethyl)methylammonium methyl sulfate / citric acid, 2-hydroxyethyltrimethylammonium acetate / citric acid, 2-hydroxyethyltrimethylammonium lactate / citric acid, 2-hydroxyethyltrimethylammonium salicylate / citric acid, tetrabutylammonium chloride / citric acid, 1,3-dimethylimidazolium methyl sulfate / citric acid, 1,2,3-trimethylimidazolium methyl sulfate / citric acid,1-Ethyl-3-methylimidazolium acetate / citric acid, 1-ethyl-3-methylimidazolium dicyanamide / citric acid, 1-ethyl-3-methylimidazolium methyl sulfate / citric acid, 1-ethyl-3-methylimidazolium thiocyanate / citric acid, 1-propyl-3-methylimidazolium acetate / citric acid, 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / citric acid, 1-butyl-3-methylimidazolium acetate / citric acid, 1-butyl-3-methylimidazolium dicyanamide / citric acid, 1-butyl-3-methylimidazolium thiocyanate / citric acid, 1-butyl-3-methylimidazolium bromide / citric acid, 1-butyl-3-methylimidazolium hexafluorophosphate / citric acid, 1-butyl-3-methylimidazolium tetrafluoroborate / citric acid, 1-octyl-3-methylimidazolium acetate / citric acid, 1-octyl-3-methylimidazolium bromide / citric acid, 1-octyl-3-methylimidazolium tetrafluoroborate / citric acid, 1-methyl-1-butylpyrrolidinium dicyanamide / citric acid, 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / citric acid, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / citric acid, 1-ethyl-3-methylpyridinium ethyl sulfate / citric acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / citric acid, 1-butylpyridinium tetrafluoroborate / citric acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, tributylmethylammonium dicyanamide / acetylenedicarboxylic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, tris(2-hydroxyethyl)methylammonium methyl sulfate / acetylenedicarboxylic acid, 2-hydroxyethyltrimethylammonium acetate / acetylenedicarboxylic acid2-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 Dicyanamide / Acetylenedicarboxylic Acid, 1-Ethyl-3-methylimidazolium Methyl Sulfate / 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 Dicyanamide / 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 / 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, 1-Methyl-1-butylpiperidinium Bis(trifluoromethylsulfonyl)imide / Acetylenedicarboxylic Acid, 1-Ethyl-3-methylpyridinium Ethyl Sulfate / Acetylenedicarboxylic 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 methyl sulfate / oxalic acid, 2-hydroxyethyltrimethylammonium 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 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 acid1-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 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-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, 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 methyl sulfate / 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 / 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 acid1-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 methyl sulfate / phthalic acid, 2-hydroxyethyltrimethylammonium 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-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 acidExamples 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.

[0048] 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 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 methyl sulfate / 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 / citraconic acid, 1-butyl-3-methylimidazolium thiocyanate / citraconic acid, 1-butyl-3-methylimidazolium bromide / citraconic acid, 1-butyl-3-methylimidazolium 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 / acetylenedicarboxylic acid, Tributylmethylammonium dicyanamide / acetylenedicarboxylic acid, Tributylmethylammonium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, Tris(2-hydroxyethyl)methylammonium methyl sulfate / 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 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, 1-Propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, 1-Butyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-Butyl-3-methylimidazolium dicyanamide / 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 / 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, 1-methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, 1-ethyl-3-methylpyridinium ethyl sulfate / acetylenedicarboxylic 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 methyl sulfate / oxalic acid, 2-hydroxyethyltrimethylammonium 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 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 / 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(trifluoromethylsulfonyl)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 methyl sulfate / maleic acid, 1-ethyl-3-methylimidazolium thiocyanate / maleic acid, 1-propyl-3-methylimidazolium acetate / maleic acid1-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 / 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 methyl sulfate / 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 thi, Oxyanate / 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 methyl sulfate / Phthalic acid, 2-Hydroxyethyltrimethylammonium 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 - 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, 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 may be mentioned.,

[0049] In an even more preferred embodiment, specific examples of the combination of the ionic liquid and the 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.,

[0050] The mixing ratio of the ionic liquid to the acid (ionic liquid / acid) is preferably 0.10 to 1.0 in terms of equivalent ratio, more preferably 0.20 to 1.0. This is because when the equivalent ratio is less than 0.10, the density of the cured film decreases, and when it exceeds 1.0, the storage stability tends to decrease.

[0051] The acid can be used alone or in combination of two or more. The content of the acid is preferably 0.00020 to 10.0% by mass, more preferably 0.005 to 10.0% by mass, and still more preferably 0.001 to 8.0% by mass based on the total mass of the composition according to the present invention.

[0052] (IV) Solvent The solvent is not particularly limited as long as it can uniformly dissolve or disperse the above-mentioned components (I) to (III) and additives added as required. 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 alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether 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; cyclic esters such as γ-butyrolactone, etc. Preferably, they are PGME, 3-methoxybutanol, 1,3-butanediol, PGMEA, ethyl lactate, butyl acetate, and 3-methoxybutyl acetate. The solvents can be used alone or in combination of two or more thereof.

[0053] The solvent content of the composition according to the present invention can be appropriately selected according to the mass average molecular weight, its distribution, and structure of the polysiloxane used, so as to improve workability depending on the coating method employed, and also taking into account the permeability of the solution into the fine grooves and the film thickness required outside the grooves. The content of the solvent is preferably 50 to 98% by mass, more preferably 60 to 98% by mass, based on the total mass of the composition according to the present invention.

[0054] The composition according to the present invention essentially comprises the above-mentioned (I) to (IV), but additional compounds can be combined as needed. The materials that can be combined are described as follows. The total amount of components other than (I) to (IV) in the entire composition is preferably 10% or less, more preferably 5% or less, based on the total mass of the composition.

[0055] The composition according to the present invention may contain other additives as needed. Examples of such additives include surfactants, adhesion enhancers, defoamers, heat-curing accelerators, and the like.

[0056] Surfactants are added for the purpose of improving coating characteristics, developability, etc. Examples of surfactants that can be used in the present invention include nonionic surfactants, anionic surfactants, amphoteric surfactants, and the like.

[0057] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters; polyoxyethylene fatty acid monoesters; polyoxyethylene polyoxypyropylene block polymers; acetylene alcohols; acetylene alcohol derivatives such as polyethoxylates of acetylene alcohols; acetylene glycols; acetylene glycol derivatives such as polyethoxylates of acetylene glycols; fluorine-containing surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Limited), MEGAFACE (trade name, manufactured by DIC Corporation), and Sulfron (trade name, manufactured by Asahi Glass Co., Ltd.); and organosiloxane surfactants such as KP341 and KF-53 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol derivatives include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0058] Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkylbenzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, and ammonium salts or organic amine salts of alkyl sulfuric acid.

[0059] Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauric acid amidopropyl hydroxysulfobetaine.

[0060] These surfactants can be used alone or in combination of two or more, and the blending amount is usually 50 to 10,000 ppm, preferably 100 to 8,000 ppm, based on the composition according to the present invention.

[0061] The adhesion enhancer has an effect of preventing the pattern from peeling off due to the stress applied after firing when a cured film is formed using the composition according to the present invention. As the adhesion enhancer, imidazoles, silane coupling agents, etc. are preferable. Among imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2-aminoimidazole are preferable, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole are particularly preferably used.

[0062] Examples of the antifoaming agent include alcohols (C1~ 18 ), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurate, polyethers such as polyethylene glycol (PEG) (Mn 200 to 10,000), polypropylene glycol (PPG) (Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil, and the above-mentioned organosiloxane-based surfactants. These can be used alone or in combination of a plurality, and the addition amount is preferably 0.1 to 3% by mass based on the total mass of the polysiloxane.

[0063] Examples of the heat curing accelerator include heat base generators, heat acid generators, and the like. In the present invention, the heat curing accelerator does not include ionic liquids. Usually, by including a heat curing accelerator, the curing rate during heating of the coating film can be increased. However, in the present invention, since the ionic liquid functions to accelerate the curing of the polysiloxane, curing can be achieved even without including a heat curing accelerator. Therefore, the content of the heat curing accelerator is preferably 0.01% by mass or less, more preferably 0.001% by mass. Not including a heat curing accelerator is also a preferred embodiment of the present invention.

[0064] The composition according to the present invention can also be used as a photosensitive composition by further including a diazonaphthoquinone derivative, a photoacid generator, a photobase generator, and the like. The composition according to the present invention preferably includes a photoacid generator or a photobase generator, and more preferably includes a photoacid generator. In the present invention, the photoacid generator or the photobase generator refers to a compound that causes bond cleavage upon exposure to generate an acid or a base. The generated acid or base is considered to contribute to the polymerization of the polysiloxane. Here, examples of the light include visible light, ultraviolet light, infrared light, X-rays, electron beams, alpha rays, or gamma rays. In the present invention, the photoacid generator does not include a diazonaphthoquinone derivative.

[0065] The photoacid generator can be arbitrarily selected from commonly used ones. For example, diazomethane compounds, triazine compounds, sulfonic acid esters, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, sulfonimide compounds, and the like can be mentioned.

[0066] Specifically usable photoacid generators include, among others, 4-methoxyphenyldiphenylsulfonium hexafluorophosphate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium -p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium -p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyl -p-toluenesulfonate, N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, 5-norbornene-2,3-dicarboximidyl triflate, 5-norbornene-2,3-dicarboximidyl -p-toluenesulfonate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthylimide, N-(nonafluorobutylsulfonyloxy)naphthylimide, and the like.

[0067] Photo base generators include polysubstituted amide compounds having an amide group, lactams, imide compounds or those containing their structures. In addition, an ionic photo-base generator containing an amide anion, a methide anion, a borate anion, a phosphate anion, a sulfonate anion, a carboxylate anion, or the like as an anion can also be used.

[0068] Method for manufacturing a cured film The method for manufacturing a cured film according to the present invention includes applying the composition according to the present invention to a substrate to form a coating film, and heating the coating film. In the present invention, "on the substrate" includes cases where the composition is directly applied to the substrate and cases where the composition is applied to the substrate via one or more intermediate layers. The method for forming the cured film will be described in the order of steps as follows.

[0069] (1) Coating step The shape of the substrate is not particularly limited and can be arbitrarily selected according to the purpose. However, since the composition according to the present invention can easily penetrate into narrow groove portions and the like and can form a uniform cured film even inside the grooves, it can be applied to a substrate having groove portions or holes with a high aspect ratio. Specifically, it can be applied to a substrate having at least one groove with a width of 0.2 μm or less at the deepest part and an aspect ratio of 2 or more. Here, the shape of the groove is not particularly limited, and the cross section may be any shape such as a rectangular shape, a forward taper shape, a reverse taper shape, a curved surface shape, etc. Both end portions of the groove may be open or closed.

[0070] As a representative example of a substrate having at least one groove with a high aspect ratio, a substrate for an electronic device equipped with a transistor element, a bit line, a capacitor, etc. can be mentioned. In the production of such an electronic device, there may be included a through-hole plating step of forming a hole that penetrates up and down the encapsulating material for the fine groove, following steps such as forming an insulating film between a transistor element and a bit line called PMD, between a transistor element and a capacitor, between a bit line and a capacitor, or between a capacitor and a metal wiring, or forming an insulating film between a plurality of metal wirings called IMD, or encapsulating an isolation groove.

[0071] Coating can be performed by any method. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, and the like. As the substrate on which the composition is coated, an appropriate substrate such as a silicon substrate, a glass substrate, or a resin film can be used. Various semiconductor elements and the like may be formed on these substrates as needed. When the substrate is a film, gravure coating can also be used. If desired, a separate drying step can be provided after the coating film. Further, if necessary, the coating step can be repeated once or more to make the film thickness of the formed coating film as desired.

[0072] (2) Pre-baking step After forming a coating film by applying the composition, the coating film can also be pre-baked (pre-heat treated) in order to dry the coating film and reduce the residual amount of solvent in the coating film.

[0073] (3) Curing step In the case of a non-photosensitive composition, then, a cured film is formed by heating the coating film. Here, in the present invention, the cured film means one having an S2 / S1 ratio of less than 0.003. For the heating device used in the curing process, a hot plate or an oven can be used. The heating temperature in this curing process is not particularly limited as long as it is the temperature at which the cured film is formed and can be arbitrarily determined. However, if silanol remains, the chemical resistance of the cured film may become insufficient or the dielectric constant of the cured film may increase. From such a viewpoint, a relatively high temperature is generally selected as the heating temperature. However, when using the composition according to the present invention, it can be cured at a relatively low temperature. Specifically, it is preferably heated at 500 °C or lower, more preferably 300 °C or lower. On the other hand, in order to promote the curing reaction, the heating temperature is preferably 120 °C or higher, more preferably 140 °C or higher, and still more preferably 170 °C or higher. Also, the heating time is not particularly limited. When using a hot plate, it is preferably 1 to 60 minutes, more preferably 1 to 30 minutes. The curing process is preferably carried out in an air atmosphere.

[0074] In this curing process, void generation may occur. In particular, when the organic groups contained in the polysiloxane decrease, void generation tends to increase. However, when using the composition of the present invention, even when the organic groups contained in the polysiloxane are few, the void generation can be suppressed.

[0075] In the case of a photosensitive composition, after forming a coating film, light irradiation is performed on the surface of the coating film. As the light source used for light irradiation, any of those conventionally used in the pattern formation method can be used. Examples of such light sources include lamps such as high-pressure mercury lamps, low-pressure mercury lamps, metal halides, xenon, laser diodes, and LEDs. As the irradiation light, ultraviolet rays such as g-line, h-line, and i-line are usually used. Except for ultra-fine processing such as semiconductors, for patterning of several μm to several tens of μm, light of 360 to 430 nm (high-pressure mercury lamp) is generally used.

[0076] To irradiate light in a pattern, a general photomask can be used. Such a photomask can be arbitrarily selected from well-known ones. The environment during irradiation is not particularly limited, but generally, the ambient atmosphere (in air) or nitrogen atmosphere may be used.

[0077] After exposure, in order to promote the reaction between polymers in the film by the acid or base generated at the exposed sites, especially in the case of a negative type, post-exposure baking can be carried out as needed. This heat treatment, unlike the heat treatment described later, is not carried out to completely cure the coating film, but is carried out so that only the desired pattern remains on the substrate after development, and the other parts can be removed by development. When post-exposure baking is carried out, a hot plate, an oven, a furnace, etc. can be used. Since it is not preferable that the acid or base in the exposed area generated by light irradiation diffuses to the unexposed area, the heating temperature should not be excessively high. From such a viewpoint, the range of the post-exposure heating temperature is preferably 40°C to 150°C, and more preferably 60°C to 120°C. In order to control the curing rate of the composition, stepwise heating can also be applied as needed. Also, the atmosphere during heating is not particularly limited, but for the purpose of controlling the curing rate of the composition, it can be selected from an inert gas such as nitrogen, under vacuum, under reduced pressure, in oxygen gas, etc. The heating time is preferably not less than a certain value in order to maintain higher uniformity of the temperature history in the wafer plane, and is preferably not excessively long in order to suppress the diffusion of the generated acid or base. From such a viewpoint, the heating time is preferably 20 seconds to 500 seconds, and more preferably 40 seconds to 300 seconds.

[0078] After exposure, the coating film is developed. As the developer used in the development, any developer conventionally used for developing a photosensitive composition can be used. Preferred developers include alkaline developers that are aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), aqueous ammonia, alkylamines, alkanolamines, and heterocyclic amines. A particularly preferred alkaline developer is an aqueous TMAH solution. The developing method can also be arbitrarily selected from conventionally known methods. Specifically, methods such as dipping in a developer, paddle, shower, slit, cap coating, and spray can be mentioned. By this development, a pattern can be obtained. After development with the developer, it is preferable to perform water washing. Thereafter, if necessary, a step of overall exposure (flood exposure) can also be performed. The coating film is cured by heating the pattern film obtained after development. The heating conditions are the same as those in (3) described above.

[0079] The cured film formed using the composition according to the present invention can achieve excellent transparency, chemical resistance, environmental resistance, electrical insulation, heat resistance, etc. Therefore, it can be suitably used in various fields as an interlayer insulating film for low-temperature polysilicon or a buffer coat film for an IC chip, a transparent protective film, etc.

[0080] The method for manufacturing an electronic device according to the present invention includes the method for manufacturing the cured film according to the present invention described above.

[0081] [Examples] The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited by these examples and comparative examples.

[0082] Gel permeation chromatography (GPC) was measured using an allianceTM e2695 type high-speed GPC system (Waters Japan K.K.) and a Super Multipore HZ-N type GPC column (Tosoh Corporation). The measurement was performed under the measurement conditions of a flow rate of 0.6 milliliters per minute and a column temperature of 40 °C, using monodisperse polystyrene as a standard sample and tetrahydrofuran as a developing solvent. After that, the mass average molecular weight (hereinafter sometimes referred to as Mw) was calculated as the relative molecular weight to the standard sample.

[0083] Synthesis Example 1: Polysiloxane A 107 g (0.786 mol) of methyltriethoxysilane, 96 g (0.484 mol) of phenyltriethoxysilane, and 300 g of PGMEA were charged into a four-necked flask and dissolved. Next, 48 g of a 44 mass% aqueous sodium hydroxide solution was added, and the mixture was stirred at 500 rpm and 40 °C for 2 hours. Next, neutralization was carried out with aqueous acetic acid, and the mixture was stirred for 1 hour. Thereafter, the reaction solution was transferred to a separatory funnel and allowed to stand for 30 minutes to separate the organic solvent phase and the aqueous phase. The aqueous phase was discarded, and 100 g of pure water was newly added to the organic solvent phase in the separatory funnel and shaken to extract and wash the alkali component and the water-soluble component remaining in the organic solvent phase. This washing operation was carried out 3 times. After that, the organic solvent phase washed with pure water was recovered to obtain a polysiloxane A solution. The mass average molecular weight of polysiloxane A contained in the organic solvent phase was 2,400, and S2 / S1 was 0.031. Here, S2 / S1 was measured in the same manner as the measurement method of S2 / S1 of the cured film described later, except that heating was not performed, using the polysiloxane A solution.

[0084] Synthesis Example 2: Polysiloxane B Into a four-necked flask, 53.7 g (0.394 mol) of methyltrimethoxysilane, 173.7 g (0.876 mol) of phenyltrimethoxysilane, and 300 g of PGMEA are charged and dissolved. Next, 48 g of a 44 mass% aqueous sodium hydroxide solution is added, and the mixture is stirred at 500 rpm at room temperature for 2 hours. Next, neutralization is carried out with aqueous acetic acid, and the mixture is stirred for 1 hour. Thereafter, the reaction solution is transferred to a separatory funnel and allowed to stand for 30 minutes to separate the organic solvent phase and the aqueous phase. The aqueous phase is discarded, 100 g of pure water is newly added to the organic solvent phase in the separatory funnel and shaken to extract and wash the alkali component and water-soluble component remaining in the organic solvent phase. This washing operation is carried out 3 times. Thereafter, the organic solvent phase washed with pure water is recovered to obtain a polysiloxane B solution. The mass average molecular weight of polysiloxane B contained in the organic solvent phase is 1,600, and S2 / S1 is 0.028.

[0085] Synthesis Example 3: Polysiloxane C Into a four-necked flask, 138.9 g (1.02 mol) of methyltrimethoxysilane, 49.8 g (0.251 mol) of phenyltrimethoxysilane, and 300 g of PGMEA are charged and dissolved. Next, 48 g of a 44 mass% aqueous sodium hydroxide solution is added, and the mixture is stirred at 500 rpm at room temperature for 2 hours. Next, neutralization is carried out with aqueous acetic acid, and the mixture is stirred for 1 hour. Thereafter, the reaction solution is transferred to a separatory funnel and allowed to stand for 30 minutes to separate the organic solvent phase and the aqueous phase. The aqueous phase is discarded, 100 g of pure water is newly added to the organic solvent phase in the separatory funnel and shaken to extract and wash the alkali component and water-soluble component remaining in the organic solvent phase. This washing operation is carried out 3 times. Thereafter, the organic solvent phase washed with pure water is recovered. The mass average molecular weight of polysiloxane C contained in the organic solvent phase is 1,800, and S2 / S1 is 0.032.

[0086] Preparation of Polysiloxane Composition Polysiloxane compositions of Examples 1 to 5 and Comparative Examples 1 to 3 are prepared with the compositions and contents shown in Table 1 below. In the table, the numerical values of the compositions mean mass%.

Table 1

[0087] Storage stability For the polysiloxane composition, the Mw was measured immediately after preparation and after storage at 40 °C for 7 days, and the storage stability was evaluated by the following formula. The results are shown in Table 1. Storage stability (%) = (Mw (after storage) - Mw (before storage)) / Mw (before storage) × 100

[0088] Film sag amount The polysiloxane composition is applied to a 4-inch Si wafer at 1000 rpm using a spin coater (1HDX2 manufactured by Mikasa Co., Ltd.). The coating film thickness is measured at 19 points on the diameter using a spectroscopic ellipsometer (M-2000V manufactured by JA Woollam Co., Ltd.), and the average value is taken. The coated wafer is cured in air at 200 °C for 2 minutes. The cured film thickness is measured in the same manner as the coating film thickness. The film sag amount is evaluated by the following formula. The results are shown in Table 1. Film sag amount (%) = (coating film thickness - cured film thickness) / coating film thickness × 100

[0089] S2 / S1 after curing The polysiloxane composition is dropped onto a 4-inch Si wafer, spin-coated at 1000 rpm, and then cured on a hot plate at 150 °C for 2 minutes. The FT-IR spectrum is measured at room temperature using FTIR-6100 (JASCO). Considering the noise, baseline correction is performed, and the absorption band (S2) attributed to Si-OH having a peak in the range of 900 ± 100 cm -1 and the absorption band at 1100 ± 100 cm -1Measure the area intensity of the absorption band (S1) attributed to Si-O that has a peak within the range, and calculate the value of S2 / S1. The results are shown in Table 1. Note that the tails of the absorption band attributed to Si-OH and the tail of the absorption band attributed to Si-O may overlap. In that case, the wavenumber corresponding to the minimum point between the two absorption bands in the spectrum is used as the boundary. The same applies when the tails of other absorption bands overlap with the tails of the absorption bands attributed to Si-OH or Si-O.

[0090] Relative diffuse reflectance Drop the polysiloxane composition onto a 4-inch Si wafer. After spin-coating at 1000 rpm, cure it on a hot plate at 200°C for 2 minutes. Attach the integrating sphere accessory ISR-2600Plus (Shimadzu Corporation) to the spectrophotometer UV-2600 (Shimadzu Corporation), and measure the relative diffuse reflectance (%) when light with a wavelength of 400 nm is incident from the side of the polysiloxane cured film (incident light 0°), using barium sulfate as the standard plate and setting the standard plate as 100%. The results are shown in Table 1.

[0091] Appearance of the cured film When visually observing the appearance of the cured films after applying the compositions of Example 1 and Comparative Example 1 to a 4-inch Si wafer at 1000 rpm using a spin coater and curing them by heating on a hot plate at 200°C for 2 minutes, a uniform cured film is formed in Example 1, while coating unevenness is observed in Comparative Example 1.

[0092] Example 6 To a solution containing 100 parts by mass of the polysiloxane A obtained in Synthesis Example 1, 0.003 parts by mass of ionic liquid A, 0.006 parts by mass of maleic acid, 1.0 part by mass of “NAI-105” (Midori Chemical Co., Ltd.) as a photoacid generator, and 0.3 part by mass of “KF-53” (Shin-Etsu Chemical Co., Ltd.) as a surfactant were added, and PGMEA was added to prepare a solution in which the components other than the solvent were 35% by mass, and a composition was obtained. The composition was applied onto a silicon wafer by spin coating, and after application, pre-baked on a hot plate at 100 °C for 90 seconds and adjusted to have an average film thickness of 2 μm. Exposure was carried out using a g, h-line exposure machine, and post-exposure heating was carried out on a hot plate at 100 °C for 90 seconds. Development was carried out using a 2.38% by mass aqueous TMAH solution, and rinsing with pure water was carried out for 30 seconds. Since a 10-μm contact hole (C / H) pattern was missing, it was found that the composition was negative photosensitive. The substrate having the C / H pattern was cured on a hot plate at 200 °C for 2 minutes, and when the elastic modulus was measured using an indentation hardness measuring instrument “ENT-2100” (Elionix, Inc.), it was 3.82 GPa.

Claims

1. A polysiloxane comprising a repeating unit represented by formula (Ia) and having a silanol at a terminal or side chain, 【Chemical 1】 wherein, R １ is a hydrogen, a linear, branched or cyclic, saturated or unsaturated aliphatic hydrocarbon group having a valence of 1 to 3, or an aromatic hydrocarbon group having a valence of 1 to 3 of C １－３０ , or an aromatic hydrocarbon group having a valence of 1 to 3 of C ６－３０ , and The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or C １－８ alkoxy, In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced, or one or more methylenes are replaced by oxy, imide or carbonyl, provided that R １ is not hydroxy or alkoxy, R １ When R is divalent or trivalent, R １ links Si atoms included in a plurality of repeating units) When the polysiloxane is measured and analyzed by the FT-IR method, the area intensity S1 of the absorption band attributed to Si—O in the range of 1100 ± 100 cm －１ and the ratio S2 / S1 of the area intensity S2 of the absorption band attributed to SiOH in the range of 900 ± 100 cm －１ is 0.010 to 0.10, the polysiloxane, (II) an ionic liquid, (III) an acid, and (IV) a solvent are included, and it is a polysiloxane composition.

2. R １ is hydrogen, C １－６ linear, branched or cyclic alkyl, or C ６－１０ aryl of Claim 1, the composition according to.

3. The composition according to claim 1 or 2, wherein the cation of the ionic liquid (II) is 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.

4. The composition according to any one of claims 1 to 3, wherein the anion of the ionic liquid (II) is 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.

5. The composition according to any one of claims 1 to 4, wherein the mass average molecular weight of the polysiloxane (I) measured by gel permeation chromatography is 500 to 10,000.

6. The composition according to any one of claims 1 to 5, wherein the mixing ratio of the ionic liquid (II) to the polysiloxane (I) (ionic liquid / polysiloxane) is 0.000010 to 0.10 by mass ratio.

7. The composition according to any one of claims 1 to 6, wherein the mixing ratio of the ionic liquid (II) to the acid (III) (ionic liquid / acid) is 0.10 to 1.0 by equivalent ratio.

8. The composition according to any one of claims 1 to 7, wherein the acid (III) is an organic acid.

9. The composition according to any one of claims 1 to 8, wherein (IV) 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.

10. The composition according to any one of claims 1 to 9, wherein (IV) the content of the solvent is 50 to 98% by mass based on the total mass of the composition.

11. The composition according to any one of claims 1 to 10, further comprising a photoacid generator or a photobase generator.

12. A method for producing a cured film, comprising applying the composition according to any one of claims 1 to 11 to a substrate to form a coating film, and heating the coating film.

13. The method for producing a cured film according to claim 12, wherein the heating is performed at a temperature of 120°C or higher.

14. A method for producing an electronic device, comprising the method for producing a cured film according to claim 12 or 13.

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