Polysiloxane composition

Abstract

[Problem] To provide a polysiloxane composition which can be cured at low temperatures and has excellent storage stability. [Solution] This polysiloxane composition contains (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 and also to a method for producing a film using the polysiloxane composition, a film using the polysiloxane composition, and a method for producing an electronic device including the film. Background Art

[0002] It is known that polysiloxane has high temperature resistance. In the case of forming a cured film from a composition containing polysiloxane, the coating film is heated at a high temperature to rapidly carry out the condensation reaction of the silanol group in the polysiloxane and the reaction of the polymer having an unsaturated bond to cure. In the case of residual unreacted reactive groups, the chemical reagents used in the manufacturing process of the device will react. From the perspective of the influence on other materials in the substrate and the device conditions, it is desired to develop a composition containing polysiloxane that can be cured at a lower temperature.

[0003] For the purpose of curing epoxy resin at low temperature, a combination of epoxy resin, anionic polymerizable curing agent and ionic liquid has been proposed (for example, Patent Document 1). However, in a comparative example not containing anionic polymerizable curing agent, curing did not occur.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-14781 Summary of the invention

[0007] Technical Problems to be Solved by the Invention

[0008] The present invention has been made based on the above circumstances, and provides a polysiloxane composition that can be cured at a low temperature and has excellent storage stability. Another object of the present invention is to provide a method for producing a cured film and an electronic device using the polysiloxane composition.

[0009] Means for solving technical problems

[0010] The polysiloxane composition of the present invention comprises (I) polysiloxane, (II) ionic liquid, (III) acid and (IV) solvent;

[0011] The polysiloxane comprises a repeating unit represented by formula (Ia), and has a silanol at the end or in the side chain;

[0012]

[0013] Among them, R 1 Hydrogen, 1-3 valent C 1-30 A straight-chain, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or a 1- to 3-valent C 6-30Aromatic hydrocarbon groups,

[0014] The above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group are unsubstituted or substituted with fluorine, hydroxyl or C 1-8 Alkoxy,

[0015] In the above aliphatic hydrocarbon group and the above aromatic hydrocarbon group, the methylene group is not replaced, or one or more methylene groups are replaced by an oxy group, an imide group or a carbonyl group, provided that R 1 Neither hydroxy nor alkoxy,

[0016] R 1 When it is bivalent or trivalent, R 1 The Si contained in multiple repeating units are linked to each other.

[0017] When the polysiloxane is measured and analyzed by FT-IR, the -1 The area intensity S1 of the absorption band attributed to Si-O is in the range of 900±100cm -1 In the range of , the ratio S2 / S1 of the area intensity S2 of the absorption band attributed to SiOH is 0.010 to 0.10.

[0018] Furthermore, the method for producing a cured film of the present invention includes the steps of applying the composition on a substrate to form a coating film, and heating the coating film.

[0019] In addition, the method for producing an electronic device of the present invention includes the above-mentioned method for producing a cured film.

[0020] Effects of the Invention

[0021] The polysiloxane composition of the present invention can be cured at a temperature lower than the temperature range used by a general heat-curable composition. The polysiloxane composition of the present invention has excellent storage stability. In addition, the film reduction amount of the obtained cured film is also small, the film thickness uniformity is also excellent, and the elastic modulus is small, so it can follow the deformation of the substrate. Furthermore, when applied to a substrate with a large aspect ratio, the embedding property is excellent. The obtained cured film is also excellent in flatness and electrical insulation properties, and therefore can be preferably used in optical devices such as interlayer insulating films, passivation films, substrate flattening films, anti-reflection films, optical filters, high-brightness light-emitting diodes, touch panels, solar cells, and optical waveguides of semiconductor devices. DETAILED DESCRIPTION

[0022] Modes for Carrying Out the Invention

[0023] [definition]

[0024] In this specification, unless otherwise specified or described, the definitions and examples described in this paragraph shall apply.

[0025] The singular form includes the plural form, and "one" or "it" means "at least one." A certain conceptual element may appear in multiple forms, and when the amount (for example, mass % or mol %) is described, the amount means the sum of the multiple forms.

[0026] "And / or" includes all combinations of elements and also includes use in a single form.

[0027] When "to" or "-" is used to express a numerical range, both end points are included and the unit is common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0028] "Cx-y", "Cx to Cy" and "Cx" etc. indicate the number of carbon atoms in a molecule or a substituent. 1-6 The alkyl group represents an alkyl chain having 1 or more and 6 or less carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0029] When a polymer has multiple repeating units, these repeating units are copolymerized. These copolymerizations may be cross-copolymerization, random copolymerization, block copolymerization, graft copolymerization, or any of their mixed forms. When a polymer or resin is represented by a structural formula, n or m, etc. recorded outside the brackets, represents the number of repetitions.

[0030] The unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0031] The additive refers to the compound itself having the function (for example, in the case of a base generator, it is the compound itself that generates a base). The compound may be dissolved or dispersed in a solvent, or may be added to the composition. As one embodiment of the present invention, such a solvent is preferably included in the composition of the present invention as a solvent (IV) or other component.

[0032] Embodiments of the present invention will be described in detail below.

[0033] Polysiloxane composition

[0034] The polysiloxane composition of the present invention (hereinafter sometimes simply referred to as a composition) comprises (I) a polysiloxane having a specific structure, (II) an ionic liquid, (III) an acid, and (IV) a solvent. Each component contained in the composition of the present invention is described in detail below.

[0035] (I) Polysiloxane

[0036] The polysiloxane used in the present invention includes a repeating unit represented by the following formula (Ia), and has a silanol at the terminal or side chain thereof.

[0037] Here, silanol refers to a polysiloxane in which an OH group is directly bonded to the Si skeleton, and is a polysiloxane containing repeating units of formula (Ia) in which a hydroxyl group is directly bonded to a silicon atom. 0.5 -Bond-O 0.5 H to form silanol. The silanol content in polysiloxane varies depending on the synthesis conditions of polysiloxane, such as the monomer ratio or the type of reaction catalyst. The silanol content can be evaluated by quantitative infrared absorption spectrum measurement. The absorption band attributed to silanol (SiOH) is at 900±100cm -1 The absorption band appears as an absorption band having a peak in the range of . When the content of silanol is high, the intensity of the absorption band becomes high.

[0038] When the polysiloxane used in the present invention is measured and analyzed by FT-IR, the wavelength of 1100±100cm -1 The area intensity S1 of the absorption band attributed to Si-O is in the range of 900±100cm -1 In the range of , the ratio S2 / S1 of the area intensity S2 of the absorption band attributed to SiOH is 0.010 to 0.10, preferably 0.015 to 0.090, and more preferably 0.020 to 0.080.

[0039] The area intensity of the absorption band is determined by taking into account the noise of the infrared absorption spectrum. In a typical infrared absorption spectrum of polysiloxane, a band of 900 ± 100 cm -1 The absorption band of Si-OH is attributed to the peak in the range of 1100±100cm -1 The absorption band that has peak and belongs to Si-O in the range of.The area intensity of these absorption bands can be measured in the form of the area of ​​considering baseline, and the baseline has considered noise etc.Although there will be the situation that the lower end of the absorption band belonging to Si-OH overlaps with the lower end of the absorption band belonging to Si-O, in this case, the wave number corresponding to the minimum point between the two absorption bands in the spectrum is regarded as the boundary.The situation that the lower end of other absorption bands overlaps with the lower end of the absorption band belonging to Si-OH or Si-O is also the same.

[0040] Formula (Ia) is as follows:

[0041]

[0042] Among them, R 1 Hydrogen, 1-3 valent C 1-30A straight-chain, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or a 1- to 3-valent C 6-30 The aromatic hydrocarbon group is preferably hydrogen, C 1-6 A straight-chain, branched or cyclic alkyl group or a C 6-10 The aryl group is more preferably hydrogen, methyl, ethyl or phenyl, more preferably methyl or phenyl.

[0043] The above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group are unsubstituted or substituted with fluorine, hydroxyl or C 1-8 Alkoxy,

[0044] In the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group, the methylene group is not replaced, or one or more methylene groups are replaced by an oxy group, an imide group or a carbonyl group, provided that R 1 Neither hydroxy nor alkoxy;

[0045] R 1 When it is bivalent or trivalent, R 1 The Si atoms contained in a plurality of repeating units are linked to each other.

[0046] In formula (Ia), R 1 When it is a univalent base, as R 1 , in addition to hydrogen, for example: (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 amino or imide structures such as isocyanate and amino, (vii) oxygen-containing groups having epoxy structures, or having acryloyl structures or methacryloyl structures such as glycidyl. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl and isocyanate. As fluoroalkyl groups, perfluoroalkyl groups are preferred, especially trifluoromethyl or pentafluoroethyl. Since the raw materials are easily available, the hardness of the cured film is high and it has a high resistance to chemical reagents, R 1 Methyl is preferred. R is also preferred because it increases the solubility of polysiloxane in solvents and makes the cured film less prone to cracking. 1 It is phenyl.

[0047] R 1 When it is a divalent or trivalent group, R 1Preferred are, for example, (i) a group formed by removing two or three hydrogen atoms from alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane and decane, (ii) a group formed by removing two or three hydrogen atoms from cycloalkanes such as cycloheptane, cyclohexane and cyclooctane, (iii) a group formed by removing two or three hydrogen atoms from aromatic compounds consisting only of hydrocarbons such as benzene and naphthalene, and (iv) a group formed by removing two or three hydrogen atoms from nitrogen- and / or oxygen-containing cyclic aliphatic hydrocarbon compounds containing amino groups, imino groups and / or carbonyl groups such as piperidine, pyrrolidine and isocyanurate. (iv) is more preferred in order to improve pattern collapse and enhance adhesion to the substrate.

[0048] 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 is preferably substantially composed of repeating units represented by formula (Ia), more preferably composed of repeating units represented by formula (Ia).

[0049] The polysiloxane used in the present invention may further contain a repeating unit represented by the following formula (Ib):

[0050]

[0051] Among them, R 2 are independently hydrogen, a monovalent to trivalent C 1～30 A straight-chain, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or a 1- to 3-valent C 6～30 The aromatic hydrocarbon group is preferably hydrogen, C 1-6 A straight-chain, branched or cyclic alkyl group or a C 6-10 aryl, more preferably hydrogen, methyl, ethyl or phenyl, and further preferably R 2 It is methyl.

[0052] The above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group are unsubstituted or substituted with fluorine, hydroxyl or C 1-8 Alkoxy,

[0053] In the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group, the methylene group is not replaced, or one or more methylene groups are replaced by an oxy group, an imide group or a carbonyl group, provided that R 2 Neither hydroxy nor alkoxy,

[0054] R 2 When it is bivalent or trivalent, R 2 The Si atoms contained in a plurality of repeating units are linked to each other.

[0055] By having a repeating unit of formula (Ib), the polysiloxane can partially form a linear structure. However, since heat resistance decreases, the linear structure portion is preferably less. Specifically, the number of repeating units of formula (Ib) is preferably 20% or less, more preferably 10% or less, based on the total number of repeating units of the polysiloxane.

[0056] The polysiloxane used in the present invention may further contain a repeating unit represented by the following formula (Ic), but from the viewpoint of compatibility with solvents, suppression of crack generation, and low elastic modulus, the repeating unit represented by formula (Ic) is preferably as small as possible. Specifically, based on the total number of repeating units contained in the polysiloxane molecule, it is preferably 10% or less, and more preferably 5% or less. In a preferred embodiment, the polysiloxane used in the present invention preferably does not substantially contain a repeating unit represented by formula (Ic), and more preferably does not contain a repeating unit represented by formula (Ic), that is, 0%.

[0057]

[0058] The polysiloxane used in the present invention may contain repeating units other than the repeating units represented by (Ia), (Ib) and (Ic), but 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. It is also a preferred embodiment of the present invention that the polysiloxane contains no repeating units other than the above.

[0059] 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 viewpoint of solubility in organic solvents, coating properties on substrates, and solubility in alkaline developers. The mass average molecular weight here is a polystyrene-equivalent mass average molecular weight, which can be measured by gel permeation chromatography using polystyrene as a standard.

[0060] The polysiloxane may 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.

[0061] Such polysiloxane can be obtained, for example, by subjecting a silicon compound represented by the following formula (ia) to hydrolysis and condensation in the presence of an acidic catalyst or a basic catalyst as required;

[0062] R 1 '[Si(OR a )3] p (ia)

[0063] Wherein, p is an integer from 1 to 3,

[0064] R 1 ' is hydrogen, 1 to 3 valent C 1-30 A straight-chain, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or a 1- to 3-valent C 6-30 Aromatic hydrocarbon groups,

[0065] The above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group are unsubstituted or substituted with fluorine, hydroxyl or C 1-8 Alkoxy,

[0066] In the above-mentioned aliphatic hydrocarbon group and the above-mentioned aromatic hydrocarbon group, the methylene group is not replaced, or one or more methylene groups are replaced by an oxy group, an imide group or a carbonyl group, provided that R 1 'Neither hydroxy nor alkoxy,

[0067] R a C 1-10 The alkyl group is preferably methyl, ethyl, n-propyl, isopropyl and n-butyl.

[0068] Specific examples of the silicon compound represented by the general formula (ia) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, Oxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, tris(3-triethoxysilylpropyl)isocyanurate, tris(3-trimethoxysilylethyl)isocyanurate, etc., among which methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane and phenyltrimethoxysilane are preferred.

[0069] Here, the silicon compounds may be used in combination of two or more types.

[0070] (II) Ionic Liquids

[0071] The composition of the present invention comprises an ionic liquid.

[0072] 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 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.

[0073] The ionic liquid used in the present invention is preferably a basic ionic liquid, preferably composed of a combination of a strong base and a weak acid.

[0074] The cation of the ionic liquid is preferably at least one cation selected from the group consisting of imidazolium ions, pyrrolidinium ions, piperidinium ions, pyridinium ions and ammonium ions, and more preferably an imidazolium ion.

[0075] The imidazolium salt ion is preferably represented by the following formula (A):

[0076]

[0077] in,

[0078] R 11 , R 12 , R 13 , R 14 and R 15 are independently hydrogen, a linear or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl or C 6-14 Aryl.

[0079] Specific examples of imidazolium salt ions include 1-methylimidazolium salt, 1-methyl-2-ethylimidazolium salt, 1-methyl-3-octylimidazolium salt, 1,2-dimethylimidazolium salt, 1,3-dimethylimidazolium salt, 2,3-dimethylimidazolium salt, 3,4-dimethylimidazolium salt, 1,2,3-trimethylimidazolium salt, 1,3,4-trimethylimidazolium salt, 1,3,4,5-tetramethylimidazolium salt, 1-ethylimidazolium salt, 1-ethyl-2-methylimidazolium salt, 1-ethyl-3-methylimidazolium salt, 1-ethyl-2,3-dimethylimidazolium salt, 2 -ethyl-3,4-dimethylimidazolium salt, 1-propylimidazolium salt, 1-propyl-2-methylimidazolium salt, 1-propyl-3-methylimidazolium salt, 1-propyl-2,3-dimethylimidazolium salt, 1,3-dipropylimidazolium salt, 1-butylimidazolium salt, 1-butyl-2-methylimidazolium salt, 1-butyl-3-methylimidazolium salt, 1-butyl-4-methylimidazolium salt, 1-butyl-2,3-dimethylimidazolium salt, 1-butyl-3,4-dimethylimidazolium salt, 1-butyl-3,4,5-trimethylimidazolium salt, 1-butyl-2-ethylimidazolium salt, 1- Butyl-3-ethylimidazolium salt, 1-butyl-2-ethyl-5-methylimidazolium salt, 1,3-dibutylimidazolium salt, 1,3-dibutyl-2-methylimidazolium salt, 1-pentylimidazolium salt, 1-pentyl-2-methylimidazolium salt, 1-pentyl-3-methylimidazolium salt, 1-pentyl-2,3-dimethylimidazolium salt, 1-hexylimidazolium salt, 1-hexyl-2-methylimidazolium salt, 1-hexyl-3-methylimidazolium salt, 1-hexyl-2,3-dimethylimidazolium salt, 1-octyl-2-methylimidazolium salt, 1-octyl-3-methylimidazolium salt, 1-decyl-3 -methylimidazolium salt, 1-dodecyl-3-methylimidazolium salt, 1-tetradecyl-3-methylimidazolium salt, 1-hexadecyl-3-methylimidazolium salt and 1-benzyl-3-methylimidazolium salt, preferably 1-ethyl-3-methylimidazolium salt, 1-ethyl-2,3-dimethylimidazolium salt, 1,3-dimethylimidazolium salt, 1,2,3-trimethylimidazolium salt, 1-propyl-3-methylimidazolium salt, 1-propyl-2,3-dimethylimidazolium salt, 1-butyl-3-methylimidazolium salt, 1-butyl-2,3-dimethylimidazolium salt, 1-octyl-3-methylimidazolium salt.

[0080] The pyrrolidinium salt ion is preferably represented by the following formula (B):

[0081]

[0082] in,

[0083] R 21 , R 22 , R 23 , R24 , R 25 and R 26 are independently hydrogen, a linear or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl or C 6-14 Aryl.

[0084] Specific examples of pyrrolidinium salt ions include 1-methyl-1-ethylpyrrolidinium salt, 1-methyl-1-propylpyrrolidinium salt, 1-methyl-1-butylpyrrolidinium salt, 1-methyl-1-pentylpyrrolidinium salt, 1-methyl-1-hexylpyrrolidinium salt and 1-methyl-1-octylpyrrolidinium salt, preferably 1-methyl-1-propylpyrrolidinium salt.

[0085] The piperidinium salt ion is preferably represented by the following formula (C):

[0086]

[0087] in,

[0088] R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 are independently hydrogen, a linear or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl or C 6-14 Aryl.

[0089] Specific examples of piperidinium salt ions include 1-methyl-1-ethylpiperidinium salt, 1-methyl-1-propylpiperidinium salt, 1-methyl-1-butylpiperidinium salt, 1-methyl-1-pentylpiperidinium salt, 1-methyl-1-hexylpiperidinium salt and 1-methyl-1-octylpiperidinium salt, preferably 1-methyl-1-butylpiperidinium salt.

[0090] The pyridinium salt ion is preferably represented by the following formula (D):

[0091]

[0092] in,

[0093] R 41 , R 42 , R 43 , R 44 , R 45 and R 46 are independently hydrogen, a linear or branched C 1-18 Alkyl, cyclic C 5-12 Alkyl or C6-14 Aryl.

[0094] Specific examples of pyridinium salt ions include 1-methylpyridinium salt, 1-ethylpyridinium salt, 1-propylpyridinium salt, 1-butylpyridinium salt, 1-pentylpyridinium salt, 1-hexylpyridinium salt, 1-octylpyridinium salt, 1-methyl-3-ethylpyridinium salt, 1-methyl-4-ethylpyridinium salt, 1-methyl-3-butylpyridinium salt, 1-methyl-4-butylpyridinium salt, 1-ethyl-3-methylpyridinium salt, 1-ethyl-4-methylpyridinium salt, 1-propyl-3-methylpyridinium salt, 1-propyl-4-methylpyridinium salt, 1-butyl-3-methylpyridinium salt, 1-butyl-4-methylpyridinium salt, 1-hexyl-4-methylpyridinium salt and 1-octyl-4-methylpyridinium salt, preferably 1-butylpyridinium salt and 1-ethyl-4-methylpyridinium salt.

[0095] The ammonium ion is preferably represented by the following formula (E):

[0096]

[0097] in,

[0098] R 51 , R 52 , R 53 and R 54 are independently linear or branched C 1-18 Alkyl, linear or branched C 1-18 Hydroxyalkyl, cyclic C 5-12 Alkyl or C 6-14 Aryl.

[0099] Specific examples of ammonium ions include trimethylethylammonium, trimethylbutylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trihexylmethylammonium, trioctylmethylammonium, tetrabutylammonium, 2-hydroxyethyltrimethylammonium and tris(2-hydroxyethyl)methylammonium, preferably tetrabutylammonium, tributylmethylammonium and 2-hydroxyethyltrimethylammonium.

[0100] 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, methylsulfate ion, ethylsulfate ion, hydrogen sulfate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, bis(trifluoromethylsulfonyl)imide ion, bis(fluorosulfonyl)imide ion, methylcarbonate ion, bicarbonate ion, diethylphosphate ion, dibutylphosphate ion, hexafluorophosphate ion, tetrafluoroborate ion, chloride ion and bromide ion, and more preferably acetate ion, dicyanamide ion, cyanamide ion, chloride ion and bromide ion.

[0101] In a preferred embodiment, specific examples of ionic liquids include trimethylbutylammonium bis(trifluoromethylsulfonyl)imide, tributylmethylammonium dicyanamide, tributylmethylammonium bis(trifluoromethylsulfonyl)imide, tri(2-hydroxyethyl)methylammonium methylsulfate, 2-hydroxyethyltrimethylammonium acetate, 2-hydroxyethyltrimethylammonium lactate, 2-hydroxyethyltrimethylammonium salicylate, tetrabutylammonium chloride, 1,3-dimethylimidazolium methylsulfate, 1,2,3-trimethylammonium Methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium methylsulfate, 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-dimethyl Imidazolium 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 embodiment, in the ionic liquid, the cation is an imidazolium salt ion and the anion is acetate, as specific examples, 1-ethyl-3-methylimidazolium acetate, 1-propyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate and 1-octyl-3-methylimidazolium acetate.

[0102] The ionic liquid has a catalytic effect of accelerating the curing of polysiloxane, and it is believed that the curing can be completed even at a relatively low temperature.

[0103] The mixing ratio of the ionic liquid to the polysiloxane (ionic liquid / polysiloxane) is preferably 0.000010 to 0.10, more preferably 0.000020 to 0.10 in terms of mass ratio. This is because the low-temperature curing effect is further exerted by setting the content in this range, and the density of the cured film tends to be higher.

[0104] Compared with a commonly used curing accelerator (eg, a thermal base generator), an ionic liquid can be uniformly present in the composition, and thus is considered to have an effect of inhibiting voids. By including an ionic liquid in the composition, it is expected to improve the adhesion to the substrate.

[0105] The ionic liquid may 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 of the present invention.

[0106] (III) Acid

[0107] The composition of the present invention comprises an acid.

[0108] The acid may be an inorganic acid or an organic acid, and is preferably an organic acid, more preferably a carboxylic acid, further preferably a monocarboxylic acid or a dicarboxylic acid, and further more preferably a dicarboxylic acid.

[0109] Examples of the monocarboxylic acid include acetic acid, formic acid, propionic acid, butyric acid, valeric acid, and acrylic acid, and acetic acid is preferred.

[0110] 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, acetylene dicarboxylic acid, itaconic acid, mesaconic acid, 3-aminohexane dicarboxylic acid, and malonic acid. Oxalic acid, maleic acid, fumaric acid, phthalic acid, succinic acid, malic acid, citraconic acid, acetylene dicarboxylic acid, or malonic acid is preferred. Oxalic acid, maleic acid, fumaric acid, phthalic acid, citraconic acid, or acetylene dicarboxylic acid is more preferred.

[0111] The acid preferably sublimates when heated for curing and has high sublimability. 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 amount of the cured film remaining is reduced due to the sublimation of the acid.

[0112] Not bound by theory, as mentioned above, ionic liquids function as catalysts that promote the curing of polysiloxanes at low temperatures. Compositions comprising ionic liquids, polysiloxanes and solvents may also be cured, gelled, etc., even in long-term storage at room temperature. In contrast, it is believed that by combining acids, the catalytic action of ionic liquids can be suppressed and good storage stability can be exerted. It is believed that it is because the acid sublimates when heated for curing, showing the catalytic action of ionic liquids, and can be cured at a lower temperature. In order to exert better storage stability and low temperature curing, in the present invention, it is preferred to include a combination of ionic liquids and carboxylic acids, more preferably include a combination of ionic liquids and oxalic acid, maleic acid, fumaric acid, phthalic acid, citraconic acid or acetylene dicarboxylic acid, and further preferably include a combination of ionic liquids and maleic acid in which cations are imidazolium salt ions and anions are acetate ions.

[0113] 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 dicyanamide / acetic acid, 1-ethyl-3-methylimidazolium methylsulfate / 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 methylsulfate / 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 methylsulfate / glutaric acid, 2-hydroxyethyltrimethylammonium acetate / glutaric acid, 2-hydroxyethyltrimethylammonium acetate / glutaric acid, Ethyltrimethylammonium 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 methylsulfate / 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 / citraconic acid, tributylmethylammonium dicyanamide / citraconic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / citraconic acid, tri(2-hydroxyethyl)methylammonium methylsulfate / citraconic acid, 2-hydroxyethyltrimethylammonium acetate / citraconic acid, 2-hydroxyethyltrimethylammonium lactate / citraconic acid, 2-hydroxyethyltrimethylammonium salicylate / citraconic acid, tetrabutylammonium chloride / citraconic acid, 1,3-dimethylimidazolium methylsulfate / citraconic acid, 1,2,3-trimethylimidazolium methylsulfate / 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 dicyano Amine / 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 salt / 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 ethylsulfide acid salt / 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, tri(2 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 methylsulfate / acetylenedicarboxylic acid, 1,2,3-Trimethylimidazolium methylsulfate / acetylenedicarboxylic acid, 1-Ethyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-Ethyl-3-methylimidazolium dicyanamide / 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 dicyanamide / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium thiocyanate / acetylenedicarboxylic acid, 1-butyl-3-methylimidazolium bromide / acetylenedicarboxylic acid, -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-butyl 1-Methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, 1-Methyl-1-butylpiperidinium bis(trifluoromethylsulfonyl)imide / acetylenedicarboxylic acid, 1-Ethyl-3-methylpyridinium ethylsulfate / 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 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 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, Cyanamide / 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 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, tri(2-hydroxyethyl)methylammonium methylsulfate / maleic acid, 2-hydroxyethyltrimethylammonium acetate / maleic acid, 2-hydroxyethyltrimethylammonium lactate / maleic acid, 2-hydroxyethyltrimethylammonium salicylate / maleic acid, tetrabutylammonium chloride / maleic acid, 1,3-dimethylimidazolium methylsulfate / maleic acid, 1,2,3-trimethylimidazolium methylsulfate / 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 tetrafluoroborate / maleic acid, -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-Methylsulfonyl)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, Tributylmethyl 2-Hydroxyethyltrimethylammonium acetate / fumaric acid, 2-Hydroxyethyltrimethylammonium lactate / fumaric acid, 2-Hydroxyethyltrimethylammonium salicylate / fumaric acid, Tetrabutylammonium chloride / fumaric acid, 1,3-Dimethylimidazolium methylsulfate / fumaric acid, 1,2,3-Trimethylimidazolium methylsulfate / fumaric acid, 1-Ethyl-3-methylimidazolium acetate / fumaric acid, 1-Ethyl-3-methylimidazolium dicyanamide / fumaric acid, 1-Ethyl-3-methylimidazolium methylsulfate / 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 imidazolium 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 methylsulfate / phthalic acid, 1,2,3-trimethylimidazolium methylsulfate / phthalic acid, 1-ethyl-3-methylimidazolium acetate / phthalic acid, 1-ethyl-3-methylimidazolium dicyanamide / phthalic acid, 1-ethyl-3-methylimidazolium methylsulfate / 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, -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.

[0114] 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, tri(2-hydroxyethyl)methylammonium methylsulfate / citraconic acid, 2-hydroxyethyltrimethylammonium acetate / citraconic acid, 2-hydroxyethyltrimethylammonium lactate / citraconic acid, 2-hydroxyethyltrimethylammonium salicylate / citraconic acid, tetrabutylammonium chloride / citraconic acid, 1,3-dimethylimidazolium methylsulfate / citraconic acid, 1,2,3-trimethylimidazolium methylsulfate / citraconic acid. 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 / citraconic acid, 1-butyl-3-methylimidazolium thiocyanate / citraconic acid, 1-butyl-3-methylimidazolium bromide / citraconic acid, 1-butyl 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 Trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / Citraconic acid, 1-butylpyridinium tetrafluoroborate / Citraconic acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide / Ethylenedicarboxylic acid, tributylmethylammonium dicyanamide / Ethylenedicarboxylic acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / Ethylenedicarboxylic acid, tri(2-hydroxyethyl)methylammonium methylsulfate / Ethylenedicarboxylic acid, 2-hydroxyethyltrimethylammonium acetate / Ethylenedicarboxylic acid, 2-hydroxyethyltrimethylammonium lactate / Ethylenedicarboxylic acid, 2-hydroxyethyltrimethylammonium salicylate / Ethylenedicarboxylic acid, tetrabutylammonium chloride / Ethylenedicarboxylic acid, 1,3-dimethylimidazolium methylsulfate / Ethylenedicarboxylic acid, 1,2,3-Trimethylimidazolium methylsulfate / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium acetate / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium dicyanamide / acetylenedicarboxylic acid, 1-ethyl-3-methylimidazolium methylsulfate / 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 Imidazolium 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, tri(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-Trimethylimidazolium methylsulfate / oxalic acid, 1-ethyl-3-methylimidazolium acetate / oxalic acid, 1-ethyl-3-methylimidazolium dicyanamide / oxalic acid, 1-ethyl-3-methylimidazolium methylsulfate / 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 / oxalic acid methylsulfonyl)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, tetrabutylammonium chloride / maleic acid, 1,3-dimethylimidazolium methylsulfate / maleic acid, 1,2,3-Trimethylimidazolium methylsulfate / 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 ethyl bromide / 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 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 ethylsulfate / Maleic Acid, 1-Butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / Maleic Acid, 1-Butylpyridinium tetrafluoroborate / Maleic Acid, Trimethylbutyl ammonium bis(trifluoromethylsulfonyl)imide / fumaric acid, tributylmethylammonium dicyanamide / fumaric acid, tributylmethylammonium bis(trifluoromethylsulfonyl)imide / fumaric acid, tri(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 methylsulfate / fumaric acid, 1,2,3-Trimethylimidazolium methylsulfate / fumaric acid, 1-ethyl-3-methylimidazolium acetate / fumaric acid, 1-ethyl-3-methylimidazolium dicyanamide / fumaric acid, 1-ethyl-3-methylimidazolium methylsulfate / 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 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 acid, 1-butyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide / fumaric acid, 1-butylpyridinium tetrafluoroborate / fumaric acid, trimethylbutylammonium bis(trifluoromethylsulfonyl)imide Amine / 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 methylsulfate / phthalic acid, 1-ethyl-3-methylimidazolium acetate / phthalic acid, 1-ethyl-3-methylimidazolium dicyanamide / phthalic acid, 1-ethyl-3-methylimidazolium methylsulfate / 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. ,

[0115] In a further 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.

[0116] The mixing ratio of the ionic liquid to the acid (ionic liquid / acid) is preferably 0.10 to 1.0, more preferably 0.20 to 1.0, in terms of equivalent ratio. This is because 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.

[0117] The acid may 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 even more preferably 0.001 to 8.0% by mass, based on the total mass of the composition of the present invention.

[0118] (IV) Solvent

[0119] The solvent is not particularly limited as long as it can evenly dissolve or disperse the above-mentioned components (I) to (III) and additives added as needed. Examples of the solvent 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 acetate. Alkyl ether acetates, 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, glycerol, 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, and preferably PGME, 3-methoxybutanol, 1,3-butanediol, PGMEA, ethyl lactate, butyl acetate, and 3-methoxybutyl acetate. The solvents may be used alone or in combination of two or more.

[0120] The solvent content of the composition of the present invention is appropriately selected based on the mass average molecular weight, distribution and structure of the polysiloxane used, in order to improve workability according to the coating method adopted, and in consideration of 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 of the present invention.

[0121] The composition of the present invention must have the above (I) to (IV), but other compounds may be combined as needed. The following is an explanation of these combinable materials. It should be noted that the total amount of components other than (I) to (IV) in the entire composition is preferably less than 10% relative to the total mass of the composition, and more preferably less than 5%.

[0122] The composition of the present invention may contain other additives as necessary. Examples of such additives include surfactants, adhesion enhancers, defoamers, and thermal curing accelerators.

[0123] The surfactant is added for the purpose of improving coating properties, developing properties, etc. Examples of the surfactant that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0124] 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, and polyoxyethylene polyoxypropylene block polymers; acetylene alcohol derivatives such as acetylene alcohol and polyethoxylates of acetylene alcohol; acetylene glycol derivatives such as acethylene glycol and polyethoxylates of acetylene glycol; fluorine-containing surfactants such as FLUORAD (trade name, manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (trade name, manufactured by DIC Corporation), and SURFLON (trade name, manufactured by Asahi Glass Co., Ltd.); and organosilicone surfactants such as KP341 and KF-53 (trade name, 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-octyne-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.

[0125] Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyldiphenylether disulfonic acid, ammonium salts or organic amine salts of alkyldiphenylether sulfonic acid, ammonium salts or organic amine salts of alkylbenzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfate, and ammonium salts or organic amine salts of alkyl sulfate.

[0126] Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauramide propyl hydroxysulfobetaine.

[0127] These surfactants may be used alone or in combination of two or more. The amount thereof blended is usually 50 to 10,000 ppm, preferably 100 to 8,000 ppm, based on the composition of the present invention.

[0128] When the composition of the present invention is used to form a cured film, the adhesion enhancer has the effect of preventing pattern peeling due to stress applied after firing. As the adhesion enhancer, imidazoles or silane coupling agents are preferred, and among the imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, and 2-aminoimidazole are preferred, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferred.

[0129] Examples of the defoaming agent include alcohol (C 1～18), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glyceryl monolaurate, polyethers such as polyethylene glycol (PEG) (Mn: 200-10000), polypropylene glycol (PPG) (Mn: 200-10000), silicone compounds such as dimethyl silicone oil, alkyl modified silicone oil, fluorosilicone oil, and the above-mentioned organosiloxane surfactants. These can be used alone or in combination, and the addition amount is preferably 0.1-3% by mass based on the total mass of polysiloxane.

[0130] As a heat curing accelerator, there can be cited: a hot alkali generator, a hot acid generator, etc. In the present invention, as far as the heat curing accelerator is concerned, an ionic liquid is not included. Usually, by including a heat curing accelerator, the curing speed of the coating film when heated can be increased, but in the present invention, because the ionic liquid plays a function of promoting the curing of polysiloxane, even if the heat curing accelerator is not included, the curing can also be performed, so the content of the heat curing accelerator is preferably 0.01% by mass or less, more preferably 0.001% by mass. Not containing a heat curing accelerator is also one of the preferred embodiments of the present invention.

[0131] The composition of the present invention further comprises a naphthoquinone diazide derivative, a photoacid generator, a photobase generator, etc., and therefore can also be used as a photosensitive composition. The composition of the present invention preferably comprises a photoacid generator or a photobase generator, and more preferably comprises a photoacid generator. In the present invention, a photoacid generator or a photobase generator refers to a compound that generates an acid or a base due to bond breakage caused by exposure. The acid or base generated is believed to contribute to the polymerization of polysiloxane. Here, as light, there can be cited: visible light, ultraviolet light, infrared light, X-rays, electron beams, α rays or γ rays, etc. In the present invention, as far as the photoacid generator is concerned, a naphthoquinone diazide derivative is not included.

[0132] The photoacid generator can be arbitrarily selected from commonly used photoacid generators, for example, diazomethane compounds, triazine compounds, sulfonates, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, sulfonimide compounds and the like.

[0133] Including the above substances, as specific photoacid generators that can be used, there are 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluoroarsenate, 4-phenylthiophenyl diphenyl p-toluenesulfonate, N-(trifluoromethylsulfonyloxy) succinimide, N-(trifluoromethylsulfonyloxy) phthalimide, 5-norbornene-2,3-dicarboximido trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximido p-toluenesulfonate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, N-(trifluoromethylsulfonyloxy) diphenyl maleimide, N-(trifluoromethylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dicarboximidamide, N-(trifluoromethylsulfonyloxy) naphthalimide, N-(nonafluorobutylsulfonyloxy) naphthalimide, and the like.

[0134] Examples of the photobase generator include polysubstituted amide compounds, lactams, imide compounds, and compounds containing structures thereof having an amide group.

[0135] In addition, an ionic photobase generator containing an amide anion, a methyl anion, a borate anion, a phosphate anion, a sulfonate anion, a carboxylate anion, or the like as an anion may also be used.

[0136] Method for producing cured film

[0137] The method for producing a cured film of the present invention comprises the steps of applying the composition of the present invention on a substrate to form a coating film, and the step of heating the coating film. In the present invention, "on a substrate" includes the case where the composition is directly applied to the substrate, and / or the case where the composition is applied to the substrate via one or more intermediate layers. The method for forming a cured film is described below in order of steps.

[0138] (1) Coating process

[0139] The shape of the substrate is not particularly limited and can be selected arbitrarily according to the purpose. However, the composition of the present invention has the characteristics of being easy to penetrate into narrow grooves and the like and forming a uniform cured film inside the grooves, so it can be applied to substrates with grooves or holes with a large aspect ratio. Specifically, it can be applied to substrates having at least one groove with a width of less than 0.2 μm at the deepest part and an aspect ratio of more than 2. The shape of the groove is not particularly limited here, and the cross-section can be any shape such as a rectangle, a positive cone, an inverted cone, a curved surface, etc. The two end portions of the groove can be open or closed.

[0140] Representative examples of substrates having at least one groove with a large aspect ratio include substrates for electronic devices having semiconductor tube elements, bit lines, capacitors, etc. For the production of such electronic devices, an insulating film is formed between a semiconductor tube element called PMD and a bit line, between a semiconductor tube element and a capacitor, between a bit line and a capacitor, or between a capacitor and a metal wiring, or an insulating film is formed between a plurality of metal wirings called IMD, or a separation groove is buried, followed by a through hole plating step of forming a hole that penetrates the buried material of the fine groove from top to bottom.

[0141] Coating can be carried out by any method. Specifically, it can be arbitrarily selected from dip coating, roller coating, rod coating, brush coating, spray coating, blade coating, blow coating, spin coating and slit coating etc. In addition, as the substrate of the coating composition, suitable substrates such as silicon substrate, glass substrate, resin film can be used. Various semiconductor devices etc. can also be formed on these substrates as required. When the substrate is a film, gravure coating can also be utilized. Drying process can also be set separately after coating according to expectation. In addition, 1 coating process or repeating more than 2 times can also be carried out as required to make the formed coating become the expected film thickness.

[0142] (2) Pre-baking process

[0143] After a coating film is formed by applying the composition, the coating film may be pre-baked (pre-heating treatment) in order to dry the coating film and reduce the amount of residual solvent in the coating film.

[0144] (3) Curing process

[0145] In the case of a non-photosensitive composition, the coating film is then heated to form a cured film. Here, in the present invention, the cured film means that the S2 / S1 ratio is less than 0.003.

[0146] The heating device used in the curing process can use a heating plate or an oven. As the heating temperature in the curing process, there is no particular limitation as long as it is a temperature at which a cured film can be formed, and it can be determined arbitrarily. However, if silanol remains, the chemical resistance of the cured film becomes insufficient, and the dielectric constant of the cured film may become higher. From such a viewpoint, a relatively high temperature is usually selected for the heating temperature, but when the composition of the present invention is used, curing can be performed at a lower temperature. Specifically, it is preferably heated at 500°C or less, and more preferably at 300°C or less. On the other hand, in order to promote the curing reaction, the heating temperature is preferably 120°C or more, more preferably 140°C or more, and further preferably 170°C or more. In addition, the heating time is not particularly limited, and when a heating plate is used, it is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes. The curing process is preferably carried out under an atmospheric atmosphere.

[0147] In this curing process, holes may be generated. In particular, if the polysiloxane contains fewer organic groups, there is a tendency for the generation of holes to increase. However, when the composition of the present invention is used, the generation of holes can be suppressed even when the polysiloxane contains fewer organic groups.

[0148] In the case of a photosensitive composition, after forming a coating film, the coating film surface is subjected to light irradiation. As the light source for light irradiation, any light source used in the previous pattern forming method can be used. As such a light source, there can be cited: a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide, a xenon lamp or a laser diode, an LED, etc. As the irradiation light, ultraviolet rays such as g-line, h-line, and i-line can usually be used. In addition to ultrafine processing such as semiconductors, in patterning of several μm to tens of μm, 360-430nm light (high-pressure mercury lamp) is generally used.

[0149] In order to irradiate light in a pattern, a common photomask can be used. Such a photomask can be arbitrarily selected from known photomasks. The environment during irradiation is not particularly limited, and generally, it can be an ambient atmosphere (in the air) or a nitrogen atmosphere.

[0150] After exposure, the acid or alkali generated at the exposure site will promote the reaction between polymers in the film, so in the case of negative type, post-exposure heating can be performed as needed. This heating treatment is different from the heating process described later. It is not performed to completely cure the coating film, but only the expected pattern can remain on the substrate after development, and the rest of it can be removed by development. In the case of post-exposure heating, a heating plate, an oven or a furnace can be used. Since the acid or alkali in the exposure area generated by light irradiation will diffuse to the unexposed area, it is not preferred, so the heating temperature should not be too high. From this point of view, the range of the heating temperature after exposure 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, staged heating can also be applied as needed. In addition, the atmosphere during heating is not particularly limited. For the purpose of controlling the curing rate of the composition, it can be selected from inert gases such as nitrogen, vacuum, reduced pressure, oxygen, etc. In order to maintain the uniformity of the temperature history in the wafer surface at a higher level, the heating time is preferably above a certain level, and in order to suppress the diffusion of the generated acid or alkali, the heating time is preferably not too long. From such a viewpoint, the heating time is preferably 20 seconds to 500 seconds, more preferably 40 seconds to 300 seconds.

[0151] After exposure, the coating is developed. As the developer used in the development, any developer used in the development of the photosensitive composition in the past can be used. As preferred developers, there are alkaline developers of aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), ammonia water, alkylamines, alkanolamines, heterocyclic amines, etc., and a particularly preferred alkaline developer is a TMAH aqueous solution. The development method can be arbitrarily selected from the methods known in the past. Specifically, there can be cited methods such as dipping (dip) in the developer, paddle immersion (paddle), showering, slit, cap coating, and spraying. A pattern can be obtained by this development, and after development with a developer, it is preferably washed with water.

[0152] Thereafter, a flood exposure step may be performed as necessary.

[0153] The pattern film obtained after development is heated to cure the coating film. The heating conditions are the same as those in (3) above.

[0154] The cured film formed using the composition of the present invention can achieve excellent transparency, chemical resistance, environmental resistance, electrical insulation, heat resistance, etc. Therefore, it can be preferably used in many aspects as an interlayer insulating film for low-temperature polysilicon, a buffer coating film for IC chips, a transparent protective film, etc.

[0155] The method for producing an electronic device of the present invention includes the method for producing a cured film of the present invention described above.

[0156] [Example]

[0157] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[0158] Gel permeation chromatography (GPC) was measured using Alliance (trademark) e2695 high-speed GPC system (Japan Waters K.K.) and Super Multipore HZ-N GPC column (Tosoh Corporation). The measurement was carried out using monodisperse polystyrene as a standard sample, tetrahydrofuran as a developing solvent, and under the measurement conditions of a flow rate of 0.6 ml / min and a column temperature of 40°C, and on this basis, the mass average molecular weight (hereinafter referred to as Mw) was calculated as the molecular weight relative to the standard sample.

[0159] Synthesis Example 1: Polysiloxane A

[0160] 107g (0.786 mol) of methyltriethoxysilane, 96g (0.484 mol) of phenyltriethoxysilane and 300g of PGMEA were added to a four-necked flask to dissolve them. Then 48g of 44% sodium hydroxide aqueous solution was added and stirred at 500rpm and 40°C for 2 hours. Then it was neutralized with acetic acid water and stirred for 1 hour. After that, the reaction solution was moved to a separatory funnel and allowed to stand for 30 minutes to separate the organic solvent phase from the aqueous phase. The aqueous phase was discarded, and 100g of pure water was added to the organic solvent phase in the separatory funnel and shaken, and the alkaline components and water-soluble components remaining in the organic solvent phase were extracted and washed. This washing operation was performed three times. The organic solvent phase washed with pure water was then 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. In addition, S2 / S1 here is measured by using the polysiloxane A solution and in the same manner as the method for measuring S2 / S1 of a cured film described later, except that heating is not performed.

[0161] Synthesis Example 2: Polysiloxane B

[0162] 53.7g (0.394 mol) of methyltrimethoxysilane, 173.7g (0.876 mol) of phenyltrimethoxysilane and 300g of PGMEA were added to a four-necked flask to dissolve it. Then 48g of 44% by mass sodium hydroxide aqueous solution was added and stirred at room temperature for 2 hours at 500rpm. Then it was neutralized with acetic acid water and stirred for 1 hour. After that, the reaction solution was moved to a separatory funnel and left to stand for 30 minutes to separate the organic solvent phase from the aqueous phase. The aqueous phase was discarded, and 100g of pure water was added to the organic solvent phase in the separatory funnel and shaken, and the alkaline components and water-soluble components remaining in the organic solvent phase were extracted and washed. This washing operation was performed three times. After that, the organic solvent phase washed with pure water was recovered to obtain a polysiloxane B solution. The mass average molecular weight of polysiloxane B contained in the organic solvent phase was 1,600, and S2 / S1 was 0.028.

[0163] Synthesis Example 3: Polysiloxane C

[0164] 138.9g (1.02 mol) of methyltrimethoxysilane, 49.8g (0.251 mol) of phenyltrimethoxysilane and 300g of PGMEA were added to a four-necked flask to dissolve it. Then 48g of 44% by mass sodium hydroxide aqueous solution was added and stirred at room temperature for 2 hours at 500rpm. Then it was neutralized with acetic acid water and stirred for 1 hour. After that, the reaction solution was moved to a separatory funnel and left to stand for 30 minutes to separate the organic solvent phase from the aqueous phase. The aqueous phase was discarded, and 100g of pure water was added to the organic solvent phase in the separatory funnel and shaken to extract and wash the alkali components and water-soluble components remaining in the organic solvent phase. This washing operation was performed three times. The organic solvent phase washed with pure water was then recovered. The mass average molecular weight of polysiloxane C contained in the organic solvent phase was 1,800, and S2 / S1 was 0.032.

[0165] Preparation of polysiloxane composition

[0166] The polysiloxane compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were prepared with the compositions and contents shown in Table 1. In the table, the numerical values ​​of the compositions are expressed in mass %.

[0167] [Table 1]

[0168]

[0169] In the table,

[0170] Ionic liquid A: 1-ethyl-3-methylimidazolium acetate (EMIMAc);

[0171] Ionic liquid B: 1-butyl-3-methylimidazolium dicyanamide;

[0172] Ionic liquid C: 2-hydroxyethyltrimethylammonium acetate;

[0173] Ionic liquid D: 1-methyl-1-butylpyrrolidinium dicyanamide;

[0174] Thermal alkali generator A: manufactured by SANAPRO Co., Ltd.

[0175] Storage stability

[0176] The polysiloxane composition was measured for Mw 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.

[0177] Storage stability (%) = (Mw (after storage) - Mw (before storage)) / Mw (before storage) × 100

[0178] Film reduction rate

[0179] The polysiloxane composition was applied to a 4-inch Si wafer using a spin coater (1HDX2 manufactured by MIKASA Co., Ltd.) at 1000 rpm. The coating film thickness was measured at 19 points on the diameter using a spectroscopic ellipsometer (M-2000V manufactured by JA Woolam Co., Ltd.), and the average value was taken. The coated wafer was cured at 200°C for 2 minutes in the atmosphere. The cured film thickness was measured in the same manner as the coating film thickness. The film reduction rate was evaluated by the following formula. The results are shown in Table 1.

[0180] Film reduction rate (%) = (coating film thickness - cured film thickness) / coating film thickness × 100

[0181] S2 / S1 after curing

[0182] The polysiloxane composition was dropped onto a 4-inch Si wafer and spin-coated at 1000 rpm, and then cured on a hot plate at 150°C for 2 minutes. FT-IR spectra were measured at room temperature using FTIR-6100 (JASCO). The noise was taken into account and baseline correction was performed, and the measurement was performed at 900±100cm -1 The absorption band (S2) of Si-OH and the absorption band (S3) of 1100±100cm -1 The area intensity of the absorption band (S1) having a peak in the range of 1.5 and attributable to Si-O was calculated to obtain the value of S2 / S1. The results are shown in Table 1.

[0183] It should be noted that the lower end of the absorption band belonging to Si-OH may overlap with the lower end of the absorption band belonging to Si-O. In this case, the wave number corresponding to the minimum point between the two absorption bands in the spectrum is regarded as the boundary. The same is true for the lower end of other absorption bands overlapping with the lower end of the absorption band belonging to Si-OH or Si-O.

[0184] Relative diffuse reflectivity

[0185] The polysiloxane composition was dropped onto a 4-inch Si wafer, spin-coated at 1000 rpm, and then cured on a 200°C hot plate for 2 minutes. The spectrophotometer UV-2600 (Shimadzu Corporation) was equipped with an integrating sphere device ISR-2600Plus (Shimadzu Corporation), and barium sulfate was used as a standard plate, and the standard plate was set as 100%. The relative diffuse reflectance (%) when a light with a wavelength of 400 nm was incident from the polysiloxane cured film side (incident light 0°) was measured. The results are shown in Table 1.

[0186] Cured film appearance

[0187] The compositions of Example 1 and Comparative Example 1 were respectively applied onto a 4-inch Si wafer at 1000 rpm using a spin coating method, and cured by heating on a hot plate at 200° C. for 2 minutes. The appearance of the cured film was visually observed, and a uniform cured film was formed in Example 1, but uneven coating was observed in Comparative Example 1.

[0188] Example 6

[0189] In 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 parts by mass of "NAI-105" (Midori Kagaku Co., Ltd.) as a photoacid generator, 0.3 parts by mass of "KF-53" (Shin-Etsu Chemical Co., Ltd.) as a surfactant, and PGMEA are added to prepare a solution in which the components other than the solvent are 35% by mass to obtain a composition. The composition is applied on a silicon wafer by spin coating, and after coating, it is pre-baked on a hot plate at 100°C for 90 seconds to adjust the average film thickness to 2μm. Exposure is performed using a g and h line exposure machine, and post-exposure is performed on a hot plate at 100°C for 90 seconds, and developed using a 2.38% by mass TMAH aqueous solution, and rinsed with pure water for 30 seconds. Because a 10μm contact hole (C / H) pattern is formed, it can be seen that the composition is negatively sensitive. The substrate having the C / H pattern was cured for 2 minutes on a hot plate at 200° C., and the elastic modulus was measured using an indentation hardness tester “ENT-2100” (ELIONIX Corporation) to find that it was 3.82 GPa.

Claims

1. A polysiloxane composition comprising (I) polysiloxane, (II) ionic liquid, (III) acid and (IV) solvent; The (I) polysiloxane comprises a repeating unit represented by formula (Ia), and has a silanol at the end or side chain thereof; in, R 1 Hydrogen, 1-3 valent C 1-30 A straight-chain, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or a 1- to 3-valent C 6-30 Aromatic hydrocarbon groups, The aliphatic hydrocarbon group and the aromatic hydrocarbon group are unsubstituted or substituted with fluorine, hydroxyl or C 1-8 Alkoxy; In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, the methylene group is not replaced, or one or more methylene groups are replaced by an oxy group, an imide group or a carbonyl group, provided that R 1 Neither hydroxy nor alkoxy; R 1 When it is bivalent or trivalent, R 1 Connecting Si contained in multiple repeating units to each other; When the polysiloxane is measured and analyzed by FT-IR method, the wavelength of 1100±100cm -1 The area intensity S1 of the absorption band attributed to Si-O is in the range of 900±100cm -1 The ratio S2 / S1 of the area intensity S2 of the absorption band attributed to SiOH is within the range of 0.010 to 0.

10.

2. The polysiloxane composition according to claim 1, wherein R 1 For hydrogen, C 1-6 A straight-chain, branched or cyclic alkyl group or C 6-10 The aromatic group.

3. The polysiloxane composition according to claim 1 or 2, wherein (II) The cation of the ionic liquid is at least one cation selected from the group consisting of imidazolium ions, pyrrolidinium ions, piperidinium ions, pyridinium ions and ammonium ions.

4. The polysiloxane composition according to any one of claims 1 to 3, wherein (II) The anion of the ionic liquid 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, methylsulfate ion, ethylsulfate ion, hydrogen sulfate ion, methanesulfonate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, bis(trifluoromethylsulfonyl)imide ion, bis(fluorosulfonyl)imide ion, methylcarbonate ion, hydrogencarbonate ion, diethylphosphate ion, dibutylphosphate ion, hexafluorophosphate ion, tetrafluoroborate ion, chloride ion and bromide ion.

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

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

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

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

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

11. The polysiloxane composition according to any one of claims 1 to 10, wherein It further comprises a photoacid generator or a photobase generator. 12 . A method for producing a cured film, comprising the steps of applying the polysiloxane composition according to claim 1 on 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 of manufacturing an electronic device, wherein: The method for producing a cured film comprising claim 12 or 13.

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