JP2000119600A - Composition for membrane formation, production of membrane and porous membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for forming membranes of low dielectric constant having excellent adhesion and uniformity of coated membrane by using a hydrolyzate of a specific compound or the like, a compound that is compatible to the hydrolyzate component and has a specific boiling point, and a low-boiling organic solvent of ester. SOLUTION: The objective composition for forming coated membranes comprises (A) a hydrolyzate of a compound represented by the formula: R1nSi(OR2)4-n (R1 and R2 are each a monovalent organic group; n is 0-2) and its partial condensate or one of them, (B) a compound that is compatible to or dispersible in the component A and has a boiling point or decomposition point of 250-450 deg.C, and (C) an ester-based organic solvent boiling at a temperature of <=250 deg.C. In a preferred embodiment, this composition includes a metal chelate compound of the formula: R31tM(OR32)4-t (R31 is a chelating agent; M is Ti, Zr, Al, Sn, Sb, Nb or the like; R32 is an alkyl, an aryl; t is 1-4). A porous membrane is obtained by curing this composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition, and more particularly, to a low-dielectric-constant film-forming composition having excellent adhesion, uniformity of a coating film, and the like. And a porous membrane obtained by the above method.

[0002]

Conventionally, as an interlayer insulating film in semiconductor devices and the like, silica is formed Te than by a vacuum process such as CVD (SiO ₂₎ film is often used. And in recent years,
In order to form a more uniform interlayer insulating film, S
A coating-type insulating film called a OG (Spin on Glass) film, which is mainly composed of a hydrolysis product of tetraalkoxylan, has also been used. Also, with the high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant, which is mainly composed of organopolysiloxane and is called organic SOG, has been developed. However, with further higher integration of semiconductor devices and the like, more excellent wiring delay between conductors has become a problem, and therefore, a material for an interlayer insulating film having a lower dielectric constant has been required.

[0003] Japanese Patent Application Laid-Open No. 6-181201 discloses a coating composition for forming an insulating film having a lower dielectric constant as an interlayer insulating film material. Such a coating composition has a low water absorption and is intended to provide an insulating film of a semiconductor device having excellent crack resistance, and the constitution is
Titanium, zirconium, niobium and tantalum; an organometallic compound containing at least one element selected from the group consisting of polycondensation of an organosilicon compound having at least one alkoxy group in the molecule; It is a coating type composition for forming an insulating film mainly comprising an oligomer. However, the dielectric constant of the conventional inorganic interlayer insulating film material is 3.0 or more, which is insufficient for high integration.

An object of the present invention is to provide a material for an interlayer insulating film which has improved dielectric constant characteristics and a good balance of adhesion to a base and the like. Hereinafter, the present invention will be described in detail. The present invention relates to (A) a hydrolyzate of a compound represented by the following general formula (1) and / or a partial condensate thereof: R ¹ _n Si (OR ² ) _4-n (1) (R ¹ and R ^{1 2} may be the same or different and each represents a monovalent organic group, and n represents an integer of 0 to 2.) (B) Compatible or dispersed in the component (A), and has a boiling point or decomposition temperature. And (C) an ester organic solvent having a boiling point of less than 250 ° C., and a film formed by applying the composition to a substrate and heating the composition. And a porous membrane obtained by the method.

(A) Component In the general formula (1), examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group. In the general formula (1), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and preferably have 1 to 5 carbon atoms, and these alkyl groups may be chain-like or branched. And a hydrogen atom may be substituted with a fluorine atom or the like. Examples of the aryl group include a phenyl group and a naphthyl group. In the general formula (1), n is 1 or 2
It is preferable to use Specific examples of the compound represented by the general formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-s
ec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri- sec-butoxysilane, ethyl tri-tert
-Butoxysilane, ethyltriphenoxysilane, n-
Propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane,
n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-
sec-butoxysilane, n-propyltri-tert
-Butoxysilane, n-propyltriphenoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, i-propyltri-n-propoxysilane, i-propyltri-iso-propoxysilane, i-propyltri- n-butoxysilane, i-propyltri-sec-butoxysilane, i-propyltri-tert-butoxysilane, i-propyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri- n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec-butoxysilane, n-butyltri-te
rt-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyl-i-triethoxysilane, sec-butyl-tri-
n-propoxysilane, sec-butyl-tri-iso
-Propoxysilane, sec-butyl-tri-n-butoxysilane, sec-butyl-tri-sec-butoxysilane, sec-butyl-tri-tert-butoxysilane, sec-butyl-triphenoxysilane, t-butyltrimethoxy Silane, t-butyl triethoxy silane, t-butyl tri-n-propoxy silane, t-butyl tri-iso-propoxy silane, t-butyl tri-n-butoxy silane, t-butyl tri sec-butoxy silane, t-butyl tri-tert-butoxy silane, t-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-
Propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec-butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane,
Dimethyl-di-iso-propoxysilane, dimethyl-
Di-n-butoxysilane, dimethyl-di-sec-butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n
-Propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n-butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-te
rt-butoxysilane, diethyldiphenoxysilane,
Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di-n-propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di -N-butoxysilane, di-n-propyl-di-sec-butoxysilane,
Di-n-propyl-di-tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-
Propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso-propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxy Silane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di-iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n -Butyldiethoxysilane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl -Di-sec-butoxysilane, di-n-
Butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl-di-n-propoxysilane, Di-s
ec-butyl-di-iso-propoxysilane, di-s
ec-butyl-di-n-butoxysilane, di-sec-
Butyl-di-sec-butoxysilane, di-sec-butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, Di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl-di-sec-butoxy Silane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane,
Diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxysilane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-
Butoxysilane, diphenyl-di-tert-butoxysilane, diphenyldiphenoxysilane, divinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- One or more kinds of glycidoxypropyltriethoxysilane, γ-trifluoropropyltrimethoxysilane, γ-trifluoropropyltriethoxysilane and the like can be mentioned.

In the film forming composition of the present invention, among the compounds represented by the above general formula (1), it is particularly preferable to use an alkyltrialkoxysilane with n = 1.
Further, it is preferable to use methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
It is particularly preferable to use the above. Use of the alkylalkoxysilane in such a range is preferable in that a film-forming composition that becomes a cured product having higher heat resistance can be obtained. Further, when the compound represented by the general formula (1) is hydrolyzed and partially condensed, it is preferable to use 0.3 to 1.2 mol of water per 1 mol of the alkoxysilyl group, It is particularly preferred to add 1.0 mol of water. When the amount of water to be added is within the range of 0.3 to 1.2 mol, there is no possibility that the uniformity of the coating film is reduced, and the storage stability of the film-forming composition is reduced. Is also less. When the component (A) is a partial condensate of the compound represented by the general formula (1), the weight average molecular weight in terms of polystyrene is preferably 500 to 100,000.

(B) Component In the present invention, the compound having a boiling point or a decomposition temperature of 250 to 450 ° C., which is compatible or dispersed in the component (A), has a polyalkylene oxide structure,
A compound having a sugar chain structure, a vinylamide polymer,
Examples thereof include (meth) acrylate polymers, aromatic vinyl polymers, dendrimers, lipophilic compounds and dispersants, and ultrafine particles. Compound having a polyalkylene oxide structure Here, examples of the polyalkylene oxide structure include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene glycol, polyoxypropylene glycol, Polyoxyalkylene glycols such as polyoxytetramethylene glycol and polyoxybutylene glycol, polyalkylene oxides, random or block copolymers containing two or more polyalkylene oxides, ether-type compounds such as polyoxyethylene polyoxypropylene alkyl ether, Polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Sorbitol fatty acid ester, ether ester type compounds such as polyoxyethylene fatty acid alkanolamide sulfate, polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester And the like.

Compounds having a sugar chain structure As the compounds having a sugar chain structure, cyclodextrin,
Starch, sucrose ester, oligosaccharide, glucose, fructose, mannitol, starch sugar, D-sorbitol, dextran, xanthan gum, curdlan, pullulan, cycloamylose, isomerized sugar, maltitol, cellulose acetate, cellulose, carboxymethyl cellulose −
, Hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, carboxymethylcellulose, chitin and chitosan.

[0009]

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It is preferable that the compound having a sugar chain structure used in the present invention is modified in part or all of a hydroxyl group or an amino group. Examples of chemical modification of the hydroxyl group include etherification, esterification, modification including a trialkylsilyl bond and a urethane bond. Examples of the chemical modification of the amino group include introduction of an amide bond, a urea bond, and an imide bond. Among the compounds having a sugar chain structure, cyclodextrin is preferred because the pore size after decomposition is small and control thereof is possible, and as the chemical modification, trialkyl ether modification or urethanation is preferable, and trialkyl ether modification is particularly preferable. In order to modify the hydroxyl group of a compound having a sugar chain structure with a trialkyl ether group, a compound having a sugar chain structure may be reacted with a trimethylsilylating agent such as trimethylchlorosilane or trimethylchlorosilylacetamide. May be substituted for 5 to 100% of the hydroxyl groups of the compound having
In order to modify a compound having a sugar chain structure with a trimethylsil group, a compound having a sugar structure may be reacted with diazomethane and an alkyl iodide. Usually, 5 to 100% of the hydroxyl groups of a compound having a sugar chain structure is removed. What is necessary is just to substitute. In order to modify a hydroxyl group with a compound having a sugar chain structure with a urethane group, a compound having a sugar chain structure may be reacted with a urethane agent such as phenyl isocyanate or hexyl isocyanate, and the hydroxyl group of cyclodextrin is usually used. 5-
The reaction may be 100%.

Vinylamide Polymers Examples of vinylamide polymers include poly (N-vinylacetamide), poly (N-vinylpyrrolidone, poly (2-methyl-2-oxazoline), and poly (N, N-dimethylacrylamide). (Meth) acrylate-based polymers Examples of (meth) acrylate-based polymers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate. )
Based on (meth) acrylates such as benzyl acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylamidohydroxypropyl (meth) acrylate Examples of the polymer include radically polymerizable monomers. Aromatic vinyl polymer Examples of the aromatic vinyl polymer include polystyrene, poly (methylstyrene), and poly (α-methylstyrene). Dendrimer Examples of the dendrimer include benzyl ether type, phenylacetylene, polyamine type and polyamide type, and polyamine type is preferable from the viewpoint of thermal decomposition.

Lipophilic compound and dispersant The lipophilic compound and dispersant are not compatible with component (A) in a wide composition range by using the lipophilic compound alone. It is compatible in the composition range. As the lipophilic compound, polycarboxylic acid esters such as didecyl phthalate, diundecyl phthalate, didodecyl phthalate, ditridecyl phthalate,
Tris (2-ethylhexyl) trimellitate, tridecyl trimellitate, tridodecyl trimellitate, tetrabutyl pyromellitate, tetrahexyl trimellitate, tetraoctyl pyromellitate, bis (2-ethylhexyl) dodecandioate, bisdecyl Dodecandioate and the like can be mentioned. Examples of dispersants that make these lipophilic compounds compatible include higher alcohols such as octanol, lauryl alcohol, decyl alcohol, and undecyl alcohol. The amount of the higher alcohol used as a dispersant can be used in the range of 0.1 to 10 times (weight) the lipophilic compound. Ultra-fine particles Ultra-fine particles are polymer particles having a particle size of 100 nm or less, the particle size of which is controlled by ordinary emulsion polymerization, such as the type of emulsifier, the concentration of the emulsifier, and the stirring speed. It is prepared from a monomer of a (meth) acrylate compound using a crosslinkable monomer for controlling the particle size. The amount of the component (B) is usually 5 to 75% by weight based on the component (A). When the use ratio of the component (B) is 5% by weight or less, the effect of lowering the dielectric constant is small.
If it is at least 5% by weight, the mechanical strength will decrease.

(C) Ester organic having a boiling point of less than 250 ° C.
Ester organic solvents having a solvent boiling point of less than 250 ° C. include methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, and acetic acid. sec-butyl,
N-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-pentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, n-butyl lactate, n-pentyl lactate , Diethyl malonate, methyl maleate, diethyl oxalate, ethyl carbonate, ethylene carbonate, methyl benzoate, ethyl benzoate and the like. Among these ester organic solvents, methyl acetoacetate, ethyl acetoacetate, γ-butyrolactone and the like are preferable. In addition, two or more ester-based organic solvents can be used, and examples thereof include a combination of methyl acetoacetate and γ-butyrolactone.

In the present invention, an organic solvent other than the ester organic solvent having a boiling point of less than 250 ° C. can be used in combination. Organic solvents other than ester organic solvents having a boiling point of less than 250 ° C. include n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane,
Aliphatic hydrocarbon solvents such as 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, propylbenzene, isopropylbenzene, diethylbenzene, Aromatic hydrocarbon solvents such as isobutylbenzene, triethylbenzene, diisopropylbenzene, amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n- Pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2
-Methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, s
ec-octanol, nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethyl nonyl alcohol, s
mono-alcohol solvents such as ec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol; ethylene Glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2-methyl-2,
4-pentanediol, pentanediol-2,4, hexanediol-2,5, heptanediol-2,4,
Polyhydric alcohol solvents such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone;
Methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, ethyl butyl ketone, methyl hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2,
Ketone solvents such as 4-pentanedione, acetonylacetone, acetophenone, fuenchon;

Ethyl ether, isopropyl ether,
n-butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolan, 4-methyldioxolan,
Dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene Glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether,
Ether solvents such as diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol dibutyl ether, monopropylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; Nitrogen compound solvents such as methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide Compound solvents such as sulfur, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone, etc. It can be mentioned.

Component (D) In the present invention, it is preferable to use a metal chelate compound (D) in addition to the components (A) to (C).
In R ³¹ of the general formula (2), examples of the chelating agent include acetylacetone, methyl acetoacetate, and ethyl acetoacetate. In R ³² of the formula (2), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and preferably have 1 to carbon atoms
5, and these alkyl groups may be chain-like or branched, and a hydrogen atom may be substituted with a fluorine atom or the like. ^Examples of the aryl group in R ³² of the general formula (2) include a phenyl group and a naphthyl group. M in the general formula (2) includes titanium, zirconium, aluminum, tin, antimony, lead and the like.
Of these, it is preferable to use titanium or zirconium.

Specific examples of the component (B) in which M is titanium or zirconium include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy.
Mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-
n-butoxy mono (acetylacetonate) titanium,
Tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, diethoxy bis (acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) Titanium, di-i-propoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonato) titanium, di-sec-butoxybis (acetylacetonato) titanium, di-t-butoxy. Bis (acetylacetonato) titanium, monoethoxytris (acetylacetonato) titanium, mono-n-propoxytris (acetylacetonato) titanium, mono-i-propoxytris (acetylacetonato) titanium, mono-n -Butoxy tris (acetylacetonate) Emissions, mono -sec- butoxy tris (acetylacetonate) titanium, mono -t- butoxy tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, triethoxy ·
Mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate)
Titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) Acetate) titanium, di-n-propoxy bis (ethylacetoacetate) titanium, di-i
-Propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) ) Titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate)
Titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) Titanium chelate compounds such as titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy Mono (acetylacetonato) zirconium, tri -sec- butoxy mono (acetylacetonate) zirconium, tri -t- butoxy mono (acetylacetonate) zirconium, diethoxy-bis (acetylacetonate) zirconium,
Di-n-propoxybis (acetylacetonato) zirconium, di-i-propoxybis (acetylacetonato) zirconium, di-n-butoxybis (acetylacetonato) zirconium, di-sec-butoxybis ( Acetylacetonato) zirconium, di-t-butoxybis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxy・ Tris (acetylacetonate) zirconium,
Mono-n-butoxy tris (acetylacetonate)
Zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri- n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium,
Tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) Zirconium, di-i-propoxybis (ethylacetoacetate) zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-
t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, mono-n-propoxytris (ethylacetoacetate) zirconium, mono-i-propoxytris (ethylacetoacetate) zirconium Mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-
Butoxy / tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) bis (ethylacetoacetate) zirconium, tris (acetylacetate) One or more zirconium chelate compounds such as (nate) mono (ethyl acetoacetate);

In particular, (iso-propoxy) _4-t titanium (acetylacetone) _t , (t is an integer of 1 to 4, the same applies hereinafter), (iso-propoxy) _4-t titanium (ethyl acetyl acetate) _t , (N-butoxy) _4-t titanium (acetylacetone) _t , (n-butoxy) _4-t titanium (ethyl acetylacetate) _t , (t-butoxy) _4-t zirconium (acetylacetone) _t , (t-
Butoxy) _4-t zirconium (ethyl acetylacetate) One or more of _t is preferable as the chelate compound.

The amount of the chelate compound represented by the general formula (2) is 100 parts by weight of a hydrolyzate of the alkylalkoxylane represented by the general formula (1) and / or a partial condensate thereof (solids Conversion), usually 0.5 to
300 mmol, preferably 0.5 to 200 mmo
1, more preferably a value within the range of 1 to 100 mmol. When the amount of the chelate compound represented by the general formula (2) is in the range of 0.5 to 300 mmol, the thickness of the cured coating film becomes uniform, and the dielectric constant of the cured coating film. This is because it is possible to reduce

(E) Heat-resistant polymer The heat-resistant polymer that can be used in the present invention includes:
The 5% weight loss temperature, that is, the heat-resistant polymer was added to an aluminum pan, dried at 350 ° C. for 60 minutes, and then dried in air using an SSC5200 thermogravimetric analyzer (TGA) manufactured by Seiko Instruments Inc. The 5% weight loss temperature measured at a heating rate of 10 ° C./min is 500 ° C. or higher, preferably 520 ° C. or higher. Specific examples include polyimide, polyarylene, hydantoin-based polymer, polyquinoxaline, polyoxadiazole, and fluorine-based polymer. Of these, it is preferable to use polyimide and polyarylene. In the present invention, the heat-resistant polymer preferably has a group such as a hydrolyzable silyl group, a carboxyl group, a carboxylic anhydride group, and a phenolic hydroxyl group.

<Polyimide> Among the components (E), preferred are a polyamic acid having a carboxylic acid anhydride group or a carboxyl group and / or a polyimide having a carboxylic acid anhydride group (hereinafter referred to as “specific polyimide”).
). Specifically, such a specific polyimide has a carboxylic acid anhydride group represented by the following general formula (3) (hereinafter referred to as a “carboxylic acid anhydride group (3)”) at at least one terminal of a polymer molecular chain. ] And a repeating unit represented by the following general formula (4) (hereinafter, referred to as “repeating unit (4)”) or a repeating unit represented by the following general formula (5) (hereinafter, referred to as “repeating unit (4)”). "Repeated unit (5)").

General formula (3)

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Formula (4)

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General formula (5)

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[In the general formulas (3), (4) and (5), R ³ represents a tetravalent organic group, and R ⁴ represents a divalent organic group. In the general formulas (3), (4) and (5), the tetravalent organic group for R ³ may be any of an aliphatic organic group, an alicyclic organic group and an aromatic organic group. However, an aromatic organic group having 6 to 120 carbon atoms is particularly preferable. Examples of the tetravalent aromatic organic group include:

[0026]

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[0027]

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(Wherein, R ^{5 to} R ¹⁰ may be the same or different from each other, and include a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, etc.), a fluoroalkyl group (eg, trifluoromethyl group, etc.) or phenyl A group). The divalent organic group for R ⁴ may be any of an aliphatic organic group, an alicyclic organic group, and an aromatic organic group, and is preferably an aromatic organic group having 6 to 120 carbon atoms. As the divalent aromatic organic group, for example,

[0029]

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[0030]

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[0031]

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(Wherein R ^{11 to} R ¹⁶ may be the same or different from each other, and include a hydrogen atom, an alkyl group (eg, a methyl group,
Ethyl group), a fluoroalkyl group (for example, a trifluoromethyl group or the like) or a phenyl group) and the like. One or more kinds of the repeating unit (4) in the polyamic acid and the repeating unit (5) in the polyimide can be present. In the present invention, the polyamic acid may be partially imidized,
In this case, the imidation ratio is less than 50%, and the polyimide may not be partially imidized, and the imidation ratio of the polyimide is 50% or more, preferably 90% or more. Here, the imidation ratio indicates the ratio of the repeating unit (5) to the total of the repeating unit (4) and the repeating unit (5).

The method for synthesizing component (E) in the present invention may be any of various methods, and is not particularly limited. For example, (a) tetracarboxylic dianhydride and a diamine compound may be used in an excess amount. Polycondensation in an organic solvent under the condition that tetracarboxylic dianhydride is present to obtain a polyamic acid solution, (b) the polyamic acid obtained by the method (a) And a method of obtaining a solution of a polyimide having a carboxylic acid anhydride group by a dehydration ring-closing reaction by a thermal method or a chemical method. Among these methods, the method (b) is particularly preferable.

Specific examples of the tetracarboxylic dianhydride used in the above method (a) include 2,2 ', 3,3'
-Biphenyltetracarboxylic dianhydride, 2,3
3 ′, 4′-biphenyltetracarboxylic dianhydride,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 9,9-bis (2,3-dicarboxyphenyl)
Fluorene dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,
3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,1
3,3,3-hexafluoropropane dianhydride, 9,9
-Bis [4- (2,3-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9-bis [4- (3
4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride Object, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] -1,
Examples thereof include 1,1,3,3,3-hexafluoropropane dianhydride.

Specific examples of the diamine compound used in the above method (a) include 9,9-bis (2-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, , 9-bis (4-aminophenyl) fluorene, 9,9-bis [4- (2-aminophenoxy) phenyl] fluorene, 9,9-bis [4-
(3-aminophenoxy) phenyl] fluorene, 9,
9-bis [4- (4-aminophenoxy) phenyl] fluorene, 2,2-bis (2-aminophenyl) -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis (3-aminophenyl) -1,1,1,3,3
3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2′-diaminodiphenyl ether, 2,3′-diaminodiphenyl ether, 2 ,
4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether,
2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-
Diaminobiphenyl, 3,4′-diaminobiphenyl,
4,4'-diaminobiphenyl, 4,4'-diamino-
2,2′-bis (trifluoromethyl) biphenyl,
2,2'-diamino-4,4'-bis (trifluoromethyl) biphenyl, 2- (3-aminophenyl) -3 '
-Aminobiphenyl, 2,2'-bis (3-aminophenyl) biphenyl 9,9-bis [3-phenyl-4- (4-amino-2-
Trifluoromethylphenoxy) phenyl] fluorene.

The organic solvent used in the above methods (a) and (b) is not particularly limited as long as it is inert to the reaction raw materials and the obtained component (E) and can dissolve them. Without limitation, for example, N, N
Aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetramethylurea, and γ-butyrolactone; phenol solvents such as phenol and cresol, and ketone solvents such as cyclohexanone. Can be mentioned. These organic solvents can be used alone or in combination of two or more. In synthesizing the polyamic acid by the method (a), the total concentration of the tetracarboxylic dianhydride and the diamine compound is usually 1 to 50% by weight, preferably 2 to 30% by weight based on the total weight of the solution.
% By weight, usually 150 ° C. or lower, preferably 0 to 12%.
React at 0 ° C. In the method (b),
The temperature of the thermal imidization reaction when synthesizing polyimide is
Usually, it is 50 to 400 ° C, preferably 100 to 350 ° C, and the temperature of the chemical imidization reaction is usually 0 to 200 ° C.
° C.

The carboxylic acid anhydride group (3) of the specific polyimide in the present invention is usually present at both ends of the molecular chain of polyacic acid or polyimide, but may be present at only one of the molecular chain ends. In the present invention, the content of the carboxylic acid anhydride group (3) of the specific polyimide is usually 0.01 to 30% by weight, preferably 0.05 to 25% by weight.
%, Particularly preferably 0.1 to 20% by weight.

The specific polyimide in the present invention is:
In some cases, it may further have a hydrolyzable silyl group, a carboxyl group, and a phenolic hydroxyl group. As a method for synthesizing the specific polyimide having a hydrolyzable silyl group, for example, (c) in the polycondensation of the tetracarboxylic dianhydride and the diamine compound in the method (a), the carboxylic acid anhydride group A silane compound having a decomposable group and / or a silane compound having a functional group capable of reacting with a carboxyl group and a hydrolyzable group (hereinafter, these silane compounds are collectively referred to as “functional silane compound”
That. (D) following the polycondensation of the tetracarboxylic dianhydride and the diamine compound in the method (a), a functional silane compound is added, and the functional silane compound and the polyamic acid are added. How to react,
(E) a method of subjecting the polyamic acid having a hydrolyzable silyl group obtained by the method (c) or (d) to a dehydration ring closure reaction by a thermal method or a chemical method in an organic solvent, (B) a method of adding a functional silane compound and reacting the functional silane compound with a polyimide following the method of (b); A silane compound having an amino group and a hydrolyzable group, for example, the following general formula

[0039]

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[Where R ³⁵ is an organic group having 1 to 8 carbon atoms;
³⁴ represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms; R ³³ represents a divalent organic group (preferably a phenylene group or an alkylene group having 1 to 10 carbon atoms);
m is an integer of 0 to 2. (H) dehydrating a polyamic acid having a hydrolyzable silyl group obtained by the method (g) by a thermal method or a chemical method in an organic solvent. And the like. The use ratio of the silane compound having two amino groups and the hydrolyzable group in the method (g) is usually 5
0 mol% or less, preferably 30 mol% or less. Among the methods (c) to (h), the method (d), (f) or (g) is preferable, and the method (d) or (f) is particularly preferable.

The functional silane compound used in the above method (c), (d) or (f) includes, for example,
Carboxylic acid anhydride group-containing silanes such as acid anhydride of 3,4-dicarboxyphenyltrimethoxysilane and acid anhydride of 3,4-dicarboxybenzyltrimethoxysilane;
Mercaptosilanes such as mercaptomethyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-
Aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, (2-aminoethylamino) methyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-
Aminoethylamino) propyldimethoxymethylsilane, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, N- (3-trimethoxysilylpropyl) urea, N- (3-triethoxysilylpropyl ) Urea, 2- (2-aminoethylthio) ethyltrimethoxysilane, 2- (2-aminoethylthio) ethyltriethoxysilane, 2- (2-aminoethylthio) ethyldimethoxymethylsilane, 2- (2
-Aminoethylthio) ethyldiethoxymethylsilane,
Aminosilanes such as 2-aminophenyltrimethoxysilane, 2-aminophenyltriethoxysilane, 3-aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 4-aminophenyltrimethoxysilane, and 4-aminophenyltriethoxysilane , Bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, 3-cyclohexylaminopropyltrimethoxysilane, 3-cyclohexylaminopropyldimethoxymethylsilane,
3-phenylaminopropyltrimethoxysilane, 3-
Phenylaminopropyldimethoxymethylsilane, 3-
Benzylaminopropyltrimethoxysilane, 3-benzylaminopropyldimethoxymethylsilane, 3- (p
-Vinylbenzylamino) propyltrimethoxysilane, 3- (p-vinylbenzylamino) propyldimethoxymethylsilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyldimethoxymethylsilane, 3-piperazinopropyltrimethoxy Iminosilanes such as silane and 3-piperazinopropyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycid Epoxy silanes such as xypropyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane; 3-isocyanate Trimethoxysilane, 3-isocyanate propyl triethoxysilane,
3-isocyanatopropyldimethoxymethylsilane,
Isocyanate silanes such as 3-isocyanatopropyldiethoxymethylsilane and the like can be mentioned. These functional silane compounds can be used alone or in combination of two or more. In the present invention, the specific polyimide preferably has a structure in which 50 mol% or more of the repeating unit has a fluorene skeleton, from the viewpoint of improving the performance of the obtained film.

<Polyarylene> Polyarylene which can be used as the component (E) of the present invention has a repeating structural unit having a phenylene group in the main chain represented by the following general formula (6).

General formula (6)

Embedded image Here, X in the repeating structural unit represented by the general formula (6) is a divalent organic group, preferably -CYY'-.
(Where Y to Y ′ are the same or different and represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group, a halogenated alkyl group and an aryl group) or a fluorenylene group. Among Y to Y ′ of —CYY′— of the repeating structural unit represented by the general formula (6), examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. As a basis,
A trifluoromethyl group, a pentafluoroethyl group, a heptafluoroisopropyl group, and the like, and examples of the aryl group include a phenyl group, a biphenyl group, a tolyl group, a pentafluorophenyl group, and preferably a phenyl group.

R ^{17 to} R ²⁴ in the repeating structural unit represented by the above general formula (6) are the same or different and are a hydrogen atom, a halogen atom, or a monovalent organic group (preferably an alkyl group, At least one monovalent organic group selected from the group consisting of a halogenated alkyl group, an allyl group and an aryl group). Here, R ¹⁷ in the above general formula (I)
Of R to R ²⁴ , a halogen atom is a fluorine atom and the like, and an alkyl group is a methyl group and an ethyl group.
Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group, preferably, a trifluoromethyl group. Examples of the allyl group include a propenyl group. Examples of the aryl group include a phenyl group. Further, R ^{25 to} R ²⁸ in the general formula (6) are the same or different and are a hydrogen atom, a halogen atom or a monovalent organic group. At least one of R ^{25 to} R ²⁸ is a group capable of reacting with a metal alkoxide.

Examples of the group capable of reacting with the metal alkoxide preferably include a hydroxyl group, a carboxyl group and an alkoxysilyl group. It may be a structure. The group capable of reacting with the metal alkoxide may be a precursor protected by a protecting group, and this precursor can be converted back into a group capable of reacting with the metal alkoxide after polymerization. Examples of a method for protecting a hydroxyl group or a reactive organic group include a method of esterifying a hydroxyalkyl group and a hydroxyl group with a carboxylic acid derivative, and a method of carbonate formation with di-t-butyl dicarbonate and the like. The carboxyl group may be esterified with an alcohol, isobutene, or the like. Examples of the halogen atom include a fluorine atom, and examples of the organic group include an alkyl group such as a methyl group, an ethyl group and a propyl group, a halogenated alkyl group such as a trifluoromethyl group and a hexafluoroethyl group, and a phenyl group. And an alkoxysilyl group such as an aryl group, a carboxyl group, and a trifluoromethoxy group.

The molar ratio between r and s in the general formula (6) is
0-100 / 100-0, preferably 5-95 / 95-
5, more preferably 50 to 90/50 to 10.
That is, the polyarylene used in the polymer composition of the present invention has a left side (r side) of 10 in the repeating structural unit.
It may be 0 mol%, the right side (s side) may be 100 mol%, or a copolymer thereof.

The polyarylene used in the polymer composition of the present invention has a polystyrene reduced weight average molecular weight of 1,
000-1,000,000, preferably 1,500-
200,000. If it is less than 1,000, the coating properties are insufficient, while if it exceeds 1,000,000,
Insufficient solubility.

The polyarylene used in the present invention comprises at least a phenylene group-containing compound represented by the following general formula (7) and / or another copolymerizable compound represented by the following general formula (8). One is produced by (co) polymerizing in a polymerization solvent in the presence of a catalyst system containing a transition metal compound catalyst.

General formula (7)

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[In the formula, X and R ^{17 to} R ²⁴ are the same as those in the general formula (6), R ^{29 to} R ³⁰ are the same or different, and a halogen atom or —OSO ₂ Z (where Z is An alkyl group, a halogenated alkyl group or an aryl group). Where R ^{29 to} R
Examples of the ³⁰ halogen atoms include a chlorine atom, a bromine atom and an iodine atom. In the general formula (7), -OSO
_The alkyl group constituting Z in ₂ Z is a methyl group,
Examples of the ethyl group include a trifluoromethyl group as the halogenated alkyl group, and examples of the aryl group include a phenyl group, a p-tolyl group, and a p-fluorophenyl group.

Specific examples of the phenylene group-containing compound represented by the general formula (7) include 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane and bis (4-methylsulfonyloxyphenyl) ) Methane, bis (4-methylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) hexafluoropropane,
2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9- Screw (4-
Methylsulfonyloxyphenyl) fluorene, 9,9
-Bis (4-methylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene,
9,9-bis (4-methylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-methylsulfonyloxy-3) -Methylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-methylsulfonyloxy-3) -Fluorophenyl) diphenylmethane, bis (4-methylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4
-Methylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4
-Methylsulfonyloxyphenyl) methane, bis (4
-Methylsulfonyloxy-3-methylphenyl) methane, bis (4-methylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-methylsulfonyloxy-3-propenylphenyl) methane, bis (4 -Methylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-methylsulfonyloxyphenyl) phenylmethane and the like.

Specific examples of the phenylene group-containing compound represented by the general formula (7) include 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane and bis (4-trifluoromethylsulfone). Phonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane, 2,2
-Bis (4-trifluoromethylsulfonyloxy-3)
-Methylphenyl) hexafluoropropane, 2,2-
Bis (4-trifluoromethylsulfonyloxy-3-
Propenylphenyl) hexafluoropropane, 2,2
-Bis (4-trifluoromethylsulfonyloxy-
3,5-dimethylphenyl) hexafluoropropane,
9,9-bis (4-trifluoromethylsulfonyloxyphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4-trifluoro Methylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) fluorene, 9,9
-Bis (4-trifluoromethylsulfonyloxy-3)
-Phenylphenyl) fluorene, bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (4-trifluoro Methylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl)
Fluorene, 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-trifluoromethylsulfonyloxyphenyl) methane, bis (4-trifluoromethylsulfonyloxy) -3-methylphenyl) methane, bis (4
-Trifluoromethylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane,
Bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-trifluoromethylsulfonyloxyphenyl) and the like can be mentioned.

Specific examples of the phenylene group-containing compound represented by the general formula (7) include 2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane and bis (4-phenylsulfonyloxyphenyl) ) Methane, bis (4-phenylsulfonyloxyphenyl)
Diphenylmethane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane, 2,2-bis (4-phenylsulfonyloxy-
3-propenylphenyl) hexafluoropropane,
2,2-bis (4-phenylsulfonyloxy-3,5
-Dimethylphenyl) hexafluoropropane, 9,9
-Bis (4-phenylsulfonyloxyphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (4
-Phenylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene, 9,
9-bis (4-phenylsulfonyloxy-3-phenylphenyl) fluorene, bis (4-phenylsulfonyloxy-3-methylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) Diphenylmethane, bis (4-phenylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (4-phenylsulfonyloxy-3,5-difluorophenyl) Diphenylmethane, 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-
Bis (4-phenylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (4-phenylsulfonyloxyphenyl) methane, bis (4-phenylsulfonyloxy-3-methylphenyl) methane, bis (4
-Phenylsulfonyloxy-3,5-dimethylphenyl) methane, bis (4-phenylsulfonyloxy-3)
-Propenylphenyl) methane, bis (4-phenylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (4-phenylsulfonyloxyphenyl) phenylmethane and the like.

Specific examples of the phenylene group-containing compound represented by the general formula (7) include 2,2-bis (p-tolylsulfonyloxyphenyl) hexafluoropropane and bis (p-tolylsulfonyloxyphenyl) ) Methane, bis (p-tolylsulfonyloxyphenyl) diphenylmethane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) hexafluoropropane,
2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) hexafluoropropane, 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane, 9,9- Screw (p-
Tolylsulfonyloxyphenyl) fluorene, 9,9
-Bis (p-tolylsulfonyloxy-3-methylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) fluorene,
9,9-bis (p-tolylsulfonyloxy-3-propenylphenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene, bis (p-tolylsulfonyloxy-3) -Methylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3) -Fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-difluorophenyl) diphenylmethane, 9,9-bis (p
-Tolylsulfonyloxy-3-fluorophenyl) fluorene, 9,9-bis (p-tolylsulfonyloxy-3,5-difluorophenyl) fluorene, bis (p
-Tolylsulfonyloxyphenyl) methane, bis (p
-Tolylsulfonyloxy-3-methylphenyl) methane, bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane, bis (p-tolylsulfonyloxy-3-propenylphenyl) methane, bis (p -Tolylsulfonyloxyphenyl) trifluoromethylphenylmethane, bis (p-tolylsulfonyloxyphenyl) phenylmethane and the like.

In the present invention, at least two kinds of the phenylene group-containing compounds represented by the general formula (7) can be copolymerized. In this case, the preferred combination is 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane / 9,9-bis (4
-Methylsulfonyloxyphenyl) fluorene, 2,
2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane / bis (4-methylsulfonyloxyphenyl) diphenylpropane, 9,9-bis (4-
Methylsulfonyloxyphenyl) fluorene / bis (4-methylsulfonyloxyphenyl) diphenylpropane, 2,2-bis (4-methylsulfonyloxy-
3-propenylphenyl) propane / 2,2-bis (4
-Methylsulfonyloxyphenyl) hexafluoropropane, 2,2-bis (4-methylsulfonyloxy-
3-propenylphenyl) propane / 2,2-bis (4
-Methylsulfonyloxyphenyl) propane, 2,2
-Bis (4-methylsulfonyloxyphenyl) hexafluoropropane / 2,2-bis (4-methylsulfonyloxyphenyl) propane and the like.

On the other hand, the other copolymerizable compound is at least one of the compounds represented by the following general formula (8).
Species are preferred.

General formula (8)

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[0058] wherein, R ²⁵ to R ²⁸ are the same or different, it is the same as R ²⁵ to R ²⁸ in the general formula (6), R ²⁹ ~
R ³⁰ is the same or different and is the same as R ^{29 to} R ^{30 in} formula (7), and p is 1 or 2. ]

Here, as other copolymerizable compounds represented by the general formula (8), for example, p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-dimethylsulfonyloxy Benzene, 2,5-
Dichlorotoluene, 2,5-dibromotoluene, 2,5
-Diiodotoluene, 2,5-dimethylsulfonyloxybenzene, 2,5-dichloro-p-xylene, 2,5
-Dibromo-p-xylene, 2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride,
2,5-dibromobenzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-
2,3,5,6-tetrafluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluorobenzene,
Examples thereof include 1,4-diiodo-2,3,5,6-tetrafluorobenzene, and preferably p-dichlorobenzene, p-dimethylsulfonyloxybenzene, and 2,5-
Dichlorotoluene and 2,5-dichlorobenzotrifluoride.

Other copolymerizable compounds represented by the above general formula (8) include 4,4'-dimethylsulfonyloxybiphenyl and 4,4'-dimethylsulfonyloxy-3,3'-di Propenyl biphenyl, 4,4'-dibromobiphenyl, 4,4'-diiodobiphenyl, 4,
4'-dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,4'-dimethylsulfonyloxy-
3,3'-difluorobiphenyl, 4,4'-dimethylsulfonyloxy-3,3 ', 5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl, 4,4-methylsulfonyloxy And preferably 4,4'-dimethylsulfonyloxybiphenyl, 4,4'-dibromobiphenyl, 4,4'-diiodobiphenyl,
4'-dimethylsulfonyloxy-3,3'-dipropenylbiphenyl.

Other copolymerizable compounds represented by the general formula (8) include m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, and 2,4. -Dichlorotoluene,
2,4-dibromotoluene, 2,4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,
4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzo Trifluoride, 1,3-dibromo-
2,4,5,6-tetrafluorobenzene and the like, preferably m-dichlorobenzene, 2,4-dichlorotoluene, 3,5-dimethylsulfonyloxytoluene, and 2,4-dichlorobenzotrifluoride. .

Other copolymerizable compounds represented by the above general formula (8) include o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3 -Dichlorotoluene,
2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4 -Dimethylsulfonyloxybenzene, 3,4-dichlorobenzotrifluoride, 3,4-dibromobenzotrifluoride, 3,
Examples thereof include 4-diiodobenzotrifluoride and 1,2-dibromo-3,4,5,6-tetrafluorobenzene, and preferably o-dichlorobenzene and 3,4-dichlorobenzotrifluoride.

The catalyst used for producing the polyarylene used in the present invention is a catalyst system containing a transition metal compound. As the catalyst system, a transition metal salt and a ligand or a ligand are used. The transition metal (salt) and the reducing agent are essential components, and a “salt” may be added to increase the polymerization rate. Here, transition metal salts include nickel compounds such as nickel chloride, nickel bromide, nickel iodide, and nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide, and palladium iodide; iron chloride; and iron bromide. And iron compounds such as iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferred. Examples of the ligand include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, and 1,3-bis (diphenylphosphino) propane. 2 '
-Bipyridine is preferred. The above-mentioned ligands may be used alone.
Alternatively, two or more kinds can be used in combination.

Further, as the transition metal (salt) to which a ligand has been previously coordinated, for example, nickel chloride 2 triphenylphosphine, nickel bromide 2 triphenylphosphine, nickel iodide 2 triphenylphosphine, nickel nitrate 2 -Triphenylphosphine, nickel chloride 2,2 'bipyridine, nickel bromide 2,2' bipyridine, nickel iodide 2,2 'bipyridine, nickel nitrate 2,2' bipyridine, bis (1,5-cyclooctadiene) nickel , Tetrakis (triphenylphosphine)
Nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like can be mentioned, and nickel chloride2triphenylphosphine and nickel chloride2,2'bipyridine are preferable.

Examples of the reducing agent that can be used in the catalyst system of the present invention include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, etc., and zinc and manganese are preferred. These reducing agents can be activated and used by bringing them into contact with an acid or an organic acid. The “salt” that can be used in the catalyst system of the present invention includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and sodium sulfate, potassium fluoride, potassium chloride, and bromide. Potassium compounds such as potassium, potassium iodide, and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate; and sodium bromide, iodine Sodium, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.

The proportion of each component used in the catalyst system is such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is the compound represented by the above formula (7) and the compound represented by the above formula (8). It is usually 0.0001 to 10 mol, preferably 0.01 to 0.5 mol, per 1 mol of the total amount of at least one other copolymerizable compound represented. If the amount is less than 0.0001 mol, the polymerization reaction does not sufficiently proceed, while if it exceeds 10 mol, there is a problem that the molecular weight is reduced. When using a transition metal salt and a ligand in the catalyst system,
The usage ratio of this ligand is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the transition metal salt. If the amount is less than 0.1 mol, the catalytic activity becomes insufficient, while if it exceeds 100 mol, there is a problem that the molecular weight is reduced. Also, the proportion of the reducing agent used in the catalyst system is
The compound represented by the general formula (7) and the general formula (8)
Is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the total amount of at least one other copolymerizable compound represented by the formula: If the amount is less than 0.1 mol, the polymerization does not proceed sufficiently. On the other hand, if it exceeds 100 mol, there is a problem that purification of the obtained polymer becomes difficult. Furthermore, when a “salt” is used in the catalyst system, the proportion used is
The compound represented by the general formula (7) and the general formula (8)
The total amount of at least one other copolymerizable compound represented by 1 mol, usually 0.001 to 100 mol,
Preferably it is 0.01 to 1 mol. If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient.
If it exceeds 100 mol, there is a problem that purification of the obtained polymer becomes difficult.

Examples of the polymerization solvent usable in the present invention include, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2
-Pyrrolidone, γ-butyrolactone, γ-butyrolactam, etc., and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide,
-Methyl-2-pyrrolidone is preferred. These polymerization solvents are preferably used after being sufficiently dried. The concentration of at least one compound of the compound represented by the general formula (7) and the other copolymerizable compound represented by the general formula (8) in the polymerization solvent is usually 1 to 100% by weight, preferably 5 to 40% by weight. The polymerization temperature at the time of (co) polymerizing the polyarylene used in the present invention is usually 0 to 200 ° C, preferably 50 to 80 ° C. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

When the polyarylene used in the present invention is a copolymer, it may be a random copolymer or a block copolymer. Here, in order to obtain a random copolymer, a phenylene group-containing compound represented by the above general formula (7) and (8) another compound copolymerizable therewith are polymerized at the start of polymerization, immediately before or immediately after polymerization. Examples of the method include the method of causing the system to exist. In order to obtain a block copolymer, a phenylene group-containing compound represented by various general formulas (7) and (8) another compound copolymerizable with the phenylene group-containing compound may be prepared by preparing a catalyst containing a transition metal compound in advance. A method of polymerizing in the presence of a system and then mixing and polymerizing the reaction solution, or a method of purifying the reaction solution once and polymerizing again in the presence of a catalyst system containing a transition metal compound, or A phenylene group-containing compound represented by the above general formula (7), and (8) any one of other compounds copolymerizable therewith in advance in the presence of a catalyst system containing a transition metal compound in advance. And a method in which another copolymerization component is added in the middle to carry out polymerization.

The structure of the polyarylene used in the present invention is, for example, 900 to 900 according to an infrared absorption spectrum.
675cm ^-1, 1,300~1,000cm ^-1, 1,5
00~1,400cm ^-1, 3,100~3,000cm
^-1 can be confirmed, and their composition ratios can be known by elemental analysis. Further, the structure can be confirmed from a peak at 6.0 to 8.5 ppm by a nuclear magnetic resonance spectrum.

Logarithmic viscosity [η] of component (E) in the present invention (N-methylpyrrolidone, 30 ° C., 0.5 g / d
l) is usually 0.05 to 5 dl / g, preferably 0.1 to 5 dl / g.
1-3 dl / g. In the present invention, the component (E) can be used alone or in combination of two or more. The mixing ratio of the component (E) in the present invention is usually based on 100 parts by weight of the component (A) after hydrolysis and condensation.
5 to 1000 parts by weight, preferably 10 to 800 parts by weight,
More preferably, it is 15 to 600 parts by weight. In this case, if the blending ratio of the component (B) is less than 5 parts by weight, cracks may occur during curing of the obtained thermosetting resin composition, and if it exceeds 1000 parts by weight, the moisture resistance of the cured product may be reduced. Tends to decrease.

(F) Component In the present invention, it is preferable to use water in addition to the components (A) to (E). The proportion of water used is an equivalent in the range of 0.1 to 1 with respect to the sum of the alkoxy or allyloxy groups of the component (A) and the component (B).

Component (G) In the present invention, a curing catalyst may be used in addition to the components (A) to (F). Examples of the curing catalyst include: alkali metal salts such as naphthenic acid, octylic acid, nitric acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid: alkaline compounds such as sodium hydroxide and potassium hydroxide;
Acidic compounds such as phosphoric acid, p-toluenesulfonic acid and phthalic acid; 1,2-ethylenediamine, 1,6-hexylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, Amines such as p-phenylenediamine, ethanolamine, triethylamine, N-methylmorpholine, and various modified amines used as curing agents for epoxy resins; 3-aminopropyltriethoxysilane, 3- (2-aminoethylamino) Amino group-containing silane compounds such as propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, and 3-anilinopropyltrimethoxysilane; (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCO
OCH ₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (O
COC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂
Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₈ H ₁₇ )
₂ , carboxylic acid type organotin compounds such as Sn (OCOC ₈ H ₁₇ ) ₂ ;
(C ₄ H ₉ ) ₂ Sn (SCH ₂ COO) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C
₈ H ₁₇ ) ₂ Sn (SCH ₂ COO) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO) ₂ , (C ₈ H
₁₇ ) ₂ Sn (SCH ₂ COOCH ₂ CH ₂ OCOCH ₂ S) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO
CH ₂ CH ₂ CH ₂ CH ₂ OCOCH ₂ S) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ )
_{2, (C 8 H 17)} 2 Sn (SCH 2 COOC 12 H 25) 2,

[0073]

Embedded image

Mercaptide-type organotin compounds such as (C ₄ H ₉ )
₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S,

[0075]

Embedded image

(C ₄ H ₉ ) ₂ S
n = O, (C ₈ H ₁₇ ) ₂ Sn = O and other oxide-type organic tin oxides, and reaction products of ethyl silicate, dimethyl maleate, diethyl maleate, ester compounds such as dioctyl phthalate, etc. Organic tin compounds and the like can be mentioned.

The composition of the present invention can be produced by mixing the above components (A) to (D) and, if necessary, other components. In order to form a film using the composition of the present invention, first, the composition of the present invention is applied to a substrate to form a coating film. Here, examples of the substrate on which the composition of the present invention can be applied include semiconductors, glass, ceramics, and metals, and examples of the application method include spin coating, dipping, and roller blades. here,
The thickness of the coating film to be formed is usually 0.1 mm in the case of an interlayer insulating film.
2 to 20 μm. Next, the formed coating film is heated, and the heating temperature at this time is lower than the boiling point or decomposition temperature of the component (C) and the component (E) used as required. In the present invention, the component (A) and the component (B)
It is necessary to select heating conditions for the coating film so that the cured film of the component has pores. As the heating method, the formed coating film is heated at a temperature lower than the boiling point or the decomposition temperature of the component (C) to partially cure the components (A) and (B),
Then, a method of heating from a temperature equal to or higher than the boiling point or the decomposition temperature of the component (C) to a final curing temperature to obtain a porous cured product may be mentioned. Usually, the boiling point or decomposition temperature of the component (C) is from 250 to 450 ° C., and thus the coating film includes a step of being finally heated to this temperature or higher.

In the method for producing a film of the present invention, the film-forming composition is heated under reduced pressure.
Heating under reduced pressure of 5 torr or less. By heating (reacting) the film-forming composition under such reduced pressure, the effect of oxygen can be eliminated, and the dielectric constant of the obtained film can be made lower. Note that the reduced pressure state can be achieved by using a vacuum oven as an example.

In the method for producing a film of the present invention, the film-forming composition is heated in an inert gas. Examples of the inert gas include a nitrogen gas and an argon gas. Is preferably in nitrogen (including a nitrogen atmosphere). In the present invention, it is preferable to use the inert gas so that the oxygen concentration has a value of, for example, 5 ppm or less. By heating (reacting) in an inert gas in this manner, the influence of oxygen can be eliminated, and the dielectric constant of the obtained film can be made lower. That is, by lowering the surrounding oxygen concentration during heating, deterioration of the film due to thermal oxidation is suppressed, and the dielectric constant of the film can be set to a lower value. The film obtained by heating the composition of the present invention by the method of the present invention usually has pores on the order of 10 nm, and has a porosity of 5 to 70%. The dielectric constant of the film is usually 2.5 to 1.2. The film of the present invention is suitable as an insulating film, and is particularly suitable as an interlayer insulating film for highly integrated circuits.

[0080]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below based on examples. However, the following description generally shows an example of the embodiment of the present invention, and the present invention is not limited by the description without any particular reason. Parts and% in Examples and Comparative Examples indicate parts by weight and% by weight, respectively, unless otherwise specified.

Production Example 1 (Synthesis of Component (B)) 25.2 parts of 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride and 9,9-bis (4-aminophenyl)
27.7 parts of fluorene and γ-butyrolactone 450
After reacting at 23 ° C for 2 hours in the part,
For 3 hours. Next, in the presence of toluene, the imidation reaction was allowed to proceed while azeotropically distilling off water in the reaction solution with toluene. At the stage when water was no longer distilled off, it was confirmed from the infrared absorption spectrum that the reaction was completed.
A 10% solution of the component (B) was obtained.

Example 1 (1) 92.3 g of methyltrimethoxysilane, 7.2 g of phenyltrimethoxysilane, 9.4 g of titanium diisopropoxybis (ethylacetoacetate) and 278 g of ethyl acetoacetate were mixed at 60 ° C. After the addition, 15.5 g of ion-exchanged water was added over 1 hour, and the mixture was further reacted at 60 ° C. for 1 hour, and then methanol in the reaction solution was distilled off under reduced pressure. (2) 56.1 g of a 10% solution of the component (B) and titanium diisopropoxybis (ethylacetoacetate) 7.
After reacting 6 g with 152 g of γ-butyrolactone at 60 ° C. for 1 hour, a solution containing 1.9 g of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 1 hour, followed by di-isopropoxybis (ethyl acetoacetate). ) Titanium 14.0
And 1.9 parts of ion-exchanged water. (3) The reaction solution obtained in (1) and the reaction solution obtained in (2) were mixed and reacted at 60 ° C. for 1 hour to obtain a composition having a solid content of 10%. (4) A polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer (Newpole P manufactured by Sanyo Chemical Co., Ltd.) is added to 15 g of the composition obtained in the above (3).
E61) was mixed with 1 g to obtain a film-forming composition. (5) The obtained film-forming composition is applied on an ITO substrate by spin coating to a film thickness of 1.45 μm, heated at 80 ° C. for 5 minutes, then at 200 ° C. for 5 minutes, and further heated at 340 under vacuum. ℃, 360 ℃, 380 ℃ in order
The mixture was heated for 0 minute each and further heated at 450 ° C. for 1 hour to obtain a colorless and transparent film. When the cross section of the ITO substrate after film formation was observed with a scanning electron microscope, formation of pores of 10 nm or less was confirmed. Further, the obtained film was evaluated as follows. Table 1 shows the results.

(Evaluation of Film Forming Composition) Uniformity of coating film The appearance of the obtained film was visually observed, and further, a stylus type surface roughness meter (Dektak303, manufactured by Japan Vacuum Engineering Co., Ltd.)
Using 0), the surface roughness (Ra) of the coating film was measured. Then, the appearance of the coating film and the obtained surface roughness (R
From the result of a), the uniformity of the coating film was evaluated according to the following criteria. Table 1 shows the evaluation results. 〇: No repelling or unevenness in appearance, and surface roughness (R
The value of a) is less than 200 angstroms. Δ: No repelling or unevenness in appearance, and surface roughness (R
The value of a) is 200 Å or more. X: There are repelling and unevenness in appearance.

2. Oxygen plasma ashing property The absorption intensity of organic groups in the obtained film was measured using a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by JEOL Ltd.
JIR-5500). Next, using a barrel-type oxygen plasma ashing device, the coating film was subjected to oxygen plasma treatment under the conditions of 1 torr, 800 W, and 500 Sccm for 20 minutes. then,
1270c of organic group in coating film after oxygen plasma treatment
The intensity of the bending vibration of the methyl group bonded to Si near m ⁻¹ was measured using the FT-IR. From the change in the intensity measured in this way, the oxygen plasma ashing property was evaluated according to the following criteria. Table 1 shows the evaluation results. 〇: Change in absorption strength of organic group is less than 40% Δ: Change in absorption strength of organic group is 40% or more and less than 60% ×: Change in absorption strength of organic group is 60% or more

3. Adhesion test PCT (Pressure C)
oak Test (PC-2, Hirayama Seisakusho)
42HS-A), 121 ° C., 100% RH, 2
The wet heat treatment was performed under atmospheric pressure conditions. Thereafter, the coating film subjected to the wet heat treatment was subjected to a grid test (tape peel test) in accordance with JIS K5400. Then, the same test was repeated three times, and out of the 100 grids, the average value (n) of the grids that did not peel and did not peel off from the silicon wafer as the base was calculated, and the adhesion to the ground was calculated as the adhesion. evaluated. Table 1 shows the measurement results. 〇: n is 100 Δ: n is 50 or more ×: n is less than 50

[0086] 4. Dielectric constant HP164 manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was applied to the obtained film at a frequency of 100 kHz.
The dielectric constant of the coating film was measured using a 51B electrode and an HP4284A precision LCR meter. Table 1 shows the results
Shown in

5. Heat resistance The obtained film-forming composition was subjected to SSC5200 thermogravimetric analysis (TGA) manufactured by Seiko Electronic Industry Co., Ltd.
The film-forming composition was heated in a nitrogen atmosphere at a heating rate of 10 ° C./min, and the 5% weight loss temperature of the film forming composition was measured. 6. Density The density was determined from the volume of the coating film and the weight of the coating film from the thickness of the film coated on the silicon wafer by spin coating. 7. Porosity The porosity was determined from the following formula from a density comparison with a coating film applied to a silicon wafer to which no porogen was added. Porosity (%) = (1− (density of pore-forming coating film / density of pore-forming agent-free coating film). The coating film without a pore-forming material refers to a film obtained in the same manner as in the examples except that the component (C) is not added in the examples. Was stored at normal temperature for one month, and the uniformity of the coating film of the preserved product was evaluated in the same manner as in the above-mentioned "uniformity of coating film". .

Example 2 15 g of the composition obtained in Example 1 (3), 50 g of a hydroxyl group
% Of cyclodextrin substituted with a trimethylsilyl group was mixed to obtain a film-forming composition. The obtained film-forming composition is applied on an ITO substrate to a film thickness of 1.25 μm by a spin coating method, and is heated at 340 ° C., 360 ° C. under vacuum.
Heat in order of 380 ° C for 30 minutes each, and add 4 more
Heating at 50 ° C. for 1 hour gave a colorless and transparent film. Also,
When the cross section of the ITO substrate after film formation was observed with a scanning electron microscope, formation of pores of 10 nm or less was confirmed.
Further, the film obtained in the same manner as in Example 1 was evaluated.
Table 1 shows the results.

Example 3 15 g of the composition obtained in Example 1 (3) and tris (2-
Ethylhexyl) trimellitate 1.5 g and lauryl alcohol 3 g were mixed to obtain a film-forming composition. The obtained film-forming composition is applied on an ITO substrate by spin coating to a film thickness of 1.15 μm, heated to 200 ° C., and further heated under vacuum at 340 ° C., 360 ° C. and 380 ° C. in order of 30 ° C. The mixture was heated for 1 minute, and further heated at 450 ° C. for 1 hour to obtain a colorless and transparent film. In addition, IT after film formation
When the cross section of the O substrate was observed with a scanning electron microscope,
Formation of pores of 0 nm or less was confirmed. Example 1
The obtained film was evaluated in the same manner as described above. Table 1 shows the results.

[0090]

[Table 1]

[0091]

The composition of the present invention has excellent storage stability, and the film obtained by curing the composition has excellent uniformity of coating film, oxygen plasma ashing property, adhesion, dielectric constant and heat resistance. Excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/316 H01L 21/316 HF Term (Reference) 4J038 BA012 BA042 BA052 BA122 BA162 CC032 CG172 CK022 CK032 CR072 DF022 DF062 DJ022 DL021 DL051 JA19 JA22 JA61 JC38 KA09 MA07 NA12 NA17 NA21 PA19 5F058 AA08 AB10 AC02 AF04 AH02

Claims (7)

[Claims] 1. A (A) following general hydrolyzate of the compound represented by formula (1) and its partial condensation product or either one _{^{R 1 n Si (OR 2)}} 4-n (1) (R 1 and R ² may be the same or different and each represents a monovalent organic group, and n represents an integer of 0 to 2.) (B) Compatible or dispersed in the component (A), and has a boiling point or decomposition. A compound for forming a film, comprising: a compound having a temperature of 250 to 450 ° C .; and (C) an ester organic solvent having a boiling point of less than 250 ° C. 2. The composition according to claim 1, further comprising (D) a metal chelate compound. 3. The composition according to claim 2, wherein the metal chelate compound (D) is a compound represented by the following general formula (2). R ³¹ _t M (OR ³² ) _4-t (2) (R ³¹ is a chelating agent, M is at least one metal selected from titanium, zirconium, aluminum, tin, antimony, niobium, tantalum and lead, and R ³² is Represents an alkyl group or an aryl group, and t represents an integer of 1 to 4.) 4. The composition according to claim 1, further comprising (E) a heat-resistant polymer. 5. The composition according to claim 1, wherein (E) the heat-resistant polymer is at least one selected from polyimide and polyarylene. 6. A method for producing a film, comprising applying the composition according to claim 1 to a substrate and heating the substrate. 7. A porous film obtained by the method according to claim 6.