JP2002332346A - Polymer, its production method, and composition for film formation containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer suitably used for film formation; to provide a production method for the polymer; and to obtain a composition for film formation which contains the polymer and can give a coating film which can be baked in a short time, is excellent in heat resistance, hardness, and crack resistance, and has low dielectric properties. SOLUTION: A specific aromatic dicarboxylic acid or its ester [e.g. 4,4'-bis(2- carboxyphenylethyl)diphenyl ether] is reacted with a specific aromatic compound (e.g. diphenyl ether) in the presence of a catalyst to give a polymer having a specified structure. The polymer is dissolved in a solvent to give the composition for film formation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer suitable for forming a film useful as an interlayer insulating film in, for example, a semiconductor device, a method for producing the polymer, and a film-forming composition containing the polymer.

[0002]

2. Description of the Related Art In electronic material applications, in recent years, with high integration, multifunctionality, and high performance, circuit resistance and capacitance between wirings have increased, and not only power consumption has increased, but also delay time has increased. And the signal speed of the device is reduced, which is a major cause of crosstalk.
Therefore, it is required to reduce the parasitic resistance and the parasitic capacitance. One of the solutions is to reduce the parasitic capacitance and increase the speed of the device by covering the periphery of the wiring with a low dielectric interlayer insulating film. Trying to respond to. Also, LCD
(Liquid Crystal Display) -related applications require low transparency as well as transparency.

[0003] Polyimide is widely known as a heat-resistant organic material that meets this requirement. However, since it contains a highly polar imide group, it has problems in terms of dielectric properties, water absorption and coloring. Is not obtained. Further, in order to bake the polyimide,
Requires a firing time of about one hour.

On the other hand, polyphenylene is known as a high heat-resistant organic material containing no polar group. Although this polyphenylene has excellent heat resistance, its solubility in an organic solvent is poor. Therefore, generally, a soluble group is introduced into a side chain to increase the solubility. Examples of such polyphenylenes include polymers described in US Pat. No. 5,214,044, International Application WO 96/28491, European Patent Publication No. 629217, and the like.

[0005] These polymers have a polyparaphenylene structure mainly and partially copolymerize a flexible monomer. However, these polymers are soluble only in a specific organic solvent and when dissolved in a solvent. However, there is also a problem of a high-viscosity solution caused by rigid molecules, and the workability is not satisfactory.

Further, in order to impart solvent resistance, improve heat resistance, and improve mechanical properties, cross-linking of polyphenylene-based polymers has been studied. Cross-linking reactions utilizing acetylene bonds have been known. However, there was a problem in adhesion of the coating film. Further, introduction of an ether element into a polymer has been studied to improve the processability and solubility of the polyarylene, but there was a problem in the heat resistance of the obtained polymer.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and a polymer suitably used for film formation, a method for producing the same, and a polymer containing An object of the present invention is to provide a film-forming composition which can be fired, is excellent in heat resistance, hardness and crack resistance, and can obtain a low dielectric coating film.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, a composition obtained by dissolving a polymer having a specific repeating unit in a solvent has excellent film-forming properties. The inventor has found that it solves the problem, and has reached the present invention.

That is, the present invention firstly provides the following general formula (1)

[0010]

Embedded image

(Wherein R ^{1 to} R ⁴ are each independently a single bond, —O
_{-, - CO -, - CH} 2 -, - COO -, - CONH
_{-, - S -, - SO} 2 -, - C≡C-, phenylene group,

[0012]

Embedded image

Or a fluorenylene group, R ^{5 to} R
¹⁰ independently represents a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group or an aryl group having 1 to 20 carbon atoms, a and b each independently represent an integer of 0 to 3, c to h each independently represent an integer of 0 to 4. The present invention provides a polymer having a repeating unit represented by the formula:

Second, the following general formula (2)

[0015]

Embedded image

Wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ ,
a, c, d and e are as defined for the above formula (1), and R ¹¹ and R ¹² independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. And a compound represented by the following general formula (3)

[0017]

Embedded image

(Wherein R ³ , R ⁴ , R ⁸ , R ⁹ ,
R ¹⁰ , b, f, g and h are as defined for the above general formula (1). The present invention provides a method for producing a polymer, which comprises polymerizing the compound represented by the formula (1) in the presence of a catalyst.

Further, thirdly, a film-forming composition containing the polymer is provided.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Polymer) The polymer of the present invention is a polymer having a repeating unit represented by the following general formula (1).

[0021]

Embedded image

(Wherein R ^{1 to} R ⁴ are each independently a single bond, —O
_{-, - CO -, - CH} 2 -, - COO -, - CONH
_{-, - S -, - SO} 2 -, - C≡C-, phenylene group,

[0023]

Embedded image

Or a fluorenylene group, and R ^{5 to} R
¹⁰ independently represents a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group or an aryl group having 1 to 20 carbon atoms, a and b each independently represent an integer of 0 to 3, c to h each independently represent an integer of 0 to 4. In particular, a polymer having a bond of —C≡C— in a repeating unit represented by the general formula (1) has crosslinking reactivity. Therefore, when this is contained in a film-forming composition and applied on a substrate, a coating film is formed in a short time baking, and this coating film has better heat resistance, hardness and crack resistance, and has a lower dielectric constant. Is shown.

(Method for Producing Polymer) A polymer having a repeating unit represented by the above general formula (1) is produced as follows.

That is, the following general formula (2)

[0027]

Embedded image

Wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ ,
a, c, d and e are as defined for the above formula (1), and R ¹¹ and R ¹² independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. And a compound represented by the following general formula (3)

[0029]

Embedded image

Wherein R ³ , R ⁴ , R ⁸ , R ⁹ ,
R ¹⁰ , b, f, g and h are as defined for the above general formula (1). ) Is polymerized in the presence of a catalyst.

The compounds represented by the general formula (2) include, for example, 4,4'-dicarboxybiphenyl,
4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenylsulfone, 4,4'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylketone, 4,4'-dicarboxydiphenylacetylene, biphenyl-4, 4'-dicarboxyl dimethyl ester, biphenyl-4,4'-dicarboxyl diethyl ester, diphenyl ether-4,4'-
Dicarboxylic dimethyl ester, diphenyl ether-4,4'-dicarboxyl diethyl ester, diphenylsulfone-4,4'-dicarboxyl dimethyl ester, diphenylsulfone-4,4'-
Dicarboxylic diethyl ester, diphenylmethane-4,4′-dicarboxyl dimethyl ester,
Diphenylmethane-4,4'-dicarboxylic diethylester, diphenylketone-4,4'-dicarboxylic dimethylester, diphenylketone-4,
4′-dicarboxylic diethyl ester, diphenylacetylene-4,4′-dicarboxyl dimethyl ester, diphenylacetylene-4,4′-dicarboxyl diethyl ester,

4,4'-bis (4-carboxyphenoxy) diphenyl ether, 4,4'-bis (3-carboxyphenoxy) diphenyl ether, 4,4'-bis (2-carboxyphenoxy) diphenyl ether,
4,4'-bis (4-carboxyphenoxy) diphenyl ketone, 4,4'-bis (3-carboxyphenoxy) diphenyl ketone, 4,4'-bis (2-carboxyphenoxy) diphenyl ketone, 4,4'- Screw (4
-Carboxyphenoxy) diphenylacetylene, 4,
4′-bis (3-carboxyphenoxy) diphenylacetylene, 4,4′-bis (2-carboxyphenoxy) diphenylacetylene,

4,4'-bis (4-carboxybenzoyl) diphenyl ether, 4,4'-bis (3-carboxybenzoyl) diphenyl ether, 4,4'-bis (2-carboxybenzoyl) diphenyl ether,
4,4'-bis (4-carboxybenzoyl) diphenyl ketone, 4,4'-bis (3-carboxybenzoyl) diphenyl ketone, 4,4'-bis (2-carboxybenzoyl) diphenyl ketone, 4,4'- Screw (4
-Carboxybenzoyl) diphenylacetylene, 4,
4′-bis (3-carboxybenzoyl) diphenylacetylene, 4,4′-bis (2-carboxybenzoyl) diphenylacetylene,

4,4'-bis (phenoxy-4-carboxymethyl ester) diphenyl ether, 4,4'-
Bis (phenoxy-3-carboxymethyl ester) diphenyl ether, 4,4'-bis (phenoxy-2-
Carboxymethyl ester) diphenyl ether, 4,
4′-bis (phenoxy-4-carboxymethyl ester) diphenyl ketone, 4,4′-bis (phenoxy-
3-carboxymethyl ester) diphenyl ketone,
4,4'-bis (phenoxy-2-carboxymethyl ester) diphenyl ketone, 4,4'-bis (phenoxy-4-carboxymethyl ester) diphenylacetylene, 4,4'-bis (phenoxy-3-carboxymethyl ester) ) Diphenylacetylene, 4,4′-bis (phenoxy-2-carboxymethyl ester) diphenylacetylene,

4,4'-bis (benzoyl-4-carboxymethyl ester) diphenyl ether, 4,4'-
Bis (benzoyl-3-carboxymethyl ester) diphenyl ether, 4,4'-bis (benzoyl-2-
Carboxymethyl ester) diphenyl ether, 4,
4′-bis (benzoyl-4-carboxymethyl ester) diphenyl ketone, 4,4′-bis (benzoyl-
3-carboxymethyl ester) diphenyl ketone,
4,4'-bis (benzoyl-2-carboxymethyl ester) diphenyl ketone, 4,4'-bis (benzoyl-4-carboxymethyl ester) diphenylacetylene, 4,4'-bis (benzoyl-3-carboxymethyl ester) ) Diphenylacetylene, 4,4′-bis (benzoyl-2-carboxymethyl ester) diphenylacetylene,

4,4'-bis (phenoxy-4-carboxyethyl ester) diphenyl ether, 4,4'-
Bis (phenoxy-3-carboxyethyl ester) diphenyl ether, 4,4'-bis (phenoxy-2-
Carboxyethyl ester) diphenyl ether, 4,
4′-bis (phenoxy-4-carboxyethyl ester) diphenyl ketone, 4,4′-bis (phenoxy-
3-carboxyethyl ester) diphenyl ketone,
4,4'-bis (phenoxy-2-carboxyethyl ester) diphenyl ketone, 4,4'-bis (phenoxy-4-carboxyethyl ester) diphenylacetylene, 4,4'-bis (phenoxy-3-carboxyethyl ester) ) Diphenylacetylene, 4,4′-bis (phenoxy-2-carboxyethyl ester) diphenylacetylene,

4,4'-bis (benzoyl-4-carboxyethyl ester) diphenyl ether, 4,4'-
Bis (benzoyl-3-carboxyethyl ester) diphenyl ether, 4,4'-bis (benzoyl-2-
Carboxyethyl ester) diphenyl ether, 4,
4′-bis (benzoyl-4-carboxyethyl ester) diphenyl ketone, 4,4′-bis (benzoyl-
3-carboxyethyl ester) diphenyl ketone,
4,4'-bis (benzoyl-2-carboxyethyl ester) diphenyl ketone, 4,4'-bis (benzoyl-4-carboxyethyl ester) diphenylacetylene, 4,4'-bis (benzoyl-3-carboxyethyl ester) ) Diphenylacetylene, 4,4′-bis (benzoyl-2-carboxyethyl ester) diphenylacetylene,

4,4'-bis (2-carboxyphenylethynyl) diphenyl ether, 4,4'-bis (3-
Carboxyphenylethynyl) diphenyl ether,
4,4'-bis (4-carboxyphenylethynyl) diphenyl ketone, 4,4'-bis (2-carboxyphenylethynyl) diphenyl ketone, 4,4'-bis (3-carboxyphenylethynyl) diphenyl ketone, 4,4 '-Bis (4-carboxyphenylethynyl) diphenyl ketone, 4,4'-bis (2-carboxyphenylethynyl) diphenyl sulfone, 4,4'-
Bis (3-carboxyphenylethynyl) diphenylsulfone, 4,4′-bis (4-carboxyphenylethynyl) diphenylsulfone,

4,4'-bis (2-carboxyphenylethynyl) diphenyl ether dimethyl ester,
4'-bis (3-carboxyphenylethynyl) diphenyl ether dimethyl ester, 4,4'-bis (4-
Carboxyphenylethynyl) diphenyl ether dimethyl ester, 4,4′-bis (2-carboxyphenylethynyl) diphenyl ketone dimethyl ester,
4'-bis (3-carboxyphenylethynyl) diphenylketone dimethyl ester, 4,4'-bis (4-carboxyphenylethynyl) diphenylketone dimethyl ester, 4,4'-bis (2-carboxyphenylethynyl) diphenylsulfonedimethyl Ester, 4,
4'-bis (3-carboxyphenylethynyl) diphenylsulfone dimethyl ester, 4,4'-bis (4-
Carboxyphenylethynyl) diphenylsulfone dimethyl ester,

4,4′-bis (2-carboxyphenylethynyl) diphenyl ether diethyl ester,
4'-bis (3-carboxyphenylethynyl) diphenyl ether diethyl ester, 4,4'-bis (4-
(Carboxyphenylethynyl) diphenyl ether diethyl ester, 4,4′-bis (2-carboxyphenylethynyl) diphenyl ketone diethyl ester,
4′-bis (3-carboxyphenylethynyl) diphenyl ketone diethyl ester, 4,4′-bis (4-carboxyphenylethynyl) diphenyl ketone diethyl ester, 4,4′-bis (2-carboxyphenylethynyl) diphenyl sulfone diethyl Ester, 4,
4'-bis (3-carboxyphenylethynyl) diphenylsulfone diethyl ester, 4,4'-bis (4-
(Carboxyphenylethynyl) diphenylsulfone diethyl ester and the like. These compounds may be used alone or in combination of two or more.

Examples of the compound represented by the general formula (3) include diphenyl ether, benzophenone, diphenyl sulfone, tolan, 4,4'-diphenoxybenzene, 3,3'-diphenoxybenzene, and 4,4'-
Diphenoxy ketone, 3,3′-diphenoxy ketone,
4,4′-diphenoxydiphenyl ether, 3,3 ′
-Diphenoxydiphenyl ether, 4,4'-diphenoxybenzophenone, 3,3'-diphenoxybenzophenone, 4,4'-diphenoxydiphenylsulfone, 3,3'-diphenoxydiphenylsulfone, 4,
4′-diphenoxytran, 3,3′-diphenoxytran, 4,4′-dibenzoyldiphenyl ether,
3,3'-dibenzoyldiphenyl ether, 4,4 '
-Dibenzoylbenzophenone, 3,3'-dibenzoylbenzophenone, 4,4'-dibenzoyldiphenylsulfone, 3,3'-dibenzoyldiphenylsulfone, 4,4'-dibenzoyltran, 3,3'-dibenzoyl Tolan and the like can be mentioned. These compounds may be used alone or in combination of two or more.

The polymer of the present invention is produced by polymerizing a compound represented by the general formula (2) and a compound represented by the general formula (3) in the presence of a catalyst. At this time, the use ratio of the compound represented by the general formula (2) and the compound represented by the general formula (3) is the same as that of the compound 1 represented by the general formula (2).
The compound represented by the general formula (3) 0.8 to
It is 1.2 mol, preferably 0.9 to 1.1 mol, particularly preferably 0.95 to 1.05. When the total amount of the compound represented by the general formula (3) is less than 0.8 mol or more than 1.2 mol, the molecular weight of the obtained polymer hardly increases.

In the production method of the present invention, for example, it is preferable to react the compound represented by the general formula (2) with the compound represented by the general formula (3) in the presence of a phosphorus-containing compound as a catalyst. Examples of such phosphorus-containing compounds include polyphosphoric acid, sodium polyphosphate, potassium polyphosphate, methyl polyphosphate, ethyl polyphosphate, trimethylsilyl polyphosphate, phosphorus pentoxide-methanesulfonic acid solution, phosphorus pentoxide-trichloromethane Examples thereof include a sulfonic acid solution, a phosphorus pentoxide-trifluoromethanesulfonic acid solution, and a phosphorus pentoxide-sulfuric acid solution. These compounds may be used alone or in combination of two or more.

The use ratio of the above catalyst is preferably 1 to 1000 mol, more preferably 1 to 1 mol, based on 1 mol of the total amount of the compound represented by the general formula (2) and the compound represented by the general formula (3). １００100 mol. If it is less than 1 mol, the polymerization may not proceed sufficiently, while if it exceeds 100 mol, it is not economical.

In the production method of the present invention, the reaction can be carried out without using a solvent, but a solvent may be used if necessary. The solvent for polymerization is not particularly limited, and examples thereof include halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and diethylbenzene. Solvents: ether solvents such as diethyl ether, tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-heptanone, cyclohexanone, cyclclepentanone Ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, and γ-butyrolactone N, N- dimethylformamide, N, N- dimethylacetamide may be mentioned amide solvents such as N- methyl-2-pyrrolidone. It is preferable that these solvents are sufficiently dried and deoxygenated before use. These compounds may be used alone or in combination of two or more.

When a solvent is used, the concentration of the monomer (polymerization component) in the polymerization solvent is preferably from 10 to 99.
%, More preferably 20-99% by weight. The polymerization temperature is preferably from 0 to 150C, more preferably from 5 to 100C. The polymerization time is preferably 0.5 to 100 hours, more preferably 1 to 4 hours.
0 hours.

(Composition for Film Formation) The composition for film formation of the present invention is prepared by dissolving the polymer of the present invention in a solvent. Examples of the solvent that can be used at this time include at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ester solvents, and aprotic solvents.

Here, as the alcohol solvent, for example, methanol, ethanol, n-propanol, i-
Propanol, n-butanol, i-butanol, se
c-butanol, t-butanol, n-pentanol,
i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, se
c-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2
-Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4,
n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol,
Cyclohexanol, methylcyclohexanol, 3,
Monoalcohol solvents such as 3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;

Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,
4, hexanediol-2,5, heptanediol-
Polyhydric alcohol solvents such as 2,4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol;

Ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether,
Polyhydric alcohol partial ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether And the like. These alcohol solvents may be used alone or in combination of two or more.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone,
Ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchone, etc. Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione,
3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro- Β-diketones such as 2,4-heptanedione and the like can be mentioned. These ketone solvents may be used alone or in combination of two or more.

Examples of the amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide , N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N -Acetylpyrrolidine and the like. These amide solvents may be used alone or in combination of two or more.

Examples of the ester solvent include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, and i-acetate.
Propyl, n-butyl acetate, i-butyl acetate, acetic acid se
c-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, acetoacetate Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl acetate, propylene glycol monoethyl acetate Ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropyl acetate Glycol monomethyl ether acetate, dipropylene glycol monoethyl ether,
Glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactic acid n -Amyl, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like. These ester solvents may be used alone or in combination of two or more.

Examples of the aprotic solvents include acetonitrile, dimethyl sulfoxide, N, N, N ',
N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine,
N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1, 3-dimethyltetrahydro-2 (1H) -pyrimidinone and the like can be mentioned. These aprotic solvents may be used alone or in combination of two or more.

The film-forming composition of the present invention further comprises colloidal silica, colloidal alumina, an organic polymer other than the polymer of the present invention, as long as the effects of the present invention are not impaired.
Components such as a surfactant, a silane coupling agent, a triazene compound, a radical generator, a compound having a polymerizable double bond, and a compound having a polymerizable triple bond may be added.

The colloidal silica is, for example, a dispersion in which high-purity silicic anhydride is dispersed in the hydrophilic organic solvent, and usually has an average particle size of 5 to 30 nm, preferably 10 to 30 nm.
It has a thickness of 20 nm and a solid concentration of about 10 to 40% by weight. Examples of such a colloidal silica include, for example, methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd .;
Oscar and the like. The amount of these used is usually preferably 1 to 20 parts by weight based on 100 parts by weight of the polymer.

Examples of the colloidal alumina include alumina sols 520, 100 and 20 manufactured by Nissan Chemical Industries, Ltd.
0; alumina clear sol, alumina sol 10 and 132, manufactured by Kawaken Fine Chemical Co., Ltd .;
The amount of these used is usually preferably 1 to 20 parts by weight based on 100 parts by weight of the polymer.

Examples of the organic polymer include a polymer having a sugar chain structure, a vinylamide polymer, and (meth)
Acrylic polymer, aromatic vinyl compound polymer, dendrimer, polyimide, polyamic acid, polyamide,
Examples thereof include polyquinoxaline, polyoxadiazole, a fluoropolymer, and a polymer having a polyalkylene oxide structure.

Examples of the polymer having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure,
A polymer having a polytetramethylene oxide structure, a polybutylene oxide structure, or the like can be given.

More specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene Ether type compounds such as ethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate Such as ether ester type compounds, polyethylene glycol fatty acid esters, ethylene glycol Call fatty acid esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters.

Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures. − (X ′) _p − (Y ′) _q − − (X ′) _p − (Y ′) _q − (X ′) _r − [In the general formula, X ′ is represented by —CH ₂ CH ₂ O—. Y ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, p represents a number of 1 to 90, q represents a number of 10 to 99, and r represents a number of 0 to 90. ]

Among these, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol Ether-type compounds such as fatty acid esters can be mentioned as more preferable examples. These may be used alone or in combination of two or more. The amount of these used is usually preferably 1 to 30 parts by weight based on 100 parts by weight of the polymer.

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like. Further, a fluorine-based surfactant, a silicone-based surfactant, and the like. Examples of the surfactant include a surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant, and preferably a fluorine-based surfactant and a silicone-based surfactant.

As the fluorinated surfactant, for example,
1,1,2,2-tetrafluorooctyl (1,1,2,2
2-tetrafluoropropyl) ether, 1,1,2,2
-Tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,
2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3- Hexafluoropentyl)
Ether, sodium perfluorododecyl sulfonate,
1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfone Amido) propyl] -N, N′-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt,
At least one of terminal, main chain and side chain of perfluoroalkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate, etc. And a fluorine-based surfactant composed of a compound having a fluoroalkyl or fluoroalkylene group at the position (1).

As a commercial product, Megafac F1
42D, F172, F173, F183 [or more,
Dainippon Ink and Chemicals, Inc.], F-Top EF30
1, 303, 352 [manufactured by Shin-Akita Kasei Co., Ltd.], Florard FC-430, FC-431 [manufactured by Sumitomo 3M Limited], Asahi Guard AG710, Surflon S-
382, SC-101, SC-102, SC-1
03, SC-104, SC-105, SC-10
6 [manufactured by Asahi Glass Co., Ltd.], BM-1000, BM-110
0 [manufactured by Yusho Co., Ltd.] and NBX-15 [Neos Co., Ltd.] are commercially available. Among them, the mega fuck F1
72, BM-1000, BM-1100, NBX-15
Is particularly preferred.

Examples of the silicone-based surfactant include SH7PA, SH21PA, SH30PA, and ST9.
4PA (all manufactured by Dow Corning Toray Silicone Co., Ltd.) can be used. Among them, SH28PA and SH30PA are particularly preferable.
The amount of the surfactant to be used is preferably usually 0.00001 to 1 part by weight based on 100 parts by weight of the polymer of the present invention. These may be used alone or in combination of two or more.

As the silane coupling agent, for example,
3-glycidyloxypropyltrimethoxysilane, 3-
Aminoglycidyloxypropyltriethoxysilane, 3
-Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1-methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane , 2-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- Ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl- 1,4,7-triazadecane, 10-
Triethoxysilyl-1,4,7-triazadecane, 9
-Trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-
Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, p-tolyltrimethoxysilane, p-tolyltriethoxysilane, m-ethynylphenyltrimethoxysilane, p-ethynylphenyltrimethoxysilane, m
-Ethynylphenyltriethoxysilane, p-ethynylphenyltriethoxysilane and the like. Also,
Hydrolysates and / or condensates of these alkoxysilanes can be used. These may be used alone or in combination of two or more. These amounts are usually 0.1 to 1 based on 100 parts by weight of the polymer.
It is preferably 0 parts by weight.

As the triazene compound, for example, 1,
2-bis (3,3-dimethyltriazenyl) benzene,
1,3-bis (3,3-dimethyltriazenyl) benzene, 1,4-bis (3,3-dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis ( 3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3-dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3 ,
3-dimethyltriazenylphenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl)- 9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3- Phenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-propenyl-4- (3,3 -Dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyltriazenyl) phenyl] Fluorene, 2,7-
Bis (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3
-Dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl)
Phenyl] fluorene and the like. These are 1
One kind may be used alone, or two or more kinds may be used simultaneously.
Usually, the amount of these is preferably 1 to 10 parts by weight based on 100 parts by weight of the polymer.

Examples of the radical generator include isobutyryl peroxide, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropyl Peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-
1-methylethyl peroxy neodecanoate, di-2
Ethoxyethyl peroxydicarbonate, di (2-
Ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, t-butylperoxyneodecanoate , 2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t
-Butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexano Ethate, succinic peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylper Oxy-2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate,
m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-
Butylperoxycyclohexyl) propane, 1,1-
Bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-
3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, -Butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis ( t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Organic peroxides such as cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide;

Dibenzyl, 2,3-dimethyl-2,3-
Diphenylbutane, α, α'-dimethoxy-α, α'-
Diphenylbibenzyl, α, α′-diphenyl-α-methoxybibenzyl, α, α′-diphenyl-α, α′-
Dimethoxybibenzyl, α, α′-dimethoxy-α,
α′-dimethylbibenzyl, α, α′-dimethoxybibenzyl, 3,4-dimethyl-3,4-diphenyl-n-
Bibenzyl compounds such as hexane and 2,2,3,3-tetraphenylsuccinic nitrile can be mentioned.
These may be used alone or in combination of two or more. The amount of these used is usually preferably 0.5 to 10 parts by weight based on 100 parts by weight of the polymer.

Examples of the compound containing a polymerizable double bond include, for example, allylbenzene, diallylbenzene, triallylbenzene, allyloxybenzene, diallyloxybenzene, triallyloxybenzene, α, ω-diallyloxyalkane, α, ω-diallyl alkenes,
α, ω-diallylalkenes, allylamine, diallylamine, triallylamine, N-allylphthalimide,
Allyl compounds such as N-allylpyromellitimide, N, N'-diallylurea, triallyl isocyanurate, 2,2'-diallylbisphenol A; styrene, divinylbenzene, trivinylbenzene, stilbene, propenylbenzene, dipropenylbenzene, Tripropenylbenzene, phenylvinyl ketone, methylstyryl ketone, α, ω-divinylalkanes, α, ω-divinylalkenes, α, ω-divinylalkynes, α, ω-
Divinyloxyalkanes, α, ω-divinylalkenes, α, ω-divinylalkynes, α, ω-diacryloxyalkanes, α, ω-diacrylalkenes,
α, ω-diacrylalkenes, α, ω-dimethacryloxyalkanes, α, ω-dimethacrylalkenes,
vinyl compounds such as α, ω-dimethacrylalkenes, bisacryloxybenzene, trisacryloxybenzene, bismethacryloxybenzene, trismethacryloxybenzene, N-vinylphthalimide and N-vinylpyromellitimide;

Examples thereof include polyarylene ethers containing 2,2'-diallyl-4,4'-biphenol, and polyarylenes containing 2,2'-diallyl-4,4'-biphenol. These may be used alone or in combination of two or more. These amounts are usually 0.5 to 10 parts by weight of the polymer.
It is preferred to use parts by weight.

The compound containing a polymerizable triple bond includes, for example, the compounds represented by the general formula (2) and the compounds represented by the general formula (3). Compounds containing a polymerizable triple bond include ethynylbenzene, bis (trimethylsilylethynyl) benzene, and tris (trimethylsilylethynyl)
Benzene, triethynylbenzene, bis (trimethylsilylethynylphenyl) ether, trimethylsilylethynylbenzene, tris (phenylethynyl) benzene and the like can be mentioned. These compounds containing a polymerizable triple bond may be used alone or in combination of two or more. The amount of these used is usually preferably 1 to 20 parts by weight based on 100 parts by weight of the polymer.

The total solid content of the film-forming composition of the present invention is preferably from 1 to 30% by weight, more preferably from 2 to 20% by weight, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 1 to 30% by weight, the thickness of the coating film is in an appropriate range, and the storage stability is excellent.

When applying the film-forming composition of the present invention to a substrate (or substrate) such as a silicon wafer, SiO ₂ wafer or SiN wafer, spin coating, dipping, roll coating, spraying, etc. Is used. Thereafter, the coating film is dried at room temperature or heated at a temperature of about 80 to 600 ° C., usually for about 5 to 240 minutes, and dried and cured to form a coating film (for example, an interlayer insulating film). As a heating method at this time, a hot plate,
An oven, a furnace, or the like can be used, and the heating can be performed under air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with controlled oxygen concentration, or the like. Further, the coating film can be formed by irradiating an electron beam or an ultraviolet ray. At this time, the thickness (solid content) of a single coating is 0.02 to 1.
The thickness of about 5 μm can be formed to a thickness of about 0.05 to 3 μm by the second coating.

From the film forming composition of the present invention, a coating film can be formed by baking in a short time, and the obtained coating film is excellent in adhesion, heat resistance, film hardness, crack resistance and low dielectric property. Therefore, LSI (Large Scale Integration), system LSI, DRAM (Dynamic Random Access Memor
y), an interlayer insulating film for semiconductor devices such as SDRAM, RDRAM, and D-RDRAM, an etching stopper, a chemical mechanical polishing stopper, a protective film such as a surface coat film of a semiconductor device, an intermediate layer in a semiconductor manufacturing process using a multilayer resist,
It is useful for applications such as interlayer insulating films of multilayer wiring boards, protective films and insulating films for liquid crystal display elements.

[0077]

The present invention will now be described more specifically with reference to examples. Parts and% in Examples and Comparative Examples
Represents parts by weight and% by weight, respectively, unless otherwise specified. The evaluation of the film-forming composition in the examples was performed as follows.

(Weight average molecular weight (Mw)) Gel permeation chromatography (GPC) under the following conditions
It was measured by the method. Sample: Sample 1 using tetrahydrofuran as a solvent
g was dissolved in 100 cc of tetrahydrofuran. Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical Co., USA was used. Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters, USA Column: SHOdex A-80M manufactured by Showa Denko KK
(Length 50cm) Measurement temperature: 40 ° C Flow rate: 1cc / min

(Relative Dielectric Constant) A composition for film formation was applied on an 8-inch silicon wafer by spin coating, dried on a hot plate at 80 ° C. for 2 minutes and at 180 ° C. for 2 minutes, and further dried at 380 ° C. The film was baked for 7 minutes on a hot plate in a nitrogen atmosphere to form a coating film on the wafer, and aluminum was further evaporated on the coating film to prepare a sample for relative dielectric constant evaluation. The relative permittivity is determined by using a Yokogawa-Hewlett-Packard Co., Ltd. HP16451B electrode and HP4284A.
It was calculated from the capacitance value at 10 kHz using a precision LCR meter.

(Crack resistance) A film-forming composition is applied on an 8-inch silicon wafer by a spin coating method.
The film was dried on a hot plate at 80 ° C. for 2 minutes and at 180 ° C. for 2 minutes, and further baked on a hot plate in a nitrogen atmosphere at 380 ° C. for 7 minutes to form a coating film on the wafer. The final film thickness at this time was 5.5 μm. The wafer on which the obtained coating film is formed is immersed in pure water for 2 hours, and the appearance of the coating film is observed using a 350,000 lux surface observation lamp to determine whether cracks are observed on the coating film surface. did.

(Coating film hardness) A film forming composition was applied on an 8-inch silicon wafer by a spin coating method, dried on a hot plate at 80 ° C. for 2 minutes and at 180 ° C. for 2 minutes, and further dried at 380 ° C. Baking on a hot plate in a nitrogen atmosphere for 7 minutes to form a coating film on the wafer, and using a nano indenter XP (manufactured by Nano Instruments),
The coating film hardness was measured by a continuous rigidity measuring method.

(Heat resistance) On an 8-inch silicon wafer,
The composition for film formation was applied by a spin coating method, dried on a hot plate at 80 ° C. for 2 minutes and at 180 ° C. for 2 minutes, and further baked on a hot plate at 380 ° C. in a nitrogen atmosphere for 7 minutes. The wafer on which the obtained coating film is formed is subjected to a thermal stress measurement device (manufactured by KLA Tencor,
5 ° C from room temperature to 420 ° C using FLX-2320)
/ Min, and it was observed whether the relaxation of the stress caused by the glass transition temperature was observed.

Example 1 100 equipped with a thermometer, an argon gas inlet tube and a stirring device
200 g of methanesulfonic acid and 20 g of diphosphorus pentoxide were added to a 0 ml three-necked flask and stirred at room temperature for 2 hours. To this solution, 5.41 g of diphenyl ether and 14.58 g of 4,4′-bis (2-carboxyphenylethynyl) diphenyl ether were added, and reacted at 50 ° C. for 20 hours. The reaction solution was slowly dropped into 5 L of water while cooling with ice to precipitate a pale yellow solid. After the solid was filtered off, 1NN
Washing was performed with stirring for 1 hour in 5 L of aOH aqueous solution. The solid was separated by filtration again, dissolved in 400 g of cyclohexanone, and the insoluble matter was filtered.
The precipitate was filtered and dried to obtain a polymer A having a weight average molecular weight of 25,000.

3 g of this polymer A was added to cyclohexanone 27
g, and this solution was filtered through a Teflon (registered trademark) filter having a pore size of 0.2 μm to obtain a film-forming composition. The obtained composition was applied on a silicon wafer by a spin coating method, and each characteristic value was evaluated as described above. The relative dielectric constant of the coating film was a low value of 2.98, and no Tg was observed under heat stress. This coating did not show any cracks even after immersion in pure water. Further, the hardness of the coating film was 0.5 GPa, which was excellent in mechanical strength.

Example 2 In Example 1, 5.52 g of tolan was used in place of diphenyl ether, and 4,4'-instead of 4,4'-bis (2-carboxyphenylethynyl) diphenyl ether.
The same operation as in Example 1 was performed except that 14.47 g of bis (2-carboxybenzoyl) diphenyl ether was used, to obtain a polymer B having a weight average molecular weight of 22,000.

3 g of this polymer B was added to cyclohexanone 27
g, and the solution was filtered through a Teflon filter having a pore size of 0.2 μm to obtain a film-forming composition. The obtained composition was applied on a silicon wafer by a spin coating method, and each characteristic value was evaluated as described above. The relative dielectric constant of the coating film was a low value of 2.93, and no Tg was observed under heat stress. This coating did not show any cracks even after immersion in pure water. The hardness of the coating film is 0.6G
It was excellent in Pa and mechanical strength.

Example 3 In Example 1, 5.60 g of tolan was used in place of diphenyl ether, and 4,4'-instead of 4,4'-bis (2-carboxyphenylethynyl) diphenyl ether.
The same operation as in Example 1 was performed except that 14.40 g of bis (2-carboxyphenylethynyl) diphenyl ether was used, and a polymer C having a weight average molecular weight of 28,000 was used.
I got

Cyclohexanone 27
g, and the solution was filtered through a Teflon filter having a pore size of 0.2 μm to obtain a film-forming composition. The obtained composition was applied on a silicon wafer by a spin coating method, and each characteristic value was evaluated as described above. The relative dielectric constant of the coating film was a low value of 2.96, and no Tg was observed under heat stress. This coating did not show any cracks even after immersion in pure water. The hardness of the coating film is 0.7 G
It was excellent in Pa and mechanical strength.

Comparative Example 1 9,9-bis (4-hydroxyphenyl) fluorene 3
5.04 g and potassium carbonate (16.6 g) were placed in a flask together with 350 g of dimethylacetamide and 100 ml of toluene, and heated at 160 ° C. for 20 hours under a nitrogen atmosphere. At this time, generated steam was removed outside the system. 21.9 g of 4,4'-bisfluorobenzophenone was added to this solution.
Was added and reacted at 160 ° C. for 8 hours. After cooling the reaction solution, insolubles in the solution were removed by filtration, and then reprecipitated in methanol. After the precipitate was sufficiently washed with ion-exchanged water, the precipitate was dissolved in cyclohexanone, insolubles were removed, and the precipitate was reprecipitated in acetone. The precipitate was dried in a vacuum oven at 60 ° C. for 24 hours to obtain a polymer D having a weight average molecular weight of 24,000.

[0092] Cyclohexanone 27
g, and the solution was filtered through a Teflon filter having a pore size of 0.2 μm. The obtained composition was applied on a silicon wafer by a spin coating method, and each characteristic value was evaluated as described above. The relative dielectric constant of the coating film was as low as 2.87, but the Tg of the coating film was found at 250 ° C.

Comparative Example 2 77.04 g of methyltrimethoxysilane and 2 g of acetic acid were
After being dissolved in 290 g of isopropyl alcohol, the solution was stirred with a three-one motor to stabilize the solution temperature at 60 ° C. Next, 84 g of ion-exchanged water was added to the solution over 1 hour. Then, after reacting at 60 ° C. for 2 hours, a reaction solution (1) (condensate) was obtained.

The reaction solution was filtered with a Teflon filter having a pore size of 0.2 μm. The obtained composition was applied on a silicon wafer by a spin coating method, and each characteristic value was evaluated as described above. The relative dielectric constant of the coating is 3.44
It was a high value. In addition, cracks occurred in the coating film having a thickness of 5 μm, and the crack resistance was poor.

Reference Example 1 In Example 1, the amount of diphenyl ether used was changed to 5.
The amount was changed from 41 g to 7.02 g, and 4,4′-bis (2-
The same procedure as in Example 1 was carried out except that 12.98 g of diphenyl ether-4,4'-dicarboxyl diethyl ester was used instead of (carboxyphenylethynyl) diphenyl ether, to obtain a weight average molecular weight of 44,0.
00 polymer F was obtained.

The polymer F3g was treated with γ-butyrolactone 2
7 g, and this solution was filtered through a Teflon filter having a pore diameter of 0.2 μm to obtain a film-forming composition. The obtained composition was applied on a silicon wafer by a spin coating method, and each characteristic value was evaluated as described above. Although the dielectric constant of the coating film was relatively low at 3.02, the Tg of the coating film was found at 278 ° C.

[0095]

The polymer of the present invention is suitably used as a film-forming composition. When a film-forming composition having this polymer is applied to a substrate (or a substrate), the coating film can be formed in a short time by baking. Once formed, this coating has excellent heat resistance, hardness and crack resistance, and low dielectric properties. In particular, -C≡C-
When a film-forming composition having a polymer having a bond is used, these properties are more excellent. Therefore, the film-forming composition of the present invention is useful, for example, as a material for forming an interlayer insulating film in a semiconductor device or the like. According to the production method of the present invention, such a polymer can be easily produced.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Michinori Nishikawa 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. F term in reference (reference) 4J005 BA00 BB02 4J038 DN011 GA01 KA06 NA12 NA14 NA17 NA21 PA19

Claims (5)

[Claims] (1) The following general formula (1): (Wherein, R ^{1 to} R ⁴ are each independently a single bond, —O—, —CO
_{-, - CH 2 -, -} COO -, - CONH -, - S-,
—SO ₂ —, —C≡C—, a phenylene group, Or a fluorenylene group, R ^{5 to} R ¹⁰ independently represent a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms or an aryl group; Independently represents an integer of 0 to 3, c
To h independently represent an integer of 0 to 4; A polymer having a repeating unit represented by the formula: 2. The polymer according to claim 1, wherein the repeating unit represented by the general formula (1) has a bond of —C≡C—. 3. The following general formula (2): (Wherein, R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , a, c, d and e are as defined in claim 1 with respect to the general formula (1), and R ¹¹ and R ¹² are independently Represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.) And a compound represented by the following general formula (3): (Wherein, R ³ , R ⁴ , R ⁸ , R ⁹ , R ¹⁰ , b, f, g
And h are as defined in claim 1 for the general formula (1). The method for producing a polymer according to claim 1, wherein the compound represented by the formula (1) is polymerized in the presence of a catalyst. 4. The method according to claim 2, wherein the catalyst contains a phosphorus-containing compound. 5. A film-forming composition comprising the polymer according to claim 1.