JP2001055513A - Polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer composition that can give a cured product having low dielectric properties and improved in heat resistance, solvent resistance, mechanical strengths, etc. by mixing an aromatic polymer having aromatic rings in each repeating structural unit with a triazene compound and an organic solvent. SOLUTION: This composition comprises 100 pts.wt. aromatic polymer having aromatic rings in each repeating structural unit, 1-500 pts.wt. triazene compound having at least three -N=N-RR' groups in the molecule, and 50-10,000 pts.wt. organic solvent. The aromatic polymer is desirably a phenylene-containing (co)polymer comprising repeating structural units represented by the formula and having a weight-average molecular weight of 1,000-1,000,000. In the formulae, R and R' are each H, a 1-20C alkyl or an aryl; X is either a -CQQ'- group or fluorenylene; Q and Q' are each a haloalkyl, an alkyl, H, a halogen or an aryl; R1 to R20 are each H, a halogen or a monovalent organic group; Y is-O-, -CO-, -COO-, -CONH- or -SO2; (l) is such an integer that the related repeating units account for 5-100 mol% of the entire repeating units; (m) and (p) are each such an integer that the related repeating units account for 0-95 mol% of the entire repeating units; and (t) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic polymer having an aromatic ring in a repeating structural unit, a triazene compound having three or more triazyl groups (-N = N-NR ¹ R ² ), and an organic solvent. The present invention relates to a novel polymer composition which contains a cured product (cured film) having excellent heat resistance, low dielectric properties, solvent resistance, mechanical strength, and the like.

[0002]

2. Description of the Related Art Large-scale integrated circuits (LSIs) have become highly integrated, multifunctional, and high-performance, reflecting the progress of fine processing technology. As a result, circuit resistance and capacitance between wirings (hereinafter, sometimes referred to as “parasitic resistance” and “parasitic capacitance”, respectively) are increased, which not only increases power consumption but also increases delay time. This is a major factor in reducing the signal speed of the device. 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. I'm trying to respond. Further, the interlayer insulating film needs to have excellent heat resistance that can withstand post-processes such as a thin-film forming process at the time of manufacturing a mounting board and chip connection and pinning. In order to satisfy the above requirements of heat resistance and low dielectric constant, many developments using aromatic polymers such as polyimide, polyarylene ether, polyquinoline and polyphenylene have been attempted, and the present inventors have also proposed a method for producing polyphenylene. (For example, Japanese Patent Application No.
29068, Japanese Patent Application No. 10-29070, Japanese Patent Application No. 10-273522). However, in the case of the above-described aromatic polymer alone, solvent resistance during resist coating and stripping in a semiconductor manufacturing process and recent Cu
It does not have sufficient mechanical strength to withstand the CMP process in wiring manufacturing. Therefore, several attempts have been made to crosslink an aromatic polymer without impairing heat resistance and low dielectric constant, and one of them is a cross-linking method using a bistriazene compound (Japanese Patent Application Laid-Open No. 5-503112, Table 5
503114). However, the above method has insufficient cross-linking efficiency and cannot withstand the CMP process sufficiently.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art, and provides a heat-resistant and low-dielectric material by blending a novel triazene compound with an aromatic polymer as a crosslinking agent. Another object of the present invention is to provide an aromatic polymer composition from which a cured product (cured film) excellent in solvent resistance, mechanical strength and the like can be obtained.

[0004]

The present invention provides (A) an aromatic polymer having an aromatic ring in a repeating structural unit,
(B) a triazene compound having three or more groups represented by the formula (1) in one molecule, and -N = N-NRR '(1) wherein R and R' are the same. Alternatively, it represents a hydrogen atom, an alkyl group or an aryl group having 1 to 20 carbon atoms.) (C) It relates to a polymer composition containing an organic solvent. Here, as the aromatic polymer (A), polyimide,
At least one member selected from the group consisting of polyarylene ether, polyarylene, polyether sulfone, polyether ketone, polyquinoline, polyquinoxaline and polyoxadiazole, or phenylene comprising a repeating structural unit represented by the formula (2) Group-containing (co) polymers are preferred.

[0005]

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In the formula (2), X is -CQQ'- (where Q and Q 'are the same or different and represent a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group). And R ^{1 to} R ²⁰ are the same or different and represent a hydrogen atom, a halogen atom or a monovalent organic group, and Y is —O
-, -CO-, -COO-, -CONH-, and -S
At least one selected from the group consisting of O ₂ — groups, 1 is 5 to 100 mol%, m is 0 to 95 mol%, and n is 0 to 95 mol%
Mol% (l + m + n = 100 mol%), t is 0
Or 1. ]

In the equation (2), l is 50 to 10
0 mol%, m is preferably 0 to 50 mol%, and n is preferably 100 to 50 mol (provided that l + m + n = 100 mol%). Further, the triazene compound (B) is preferably an aromatic compound, and particularly preferably a tetratriazene compound represented by the formula (3).

[0008]

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Wherein R to R ′ are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an aryl group, and Z is a group having 1 to 20 carbon atoms.
Alkyl group, aryl group, alkenyl group, having 1 to 1 carbon atoms
P is an integer of 0 to 4; at least one selected from the group consisting of 20 halogenated alkyl groups and halogen atoms. )

Next, the present invention relates to a method for forming a cured film, which comprises applying the above-mentioned polymer composition to a substrate and heat-treating the substrate at 300 to 500 ° C. The present invention also relates to a cured product obtained by curing the polymer composition. As a use of the cured product, an insulating film or an optical film is preferable.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Aromatic polymer (A) The aromatic polymer is a polymer compound having an aromatic ring in a repeating structural unit. As the aromatic polymer (A), at least one selected from the group consisting of polyimide, polyarylene ether, polyarylene, polyether sulfone, polyether ketone, polyquinoline, polyquinoxaline and polyoxadiazole,
Alternatively, a phenylene group-containing (co) compound represented by the above formula (2)
Although a polymer is mentioned, a phenylene group-containing (co) polymer is preferable.

Phenylene group-containing (co) polymer; The phenylene group-containing (co) polymer has a repeating structural unit represented by the above formula (2). Hereinafter, in the formula (2), the structural unit enclosed by l is also referred to as “structural unit l”, the structural unit enclosed by m is referred to as “structural unit m”, and the structural unit enclosed by n is also referred to as “structural unit n”. Say.

In the formula (2), the monomer constituting the structural unit 1 (hereinafter also referred to as “monomer 1”) includes
2,2-bis (4-methylsulfonyloxyphenyl)
Hexafluoropropane, 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, 2,2-bis (4-methylsulfonyloxyphenyl) propane, 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) propane, 2,2 -Bis (4-methylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-
Bis (4-methylsulfonyloxy-3-fluorophenyl) propane, 2,2-bis (4-methylsulfonyloxy-3,5-difluorophenyl) propane, 2,
2-bis (4-trifluoromethylsulfonyloxyphenyl) propane, 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy) Phenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) propane, 2,2-
Bis (4-phenylsulfonyloxy-3-propenylphenyl) propane, 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane,
2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane, 2,2-bis (p
-Tolylsulfonyloxyphenyl) propane, 2,2
-Bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane, 2,2-
Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane, 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane, bis (p-tolylsulfonyloxy-3-fluoro) Phenyl) propane, bis (p-tolylsulfonyloxy)
3,5-difluorophenyl) propane, 9,9-bis (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) phenyl Methane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis (4-trifluoromethylsulfonyloxyphenyl) 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-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-trifluoromethylsulfone) Phonyloxy-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-trifluoromethylsulfonyloxy-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),
2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane, 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-phenylsulfur Phonyloxy-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,
2,2-bis (p-tolylsulfonyloxyphenyl)
Hexafluoropropane, 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-bis (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-dimethyl) Phenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane, bis (p-tolylsulfonyloxy-3,5-difluoro) Phenyl) 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. The monomers l can be used alone or in combination of two or more.

In the formula (2), examples of the monomer which may constitute the structural unit m (hereinafter also referred to as “monomer m”) include, for example, 4,4′-dimethylsulfonyloxybiphenyl, 4,4 ′ -Dimethylsulfonyloxy-3,3'-dipropenylbiphenyl, 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-methylsulfonyloxyoctafluorobiphenyl, 3,3'-diallyl-4,4'-bis (4-fluorobenzene Sulfonyloxy) biphenyl, 4,4'-dichloro-2,2'-trifluoromethylbiphenyl, 4,4'-dibromo-2,2'-trifluoromethylbiphenyl, 4,4'-diiodo-2,
Examples include 2'-trifluoromethylbiphenyl, bis (4-chlorophenyl) sulfone, 4,4'-dichlorobenzophenone, and 2,4-dichlorobenzophenone. The monomers m can be used alone or in combination of two or more.

Further, in the formula (2), examples of the monomer which may constitute the structural unit n (hereinafter also referred to as “monomer n”) include, for example, p-dichlorobenzene, p-dichlorobenzene,
Dibromobenzene, p-diiodobenzene, p-dimethylsulfonyloxybenzene, 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, 1,4-diiodo-
2,3,5,6-tetrafluorobenzene, 2,5-dichlorobenzoic acid, 2,5-dibromobenzoic acid, 2,5-
Methyl dichlorobenzoate, methyl 2,5-dibromobenzoate, t-butyl 2,5-dichlorobenzoate, 2,5
-T-butyl-dibromobenzoate, 3,6-dichlorophthalic anhydride and the like, and preferably p-
Dichlorobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5-dichlorobenzotrifluoride, 2,5-dichlorobenzophenone, 2,5-dichlorophenoxybenzene and the like.

Further, as the monomer n, for example,
m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 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-diiodobenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxy Phenyl, 3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2, Methyl 4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, 3,
Methyl 5-dibromobenzoate, methyl 2,4-dibromobenzoate, t-butyl 2,4-dichlorobenzoate,
Examples thereof include t-butyl 3,5-dichlorobenzoate, t-butyl 2,4-dibromobenzoate, and t-butyl 3,5-dibromobenzoate.
Dichlorobenzene, 2,4-dichlorotoluene, 3,5
-Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dichlorobenzophenone, 2,4-dichlorophenoxybenzene and the like.

In addition to the above monomers 1 to n, for example, o-dichlorobenzene, o-dibromobenzene, o-dichlorobenzene,
-Diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3 2,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxybenzene,
3,4-dichlorobenzotrifluoride, 3,4-dibromobenzotrifluoride, 3,4-diiodobenzotrifluoride, 1,2-dibromo-3,4,5
6-Tetrafluorobenzene, 4,5-dichlorophthalic anhydride and the like can be copolymerized.

The proportion of repeating structural units in the phenylene group-containing (co) polymer is such that in the above formula (2), 1 is 5 to 5.
100 mol%, m is 0 to 95 mol%, n is 0 to 95 mol%, preferably 1 is 50 to 100 mol%, and m is 0 to 5 mol%.
0 mol%, n is 0 to 50 mol (provided that l + m + n = 1
00 mol%).

The catalyst used in the production of the phenylene group-containing (co) polymer used in the present invention is preferably a catalyst system containing a transition metal compound, such as a transition metal salt and a ligand, Alternatively, a transition metal (salt) to which a ligand is coordinated, and a reducing agent may be used as essential components, and a “salt” may be added in order to increase the polymerization rate.

Here, the transition metal salt includes nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium chloride;
Examples include palladium compounds such as palladium bromide and palladium iodide, iron compounds such as iron chloride, iron bromide and 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. Phenylphosphine and 2,2'-bipyridine are preferred. The ligand is
One type may be used alone, or two or more types may 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 above-mentioned reducing agent which can be used in such a catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium and calcium, and zinc and manganese are preferred. These reducing agents can be used after being activated by contact with an acid or an organic acid.

The "salt" usable in such a catalyst system includes sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, potassium fluoride,
Potassium compounds such as potassium chloride, potassium bromide, potassium iodide, and potassium sulfate; and ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate can be given. But sodium bromide,
Preferred are sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide.

The proportion of each component used in such a catalyst system is such that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is based on 1 mol of the monomer 1 or the total amount of the monomers 1 to n. Usually, it is 0.0001 to 10 mol, preferably 0.01 to 0.5 mol. If the amount is less than 0.0001 mol, the polymerization reaction does not proceed sufficiently, while if it exceeds 10 mol, the molecular weight may be reduced.

When a transition metal salt and a ligand are used in such a catalyst system, the ligand is used in an amount of usually 0.1 to 100 mol, preferably 1 to 100 mol, per mol of the transition metal salt. 10 to 10 mol. If the amount is less than 0.1 mol, the catalytic activity becomes insufficient.
There is a problem that the molecular weight decreases.

The proportion of the reducing agent used in the catalyst system is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the monomer 1 or the total amount of the monomers 1 to n.
Is a mole. If the amount is less than 0.1 mol, the polymerization does not proceed sufficiently, and if it exceeds 100 mol, the purification of the (co) polymer obtained may be difficult.

Further, when a “salt” is used in the catalyst system,
The proportion of the monomer 1 or the monomer 1 to
It is usually 0.001 to 100 mol, preferably 0.01 to 1 mol, per 1 mol of the total amount of n. If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, and if it exceeds 100 mol, it may be difficult to purify the (co) polymer obtained.

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, 1-methyl-2-pyrrolidone are preferred. These polymerization solvents are preferably used after being sufficiently dried.

The concentration of the monomer 1 or the total amount of the monomers 1 to n in the polymerization solvent is usually 1 to 100% by weight, preferably 5 to 40% by weight.

The polymerization temperature when polymerizing the (co) polymer of the present invention is usually 0 to 200 ° C., preferably 50 to 200 ° C.
80 ° C. The polymerization time is usually 0.5 to 10
0 hours, preferably 1 to 40 hours. The phenylene group-containing (co) polymer used in the present invention generally has a weight average molecular weight in terms of polystyrene of 1,000 to 1,
1,000,000.

(B) Triazene Compound The (B) triazene compound of the present invention is a compound having three or more triazyl groups represented by the above formula (1) in one molecule. In the formula (1), R to R ′ are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an aryl group. Here, as the alkyl group having 1 to 20 carbon atoms, a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group,
n-hexyl group, n-heptyl group, n-octyl group, n
-Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. Examples of the aryl group include a phenyl group.

Preferred examples of the triazene compound (B) include a tetratriazene compound represented by the above formula (3). Here, in the formula (3), Z represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkenyl group,
It is at least one selected from the group consisting of a halogenated alkyl group having 1 to 20 carbon atoms and a halogen atom. Here, examples of the alkyl group and aryl group having 1 to 20 carbon atoms include the same groups as R to R ′. Examples of the alkenyl group include a propenyl group. 1-20 carbon atoms
Examples of the halogenated alkyl group include a trifluoromethyl group. Examples of the halogen atom include a fluoro group. In the equation (3), p is
It is an integer of 0 to 4, and the value of p in each benzene skeleton may be different. Note that R and R 'in equation (3) are the same as R and R' in equation (1).

Specific examples of the tetratriazene compound represented by the above formula (3) of the present invention include 2,7- (3,3-
Dimethyltriazenyl) -9,9-bis [4- (3,3
-Dimethyltriazenyl) phenyl] fluorene, 2,
7- (3,3-dimethyltriazenyl) -9,9-bis [3-methyl-4- (3,3-dimethyltriazenyl)
Phenyl] fluorene, 2,7- (3,3-dimethyltriazenyl) -9,9-bis [3-phenyl-4-
(3,3-dimethyltriazenyl) phenyl] fluorene, 2,7- (3,3-dimethyltriazenyl) -9,
9-bis [3-propenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7- (3,3
-Dimethyltriazenyl) -9,9-bis [3-fluoro-4- (3,3-dimethyltriazenyl) phenyl]
Fluorene, 2,7- (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3,
3-dimethyltriazenyl) phenyl] fluorene,
2,7- (3,3-dimethyltriazenyl) -9,9-
Bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene;

The tetratriazene compound represented by the formula (3) used in the present invention can generate a tetrafunctional phenyl radical by heating. Excellent effect on crosslinking with polymer.

The tetratriazene compound (B) represented by the formula (3) used in the present invention can be produced by the following steps (a) to (c). (A) A fluorene compound represented by the formula (4) (hereinafter, also referred to as “compound (4)”) is hydrochlorinated, and a hydrochloride of the fluorene compound represented by the formula (5) (hereinafter, “compound (5)”)
1st process. (B) A second step in which the hydrochloride of the fluorene compound represented by the formula (5) is diazotized to obtain a diazodium salt of a fluorene compound represented by the formula (6) (hereinafter, also referred to as “compound (6)”). (C) A third step in which a diazodium salt of a fluorene compound represented by the formula (6) is triazene-converted into a tetratriazene compound represented by the formula (3) (hereinafter, also referred to as “compound (3)”).

[0037]

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[Wherein R to R ', Z and p are the same as in the formula (3). Hereinafter, a method for producing a tetratriazene compound will be described. (A) First step: The first step is a step of hydrochlorinating a fluorene compound represented by the formula (4) to form a hydrochloride of the fluorene compound represented by the formula (5). Here, the hydrochlorination is performed using a hydrochloric acid gas or an aqueous hydrochloric acid solution in a solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, or N-methylpyrrolidone. In this case, the amount of hydrochloric acid used is the same as that of compound (4) 1
It is usually 4.0 to 12.0 mol, preferably 4.0 to 5.0 mol, per mol. The reaction conditions at this time are a temperature of 0 to 100 ° C., preferably 10 to 40 ° C., and a reaction time of 0.5 to 300 minutes, preferably about 5 to 30 minutes. By the first step, the compound (4) is converted into a hydrochloride of the fluorene compound represented by the formula (5) [compound (5)] by hydrochlorination.

(B) Second step: The second step is a step of diazotizing a hydrochloride of a fluorene compound [compound (5)] to form a diazonium salt of a fluorene compound [compound (6)]. Here, in the diazotization, after the first step, a diazotization reaction is performed using a diazotizing agent such as sodium nitrite. The amount of the diazotizing agent to be used is generally 1 to 12 mol, preferably 4 to 8 mol, per 1 mol of compound (5). The reaction conditions at this time are as follows:
30 ° C, preferably -10 to 15 ° C, reaction time 0.1 to
It is 5 hours, preferably about 0.5 to 2.5 hours. In the second step, the hydrochloride of the fluorene compound [compound (5)] is diazotized to form a diazonium salt of the fluorene compound [compound (6)].

(C) Third step: In the third step, a diazonium salt of a fluorene compound [compound (6)] is triazene-treated, and the tetratriazene compound of the present invention represented by the formula (3) [compound (3)] ]. Here, after the second step, the triazene conversion is continued by RR′NH · HC
A triazenation reaction is carried out using a triazetizing agent represented by l (where R and R 'are the same as R and R' in the formula (3)). Specific examples of the above-mentioned triazene agent include dimethylamine hydrochloride, diethylamine hydrochloride, diethylamine and the like. The amount of the triazene agent to be used is generally 1 to 12 mol, preferably 4 to 10 mol, per 1 mol of compound (6). The reaction conditions at this time are a temperature of -50 to 50 ° C, preferably -10 to 30 ° C,
The reaction time is 0.5 to 60 minutes, preferably about 1 to 30 minutes. In the third step, the diazonium salt of the fluorene compound [compound (6)] is triazinated to give the tetratriazene compound of the present invention [compound (3)]. Hereinafter, specific examples of the method for producing the tetratriazene compound of the present invention will be described.

[0041]

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In the present invention, the tetratriazene compound used as the component (B) generates a tetrafunctional phenyl radical upon heating, and thus is useful as a crosslinking agent for the aromatic polymer (A). The amount of the triazene compound (B) such as the tetratriazene compound represented by the formula (3) is usually 1 to 500 parts by weight, preferably 10 to 10 parts by weight, per 100 parts by weight of the aromatic polymer (A). 2
00 parts by weight. If the amount is less than 1 part by weight, the crosslinking effect is poor, and the solvent resistance and mechanical strength of the cured film are insufficient. On the other hand, if it exceeds 500 parts by weight, the coatability deteriorates.

(C) Organic Solvent As the solvent for dissolving the aromatic polymer (A), in particular, the phenylene group-containing (co) polymer represented by the above formula (2), for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide , N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2
-Pyrrolidone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether,
Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl amyl ketone, 4-hydroxy-4
-Methyl-2-pentanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, chloroform, Methylene chloride and the like can be mentioned, preferably cyclohexanone,
N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, γ-butyrolactone, ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and methyl amyl ketone.

The amount of the organic solvent (C) is usually 50 to 10,000 based on 100 parts by weight of the aromatic polymer (A).
00 parts by weight, preferably 100 to 1,900 parts by weight. When the amount is less than 5 parts by weight, a coating film having a sufficient thickness cannot be obtained. On the other hand, when it exceeds 10,000 parts by weight, the film does not flow sufficiently and a uniform coating film may not be obtained.

Incidentally, additives can be added to the polymer composition of the present invention, if necessary. Examples of the additive include a silane coupling agent, a methylolated melamine, and a surfactant.

The polymer composition of the present invention is excellent in storage stability as a solution, does not generate cracks during curing, and has excellent adhesion to various substrates, and has heat resistance and low dielectric constant. Excellent in solvent resistance, mechanical strength, etc. Therefore, the polymer composition of the present invention can be suitably used as an insulating material, an optical material, and the like. Examples of the insulating material include an interlayer insulating film or a flattening film between multilayer wirings of a semiconductor element, a protective film or an electric insulating film of various electric devices and electronic components, a printed board material, a sealing material, and the like. Examples of the optical material include a low-refractive material, an antireflection film, and an optical waveguide material. As other uses, it is useful as a liquid crystal alignment film, a gas permeable film, and the like, as well as an adhesive or a paint requiring heat resistance.

Further, the polymer composition of the present invention is applied to an appropriate substrate which has been previously subjected to a mold release treatment to form a thermosetting thin film, and the thin film is forcibly peeled off from the substrate before curing. A curable film can be obtained, and this thermosetting film is useful as a heat-resistant adhesive film for electric equipment and electronic parts. Alternatively, the thermosetting thin film forcibly peeled off from the substrate is cured, or the polymer thin film formed on an appropriate substrate previously subjected to a mold release treatment is heated and cured. By forcibly peeling from the cured film, a cured film can be obtained.

Further, a solution of the polymer composition of the present invention was impregnated into a suitable cloth such as a glass cloth and then dried, or a prepreg dried or a resin-free resin composition was impregnated into a suitable cloth such as a glass cloth. Prepreg is
It is also useful as a laminated material such as a copper-clad laminate. The polymer composition of the present invention is also useful as a thermosetting molding material in the form of, for example, a powder or a pellet.

The substrate used for forming a film from the polymer composition of the present invention is not particularly limited. For example, iron, nickel, stainless steel, titanium,
Metals such as aluminum, copper and various alloys; silicon nitride,
Ceramics such as silicon carbide, sialon, aluminum nitride, boron nitride, boron carbide, zirconium oxide, titanium oxide, alumina, silica, and mixtures thereof; S
semiconductors such as i, Ge, SiC, SiGE, GaAs;
Ceramic materials such as glass and porcelain; heat-resistant resins such as aromatic polyamide, polyamide imide, polyimide and wholly aromatic polyester;

The above substrate may be subjected to a release treatment in advance, if desired, and may be subjected to a chemical treatment with a silane coupling agent, a titanium coupling agent or the like, a plasma treatment, an ion plating, a sputtering, Appropriate pretreatments such as a phase reaction method and vacuum deposition can also be performed. When applying the polymer composition of the present invention to the above substrate, an appropriate coating means such as a spin coating method, a roll coating method, a casting coating method, a dip coating method, and a spray coating method can be employed. Further, the coating thickness can be appropriately controlled by selecting the coating means and adjusting the solid content concentration and the viscosity of the composition solution. The amount of the polymer composition of the present invention applied to the substrate is usually 0.01 to 100 μm in a dry film thickness.
m, preferably about 0.5 to 20 μm. As described above, in order to obtain a cured product (cured film) of the polymer composition of the present invention, the polymer composition of the present invention is applied to a substrate by spin coating or the like, and heated at a temperature of 50 to 200 ° C. Further, heating may be performed at 200 to 450 ° C. for about 10 minutes to 3 hours in an atmosphere of air, nitrogen, vacuum, or argon.

[0051]

The present invention will now be described more specifically with reference to examples. Parts and% in the examples are on a weight basis. Various evaluation items in the examples were measured as follows.

The weight average molecular weight (MPC) was measured by gel permeation chromatography (GPC), and the weight average molecular weight (M
w) was measured. An aluminum electrode pattern was formed on the obtained film by a vapor deposition method to prepare a sample for dielectric constant measurement. The dielectric constant of the coating film of this sample was measured at a frequency of 100 kHz by a CV method using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd.

The above film-forming composition was added to a heat-resistant aluminum pan, and then
Using a hot plate maintained at a temperature of 0 ° C., the aluminum pan to which the composition for film formation was added was heated for 5 minutes to disperse the organic solvent. Then, the aluminum pan is heated for 5 minutes using a hot plate maintained at a temperature of 200 ° C., and further heated for 30 minutes under nitrogen using an oven maintained at a temperature of 400 ° C. to cure the film-forming composition. I let it. The film-forming composition thus obtained was heated at a rate of 10 ° C./min in a nitrogen atmosphere using an SSC5200 thermogravimetric analyzer (TGA) manufactured by Seiko Instruments Inc. The 5% weight loss temperature of the film forming composition was measured.

Solvent resistance The substrate on which the coating film is formed is treated with cyclohexanone at 90 ° C. for 1 hour.
After immersion for 0 minutes, the residual film ratio was evaluated by the following equation. (Residual film ratio) = (Film thickness after immersion) / (Film thickness before immersion) × 1
00 (%) The modulus of elasticity of the obtained film was measured by a continuous stiffness measurement method using a nano indenter XP (manufactured by Nano Instruments).

Synthesis Example 1 (Synthesis of tetratriazene compound) 20 g of 2,7-diamino-9,9-bis (4-aminophenyl) fluorene was dissolved in 250 ml of N, N-dimethylacetamide (DMAc), and 36% hydrochloric acid was added. Aqueous solution 3
After adding 2.1 g, reprecipitation was performed using 2 liters of i-propanol, and the precipitate was filtered and dried to obtain 2,7-propanol.
The dihydro-9,9-bis (4-aminophenyl) fluorene hydrochloride was obtained. Next, 400 ml of this hydrochloride was added.
Of tetrahydrofuran and 2N hydrochloric acid aqueous solution 250
21.9 g of sodium nitrite
A / 500 ml aqueous solution was added dropwise over 30 minutes while maintaining the temperature at 0 ° C or lower, and the mixture was stirred for 1 hour. Then, an aqueous solution of sodium carbonate was slowly added to adjust the pH to 6, and then 32.4 g of dimethylamine hydrochloride and 67.3% of sodium carbonate.
g and ice water (750 ml) and stirred vigorously for 10 minutes. Next, 250 ml of methylene chloride was added,
The organic layer was washed twice with water, dried over magnesium sulfate, decolorized with activated carbon, recrystallized with chloroform, and then treated with 2,7- (3,3-dimethyltriazenyl)-
9,9-bis [4- (3,3-dimethyltriazenyl)
9 g of [phenyl] fluorene crystals were obtained. The reaction formula of the synthesis example of this tetratriazene compound is as described in the above (Chemical formula 9). ¹ H-NMR, IR of this compound
The chart is shown in FIGS.

Synthesis Example 2 (Synthesis of Aromatic Polymer Compound) An inner volume 500 equipped with an argon gas inlet tube and a thermometer
7.5 g of sodium iodide in a 3-ml three-necked flask,
1.3 g of anhydrous nickel chloride, triphenylphosphine 1
5.7 g, zinc powder 45.8 activated with acetic acid
g, 9,9-bis (4-methylsulfonyloxyphenyl) fluorene (hereinafter also referred to as “FLMs”) 40.5
g, bis (4-methylsulfonyloxyphenyl) ether (hereinafter also referred to as “PEMs”) 6.80 g,
After drying under vacuum for 24 hours, the inside of the three-necked flask was filled with argon gas. Subsequently, 150 ml of dry N, N-dimethylacetamide was added, and the mixture was stirred at 70 ° C. under a stream of argon, whereby the reaction solution turned brown. After allowing the reaction to proceed at 70 ° C. for 20 hours,
500 ml of 6% hydrochloric acid aqueous solution and 200 ml of methanol
And the precipitate was collected. The obtained precipitate was dissolved in chloroform, extracted with a 2N aqueous hydrochloric acid solution, and the chloroform layer was poured into methanol.
The precipitate was recovered and dried to obtain a white powdery polymer. Table 1 shows the physical properties of this polymer.

Synthesis Examples 3 and 4 (Synthesis of Aromatic Polymer Compound) Except that the monomer species and the charge ratio were changed as shown in Table 1,
It was synthesized in the same manner as in Synthesis Example 1. Table 1 shows the physical properties of these polymers.

[0058]

[Table 1]

* 1) TPMs; bis (4-methylsulfonyloxyphenyl) diphenylmethane * 2) AFMs; 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane

Synthesis Example 5 (Synthesis of Polyimide) 4,4′- was placed in a 100 ml 3-neck flask equipped with a stirring motor, a Dean-Stark tube, and a nitrogen inlet tube.
Oxydianiline (ODA) (1.001 g) was dissolved in m-cresol (25 ml), followed by stirring with 2,2 ',
3,3'-biphenyltetracarboxylic dianhydride (i-
1.471 g of BPDA) and a few drops of isoquinoline were added. As the temperature was increased in a nitrogen atmosphere, the monomers were dissolved by 100 ° C. to form a homogeneous system. Further, when the temperature was gradually raised to 200 ° C. within one hour, water was eliminated by the condensation reaction, and the viscosity of the polymerization system was increased. further,
The reaction was continued for 5 hours to terminate the polycondensation reaction. The polymerization system maintained a uniform solution even after standing to cool. Polymerization solution 1
The polymer was precipitated by dropping into 1 liter of methanol and collected by filtration. Further, in order to completely remove the polymerization solvent, Soxhlet extraction was performed with methanol, and the powder polymer was dried under vacuum. The polymer was obtained in almost quantitative yield. As for the structure of the polymer, it was confirmed from the infrared absorption spectrum and the ¹ H-NMR spectrum that a polyimide was obtained.

Examples 1 to 6, Comparative Example 1 (Preparation of Composition and Crosslinking of Aromatic Polymer) To 100 parts of the aromatic polymer synthesized in the above Synthesis Example, 900 parts of cyclohexanone were obtained in Synthesis Example 1. The tetratriazene compound was added to the solution shown in Table 2 to form a solution,
This is applied to each silicon wafer with a dry film thickness,
Spin coat to 1 µm, 2 minutes at 80 ° C,
After firing at 200 ° C. for 2 minutes on a hot plate, the temperature was raised from 240 ° C. to 320 ° C. over 1 hour in a nitrogen purged oven, and firing was performed at 400 ° C. for 30 minutes. Table 2 shows the evaluation results of the obtained coating films.

[0062]

[Table 2]

[0063]

According to the present invention, a cured product excellent in heat resistance, low dielectric property, solvent resistance, mechanical strength, etc. is obtained by blending a novel triazene compound as a crosslinking agent into an aromatic polymer. (Cured film) can be provided.

[Brief description of the drawings]

FIG. 1 shows the tetratriazene compound obtained in Synthesis Example 1.
It is a < ¹ > H-NMR chart.

FIG. 2 is an IR chart of the tetratriazene compound obtained in Synthesis Example 1.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kohei Goto 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 4J002 CE001 CF001 CH061 CH091 CL001 CM031 CM041 CN031 EQ036 FD146 GP00 GQ01

Claims (10)

[Claims] (A) an aromatic polymer having an aromatic ring in a repeating structural unit; (B) a triazene compound having three or more groups represented by the formula (1) in one molecule; = N-NRR '(1) wherein R and R' are the same or different and each represent a hydrogen atom, an alkyl group or an aryl group having 1 to 20 carbon atoms. Polymer composition containing. (A) The aromatic polymer is polyimide,
The polymer composition according to claim 1, which is at least one selected from the group consisting of polyarylene ether, polyarylene, polyether sulfone, polyether ketone, polyquinoline, polyquinoxaline, and polyoxadiazole. 3. The polymer composition according to claim 1, wherein (A) the aromatic polymer is a phenylene group-containing (co) polymer comprising a repeating structural unit represented by the formula (2). Embedded image [In the formula (2), X represents -CQQ'- (where Q and Q 'are the same or different and represent a halogenated alkyl group, alkyl group, hydrogen atom, halogen atom or aryl group)
And / or a fluorenylene group, wherein R ^{1 to} R ²⁰ are the same or different and represent a hydrogen atom, a halogen atom or a monovalent organic group, and Y represents —O—, —CO
—, —COO—, —CONH—, and —SO ₂ —, at least one member selected from the group consisting of
Mol%, m is 0 to 95 mol%, n is 0 to 95 mol% (provided that l + m + n = 100 mol%), and t is 0 or 1. ] 4. The polymer composition according to claim 3, wherein 1 in the formula (2) is 50 to 100 mol%, m is 0 to 50 mol%, and n is 100 to 50 mol (provided that l + m + n = 100 mol%). object. 5. The polymer composition according to claim 1, wherein (B) the triazene compound is an aromatic compound. 6. The compound according to claim 1, wherein (B) the triazene compound is a tetratriazene compound represented by the formula (3).
A polymer composition as described. Embedded image (Wherein R to R ′ are the same or different, and are at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an aryl group, and Z is an alkyl group or an aryl group having 1 to 20 carbon atoms. , An alkenyl group, a halogenated alkyl group having 1 to 20 carbon atoms, and a halogen atom, and p is an integer of 0 to 4.) 7. A method for forming a cured film, comprising applying the polymer composition according to claim 1 to a substrate and heat-treating the substrate at 300 to 500 ° C. 8. A cured product obtained by curing the polymer composition according to any one of claims 1 to 6. 9. The cured product according to claim 8, which is an insulating film. 10. The cured product according to claim 8, which is an optical film.