JP2002256146A - Material for insulation film, coating varnish for insulation film, insulation film, and semiconductor with the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for an insulation film excellent in thermal characteristic, electric characteristic, and water absorption in semiconductor usage, especially enabling low permittivity while keeping excellent heat resistance, and an insulation film using the composition. SOLUTION: This resin composition for an insulation film contains as essential components a copolymer prepared by reacting a polyamide having a repeating unit represented by general formula (A) and a reactive oligomer having a substituent reactive with the carboxy group, amino group, or hydroxy group in the polyamide, and an oligomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is used for applications such as interlayer insulating films for semiconductors, protective films, interlayer insulating films for multilayer circuits, cover coats for flexible copper clad boards, solder resist films, liquid crystal alignment films, etc. The present invention relates to an insulating film material and an insulating film which are excellent in electrical characteristics, thermal characteristics, and mechanical characteristics.

[0002]

2. Description of the Related Art In a semiconductor material, an inorganic material, an organic material, and the like are used in various parts depending on required characteristics. For example, as an interlayer insulating film for a semiconductor, an inorganic oxide film such as silicon dioxide manufactured by a chemical vapor deposition method is used. However, in recent years, the speeding up of semiconductors,
With the increase in performance, the inorganic oxide film as described above has a problem that the relative dielectric constant is high. As one of the improvement means, application of an organic material is being studied.

[0003] As organic materials for semiconductor applications, heat resistance,
A polyimide resin having excellent electrical characteristics, mechanical characteristics, and the like is used, and is used for a solder resist, a coverlay, a liquid crystal alignment film, and the like. However, in general, a polyimide resin has two carbonyl groups on an imide ring, and thus has problems in water absorption resistance and electrical characteristics. In order to solve these problems, attempts have been made to improve water absorption resistance and electric properties by introducing fluorine or a fluorine-containing group into an organic polymer, and some of them have been put to practical use.
In addition, there is a polybenzoxazole resin exhibiting better performance with respect to heat resistance, water absorption resistance, and electrical characteristics than polyimide resin, and application to various fields has been attempted. For example, those having a structure composed of 4,4'-diamino-3,3'-dihydroxybiphenyl and terephthalic acid, and those having a structure composed of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and terephthalic acid And the like.

However, more severe heat resistance, electrical characteristics,
In the advanced field where improvement of water absorption and the like is required, a material satisfying all such requirements has not yet been obtained. In other words, although excellent heat resistance is exhibited, electric characteristics such as dielectric constant are not sufficient. Further, although the electric characteristics are improved by introducing fluorine, problems such as lowering of heat resistance are caused. In particular, when an organic material is used as an interlayer insulating film for semiconductors, heat resistance, mechanical properties, and water absorption comparable to inorganic materials are required, and further lowering the dielectric constant is required.

[0005] In response to such demands for higher performance, a method of reducing the density and lowering the relative dielectric constant by providing micropores in an inorganic oxide film, which is an inorganic material, has been studied. I have. The relative dielectric constant of air is 1, and reducing the relative dielectric constant by introducing air into the film is described in US Pat. No. 3,883,452 to Scheuerlein et al. (Issued May 13, 1975). Inferred from the method of producing a foamed polymer having an average pore size of 20 μm. However, in order to be an effective insulator by introducing air into the film, the film thickness must be on the order of sub-micrometer, have an averaged relative dielectric constant, and the mechanical properties of the film itself The properties must also be able to withstand each step. At present, an inorganic material that can overcome such a problem has not yet been obtained.

On the other hand, in the case of organic materials, techniques for obtaining submicrometer-order micropores are disclosed in Hedr.
U.S. Pat. No. 5,776,990 (July 1998)
(Published on May 7) discloses that a resin having fine pores on the order of submicrometers is produced from a block copolymer. It is known that block copolymers are phase-separated on the order of submicrometer (T. Hash
imoto, M.Shibayama, M.Fujimura and H.Kawai, "Microp
hase Separation and the Polymer-polymer Interphase
in Block Polymers "in" Block Copolymers-Science
and Technology ", p.63, Ed.By DJMeier (Academi
c Pub., 1983), which indicates that polymers with low ceiling temperatures can be easily decomposed,
It is generally well known. However, in order to obtain a resin composition having micropores while satisfying not only the relative dielectric constant but also the mechanical properties, electrical properties, water absorption resistance, and heat resistance, it is necessary to use a resin, a blocking technique, and a thermally decomposable component. The choice of combinations is very limited, and none of them can satisfy all the characteristics.

[0007]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies in view of the above-mentioned conventional problems, and as a result, have found that a copolymer obtained by reacting a polyamide having a specific structure with a reactive oligomer. The inventors have found that a material for an insulating film containing a coalesced substance and an oligomer as essential components can satisfy the object of the present invention.
An object of the present invention is to provide a resin composition for an insulating film that maintains excellent heat resistance and enables a low dielectric constant in semiconductor applications, and an insulating film using the same.

[0008]

That is, the present invention provides a polyamide having a repeating unit represented by the general formula (A), and a carboxyl group, an amino group,
Or a copolymer (C) obtained by reacting a reactive oligomer (B) having a substituent capable of reacting with a hydroxyl group, and an oligomer (D) as an essential component. Further, the insulating film material and an organic solvent capable of dissolving or dispersing the insulating film material, the coating varnish capable of forming an insulating film, heat treatment of the coating varnish, condensation reaction and An insulating film made of a resin layer having polybenzoxazole as a main structure obtained by a crosslinking reaction and having fine pores, and a semiconductor using the insulating film.

[0009]

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Where m and n are m> 0, n ≧ 0, 2 ≦
m + n ≦ 1000 and 0.05 ≦ m / (m + n) ≦ 1
Is an integer satisfying the relationship X is selected from the structure represented by the formula (E), and Y is the formula (F-1), the formula (F-2),
It represents at least one group selected from the group consisting of the structures represented by Formula (G-1), Formula (G-2), Formula (H), and Formula (I). Further, X in the general formula (A) may be the same or different. Z represents a group selected from the structure represented by the formula (J). In the general formula (A), the arrangement of the repeating units may be block-like or random.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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In the formulas (E) and (J), X ₁ represents a group selected from the structure represented by the formula (K). Equation (G-
R in 1) and Formula (G-2) represents a naphthalene group, a phenyl group, or an alkyl group. In the structures represented by the formulas (E) to (J), a hydrogen atom on the benzene ring is
It may be substituted with at least one group selected from the group consisting of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, fluorine atom, and trifluoromethyl group. .

[0020]

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[0021]

BEST MODE FOR CARRYING OUT THE INVENTION First, the present invention relates to ethynyl and phenyl which are crosslinked by heating to the main chain of a polyamide (A) unit in a copolymer (C), which is an essential component of an insulating film material. Introduction of at least one skeleton of ethynyl, alkylethynyl, biphenylene, and internal acetylene, conversion of amide group to polybenzoxazole by ring-closing reaction, and crosslinking reaction of ethynyl, phenylethynyl, alkylethynyl, biphenylene, and internal acetylene skeleton By making the resin structure three-dimensional,
That a resin with high heat resistance can be obtained,

Second, the reactive oligomer (B) and the oligomer (D) in the copolymer (C), which are essential components, are
The resin is thermally decomposed and volatilized during heating to form micropores in the resin film having a polybenzoxazole resin as a main structure. Third, the reactive oligomer (B) is made of a copolymer (C) ) Is a component of
The amount introduced into the copolymer (C) is limited by its molecular weight and reactivity, but by using the oligomer (D) together,
As a component that thermally decomposes and evaporates when the resin is heated, an arbitrary amount of oligomer can be introduced into the insulating film material, whereby an arbitrary amount of oligomer can be introduced into the resin film having a polybenzoxazole resin as a main structure. The gist of the present invention is to form micropores and, as a result, to obtain a porous insulating film having both heat resistance and electrical characteristics.

In the present invention, the polyamide unit in the copolymer (C), which is an essential component, comprises at least one bisaminophenol compound having any one of the structures represented by the formula (E). , Formula (F-1), Formula (F-
2) using at least one dicarboxylic acid having any one of the structures represented by the formulas (G-1), (G-2), (H) and (I), or As the dicarboxylic acid, a combination of the above dicarboxylic acid and a dicarboxylic acid having any of the structures represented by the formula (J) is used, and the conventional acid chloride method, activated ester method, dehydration of polyphosphoric acid, dicyclohexylcarbodiimide, and the like are performed. It can be obtained by a method such as a condensation reaction in the presence of a condensing agent.

As the bisaminophenol compound having a structure represented by the formula (E) used in the present invention, 2,4
-Diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-
(Amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 3,3′- Diamino-4,4
'-Dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 3,3'
-Diamino-4,4'-dihydroxybiphenyl, 4,4 '
-Diamino-3,3'-dihydroxybiphenyl, 9,9
-Bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis (4-
((3-amino-4-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis ((4-amino-3-hydroxy) phenyl)) fluorene, 9,9-bis ((3-amino-4-hydroxy ) Phenyl)) fluorene, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 2,2-bis (3-amino-4-
Hydroxy-2-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-2-
Trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3
-Hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-6)
-Trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) propane, 2,2-bis (3-amino-
4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3
-Hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-
(Hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4- (Hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4- (Hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 3,3′-diamino-4,4′- Dihydroxy-
2,2'-bis (trifluoromethyl) biphenyl, 4,
4'-diamino-3,3'-dihydroxy-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-bis (trifluoromethyl) Biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4'-dihydroxy-6,
6'-bis (trifluoromethyl) biphenyl, 4,4 '
-Diamino-3,3'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl, 1,1'-binaphthyl-3,3'-diamino-2,2'-diol, bis (2-
((4-amino-3-hydroxy) phenoxy))-
1,1′-binaphthyl, bis (2-((3-amino-4-
Hydroxy) phenoxy))-1,1′-binaphthyl and the like. These may be used alone or in combination of two or more.

The formulas (F-1) and (F) used in the present invention
Examples of the dicarboxylic acid compound having an ethynyl skeleton having the structure represented by -2) include 3-ethynylphthalic acid,
4-ethynylphthalic acid, 2-ethynylisophthalic acid, 4
-Ethynylisophthalic acid, 5-ethynylisophthalic acid,
2-ethynyl terephthalic acid, 3-ethynyl terephthalic acid, 5-ethynyl-terephthalic acid, 2-ethynyl-1,
5-naphthalenedicarboxylic acid, 3-ethynyl-1,5-
Naphthalenedicarboxylic acid, 4-ethynyl-1,5-naphthalenedicarboxylic acid, 1-ethynyl-2,6-naphthalenedicarboxylic acid, 3-ethynyl-2,6-naphthalenedicarboxylic acid, 4-ethynyl-2,6-naphthalenedicarboxylic acid Acid, 2-ethynyl-1,6-naphthalenedicarboxylic acid, 3-ethynyl-1,6-naphthalenedicarboxylic acid,
4-ethynyl-1,6-naphthalenedicarboxylic acid, 5-
Ethynyl-1,6-naphthalenedicarboxylic acid, 7-ethynyl-1,6-naphthalenedicarboxylic acid, 8-ethynyl-1,6-naphthalenedicarboxylic acid, 3,3′-diethynyl-2,2′-biphenyldicarboxylic acid, 4,4'-
Diethynyl-2,2'-biphenyldicarboxylic acid, 5,
5′-diethynyl-2,2′-biphenyldicarboxylic acid, 6,6′-diethynyl-2,2′-biphenyldicarboxylic acid, 2,2′-diethynyl-3,3′-biphenyldicarboxylic acid, 4,4 ′ -Diethinyl-3,3'-biphenyldicarboxylic acid, 5,5'-diethynyl-3,
3′-biphenyldicarboxylic acid, 6,6′-diethynyl-3,3′-biphenyldicarboxylic acid, 2,2′-diethynyl-4,4′-biphenyldicarboxylic acid, 3,3 ′
-Diethinyl-4,4'-biphenyldicarboxylic acid,
2,2-bis (2-carboxy-3-ethynylphenyl) propane, 2,2-bis (2-carboxy-4-ethynylphenyl) propane, 2,2-bis (2-carboxy-5-ethynylphenyl) propane 2,2-bis (2-carboxy-6-ethynylphenyl) propane,
2,2-bis (3-carboxy-2-ethynylphenyl) propane, 2,2-bis (3-carboxy-4-ethynylphenyl) propane, 2,2-bis (3-carboxy-5-ethynylphenyl) propane 2,2-bis (3-carboxy-6-ethynylphenyl) propane,
2,2-bis (4-carboxy-2-ethynylphenyl) propane, 2,2-bis (4-carboxy-3-ethynylphenyl) propane, 2,2-bis (2-carboxy-4-ethynylphenyl) hexa Fluoropropane, 2,2-bis (3-carboxy-5-ethynylphenyl) hexafluoropropane, 2,2-bis (4-carboxy-2-ethynylphenyl) hexafluoropropane, 2,2-bis (4-carboxy -2-ethynylphenyl) hexafluoropropane, 4-ethynyl-1,
3-dicarboxycyclopropane, 5-ethynyl-2,
2-dicarboxycyclopropane, 1,3-bis (4-
Carboxy-phenoxy) -5-ethynyl-benzene, a structural isomer of 1,3-bis (4-carboxy-phenyl) -5-ethynyl-benzene, 5- (3
-Ethynyl-phenoxy) -isophthalic acid, 5- (1-
Ethynyl-phenoxy) -isophthalic acid, 5- (2-ethynyl-phenoxy) isophthalic acid, 2- (1-ethynyl-phenoxy) terephthalic acid, 2- (2-ethynyl-
Phenoxy) terephthalic acid, 2- (3-ethynyl-phenoxy) terephthalic acid, 5- (1-ethynyl-phenyl) -isophthalic acid, 5- (2-ethynyl-phenyl)
-Isophthalic acid, 5- (3-ethynyl-phenyl) -isophthalic acid, 2- (1-ethynyl-phenyl) -terephthalic acid, 2- (2-ethynyl-phenyl) -terephthalic acid, 2- (3-ethynyl- Phenyl) -terephthalic acid and the like, but are not limited thereto. These may be used alone or in combination of two or more. Further, two or more bisaminophenol compounds can be used in combination.

The formulas (G-1) and (G) used in the present invention
Examples of the dicarboxylic acid having the structure represented by -2) include 3-phenylethynylphthalic acid, 4-phenylethynylphthalic acid, 2-phenylethynylisophthalic acid,
-Phenylethynylisophthalic acid, 5-phenylethynylisophthalic acid, 2-phenylethynylterephthalic acid,
3-phenylethynyl terephthalic acid, 2-phenylethynyl-1,5-naphthalenedicarboxylic acid, 3-phenylethynyl-1,5-naphthalenedicarboxylic acid, 4-phenylethynyl-1,5-naphthalenedicarboxylic acid, 1-
Phenylethynyl-2,6-naphthalenedicarboxylic acid,
3-phenylethynyl-2,6-naphthalenedicarboxylic acid, 4-phenylethynyl-2,6-naphthalenedicarboxylic acid, 2-phenylethynyl-1,6-naphthalenedicarboxylic acid, 3-phenylethynyl-1,6-naphthalenedicarboxylic acid Acid, 4-phenylethynyl-1,6-naphthalenedicarboxylic acid, 5-phenylethynyl-1,6-
Naphthalenedicarboxylic acid, 7-phenylethynyl-1,
6-naphthalenedicarboxylic acid, 8-phenylethynyl-
1,6-naphthalenedicarboxylic acid, 3,3′-diphenylethynyl-2,2′-biphenyldicarboxylic acid, 4,
4'-diphenylethynyl-2,2'-biphenyldicarboxylic acid, 5,5'-diphenylethynyl-2,2'-
Biphenyldicarboxylic acid, 6,6'-diphenylethynyl-2,2'-biphenyldicarboxylic acid, 2,2'-diphenylethynyl-3,3'-biphenyldicarboxylic acid, 4,4'-diphenylethynyl-3,3 ' -Biphenyldicarboxylic acid, 5,5'-diphenylethynyl-
3,3′-biphenyldicarboxylic acid, 6,6′-diphenylethynyl-3,3′-biphenyldicarboxylic acid,
2,2′-diphenylethynyl-4,4′-biphenyldicarboxylic acid, 3,3′-diphenylethynyl-4,
4′-biphenyldicarboxylic acid, 2,2-bis (2-carboxy-3-phenylethynylphenyl) propane,
2,2-bis (2-carboxy-4-phenylethynylphenyl) propane, 2,2-bis (2-carboxy-
5-phenylethynylphenyl) propane, 2,2-bis (2-carboxy-6-phenylethynylphenyl)
Propane, 2,2-bis (3-carboxy-2-phenylethynylphenyl) propane, 2,2-bis (3-carboxy-4-phenylethynylphenyl) propane,
2,2-bis (3-carboxy-5-phenylethynylphenyl) propane, 2,2-bis (3-carboxy-
6-phenylethynylphenyl) propane, 2,2-bis (4-carboxy-2-phenylethynylphenyl)
Propane, 2,2-bis (4-carboxy-3-phenylethynylphenyl) propane, 2,2-bis (2-carboxy-4-phenylethynylphenyl) hexafluoropropane, 2,2-bis (3-carboxy- 5-phenylethynylphenyl) hexafluoropropane,
2,2-bis (4-carboxy-2-phenylethynylphenyl) hexafluoropropane, 2,2-bis (4
-Carboxy-2-phenylethynylphenyl) hexafluoropropane, 4-phenylethynyl-1,3-dicarboxycyclopropane, 5-phenylethynyl-
2,2-dicarboxycyclopropane, structural isomer of 1,3-bis (4-carboxy-phenoxy) -5-phenylethynyl-benzene, 1,3-bis (4-carboxy-phenyl) -5-phenylethynyl -Structural isomer of benzene, 5- (1-phenylethynyl-phenoxy) -isophthalic acid, 5- (2-phenylethynyl-phenoxy) -isophthalic acid, 5- (3-phenylethynyl-phenoxy) isophthalic acid, 2- (1-phenylethynyl-phenoxy) terephthalic acid, 2- (2-phenylethynyl-phenoxy) terephthalic acid, 2- (3-phenylethynyl-phenoxy) terephthalic acid, 5- (1
-Phenylethynyl-phenyl) -isophthalic acid, 5-
(2-phenylethynyl-phenyl) -isophthalic acid,
5- (3-phenylethynyl-phenyl) -isophthalic acid, 2- (1-phenylethynyl-phenyl) -terephthalic acid, 2- (2-phenylethynyl-phenyl) -terephthalic acid, 2- (3-phenylethynyl- Phenyl)
-Terephthalic acid and the like. Examples where R is an alkyl group include 3-hexynylphthalic acid, 4-hexynylphthalic acid, 2-hexynylisophthalic acid, 4-hexynylisophthalic acid, 5-hexynylisophthalic acid,
Hexynyl terephthalic acid, 3-hexynyl terephthalic acid, 2-hexynyl-1,5-naphthalenedicarboxylic acid, 3-hexynyl-1,5-naphthalenedicarboxylic acid, 4-hexynyl-1,5-naphthalene Dicarboxylic acid, 1-hexynyl-2,6-naphthalenedicarboxylic acid, 3-hexynyl-2,6-naphthalenedicarboxylic acid, 4-hexynyl-2,6-naphthalenedicarboxylic acid, 2-hexynyl-1,6 -Naphthalenedicarboxylic acid, 3-hexynyl-1,6-naphthalenedicarboxylic acid, 4-hexynyl-1,6-naphthalenedicarboxylic acid, 5-hexynyl-1,6-naphthalenedicarboxylic acid, 7-hexynyl-1 , 6-Naphthalenedicarboxylic acid, 8-hexynyl-1,6-naphthalenedicarboxylic acid, 3,3'-dihexynyl-2,2'-biphe Rujikarubon acid, the 4,4'-hexynyl-2,2'-biphenyl dicarboxylic acid, 5,5' Jihekishiniru -2,
2′-biphenyldicarboxylic acid, 6,6′-dihexynyl-2,2′-biphenyldicarboxylic acid, 2,2′-dihexynyl-3,3′-biphenyldicarboxylic acid, 4,
4'-dihexynyl-3,3'-biphenyldicarboxylic acid, 5,5'-dihexynyl-3,3'-biphenyldicarboxylic acid, 6,6'-dihexynyl-3,3'-biphenyldicarboxylic acid Acid, 2,2′-dihexynyl-4,
4'-biphenyldicarboxylic acid, 3,3'-dihexynyl-4,4'-biphenyldicarboxylic acid, 2,2-bis (2-carboxy-3-hexynylphenyl) propane, 2,2-bis ( 2-carboxy-4-hexynylphenyl) propane, 2,2-bis (2-carboxy-5)
-Hexynylphenyl) propane, 2,2-bis (2-
(Carboxy-6-hexynylphenyl) propane, 2,
2-bis (3-carboxy-2-hexynylphenyl)
Propane, 2,2-bis (3-carboxy-4-hexynylphenyl) propane, 2,2-bis (3-carboxy-5-hexynylphenyl) propane, 2,2-bis (3-carboxy- 6-hexynylphenyl) propane, 2,2-bis (4-carboxy-2-hexynylphenyl) propane, 2,2-bis (4-carboxy-3)
-Hexynylphenyl) propane, 2,2-bis (2-
Carboxy-4-hexynylphenyl) hexafluoropropane, 2,2-bis (3-carboxy-5-hexynylphenyl) hexafluoropropane, 2,2-bis (4-carboxy-2-hexynylphenyl) ) Hexafluoropropane, 2,2-bis (4-carboxy-2-
Hexynylphenyl) hexafluoropropane, 4-hexynyl-1,3-dicarboxycyclopropane, 5-
Hexynyl-2,2-dicarboxycyclopropane,
The structural isomer of 1,3-bis (4-carboxy-phenoxy) -5-hexynyl-benzene, 1,3-bis (4-
Structural isomer of carboxy-phenyl) -5-hexynyl-benzene, 5- (3-hexynyl-phenoxy) -isophthalic acid, 5- (1-hexynyl-phenoxy) -isophthalic acid, 5- (2-hexynyl-phenoxy) Isophthalic acid, 2- (1-hexynyl-phenoxy) terephthalic acid, 2- (2-hexynyl-phenoxy) terephthalic acid, 2- (3-hexynyl-phenoxy) terephthalic acid, 5- (1-hexynyl-phenyl) -isophthalic acid Acid, 5- (2-hexynyl-phenyl) -isophthalic acid, 5- (3-hexynyl-phenyl) -isophthalic acid, 2- (1-hexynyl-phenyl) -terephthalic acid, 2- (2-hexynyl-phenyl) -Terephthalic acid, 2- (3-hexynyl-phenyl) -terephthalic acid and the like. Not intended to be constant.
These may be used alone or in combination of two or more. Further, two or more bisaminophenol compounds can be used in combination.

Examples of the dicarboxylic acid having a biphenylene skeleton having a structure represented by the formula (H) used in the present invention include 1,2-biphenylenedicarboxylic acid, 1,3-biphenylenedicarboxylic acid, and 1,4-biphenylenedicarboxylic acid. Biphenylenedicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 1,6-
Biphenylenedicarboxylic acid, 1,7-biphenylenedicarboxylic acid, 1,8-biphenylenedicarboxylic acid, 2,3
-Biphenylenedicarboxylic acid, 2,6-biphenylenedicarboxylic acid, 2,7-biphenylenedicarboxylic acid and the like, and from the performance of the resulting coating film, 2,6-biphenylenedicarboxylic acid and 2,7-biphenylenedicarboxylic acid are particularly preferred. preferable. These may be used alone, or 2
You may use it in combination of types or more.

Examples of the dicarboxylic acid having the structure of the formula (I) used in the present invention include 4,4'-trandicarboxylic acid, 3,4'-trandicarboxylic acid, 3,3'-trandicarboxylic acid, , 4'-Transdicarboxylic acid, 2,
3′-Transdicarboxylic acid, 2,2′-transdicarboxylic acid and the like can be used alone or in combination of two or more.

Examples of the dicarboxylic acid having the structure represented by the formula (J) used in the present invention include isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid,
4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3
-Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-sulfonylbisbenzoic acid, 3,4'-
Sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2
-Bis (4-carboxyphenyl) propane, 2,2-
Bis (3-carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2′-dimethyl-4,4 ′ -Biphenyldicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyldicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 2,2'-bis (trifluoromethyl) -4 , 4'-biphenyldicarboxylic acid, 3,3 '
-Bis (trifluoromethyl) -4,4'-biphenyldicarboxylic acid, 2,2'-bis (trifluoromethyl)
-3,3'-biphenyldicarboxylic acid, 9,9-bis (4
-(4-carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy)
Phenyl) fluorene, 4,4'-bis (4-carboxyphenoxy) biphenyl, 4,4'-bis (3-carboxyphenoxy) biphenyl, 3,4'-bis (4-
(Carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphenoxy) biphenyl, 3,3'-
Bis (4-carboxyphenoxy) biphenyl, 3,
3′-bis (3-carboxyphenoxy) biphenyl,
4,4'-bis (4-carboxyphenoxy) -p-terphenyl, 4,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,4'-bis (4-carboxyphenoxy) -p -Terphenyl, 3,3′-bis (4-carboxyphenoxy) -p-terphenyl,
3,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,3'-bis (4-carboxyphenoxy) -m-terphenyl, 4,4'-bis (3-carboxyphenoxy) -p -Terphenyl, 4,4′-bis (3-carboxyphenoxy) -m-terphenyl,
3,4'-bis (3-carboxyphenoxy) -p-terphenyl, 3,3'-bis (3-carboxyphenoxy) -p-terphenyl, 3,4'-bis (3-carboxyphenoxy) -m -Terphenyl, 3,3'-bis (3-carboxyphenoxy) -m-terphenyl, 3
-Fluoroisophthalic acid, 2-fluoroisophthalic acid,
2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5-trifluoromethylisophthalic acid and the like can be mentioned, and these can be used alone. Or two or more kinds may be used in combination.

In the polyamide (A) of the present invention, m in the formula (A), which is the number of repeating units having a crosslinking skeleton and the number of repeating units having no crosslinking skeleton.
And n are m> 0, n ≧ 0, 2 ≦ m + n ≦ 1000,
It is an integer satisfying the relationship of 0.05 ≦ m / (m + n) ≦ 1. The sum of m and n is preferably 5 or more and 100 or less. Here, if the sum of m and n is less than 2, the film-forming property is reduced, and the mechanical strength of the film becomes insufficient. On the other hand, if it exceeds 1,000, the molecular weight becomes too large, making it difficult to dissolve in a solvent, or even if dissolved, it becomes a viscous varnish, which is not practical. It is essential that m and n are integers satisfying the relationship of 0.05 ≦ m / (m + n) ≦ 1.
It is preferable to satisfy the relationship of 5 ≦ m / (m + n) ≦ 1. When 0.05> m / (m + n), it means that the number of repeating units having a cross-linking skeleton is small, and since the number of cross-linking reaction sites is small, heat resistance is not improved, and fine pores cannot be retained. Non-uniform fine pores are not preferred.

In the formula (A), the sequence of the repeating unit is
It may be block-like or random. For example, in the case of a block-like repeating unit, a bisaminophenol compound and a dicarboxylic acid chloride having a structure selected from the formula (E) are reacted in advance to increase the molecular weight, and then the bisaminophenol compound and a compound of the formula (F-1), Formula (F-2), Formula (G-1), Formula (G-
2) It can be obtained by reacting with dicarboxylic acid chloride having a structure contributing to crosslinking selected from the group consisting of structures represented by formula (H) and formula (I). Conversely, a bisaminophenol compound and a compound of the formula (F
-1), formula (F-2), formula (G-1), formula (G-2),
A dicarboxylic acid chloride having a structure contributing to cross-linking selected from the group consisting of the structures represented by the formulas (H) and (I) is reacted in advance to increase the molecular weight, and then further reacted with a bisaminophenol compound. You may make it react with the dicarboxylic acid chloride which has a structure selected from Formula (E). In the case of a random repeating unit, a bisaminophenol compound, a dicarboxylic acid chloride having a structure selected from the formula (E), a formula (F-1), a formula (F-2), a formula (G-
1) by simultaneously reacting a dicarboxylic acid chloride having a structure contributing to crosslinking selected from the group consisting of structures represented by formulas (G-2), (H) and (I). Obtainable.

In the present invention, the reactive oligomer (B) used in the reaction with the polyamide has a reactive substituent capable of reacting with a carboxyl group, an amino group or a hydroxyl group in the polyamide structure in its structure. It is essential that the reactive substituent has a carboxyl group, an amino group or a hydroxyl group, and is an oligomer which is thermally decomposed at a temperature lower than the thermal decomposition temperature of the polyamide (A) to vaporize a decomposed product. Must. Specifically, polyoxymethylene, polyoxyethylene,
Polyoxymethylene-oxyethylene copolymer, polyoxymethylene-oxypropylene copolymer, polyoxyalkylene such as polyoxyethylene-oxypropylene copolymer, polymethyl methacrylate, polyurethane, poly α-methylstyrene, polystyrene, Preferable examples include polyester, polyetherester, and polycaprolactone. As the reactive substituent, those introduced at one or both ends of a side chain or a main chain can be used. Industrially easily available are reactive oligomers having modified main chain terminals. More specifically, 4-
Aminobenzoate esterified styrene oligomer, 4
-Aminobenzoic acid ester-terminated poly (propylene glycol) oligomer, both hydroxy-terminated poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), poly (propylene glycol) bis (2-aminopropyl) Ether) and the like.

The reactive oligomer (B) preferably has a number average molecular weight in the range of 100 to 40,000. More preferably, the number average molecular weight is in the range of 100 to 10,000. If the molecular weight is less than 100,
Since the voids after vaporization are small and easily collapsed, a decrease in the relative dielectric constant cannot be exhibited. The molecular weight is 40,
If it exceeds 000, the gap becomes too large, and the mechanical properties of the insulating film are extremely lowered, which may cause a problem that the insulating film cannot be put to practical use. The amount of the reactive oligomer (B) in the copolymer (C) is not particularly limited and can be arbitrarily set, but is preferably 5 to 40 parts by weight with respect to the polyamide (A).

In the present invention, examples of the method for producing the copolymer (C) include a conventional acid chloride method, an activated ester method, and a condensation reaction in the presence of a dehydrating condensing agent such as polyphosphoric acid and dicyclohexylcarbodiimide. Can be used. For example, in the acid chloride method, the acid chloride to be used is firstly a dicarboxylic acid and an excess amount of thionyl chloride in the presence of a catalyst such as N, N-dimethylformamide.
The reaction can be performed at room temperature to 130 ° C., excess thionyl chloride is distilled off by heating and reduced pressure, and the residue can be obtained by recrystallization with a solvent such as hexane. When the dicarboxylic acid chloride thus produced and the other dicarboxylic acid are used in combination, the acid chloride obtained in the same manner is usually used together with a bisaminophenol compound together with N-
Methyl-2-pyrrolidone, dissolved in a polar solvent such as N, N-dimethylacetamide, pyridine, after the dropwise addition of an acid acceptor such as triethylamine, reacted at room temperature to -30 ℃,
A polyamide is synthesized, and the reactive oligomer is converted to γ in advance.
-Drops dissolved in butyrolactone or the like. After completion of the dropwise addition, the mixture is returned to room temperature and stirred. The reaction solution is dropped into a mixed solution of distilled water and isopropyl alcohol, and the precipitate is collected and dried to obtain a copolymer (C) obtained by reacting the polyamide (A) with the reactive oligomer (B). I can do it.

The molar ratio of the acid chloride to the bisaminophenol compound greatly affects the molecular weight of the obtained polyamide (A) and is important for controlling the terminal group structure of the polyamide. That is, in order to cause a copolymerization reaction with the reactive oligomer (B), the terminal of the polyamide (A) must be capable of reacting with the reactive group of the reactive oligomer (B). That is, when the molar ratio of acid chloride / bisaminophenol compound is set to less than 1, the terminal of the obtained polyamide has an amino group and a hydroxyl group, and can be copolymerized with an oligomer having a carboxyl group. Further, when the molar ratio of acid chloride / bisaminophenol is larger than 1, the terminal of the obtained polyamide has a carboxyl group and can be copolymerized with a reactive oligomer having an amino group or a hydroxyl group. In this case, the terminal reactive group of the reactive oligomer (B) is more preferably an amino group having strong nucleophilicity.

At this time, as an example of converting the terminal hydroxyl group of the reactive oligomer (B) into an amino group, 4-nitrobenzoic acid chloride is usually dissolved in tetrahydrofuran together with the hydroxyl group-reactive oligomer, and an acid such as pyridine is added. By reacting at room temperature to -30 ° C in the presence of an acceptor, a 4-nitrobenzoate ester-terminated oligomer can be obtained. Thereafter, the terminal oligomer is dissolved in a solvent such as tetrahydrofuran, and reacted at room temperature in a hydrogen gas atmosphere in the presence of a palladium carbon catalyst. An aminobenzoate ester-terminated oligomer is obtained, which can be used as an amino-terminal-terminated reactive oligomer. It is also possible to synthesize and use a graft copolymer by reacting a hydroxyl group in the main chain structure of the polyamide unit with a reactive oligomer having a carboxyl group or an isocyanate group, but it is possible to use a reactive oligomer that reacts with a hydroxyl group. If there is, it is not particularly limited to these.

In the present invention, the oligomer (D), which is another essential component, may be any oligomer as long as it is thermally decomposed at a temperature lower than the thermal decomposition temperature of the polyamide (A) and a decomposition product is vaporized. An oligomer may be used, and the reactive oligomer (B) described above is also included. Specific examples include polyoxymethylene, polyoxyethylene, polyoxymethylene-oxyethylene copolymer, polyoxymethylene-oxypropylene copolymer, polyoxyalkylene such as polyoxyethylene-oxypropylene copolymer, Preferable examples include polymethyl methacrylate, polyurethane, poly α-methyl styrene, polystyrene, polyester, polyetherester, and polycaprolactone. As the reactive substituent, those introduced at one or both ends of a side chain or a main chain can be used. These organic compounds may be used alone or in combination of two or more.

The oligomer (D) has a number average molecular weight of 10
Those having a range of 0 to 10,000 are preferred. Molecular weight 1
If it is less than 00, the gap after being decomposed and vaporized is small and easily crushed, so that a decrease in the relative dielectric constant cannot be exhibited. On the other hand, if the molecular weight exceeds 10,000, the voids become too large, and the mechanical properties of the insulating film are extremely reduced.
There is a case where a problem that it cannot be put to practical use occurs. The blending amount of the oligomer (D) is not particularly limited and can be arbitrarily set, but is preferably 3 to 40 parts by weight based on 100 parts by weight of the copolymer (C).

The reactive oligomer (B) and the oligomer (D) in the copolymer (C), which are essential components, are thermally decomposed and volatilized at the time of heating the resin to form a resin having a polybenzoxazole resin as a main structure. The pores are formed in the film, and the total amount of the pores is not particularly limited, and can be arbitrarily set so as to have a desired pore volume in a resin film having a polybenzoxazole resin as a main structure.
The total amount of the reactive oligomer (B) and the oligomer (D) was 100 parts by weight of the polyamide (A).
It is preferably from 7 to 45 parts by weight. If the amount is less than 7 parts by weight, the porosity in the insulating film may be small, and it may be insufficient to reduce the dielectric constant. However, there is a possibility that the mechanical strength of the above-mentioned material may be extremely reduced, the gap may be continuous and non-uniform, and the dielectric constant may vary depending on the location.

The material for an insulating film of the present invention is obtained by mixing the copolymer (C) and the oligomer (D). In addition, various additives can be used as necessary. Examples thereof include a surfactant, a coupling agent represented by a silane group, a radical initiator that generates oxygen radicals and sulfur radicals by heating, and a catalyst such as a disulfide. And the like.

The polyamide (A) of the present invention
Can be used as a positive photosensitive resin composition by using it together with a naphthoquinonediazide compound as a photosensitive agent depending on its structure.

As a method of using the insulating film material of the present invention, the material may be dissolved in an appropriate organic solvent or evenly dispersed.
It can be used as a coating varnish.
Specifically, the insulating film material is dissolved or uniformly dispersed in an organic solvent, and applied to a suitable support, for example, a glass, fiber, metal, silicon wafer, or ceramic substrate. The application method is dipping, screen printing,
Spraying, spin coating, roll coating and the like can be mentioned. After coating, the coating is heated and dried to volatilize the solvent, and a tack-free coating film can be obtained. Then, it is preferable to convert it into a crosslinked polybenzoxazole resin by using a heat treatment. Further, by selecting a dicarboxylic acid component, a bisaminophenol component, a reactive oligomer component and an oligomer component, it can be used as a polybenzoxazole resin soluble in a solvent.

As the organic solvent for dissolving the resin composition for an insulating film of the present invention, a solvent that completely dissolves solids is preferable. For example, N-methyl-2-pyrrolidone, γ-
Butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate,
Methyl-1,3-butylene glycol acetate, 1,3
-Butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydrofuran, etc., or a mixture of two or more. Can be used. The amount used is not problematic as long as the polyamide and the organic compound can be completely dissolved, and can be adjusted according to the intended use.

The material for an insulating film of the present invention is obtained by evaporating the solvent at a temperature in the range of 80 to 200 ° C. and heating the coating in the temperature range of 200 to 500 ° C. The polyamide (A) in the insulating film material undergoes a cyclization condensation reaction and a cross-linking reaction to form a polybenzoxazole resin, and the reactive oligomer (B) and the oligomer (D) in the insulating film material Is thermally decomposed at this time, the decomposition product is vaporized and volatilized, and by forming micropores in a resin layer having a polybenzoxazole resin as a main structure, the insulating film of the present invention which is a porous insulating film is formed. Obtainable. The heat history at this time is also important for forming micropores.

The size of the micropores in the insulating film depends on the use of the insulating film and the thickness of the film, but is generally at least 1 μm or less, preferably 20 nm or less. In a semiconductor interlayer insulating film, a hole diameter is 20 nm.
If it is larger, the voids in the insulating film used between the wirings will be non-uniform, and the electrical characteristics may not be constant. there's a possibility that.

The porosity of the insulating film is not particularly limited, but is preferably 5 to 40%. If the porosity is less than 5%, a sufficient decrease in the dielectric constant may not be observed. there's a possibility that.

The insulating film material and the insulating film of the present invention include an interlayer insulating film for a semiconductor, a protective film, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film,
It can be used for forming a liquid crystal alignment film and the like.

[0048]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto. Using the films prepared in Examples and Comparative Examples,
For property evaluation, dielectric constant, heat resistance,
Glass transition temperature and water absorption were measured. Further, the cross section of the film was observed, and these results are shown in Table 1.

1. Relative permittivity According to JIS-K6911, at a frequency of 100 KHz,
Hewlett-Packard HP-4284A Pre
The measurement was performed using a cision LCR meter.

2. TG / DTA620 manufactured by Seiko Instruments Inc.
Using 0, the temperature at a weight loss of 5% was measured under a flow rate of nitrogen gas of 200 mL / min and a temperature rising rate of 10 ° C./min.

3. Glass transition temperature (Tg) Measurement frequency 1 using DMS6100 manufactured by Seiko Instruments Inc. under a nitrogen gas flow of 300 mL / min.
The measurement was performed in a tensile mode at a rate of 3 ° C./min at a rate of 3 ° C./min.

4. The weight change rate after immersing a test film having a water absorption of 5 cm square and a thickness of 10 μm in pure water at 23 ° C. for 24 hours was calculated.

5. Observation of the cross section of the film About the cross section of the film, transmission electron microscope (TEM)
Was used to observe the presence or absence of micropores and the size of the pores.

Synthesis Example 1 10 g of styrene (96 mm
l) was dissolved in 100 g of tetrahydrofuran dried under a dry nitrogen atmosphere, cooled to -78 ° C, and 1.3 M sec-butyllithium (solvent:
0.77 ml of cyclohexane) was added and the mixture was stirred for 3 hours. Continue with 0.044 g of ethylene epoxide (1.0 m
mol) and stirred for 3 hours, 3 g of methanol was added, and the solution was concentrated to remove the solvent, dissolved in 100 g of tetrahydrofuran and filtered. The obtained filtrate was concentrated under reduced pressure and dried to obtain a styrene oligomer having a hydroxyl group at a terminal and a molecular weight of 9,600.

93 g of the obtained oligomer (9.68 mm
ol) was dissolved in 80 g of tetrahydrofuran dried under a dry nitrogen atmosphere, and 1.15 g of pyridine (14.52 mm
ol) was added dropwise at 5 ° C to 20 parts of tetrahydrofuran.
2.63 g (14.52 mmol) of nitrobenzoic acid chloride
A solution of l) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and stirred at room temperature for 24 hours. afterwards,
The reaction solution was filtered to remove pyridine hydrochloride, and the solvent was removed by concentration to obtain a styrene oligomer 4-nitrobenzoate. The 4-nitrobenzoic acid ester of this styrene oligomer is converted to tetrahydrofuran 10
After dissolving in 0 g, 0.5 g of 5% palladium carbon was mixed under a hydrogen gas atmosphere, and the mixture was stirred at room temperature for 24 hours. Thereafter, the reaction solution was filtered through Celite, and the solvent was concentrated and removed to obtain a styrene oligomer having 4-aminobenzoic acid ester at the end.

"Synthesis Example 2" In Synthesis Example 1, 93 g of a styrene oligomer having a molecular weight of 9,600 (9.68 mmol) was used.
In place of 1), 38.72 g of poly (propylene glycol) monobutyl ether having a molecular weight of 4,000 (9.68 m
mol) (manufactured by Aldrich), and a 4-aminobenzoic acid ester-terminated poly (propylene glycol) oligomer was obtained in the same manner as in Synthesis Example 1 except that the terminal was 4-aminobenzoic acid ester.

Synthesis Example 3 In Synthesis Example 1, 10 g (96 mmol) of styrene was added to 49.9 g (48
0 mmol) in the same manner as in Synthesis Example 1 except that
A styrene oligomer having a terminal hydroxyl group and a molecular weight of 50,000 was obtained. 100 g of the obtained styrene oligomer (2 m
mol) was dissolved in 100 g of tetrahydrofuran dried under a dry nitrogen atmosphere, and 1.15 g of pyridine (14.5 g) was dissolved.
2 mmol) is added dropwise at 5 ° C.
To a part, 2.63 g (14.52 g) of 4-nitrobenzoic acid chloride was added.
mmol) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and stirred at room temperature for 24 hours. Thereafter, the reaction solution was filtered to remove pyridine hydrochloride, and the solvent was concentrated and removed to remove styrene oligomer 4.
-A nitrobenzoic acid ester was obtained. After dissolving the 4-nitrobenzoic acid ester of the styrene oligomer in 100 g of tetrahydrofuran, 0.5 g of 5% palladium carbon is dissolved.
Were mixed under a hydrogen gas atmosphere, and the mixture was stirred at room temperature for 24 hours. Thereafter, the reaction solution was filtered through celite, and the solvent was concentrated and removed to obtain a 4-aminobenzoic acid ester-terminated styrene oligomer whose terminal was 4-aminobenzoic acid ester.

Example 1 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
5.9 g (0.098 mol) of dried N-methyl-
Dissolve in 330 mL of 2-pyrrolidone, and add 4-ethynyl-2,6-naphthalenedicarboxylic acid chloride 2 to this solution.
7.7 g (0.1 mol) were added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 1 hour. After cooling to 10 ° C., 22.3 g of triethylamine
(0.22 mol), and 38.4 g (0.000 mol of 4-aminobenzoate ester-terminated styrene oligomer synthesized in Synthesis Example 1) was added to 100 mL of γ-butyrolactone.
(4 mol, number average molecular weight 9,600) was added at 10 ° C. under dry nitrogen. After addition, add
Stir for 20 h at 20 ° C. for 20 h. After the reaction,
The reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was filtered using 6.6 L of ion-exchanged water and 6.6 L of isopropanol.
The precipitate was collected and dried by dropwise addition to a 6 L mixed solution to obtain 80.9 g of a copolymer.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 30,000 and the molecular weight distribution was 2.23. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 36% by weight. 30.0 g of this copolymer,
4.9 g (0.510 mmol, number average molecular weight 9,600) of 4-aminobenzoic acid ester-terminated styrene oligomer synthesized in Synthesis Example 1 was dissolved in 100 g of N-methyl-2-pyrrolidone, and 0.2 μm of Teflon ( Registered trademark)
A varnish was obtained by filtration with a filter.

The varnish was applied on a silicon wafer on which aluminum was deposited by using a spin coater.
At this time, the film thickness after heat treatment is 1 to 10 μm.
The rotation speed and time of the spin coater were set. After application, 1
After drying on a hot plate at 20 ° C. for 240 seconds, the polymer was heated at 300 ° C. for 60 minutes by using an oven in which nitrogen was introduced and the oxygen concentration was controlled to 100 ppm or less, so that the polymer was reacted with the oligomer at the end. A benzoxazole resin film was obtained. Further, the oligomer group was decomposed by heating at 400 ° C. for 60 minutes to obtain a polybenzoxazole resin film having pores. Aluminum was vapor-deposited on the film to perform patterning to form an electrode having a predetermined size. The aluminum on the silicon wafer side and the capacitance by this electrode were measured. After the measurement, the electrode adjacent part of the film was etched by oxygen plasma, and the film thickness was measured by a surface roughness meter. The calculated value was 1.96. When the cross section of this film was observed by TEM, the obtained voids were discontinuous with an average pore diameter of 15 nm. Table 1 also shows the heat resistance, Tg, and water absorption.

Example 2 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
3.0 g (0.09 mol) of dried N-methyl-2
Dissolved in 330 mL of pyrrolidone, and 22.7 g (0.1 mol) of 5-ethynyl-terephthalic chloride was added to this solution.
Was added at 10 ° C. under dry nitrogen. After addition, add
The mixture was stirred for an hour, followed by 1 hour at 20 ° C. After the temperature was raised to 10 ° C., 22.3 g (0.22 mol) of triethylamine was added.
-Block-poly (propylene glycol) -Block-poly (ethylene glycol) 42.0 g (0.015 m
ol, a number-average molecular weight of 2,800) was added at 10 ° C. under dry nitrogen. After addition, at 10 ° C for 1 hour,
Subsequently, the mixture was stirred at 20 ° C. for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain a common solution. 80.3 g of polymer were obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 18,000 and the molecular weight distribution was 2.25. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 46% by weight. 30.0 g of this copolymer,
And Aldrich's polymethyl methacrylate 7.1
g (number average molecular weight: 5,000) was dissolved in 100 g of N-methyl-2-pyrrolidone and filtered through a 0.2 μm Teflon filter to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 3 9,9-bis (4-((4-
53.6 g (0.095 mol) of amino-3-hydroxy) phenoxy) phenyl) fluorene were dried in N-
It was dissolved in 330 mL of methyl-2-pyrrolidone, and 22.7 g (0.1) of 5-ethynylisophthalic chloride was added to this solution.
mol) was added at 10 ° C. under dry nitrogen. After addition, 1
Stir at 0 ° C. for 1 hour, then at 20 ° C. for 1 hour. 10 ℃
After that, 22.3 g of triethylamine (0.22 mol
l), and then add 40.0 g (0.01 m) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich to 100 mL of γ-butyrolactone.
ol, a number average molecular weight of 4000) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried.
96.7 g of a copolymer were obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 25,200 and the molecular weight distribution was 2.20. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 34% by weight. 30.0 g of this copolymer,
And 3.6 g (number average molecular weight 4,000) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co., Ltd. in N-methyl-2-pyrrolidone 100
g, and filtered through a 0.2 μm Teflon filter to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 4 30.0 g (weight average molecular weight 25,200, molecular weight distribution 2.20) of the copolymer obtained in Example 3 and 4.8 g (number average molecular weight) of polyoxypropylene manufactured by Aldrich Co. 7,500) with N-methyl-
It was dissolved in 100 g of 2-pyrrolidone and filtered through a 0.2 μm Teflon filter to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 5 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 6
9.6 g (0.19 mol) of dried N-methyl-2
Dissolved in 330 mL of pyrrolidone, and 22.7 g (0.1 mol) of 5-ethynyl-terephthalic chloride was added to this solution.
And 2,5.3 g of 2,6-naphthalenedicarboxylic acid chloride
(0.1 mol) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 1 hour. After cooling to 10 ° C., 44.5 g of triethylamine (0.5%) was added.
44 mol) and then γ-butyrolactone 10
In 0 mL, 50 g of the 4-aminobenzoic acid ester-terminated poly (propylene glycol) oligomer obtained in Synthesis Example 2
(0.02 mol, number average molecular weight 2,500) was added at 10 ° C. under dry nitrogen. After addition, 10 ° C
For 1 hour and then at 20 ° C. for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain a common solution. 138.6 g of a polymer were obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 25,000 and the molecular weight distribution was 2.25. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 27% by weight. 30.0 g of this copolymer,
Then, 4.8 g (number average molecular weight: 2,500) of 4-aminobenzoate ester-terminated poly (propylene glycol) oligomer obtained in Synthesis Example 2 was dissolved in 100 g of N-methyl-2-pyrrolidone, and 0.2 μm of Teflon was dissolved. A varnish was obtained by filtration with a filter. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 6 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
4.8 g (0.095 mol) of dried N-methyl-
Dissolve in 330 mL of 2-pyrrolidone, and add 30.3 g (0.1) of 5-phenylethynylisophthalic chloride to this solution.
mol) was added at 10 ° C. under dry nitrogen. After addition, 1
Stir at 0 ° C. for 1 hour, then at 20 ° C. for 1 hour. 10 ℃
After that, 22.3 g of triethylamine (0.22 mol
l), then add 100 mL of γ-butyrolactone
In addition, 40 g (0.01 m) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich
ol, a number average molecular weight of 4,000) was added at 10 ° C. under dry nitrogen. After addition, at 10 ° C for 1 hour,
Subsequently, the mixture was stirred at 20 ° C. for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol. 87.9 g of polymer were obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 25,000 and the molecular weight distribution was 2.20. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 36% by weight. 30.0 g of this copolymer,
And 3.8 g (number average molecular weight 4,000) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co., Ltd. were added to N-methyl-2-pyrrolidone 10
0 g, and filtered through a 0.2 μm Teflon filter to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 7 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
4.8 g (0.095 mol) of dried N-methyl-
Dissolve in 330 mL of 2-pyrrolidone and add 2,7
-27.7 g of biphenylenedicarboxylic acid dichloride (0.
1 mol) was added at 10 ° C. under dry nitrogen. After the addition,
Stirred at 10 ° C. for 1 hour, then at 20 ° C. for 1 hour. 10
° C, 22.3 g of triethylamine (0.22 mol
l) was added, and 40 g (0.01 mol of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co.) was added to 100 mL of γ-butyrolactone.
1, a number average molecular weight of 4,000) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried.
87.7 g of a copolymer were obtained.

The molecular weight of the obtained copolymer was determined by
When calculated in terms of polystyrene using GPC manufactured by
It has a weight average molecular weight of 25,300 and a molecular weight distribution of 2.21.
Was. ¹Introduction rate of reactive oligomer component by H-NMR
Was 38% by weight. 30.0 g of this copolymer, and
Aldrich poly (propylene glycol) bis
1.5 g of (2-aminopropyl ether) (number average molecule
4000) in 100 g of N-methyl-2-pyrrolidone
And filtered through a 0.2 μm Teflon filter.
I got a varnish. The obtained varnish was prepared in the same manner as in Example 1.
To prepare a sample for evaluation and summarize the measurement results in Table 1.
Was.

Example 8 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 3
4.8 g (0.095 mol) of dried N-methyl-
Dissolve in 330 mL of 2-pyrrolidone and add 4,4
30.3 g of 4'-transdicarboxylic acid chloride (0.1 m
ol) at 10 ° C. under dry nitrogen. After addition, 10
Stirred at C for 1 hour, then at 20 C for 1 hour. After the temperature was raised to 10 ° C., 22.3 g (0.22 mol) of triethylamine was used.
Is added to 100 mL of γ-butyrolactone, and poly (propylene glycol) bis (2
-Aminopropyl ether) 40 g (0.01 mol,
A solution of (number average molecular weight 4,000) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol. 90.8 g of polymer were obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 25,100 and the molecular weight distribution was 2.21. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 37% by weight. 30.0 g of this copolymer,
And 2.6 g (number average molecular weight 4000) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co., Ltd. were added to N-methyl-2-pyrrolidone 100
g, and filtered through a 0.2 μm Teflon filter to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 9 9,9-bis (4-((4-
118.6 g (0.21 mol) of amino-3-hydroxy) phenoxy) phenyl) fluorene were dried in N-
The solution was dissolved in 900 mL of methyl-2-pyrrolidone, and 22.7 g of 5-ethynylisophthalic dichloride (0.2 mL) was added to this solution.
1 mol), 5-phenylethynylisophthalic acid dichloride 30.3 (0.1 mol) and isophthalic acid dichloride 4.5 g (0.022 mol) under dry nitrogen.
C. was added. After addition, 1 hour at 10 ° C, then 20 ° C
For 1 hour. After the temperature was raised to 10 ° C., 49.5 g (0.49 mol) of triethylamine was added, and then, to 250 mL of γ-butyrolactone, 88.0 g (0.022 mol, 0.022 mol, Number average molecular weight 4.0
00) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was deionized water (15 L).
The mixture was dropped into a mixed solution of 15 L of isopropanol and the precipitate was collected and dried to obtain 211.8 g of a copolymer.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 25,000 and the molecular weight distribution was 2.20. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 33% by weight. 30.0 g of this copolymer,
And 3.5 g (number average molecular weight 3,500) of a polyoxyethylene-oxypropylene copolymer manufactured by Aldrich
-Methyl-2-pyrrolidone dissolved in 100 g,
Then, the mixture was filtered through a Teflon filter of m to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 10 9,9-Bis (4-((4
-Amino-3-hydroxy) phenoxy) phenyl) fluorene (73.4 g, 0.13 mol) was dried with N-
The residue was dissolved in 550 mL of methyl-2-pyrrolidone, and 7.5 g (0.05 g) of 5-ethynylisophthalic dichloride was added to this solution.
33 mol) and 30.3 g (0.1 mol) of 5-phenylethynylisophthalic acid dichloride were added under dry nitrogen for 10 minutes.
C. was added. After addition, 1 hour at 10 ° C, then 20 ° C
For 1 hour. After the temperature was raised to 10 ° C., 29.7 g (0.29 mol) of triethylamine was added, and then, to 150 mL of γ-butyrolactone, 52.0 g (0.013 mol of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co. Number average molecular weight 4.0
00) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was subjected to 11 L of ion-exchanged water.
And 11 L of isopropanol, and the precipitate was collected and dried to obtain 137.7 g of a copolymer.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 24,000 and the molecular weight distribution was 2.10. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 32% by weight. 30.0 g of this copolymer,
And 6.5 g (number average molecular weight 4,000) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co., Ltd. were added to N-methyl-2-pyrrolidone 10
0 g, and filtered through a 0.2 μm Teflon filter to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Comparative Example 1 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
4.8 g (0.095 mol) of dried N-methyl-
Dissolve in 330 mL of 2-pyrrolidone, and add 5-ethynyl-2,6-naphthalenedicarboxylic acid dichloride 2 to this solution.
7.7 g (0.1 mol) were added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 1 hour. After cooling to 10 ° C., 22.3 g of triethylamine
After adding (0.22 mol), the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was dropped into a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain a polymer. 53.5 g were obtained.

The molecular weight of the obtained polymer was determined in terms of polystyrene by using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 25,600 and the molecular weight distribution was 2.23. 25.0 g of this copolymer was dissolved in 100 g of N-methyl-2-pyrrolidone and filtered through a 0.2 μm Teflon filter to obtain a varnish. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Comparative Example 2 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
4.8 g (0.095 mol) of dried N-methyl-
The product was dissolved in 330 mL of 2-pyrrolidone, and 20.3 g (0.1 mol) of terephthalic acid chloride was added to the solution at 10 ° C under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 1 hour. After reaching 10 ° C., 22.3 g (0.22 mol) of triethylamine are added and then γ
A solution prepared by dissolving 28 g (0.01 mol, number average molecular weight 2,800) of poly (propylene glycol) -block-poly (ethylene glycol) both-terminal hydroxy copolymer in 3 mL of butyrolactone is added at 10 ° C. under dry nitrogen. did. After the addition, 1 hour at 10 ° C., followed by 2 hours at 20 ° C.
Stirred for 0 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol. Polymer 5
0.3 g was obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 20,100 and the molecular weight distribution was 2.22. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 33% by weight. 25.0 g of this copolymer was dissolved in 100 g of N-methyl-2-pyrrolidone, and 0.2
A varnish was obtained by filtration through a μm Teflon filter. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Comparative Example 3 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 2
7.5 g (0.075 mol) of dried N-methyl-
This was dissolved in 330 mL of 2-pyrrolidone, and 22.7 g (0.1 mol) of 5-ethynyl-terephthalic acid chloride was added to this solution.
l) was added at 10 ° C under dry nitrogen. After addition, 10 ° C
For 1 hour and then at 20 ° C. for 1 hour. After the temperature was raised to 10 ° C., 22.3 g (0.22 mol) of triethylamine was added, and then 100 mL of γ-butyrolactone was added to a poly (ethylene glycol) -block-poly (propylene glycol-poly (ethylene glycol) both hydroxy-terminated copolymer. A solution of 140 g (0.05 mol, number average molecular weight 2,800) was added under dry nitrogen at 10 ° C. After the addition, 1 hour at 10 ° C., followed by 20 hours at 20 ° C.
Stirred for hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol, and the precipitate was collected and dried to obtain a common solution. Polymer 16
0.5 g was obtained.

The molecular weight of the obtained copolymer was determined by
Using a company-manufactured GPC and calculating in terms of polystyrene
The weight average molecular weight was 7,000 and the molecular weight distribution was 2.15.
Was. ¹Introduction of reactive oligomer component by H-NMR
The rate was 72% by weight. 25.0 g of the obtained copolymer
Was dissolved in 100 g of N-methyl-2-pyrrolidone.
A varnish was obtained by filtration with a 2 μm Teflon filter.
The obtained varnish was treated in the same manner as in Example 1 to obtain a sump for evaluation.
Table 1 shows the measurement results.

Comparative Example 4 2,2-Bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
6.4 g (0.0995 mol) was dissolved in dried N-methyl-2-pyrrolidone (330 mL), and 5-N-methyl-2-pyrrolidone was added to this solution.
22.7 g of ethynyl-terephthalic acid chloride (0.1 mol
l) was added at 10 ° C under dry nitrogen. After addition, 10 ° C
For 1 hour and then at 20 ° C. for 1 hour. After the temperature was raised to 10 ° C, 22.3 g (0.22 mol) of triethylamine was added, and then 30.0 mL of γ-butyrolactone was added to 50.0 g of 4-aminobenzoic acid-terminated polystyrene (0.001 mol
1, number average molecular weight 50,000) was added at 10 ° C. under dry nitrogen. After addition, at 10 ° C for 1 hour,
Subsequently, the mixture was stirred at 20 ° C. for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was added dropwise to a mixed solution of 6.6 L of ion-exchanged water and 6.6 L of isopropanol. 81.4 g of polymer were obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 80,000 and the molecular weight distribution was 2.12. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 42% by weight. 25.0 g of this copolymer
Was dissolved in 100 g of N-methyl-2-pyrrolidone.
A varnish was obtained by filtration with a 2 μm Teflon filter.
An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Comparative Example 5 9,9-Bis (4-((4-
124.2 g (0.22 mol) of amino-3-hydroxy) phenoxy) phenyl) fluorene were dried with N-
It was dissolved in 600 mL of methyl-2-pyrrolidone, and 4,4′-biphenyldicarboxylic acid dichloride was added to the solution.
7 g (0.1 mol), terephthalic dichloride 20.3
(0.1 mol) and 4.9 g of isophthalic dichloride
(0.024 mol) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 1 hour. After cooling to 10 ° C, 49.8 g of triethylamine
(0.49 mol), and then poly (propylene glycol) bis (2-aminopropyl ether) 96.
A solution of 0 g (0.024 mol, number average molecular weight 4,000) was added at 10 ° C. under dry nitrogen. After the addition,
The mixture was stirred at 10 ° C for 1 hour, and then at 20 ° C for 20 hours. After completion of the reaction, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtered solution was dropped into a mixed solution of 18 L of ion-exchanged water and 18 L of isopropanol. 4 g were obtained.

The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation. The weight average molecular weight was 24,000 and the molecular weight distribution was 2.10. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 34% by weight. 25.0 g of this copolymer was dissolved in 100 g of N-methyl-2-pyrrolidone, and 0.2
A varnish was obtained by filtration through a μm Teflon filter. An evaluation sample was prepared from the obtained varnish in the same manner as in Example 1, and the measurement results were summarized in Table 1.

[0088]

[Table 1]

From the evaluation results of Examples and Comparative Examples summarized in Table 1, the insulating film (coating) obtained from the material for an insulating film of the present invention can be obtained while maintaining excellent heat resistance and low water absorption.
It can be seen that the dielectric constant can be reduced.

[0090]

The insulating film obtained from the insulating film material and the coating varnish of the present invention can achieve excellent thermal characteristics, electric characteristics, and water absorption. It can be suitably used for applications such as an interlayer insulating film, a protective film, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, and a liquid crystal alignment film.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/30 H01B 3/30 M CH H01L 21/312 H01L 21/312 A F term (Reference) 4J002 BC032 BC092 BG062 CH012 CH022 CK022 CL031 GQ01 4J038 CC031 CC081 CG141 CH031 DF001 DH001 DH021 DJ001 GA03 GA06 GA09 KA06 MA14 NA14 NA21 PB09 PC03 4J043 PA02 PA19 QB05 RA52 ZA46 ZB47 5F058 AA11A04 A10A03 A10A03 A04A10 CB28

Claims (18)

[Claims] 1. A polyamide having a repeating unit represented by the general formula (A) and a reactive oligomer (B) having a substituent capable of reacting with a carboxyl group, an amino group or a hydroxyl group in the polyamide structure. A material for an insulating film, comprising the reacted copolymer (C) and oligomer (D) as essential components. Embedded image In the formula, m and n are m> 0, n ≧ 0, 2 ≦ m + n ≦ 10
00 and an integer satisfying the relationship of 0.05 ≦ m / (m + n) ≦ 1. X is selected from the structure represented by the formula (E), and Y is the formula (F-1), the formula (F-2), the formula (G-1),
It represents at least one group selected from the group consisting of the structures represented by Formula (G-2), Formula (H), and Formula (I). Further, X in the general formula (A) may be the same or different. Z represents a group selected from the structure represented by the formula (J). In the general formula (A), the arrangement of the repeating units may be block-like or random. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image In the formulas (E) and (J), X ₁ represents a group selected from the structure represented by the formula (K). Equation (G-1), Equation (G-
R in 2) represents a naphthalene group, a phenyl group, or an alkyl group. In the structures represented by Formulas (E) to (J), a hydrogen atom on the benzene ring is a methyl group, an ethyl group,
It may be substituted with at least one group selected from the group consisting of propyl, isopropyl, butyl, isobutyl, t-butyl, fluorine and trifluoromethyl. Embedded image 2. The method according to claim 1, wherein Y in the general formula (A) representing the structure of the polyamide has a structure selected from the group consisting of the formulas (F-1) and (F-2). Item 4. The material for an insulating film according to Item 1. 3. The method according to claim 1, wherein Y in the general formula (A) representing the structure of the polyamide has a structure selected from the group consisting of the formulas (G-1) and (G-2). Item 4. The material for an insulating film according to Item 1. 4. The insulating film material according to claim 1, wherein Y in the general formula (A) representing the structure of the polyamide has a structure selected from the group consisting of the formula (H). 5. The insulating film material according to claim 1, wherein Y in the general formula (A) representing the structure of the polyamide has a structure selected from the group consisting of the formula (I). 6. A polyamide (A) having a reactive oligomer (B) at one or both ends of its side chain or main chain.
Polyoxyalkylene, polymethyl methacrylate, poly-α-methylstyrene, polystyrene, polyester, polyetherester, polycaprolactone and polyurethane having a reactive substituent capable of reacting with a carboxyl group, amino group, or hydroxyl group in the structure The insulating film material according to any one of claims 1 to 5, wherein the material is at least one selected from the group consisting of: 7. The insulating film material according to claim 6, wherein the reactive oligomer (B) has a number average molecular weight of 100 to 10,000. 8. The copolymer (C) is a polyamide (A) 1
The reactive oligomer (B) is 5 to 40 parts by weight with respect to 00 parts by weight.
Characterized in that it is obtained by copolymerizing parts by weight,
The material for an insulating film according to claim 1. 9. The oligomer (D) has a reactive substituent capable of reacting with a carboxyl group, an amino group or a hydroxyl group in the polyamide (A) structure at one or both ends of its side chain or main chain. Having, a group consisting of polyoxyalkylene, polymethyl methacrylate, poly α-methylstyrene, polystyrene, polyester, polyetherester, polycaprolactone and polyurethane,
And at least one selected from the group consisting of oxyalkylene, methyl methacrylate, urethane, α-methylstyrene, and styrene having at least one type of repeating unit. The material for an insulating film according to any one of the above. 10. The oligomer (D) is at least one selected from the group consisting of oxyalkylenes having at least one type of repeating unit, methyl methacrylate, urethane, α-methylstyrene, and styrene. 10. The insulating film material according to claim 9, wherein: 11. The insulating film material according to claim 9, wherein the oligomer (D) is the same as the reactive oligomer (B). 12. The oligomer (D) having a number average molecular weight of:
The insulating film material according to any one of claims 9 to 11, wherein the thickness is 100 to 10,000. 13. The copolymer (C) comprising the oligomer (D) and the copolymer (C).
13. The insulating film material according to claim 1, wherein 3 to 40 parts by weight is blended with respect to 100 parts by weight. 14. An insulating material comprising the insulating film material according to claim 1 and an organic solvent capable of dissolving or dispersing the insulating film material. A coating varnish capable of producing a film. 15. An insulating film material according to any one of claims 1 to 13, or a coating varnish according to claim 14, which is obtained by a heat treatment to cause a condensation reaction and a crosslinking reaction. An insulating film comprising a resin layer having polybenzoxazole as a main structure and having fine pores. 16. The size of a fine hole in an insulating film is 20 nm.
The insulating film according to claim 15, wherein: 17. The insulating film according to claim 15, wherein the porosity of the insulating film is 5 to 40%. 18. A semiconductor using the insulating film according to claim 15. Description: