JP2002241503A - Material for insulating film, coating varnish for insulating film and insulating film using thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an insulating film excellent in thermal characteristics, electric characteristics, low water absorption properties, especially a heat resistant insulating film having a remarkably small specific dielectric constant in semiconductor applications. SOLUTION: In a material for insulating films comprising a copolymer obtained by reacting a polyamide having a repeating unit of a specific structure with a reactive oligomer having substituents capable of reacting with carboxy groups, amino groups or hydroxy groups in the polyamide structure, the reactive oligomer is a compound having a norbornene structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a material for an insulating film, a coating varnish for an insulating film, and an insulating film using the same. More specifically, it has excellent electrical, thermal and mechanical properties and is suitable for 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. TECHNICAL FIELD The present invention relates to an insulating film material used for the above, a coating varnish for an insulating film containing the same, and an insulating film using the same.

[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 according to required characteristics. For example, as an interlayer insulating film for a semiconductor,
An inorganic oxide film such as silicon dioxide produced by a chemical vapor method is used. However, with the recent increase in speed and performance of semiconductors, 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] Organic materials for semiconductor applications include 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, since polyimide resins generally have two carbonyl groups on the imide ring, there are problems in water absorption and electrical properties. To solve these problems, attempts have been made to improve water absorption and electrical properties by introducing fluorine or a fluorine-containing group into an organic polymer, and some of them have been put to practical use. Also,
There is a polybenzoxazole resin exhibiting better performance with respect to heat resistance, water absorption, and electrical properties than polyimide resin, and application to various fields has been attempted. For example, those having a structure consisting of 4,4′-diamino-3,3′-dihydroxybiphenyl and terephthalic acid,
2,2-bis (3-amino-4-hydroxyphenyl)
There is a polybenzoxazole resin having a structure composed of hexafluoropropane and terephthalic acid.

However, more severe heat resistance, electrical characteristics,
In the advanced field where improvement of water absorption etc. 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, there is a problem that the heat resistance is lowered. 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 forming fine holes in the 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 disclosed in U.S. Pat. No. 3,883,452 to Scheuerlein et al. (May 13, 1975).
From the method of producing a foamed polymer having an average pore diameter of about 20 μm. However, in order to make an effective insulator by introducing air into the film, the film thickness needs to be on the order of sub-micrometer, has an averaged relative dielectric constant, and the mechanical properties of the film itself Must be able to withstand each step. At present, an inorganic material that overcomes such problems 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 to ick et al. (199).
(July 7, 2008) discloses that a block copolymer is formed into a resin having fine pores on the order of sub-micrometer. It is known that block copolymers undergo phase separation on the order of submicrometer (T. Hashimoto, M. Shibayama, M. Fujimura and H. Kawa).
i, Microphase Separation and the Polymer-polymer In
terphase in Block Polymers in Block Copolymers-Sci
ence 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 permittivity 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. Combinations are very limited in their choice, and none of them can satisfy all the characteristics.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention is excellent in electrical characteristics, thermal characteristics, mechanical characteristics, etc., among which excellent heat resistance is maintained and low dielectric constant is achieved. And a coating varnish for an insulating film, and an insulating film using the same.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a copolymer obtained by reacting a polyamide having a specific structure with a reactive oligomer. Finding that the material for the insulating film can meet the purpose of the present invention, further study,
The present invention has been completed.

That is, the present invention provides a copolymer comprising a polyamide comprising a repeating unit represented by the general formula (A) and a carboxyl group, an amino group or a hydroxyl group in the polyamide structure. An insulating film material comprising a copolymer obtained by reacting a reactive oligomer having a substituent which can be generated with the reactive oligomer, wherein the reactive oligomer is a compound having a norbornene structure. is there.

[0010]

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(Wherein, R _{1 to} R ₄ represent a hydrogen atom or a monovalent organic group, and X represents a tetravalent group selected from the groups represented by the formula (B).) , Two Xs may be the same or different from each other, and Y ₁ is represented by the formulas (C), (D),
At least one divalent group selected from the groups represented by the formulas (E) and (F), and Y ₂ represents a divalent group selected from the groups represented by the formula (G) And m and n
Are m> 0, n ≧ 0, 2 ≦ m + n ≦ 1000, and 0.
It is an integer satisfying 05 ≦ m / (m + n) ≦ 1, and the arrangement of the repeating units in the general formula (A) may be blockwise or random. )

[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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(However, in the formulas (B) and (G), X ₁ represents a divalent group selected from the groups represented by the formula (H). In the formula (D), R represents a naphthalene group , A phenyl group or an alkyl group, and formulas (B), (D), (E),
In the groups represented by the formulas (F), (G), and (H), the hydrogen atom on the benzene ring is a methyl group, an ethyl group,
It may be substituted with at least one group selected from a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group. )

[0019]

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The present invention also provides a coating capable of forming an insulating film, comprising the insulating material and an organic solvent capable of dissolving or dispersing the insulating material. Varnish, further comprising a resin layer having a main structure of polybenzoxazole obtained by subjecting the insulating film material or coating varnish to a heat treatment to cause a crosslinking reaction and a condensation reaction, and to form fine pores. It is an insulating film provided.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, at least one of ethynyl, phenylethynyl, alkylethynyl, biphenylene, and internal acetylene, which is crosslinked by heating, to the main chain of a polyamide unit in a copolymer which is an essential component.
By introducing a kind of skeleton and converting the amide group into polybenzoxazole by a ring-closing reaction, and by cross-linking the ethynyl, phenylethynyl, alkylethynyl, biphenylene, internal acetylene skeleton, the resin structure is made three-dimensional, thereby increasing A resin having heat resistance can be obtained. Then, the oligomers in the copolymer are thermally decomposed at the time of heating the resin and volatilized, thereby forming micropores in the resin film having a polybenzoxazole resin as a main structure, thereby achieving both heat resistance and electrical characteristics. Obtaining a porous insulating film is the gist of the present invention.

In the present invention, the polyamide unit in the copolymer, which is an essential component, comprises at least one bisaminophenol compound having any one of the tetravalent groups represented by the formula (B), Using at least one dicarboxylic acid having any of the divalent groups represented by the formulas (C), (D), (E) and (F), or as a dicarboxylic acid, The dicarboxylic acid and the formula (G)
In combination with a dicarboxylic acid having any of the divalent groups represented by the above, a conventional acid chloride method, an activated ester method, a condensation reaction in the presence of a dehydrating condensing agent such as polyphosphoric acid or dicyclohexylcarbodiimide And the like. The ethynyl, phenylethynyl,
Similarly, by combining a polyamide having at least one skeleton of alkylethynyl, biphenylene, and internal acetylene with another polyamide of a type that does not undergo a cross-linking reaction, which is conventionally used, to form an interpenetrating network structure. It is possible to obtain a resin having high heat resistance. In this case, ethynyl, phenylethynyl, alkylethynyl, biphenylene, and a polyamide having no internal acetylene skeleton are at least one of bisaminophenol compounds having any of the tetravalent groups represented by the formula (B). It can be obtained by a similar method using a species and at least one dicarboxylic acid having any of the divalent groups represented by the formula (G).

The bisaminophenol compound having a tetravalent group represented by the formula (B) used in the present invention includes:
2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoro Propane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3
-Hydroxyphenyl) propane, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone,
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-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'-di Amino-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 and the like. These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid having an ethynyl skeleton having a divalent group represented by the formula (C) used in the present invention include 3-ethynylphthalic acid, 4-ethynylphthalic acid,
2-ethynyl isophthalic acid, 4-ethynyl isophthalic acid, 5-ethynyl isophthalic 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, 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'-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) hexafluoropropane, 2,2-bis (3-carboxy-5-ethynylphenyl) hexafluoropropane, 2,2-bis (4-carboxy-2- Ethynylphenyl) hexafluoropropane, 4-ethynyl-1,3
-Dicarboxycyclopropane, 5-ethynyl-2,2
-Dicarboxycyclopropane 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.

Examples of the dicarboxylic acid having a divalent group represented by the formula (D) used in the present invention include 3-phenylethynylphthalic acid, 4-phenylethynylphthalic acid,
-Phenylethynylisophthalic acid, 4-phenylethynylisophthalic acid, 5-phenylethynylisophthalic acid,
2-phenylethynyl terephthalic 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-phenyl Ethynyl-1,6-naphthalenedicarboxylic acid, 3
-Phenylethynyl-1,6-naphthalenedicarboxylic 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, 4-phenylethynyl-1,3
-Dicarboxycyclopropane, 5-phenylethynyl-2,2-dicarboxycyclopropane and the like. In the formula (D), examples where R is an alkyl group include 3-hexynylphthalic acid, 4-hexynylphthalic acid, 2-hexynylisophthalic acid, 4-hexynylisophthalic acid, and 5-hexynylisophthalic acid. 2-hexynylterephthalic acid, 3-hexynylterephthalic acid, 2-hexynyl-1,5-naphthalenedicarboxylic acid, 3-hexynyl-1,5-naphthalenedicarboxylic acid, 4-hexynyl-1, 5-naphthalenedicarboxylic 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′-biphenyldicarboxylic acid, 4,4′-
Dihexynyl-2,2'-biphenyldicarboxylic acid,
5,5'-dihexynyl-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,
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-hexynyl) Phenyl) 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-ethynyl-2,2-dicarboxycyclopropane and the like, It is not limited to these. These may be used alone,
Also, two or more kinds may be used in combination. Also, 2
It is also possible to use a combination of two or more bisaminophenol compounds.

Examples of the dicarboxylic acid having a biphenylene skeleton having a divalent group represented by the formula (E) used in the present invention include 1,2-biphenylenedicarboxylic acid, 1,3
-Biphenylenedicarboxylic acid, 1,4-biphenylenedicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 1,
6-biphenylenedicarboxylic acid, 1,7-biphenylenedicarboxylic acid, 1,8-biphenylenedicarboxylic acid,
Examples include 2,3-biphenylenedicarboxylic acid, 2,6-biphenylenedicarboxylic acid, and 2,7-biphenylenedicarboxylic acid. From the performance of the obtained coating film, 2,6-biphenylenedicarboxylic acid, 2,7-biphenylenedicarboxylic acid Acids are particularly preferred. These may be used alone,
Also, two or more kinds may be used in combination.

Examples of the dicarboxylic acid having a divalent group represented by the formula (F) used in the present invention include 4,4′-trandicarboxylic acid, 3,4′-trandicarboxylic acid,
3′-Transdicarboxylic acid, 2,4′-trandicarboxylic acid, 2,3′-trandicarboxylic acid, 2,2′-trandicarboxylic acid, etc. can be used alone or in combination of two or more.

Examples of the dicarboxylic acid having a divalent group represented by the formula (G) used in the present invention include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid and 3,4'-biphenyl Dicarboxylic 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,
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-ter Phenyl, 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, etc., may be used alone or in combination of two or more. May be.

In the polyamide of the present invention, m and n in the formula (A), which are the number of repeating units having a crosslinking skeleton and the number of repeating units having no crosslinking skeleton, are as follows:
m and n are as follows: m> 0, n ≧ 0, 2 ≦ m + n ≦ 100
0, an integer satisfying 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 suitable for practical use. It is essential that m and n are integers satisfying 0.05 ≦ m / (m + n) ≦ 1, and further, 0.5 ≦ m /
It is preferable that (m + n) ≦ 1. 0.05> m
/ (M + n) means that the number of repeating units having a skeleton to be crosslinked is small, and since the number of crosslinking reaction sites is small, heat resistance is not improved, and micropores cannot be retained or uneven micropores. Is not preferred.

In the general formula (A), the arrangement of the repeating units may be blockwise or random. For example, in the case of a block-like repeating unit,
The bisaminophenol compound and a dicarboxylic acid chloride having a divalent group selected from the groups represented by the formula (G) are reacted in advance to increase the molecular weight, and then the bisaminophenol compound and a compound represented by the formula (G) C), by reacting with a dicarboxylic acid chloride having a divalent group that contributes to crosslinking selected from the groups represented by the formulas (D), (E) and (F). it can. Conversely, a bisaminophenol compound and a divalent group contributing to crosslinking selected from the groups represented by formulas (C), (D), (E), and (F) may be used. And a dicarboxylic acid chloride having a divalent group selected from the groups represented by the formula (G). You may. In the case of a random repeating unit, a bisaminophenol compound and a dicarboxylic acid chloride having a divalent group selected from formulas (G) and
By simultaneously reacting (C), a dicarboxylic acid chloride having a divalent group that contributes to crosslinking selected from the groups represented by the formulas (D), (E), and (F), Obtainable.

In the present invention, the reactive oligomer used in the reaction with the polyamide is a compound having a norbornene structure, and in the structure, a reaction capable of reacting with a carboxyl group, an amino group, or a hydroxyl group in the polyamide structure. It is essential that the reactive substituent has a carboxyl group or a derivative thereof, an amino group or a hydroxyl group, and may be an acid anhydride compound. The oligomer must be thermally decomposed at a temperature lower than the decomposition temperature, and the decomposition product is vaporized. Specifically, amines such as aminopropyl group-containing norbornene oligomer, 2-aminopropyl group-containing norbornene oligomer, carboxylic acids such as 1-carboxypropyl group-containing norbornene oligomer, 2-carboxypropyl group-containing norbornene oligomer,
Carboxylic acid chlorides such as 1-chloroformylpropyl group-containing norbornene oligomer, 2-chloroformylpropyl group-containing norbornene oligomer, phenyl-1-
Esters such as propylcarboxylate group-containing norbornene oligomer, phenyl-2-propylcarboxylate group-containing norbornene oligomer, and anhydrous 1,2-dicarboxypropylnorbornene oligomer can be exemplified.

The oligomer has a number average molecular weight of 135 to 135.
Those in the range of 500,000 are preferred. More preferably, the number average molecular weight is from 200 to 200,000, and still more preferably, the number average molecular weight is from 300 to 100,000.
In the range of If the molecular weight exceeds 500,000, the voids become too large and the mechanical properties of the insulating film are extremely deteriorated, which causes a problem that the insulating film cannot be put to practical use.

With respect to the blending amount of the oligomer in the copolymer, it is preferable to react 5 to 70 parts by weight of the oligomer with respect to the polyamide. More preferably, it is 5 to 50 parts by weight, and still more preferably, 5 to 40 parts by weight.
Parts by weight. Similarly, the amount of the oligomer component in the resin after the reaction preferably satisfies 5 to 70 parts by weight.
If the amount is less than 5 parts by weight, the porosity in the insulating film may be small, and it may be insufficient to reduce the dielectric constant.
If the amount exceeds 70 parts by weight, the porosity in the film may be increased, the mechanical strength of the film may be extremely reduced, the voids may be continuous and non-uniform, and the dielectric constant may vary from place to place.

In the present invention, examples of the method for producing the copolymer include methods such as 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 prepared by first reacting a dicarboxylic acid with an excess amount of thionyl chloride at room temperature to 130 ° C. in the presence of a catalyst such as N, N-dimethylformamide to obtain an excess of chloride. After the thionyl is distilled off by heating and reduced pressure, 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 combined with a bisaminophenol compound together with N-methyl-2-pyrrolidone, N, N- After dissolving in a polar solvent such as dimethylacetamide and dropping an acid acceptor such as pyridine and triethylamine, the mixture is reacted at room temperature to -30 ° C to synthesize a polyamide, and the reactive oligomer is previously dissolved in γ-butyrolactone or the like. Is dropped. 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 obtained by reacting a polyamide with a reactive oligomer.

The charged molar ratio of the acid chloride to the bisaminophenol compound greatly affects the molecular weight of the obtained polyamide 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, the terminal of the polyamide must be capable of reacting with the reactive group of the oligomer. 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 oligomer is more preferably an amino group having strong nucleophilicity.

In the material for an insulating film of the present invention, an additive may be used according to the purpose, in addition to the above copolymer. Examples of the various additives include a surfactant, a coupling agent represented by a silane-based compound, a radical initiator that generates an oxygen radical or a sulfur radical by heating, and a catalyst such as a disulfide.

The polyamide according to the present invention has a structure in which at least one of R ₁ and R ₂ and R ₃ and R ₄ in the structure of the precursor represented by the general formula (A) is H. By using a naphthoquinonediazide compound as a photosensitizer together with a naphthoquinonediazide compound, at least one of R ₁ and R ₂ , or R ₃ and R ₄ can be used as a positive photosensitive resin composition. In the case of a group having a crosslinkable group, it can be used as a negative photosensitive resin composition by using a photoinitiator.

As a method of using the material for an insulating film of the present invention, the material may be dissolved in a suitable organic solvent or uniformly 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 and a reactive oligomer component, it can be used as a polybenzoxazole resin soluble in a solvent.

As the organic solvent for dissolving or dispersing the insulating film material of the present invention, a solvent which 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
-One or a mixture of butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydrofuran, etc. Can be used. The amount used is not problematic as long as it can completely dissolve the insulating film material, and can be adjusted according to the intended use.

The material for an insulating film of the present invention is obtained by evaporating a solvent in a temperature range from 80 ° C. to 200 ° C. and heating the coating film obtained as described above in a temperature range from 200 ° C. to 500 ° C. As a result, the polyamide in the insulating film material undergoes a cyclocondensation reaction and a cross-linking reaction to become a polybenzoxazole resin, and the oligomer in the insulating film material is thermally decomposed at this time, and the decomposition product is vaporized. The insulating film of the present invention, which is a porous insulating film, can be obtained by volatilizing and forming micropores in a resin layer having a polybenzoxazole resin as a main structure. The heat history at this time is also important for forming micropores.

The size of the micropores in the insulating film having the micropores, which is composed of the resin layer having polybenzoxazole as a main structure of the present invention, depends on the use of the insulating film and the thickness of the film. In general, it is at least 1 μm or less, preferably 500 nm or less, more preferably 100 nm or less, and preferably 20 μm or less in applications such as interlayer insulating films for semiconductors.
nm or less, more preferably 5 nm or less. In the interlayer insulating film for semiconductor, the hole diameter is 20n.
If it is larger than m, the voids in the insulating film used between the wirings will be non-uniform, and the electrical characteristics will not be constant. In addition, problems such as a decrease in mechanical strength of the film and an adverse effect on adhesiveness occur. However, depending on the application of the film,
5 nm is not necessarily required because of the optimal pore size.

The porosity of the insulating film is preferably 5% to 70%. It is more preferably from 5% to 50%, and still more preferably from 5% to 40%. If the porosity is smaller than 5%, a sufficient decrease in the dielectric constant may not be observed. If the porosity is larger than 70%, the mechanical strength of the film is reduced, and problems such as adverse effects on the adhesiveness may occur.

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

[0044]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

The dielectric constant, heat resistance, and glass transition temperature of the films prepared in Examples and Comparative Examples were measured by the following methods for evaluating characteristics. Further, the cross section of the film was observed, and these results are summarized in Table 1.

1. Relative permittivity Hewlett-Packard HP-4284A Pre
The volume was measured using a Cison LCR meter and calculated.

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) Using DMS6100 manufactured by Seiko Instruments Inc., under a flow of nitrogen gas at 300 mL / min, measurement frequency 1
The measurement was performed in a tensile mode under the conditions of Hz and a heating rate of 3 ° C./min, and the peak top temperature of the loss tangent (tan δ) was defined as the glass transition temperature.

4. A 5 cm square test film having a thickness of 10 μm and a water absorption of 10 μm were immersed in pure water at 23 ° C. for 24 hours to calculate a weight change rate.

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.

Example 1 2,2-bis (3-amino-
4-Hydroxyphenyl) hexafluoropropane
022 g (2.79 mmol) were dissolved in 10 mL of dried N-methyl-2-pyrrolidone, and 4-ethynyl-2,6-naphthalenedicarboxylic acid chloride was added to the solution.
828 g (3.0 mmol) 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 heating to 10 ° C, triethylamine 0.6
68 g (6.6 mmol) was added, and then a solution of 1.47 g (0.42 mmol, number average molecular weight 3500) of 1-aminopropylnorbornene oligomer dissolved in 3 mL of γ-butyrolactone 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 20.
0 mL and 50 mL of isopropanol were dropped into a mixed solution, and the precipitate was collected and dried to obtain the copolymer 2.
8 g were obtained. When 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 22,000 and the molecular weight distribution was 2.33.
Met. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 41% by weight.

2.00 g of the obtained copolymer was dissolved in 8.00 g of N-methyl-2-pyrrolidone, and the pore size was 0.2 μm.
Was filtered through a Teflon (R) filter to obtain a varnish.
The varnish was applied on a silicon wafer on which aluminum was deposited using a spin coater. At this time, the rotation speed and time of the spin coater were set so that the film thickness after the heat treatment was 1 to 10 μm. After coating, the coating was dried on a hot plate at 120 ° C. for 240 seconds, and then heated at 300 ° C. for 60 minutes using an oven in which nitrogen was introduced and the oxygen concentration was controlled to 100 ppm or less, so that the terminal was reacted with the oligomer. A polybenzoxazole 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 is deposited on the film,
An electrode having a predetermined size was formed by patterning.
The aluminum on the silicon wafer side and the capacitance by this electrode were measured, and after the measurement, the electrode adjacent part of the film was etched with oxygen plasma, and the film thickness was measured with a surface roughness meter to obtain a dielectric constant at a frequency of 1 MHz. The calculated value was 2.54. When the cross section of this film was observed with a TEM, the obtained voids were discontinuous with an average pore diameter of 15 nm. Heat resistance, T
g and water absorption are also shown in Table 1.

(Example 2) In Example 1, 4-ethynyl-2,6-naphthalenedicarboxylic acid chloride 0.8
2.6 g of a copolymer was obtained in the same manner as in Example 1, except that 28 g (3.0 mmol) of 2-ethynyl terephthalic acid chloride was used. 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 28,000 and the molecular weight distribution was 2.51. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 42% by weight. A sample for evaluation was obtained from the obtained copolymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

(Example 3) In Example 1, 2,2-
Instead of 1.022 g (2.79 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene 1 .575
g (2.79 mmol) was carried out in the same manner as in Example 1 except that g (2.79 mmol) was used to obtain 3.2 g of a copolymer. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation, and the weight average molecular weight was 32,000.
0, molecular weight distribution 2.61. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 36% by weight.
A sample for evaluation was obtained from the obtained copolymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 4 In Example 1, 1.47 g (0.4%) of 1-aminopropylnorbornene oligomer was used.
2 mmol, number average molecular weight 3500),
1.47 g of chloroformyl norbornene oligomer
(0.42 mmol, number average molecular weight 3500) was performed in the same manner as in Example 1 except that 2.8 g of a copolymer was obtained. The molecular weight of the obtained copolymer was determined using Tosoh Corporation G
The weight-average molecular weight was 23,000 and the molecular weight distribution was 2.51 as determined in terms of polystyrene using PC.
^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 4
It was 0% by weight. A sample for evaluation was obtained from the obtained copolymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

(Example 5) In Example 1, 2,2-
1.022 g (2.79 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 1.47 g of 1-aminopropylnorbornene oligomer
1.575 g of 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene instead of (0.42 mmol, number average molecular weight 3500)
(2.79 mmol) and 1.47 g of anhydrous 1,2-dicarboxypropylnorbornene oligomer (0.42 m
mol, number average molecular weight 3500), except that 3.0 g of a copolymer was obtained. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation.
000, molecular weight distribution 2.41. ¹ H-NM
By R, the introduction ratio of the reactive oligomer component was 37% by weight. A sample for evaluation was obtained from the obtained copolymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

(Example 6) In Example 1, 4-ethynyl-2,6-naphthalenedicarboxylic acid chloride 0.8
Instead of 28 g (3.0 mmol), 0.340 g (0.15 mmol) of 5-ethynyl-terephthalic acid chloride and 0.380 g of 2,6-naphthalenedicarboxylic acid chloride
(0.15 mmol), except that 2.6 g of a copolymer was obtained. When 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 42% by weight. A sample for evaluation was obtained from the obtained copolymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

(Example 7) In Example 1, 4-ethynyl-2,6-naphthalenedicarboxylic acid chloride 0.8
Instead of 28 g (3.0 mmol), 0.909 g (3.0 mmol) of 5-phenylethynylisophthalic chloride was used.
l) was carried out in the same manner as in Example 1 except that l) was used to obtain 2.7 g of a copolymer. When 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 2.2.
It was 0. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 40% by weight. A sample for evaluation was obtained from the obtained copolymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

(Example 8) In Example 1, 4-ethynyl-2,6-naphthalenedicarboxylic acid chloride 0.8
Instead of 28 g (3.0 mmol), 0.831 g (3.0 mm) of 2,7-biphenylenedicarboxylic acid dichloride was used.
ol) was used in the same manner as in Example 1 except that 2.8 g of a copolymer was obtained. The molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation, and the weight average molecular weight was 25,300 and the molecular weight distribution was 2.
21. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 40% by weight. A sample for evaluation was obtained from the obtained copolymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Example 9 The procedure of Example 1 was repeated except that 0.8% of 4-ethynyl-2,6-naphthalenedicarboxylic acid chloride was used.
Instead of 28 g (3.0 mmol), 0.909 g (3.0 mmol) of 4,4′-trandicarboxylic acid chloride
Was used in the same manner as in Example 1 except that copolymer was used.
8 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 25,100 and the molecular weight distribution was 2.21.
Met. ^{According to 1} H-NMR, the introduction ratio of the reactive oligomer component was 39% by weight. A sample for evaluation was obtained from the obtained copolymer 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
076 g (2.94 mmol) were dissolved in 10 mL of dried N-methyl-2-pyrrolidone, and the solution was added with 5-ethynyl-2,6-naphthalenedicarboxylic acid chloride (0.1 mL).
828 g (3.0 mmol) 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 heating to 10 ° C, triethylamine 0.6
After adding 68 g (6.6 mmol) 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 subjected to 200 mL of ion-exchanged water and 500 mL of isopropanol.
1.57 g of a polymer was obtained by adding dropwise to the mixed solution of mL and collecting and drying the precipitate. When the molecular weight of the obtained polymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation, the weight average molecular weight was 23,600,
The molecular weight distribution was 2.24. An evaluation sample was obtained from the obtained polymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

Comparative Example 2 The same procedure as in Comparative Example 1 except that 5-ethynyl-2,6-naphthalenedicarboxylic acid chloride 0.8
In the same manner as in Comparative Example 1 except that 0.609 g (3 mmol) of terephthalic acid chloride was used instead of 28 g (3.0 mmol), 1.41 g of a polymer 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 23,000 and the molecular weight distribution was 2.41. An evaluation sample was obtained from the obtained polymer in the same manner as in Example 1, and the measurement results were summarized in Table 1.

[0063]

[Table 1]

From the evaluation results of Examples and Comparative Examples summarized in Table 1, the insulating film (coating) obtained from the insulating film material 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. In addition, the porosity calculated from the logarithmic mixing equation using the measured dielectric constant almost coincided with the reactive oligomer introduction rate.

[0065]

According to the present invention, it is possible to reduce the dielectric constant while maintaining excellent heat resistance and low water absorption while maintaining excellent characteristics such as electrical characteristics, thermal characteristics and mechanical characteristics. The insulating film obtained by the insulating film material and the insulating film coating varnish containing the same can be used as an interlayer insulating film for a semiconductor, a protective film, an interlayer insulating film of a multilayer circuit, a flexible copper It can be suitably used for applications such as a cover coat of a plate, a solder resist film, and a liquid crystal alignment film.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J001 DA01 DB03 DC05 DC08 DC14 DD01 DD04 EB02 EB33 EB34 EB35 EB36 EB37 EB44 EB45 EB46 EB56 EB57 EB60 EB64 EC02 EC43 EC44 EC54 EC55 EC66 EC67 EC70 EC74 GE00 J01 J07 JB18B 4J031 AA28 AA55 AB02 AC03 AC07 AD01 AF24 4J038 CM012 DH001 GA03 NA21 5F058 AC02 AH02 AH03 5G305 AA07 AA11 AB10 AB15 AB24 AB26 BA09 CA20 CA32 CB28

Claims (21)

[Claims] 1. A reaction between a polyamide having a repeating unit represented by the general formula (A) and a reactive oligomer having a substituent capable of reacting with a carboxyl group, an amino group or a hydroxyl group in the polyamide structure. An insulating film material made of a reduced copolymer, wherein the reactive oligomer is a compound having a norbornene structure. Embedded image (Wherein, R _{1 to} R ₄ represent a hydrogen atom or a monovalent organic group, X represents a tetravalent group selected from the groups represented by the formula (B), and two Xs may be the same or different, and Y ₁ is at least one selected from the groups represented by formulas (C), (D), (E), and (F).
Two divalent groups, Y ₂ represents a divalent group selected from the groups represented by the formula (G), m and n are m> 0,
n ≧ 0, 2 ≦ m + n ≦ 1000, and 0.05 ≦ m /
It is an integer satisfying (m + n) ≦ 1, and the arrangement of the repeating units in the general formula (A) may be block-like or random. ) Embedded image Embedded image Embedded image Embedded image Embedded image (However, in the formulas (B) and (G), X ₁ represents a divalent group selected from the groups represented by the formula (H). R in the formula (D)
Represents a naphthalene group, a phenyl group, or an alkyl group. Equations (B), (D), (E), (F),
In the groups represented by the formulas (G) and (H), the hydrogen atom on the benzene ring is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom Or a trifluoromethyl group, and may be substituted with at least one group. ) 2. The insulating film material according to claim 1, wherein the polyamide has a divalent group selected from the groups represented by the formula (C) as Y ₁ in the general formula (A). 3. The insulating film material according to claim 1, wherein the polyamide has a divalent group selected from the groups represented by formula (D) as Y ₁ in general formula (A). 4. The insulating film material according to claim 1, wherein the polyamide has a divalent group selected from the groups represented by the formula (E) as Y ₁ in the general formula (A). 5. The insulating film material according to claim 1, wherein the polyamide has, as Y ₁ in the general formula (A), a divalent group selected from the groups represented by the formula (F). 6. The insulating film material according to claim 1, wherein the reactive oligomer is a norbornene type and contains a hydroxyl group. 7. The insulating film material according to claim 1, wherein the reactive oligomer has a norbornene type and contains an amino group. 8. The insulating film material according to claim 1, wherein the reactive oligomer is a norbornene type and contains a carboxyl group or a carboxylic acid derivative as a substituent. 9. The insulating film material according to claim 1, wherein the reactive oligomer is a norbornene-type acid anhydride compound. 10. The reactive oligomer is polyamide 10
2. The composition according to claim 1, wherein the amount is 5 to 70 parts by weight based on 0 parts by weight.
10. The insulating film material according to any one of items 1 to 9. 11. The method according to claim 11, wherein the reactive oligomer is polyamide 10
2. The composition according to claim 1, wherein 5 to 50 parts by weight is added to 0 part by weight.
10. The insulating film material according to any one of items 1 to 9. 12. The reactive oligomer is a polyamide 10
2. The composition according to claim 1, wherein 5 to 40 parts by weight is added to 0 part by weight.
10. The insulating film material according to any one of items 1 to 9. 13. 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 for insulating films that can produce films. 14. An insulating film material according to claim 1 or a coating varnish according to claim 13, which is subjected to a heat treatment to cause a condensation reaction and a cross-linking reaction. An insulating film comprising a resin layer having polybenzoxazole as a main structure and having fine pores. 15. The insulating film according to claim 14, wherein the size of the fine holes in the insulating film is 1 μm or less. 16. The insulating film has a fine pore size of 500 n.
The insulating film according to claim 14, which is not more than m. 17. The size of a fine hole in an insulating film is 100 n.
The insulating film according to claim 14, which is not more than m. 18. The size of a fine hole in an insulating film is 20 nm.
The insulating film according to claim 14, wherein: 19. The insulating film according to claim 14, wherein the porosity of the insulating film is 5% to 70%. 20. The insulating film according to claim 14, wherein the porosity of the insulating film is 5% to 50%. 21. The insulating film according to claim 14, wherein the porosity of the insulating film is 5% to 40%.