JP2003128990A - Material for electrical insulation film, coating varnish for electrical insulation film, and electrical insulation film and semiconductor device using them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material for electrical insulation films having excellent electrical properties, thermal properties and mechanical properties, etc., and enabling themselves to be brought to lower dielectric constant, to provide a coating varnish for such films including the material, to provide such electrical insulation films using them, and to provide semiconductor devices having such electrical insulation films. SOLUTION: This material includes as a film-forming component a copolymer obtained by reaction between a polyamide with a specific structure and a reactive oligomer. The 2nd objective coating varnish comprises the material and an organic solvent. The 3rd objective electrical insulation film is composed of layer(s) of a resin with polybenzoxazole as the principal structure obtained by treating the coating varnish under heating to effect condensation reaction and crosslinking reaction and has micropores. The last objective semiconductor device has interlaminar electrical insulation film(s) for multilayer wiring use and/or a surface-protective layer consisting of the electrical insulation film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an insulating film material, an insulating film coating varnish, an insulating film using the same, and a semiconductor device. More specifically, the present invention provides
It has excellent electrical properties, thermal properties, mechanical properties, etc., and can have a low dielectric constant.
Insulating film material suitably used for interlayer insulating film of multilayer circuit, cover coat of flexible copper clad board, solder resist film, liquid crystal alignment film, etc., insulating film coating varnish containing the same and insulating film using these, It also relates to a semiconductor device having the insulating film.

[0002]

2. Description of the Related Art As materials for semiconductors, inorganic materials, organic materials 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 deposition method is used. However, with the recent increase in speed and performance of semiconductors, in the above inorganic oxide film,
The high relative dielectric constant has been a problem. The application of organic materials is being studied as one of the means for improving this.

As an organic material for semiconductor use, heat resistance,
Polyimide resins, which have excellent electrical and mechanical properties, are mentioned and are used in solder resists, coverlays, liquid crystal alignment films, and the like. However, since a polyimide resin generally has two carbonyl groups in the imide ring, it has problems in water absorption and electric characteristics. In order to solve these problems, it has been attempted to introduce water or fluorine-containing groups into the organic polymer to improve water absorption and electrical characteristics, and some of them have been put into practical use. Also,
There is a polybenzoxazole resin that shows superior performance in heat resistance, water absorption, and electrical characteristics as compared with a polyimide resin, and its application to various fields has been attempted. For example, those having a structure composed of 4,4′-diamino-3,3′-dihydroxybiphenyl and terephthalic acid, 2,2
There are polybenzoxazole resins having a structure composed of -bis (3-amino-4-hydroxyphenyl) hexafluoropropane and terephthalic acid. However,
In the advanced field where even more strict heat resistance, electrical characteristics, water absorption and the like are required, materials that satisfy all such requirements have not yet been obtained. That is, although excellent heat resistance is exhibited, electric characteristics such as a dielectric constant are not sufficient, and although introduction of fluorine improves the electric characteristics, the heat resistance is deteriorated. In particular, when an organic material is applied as an interlayer insulating film for semiconductors, it is required to have heat resistance, mechanical properties and water absorption comparable to those of inorganic materials, and further lower dielectric constant is required. To meet such demands for high performance, by forming fine pores in the inorganic oxide film, which is an inorganic material,
Methods for reducing the density and reducing the relative permittivity are being studied. The relative permittivity of air is 1, and it is disclosed in US Pat. No. 3,883,4 that air is introduced into the film to lower the relative permittivity.
By analogy with the method described in No. 52 for producing a foamed polymer having an average pore size 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 and have an averaged relative dielectric constant, and the mechanical properties of the film itself. Must also be able to withstand each process. At present, an inorganic material that overcomes such a problem has not yet been obtained.

On the other hand, as for the technique for obtaining submicrometer-order micropores in organic materials, a technique has been disclosed in which a block copolymer is heat-treated to produce a resin having submicrometer-order micropores. (U.S. Pat. No. 5,776,990).
It is known that block copolymers undergo phase separation on the order of sub-micrometer [T. Hashimoto,
M. Shibayama, M. Fujimura and H. Kawai, "Microphase Se
paration and the Polymer-polymer Interphase in Blo
ck Polymers "in" Block Copolymers-Science and Tech
nology ", p.63, Ed. By DJMeier (Academic Pub., 19
It is also well known in the field of polymer chemistry that polymers with a low ceiling temperature easily decompose. However, while satisfying not only the relative dielectric constant but also the mechanical properties, electrical properties, water absorption resistance, and heat resistance,
In order to obtain a resin composition having fine pores, the selection of the combination of resin, blocking technology, heat decomposable component, etc. is very limited, and the fact that all properties are not satisfied has not been obtained. Is.

[0005]

Under the above circumstances, the present invention provides a material for an insulating film which is excellent in electrical characteristics, thermal characteristics, mechanical characteristics, etc., and which enables a low dielectric constant. The present invention has been made for the purpose of providing a coating varnish for an insulating film containing the above, an insulating film using the same, and a semiconductor device having the insulating film.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors isolated a copolymer obtained by reacting a polyamide having a specific structure and a reactive oligomer with each other. It was found that the object can be achieved by using it as a film forming component of a film material, and the present invention has been completed based on this finding.

That is, the present invention provides (1) a polyamide having a branched structure obtained by reacting a part of the polyamide structure represented by the general formula (A) with a bisaminophenol and a polyfunctional carboxylic acid. An insulating film containing a copolymer obtained by reacting a reactive oligomer having a substituent capable of reacting with a carboxyl group, an amino group or a hydroxyl group in the polyamide structure as a film forming component. Materials for

[Chemical 11] [Wherein R _{1 to} R ₄ are each independently a hydrogen atom or a monovalent organic group, and X represents a tetravalent group selected from the groups represented by the following formula (B), X may be the same or different, and Y is at least one divalent group selected from the groups represented by the following formula (C), formula (D), formula (E) and formula (F): , Z represents a divalent group selected from the groups represented by formula (G), and m and n are m> 0 and n ≧, respectively.
0, 2 ≦ m + n ≦ 1000 and 0.05 ≦ m / (m +
n) is an integer that satisfies the relationship of ≦ 1, and the arrangement of repeating units may be either block-like or random. ]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18] [X _{1 in} Formula (B) and Formula (G) is the Formula (H)]

[Chemical 19] Represents a divalent group selected from the groups represented by: R in formula (D) is an alkyl group or formula (I)

[Chemical 20] A monovalent group selected from the groups represented by The hydrogen atom on the benzene ring in the groups represented by formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) and formula (H) is a carbon atom. It may be substituted with at least one group selected from the alkyl groups of formulas 1 to 4, a fluorine atom and a trifluoromethyl group. ] (2) Polyfunctional carboxylic acid is trimeric acid, trimesic acid, 1,3,5
-Cyclohexanetricarboxylic acid, 5,5'-bisisophthalic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, biphenylether-3,3', 5,5'-tetracarboxylic acid, 3,3 ' 2. The insulating film material according to claim 1, which is selected from 4,4 '-(1,1'-hexafluoroisopropylidenebiphenyl) tetracarboxylic acid and 1,2,3,4,5,6-benzenehexacarboxylic acid. And (3) the polyamide according to claim 1, wherein Y in the general formula (A) has a divalent group selected from the groups represented by the formula (C). The membrane material (4), wherein the polyamide (4) has a divalent group selected from the groups represented by the formula (D) as Y in the general formula (A). The insulating film material described above, (5) polyamide, as Y in the general formula (A), The first term to the insulating film material of the second term, wherein those having a divalent group selected from groups represented by (E), is (6) a polyamide,
(7) The material for an insulating film as described in the item 1 or 2, wherein Y in the general formula (A) has a divalent group selected from the groups represented by the formula (F). Any of the first to sixth items, wherein the reactive oligomer is at least one selected from polyoxyalkylene, polymethylmethacrylate, polyα-methylstyrene, polystyrene, polyester, polyetherester, polycaprolactone and polyurethane. Insulating film material,
(8) The reactive oligomer has a number average molecular weight of 100 to 4
The insulating film material according to any one of items 1 to 7, which has a number average molecular weight of 100 to 20,000, and (9) the reactive oligomer having a number average molecular weight of 100 to 20,000. The insulating film material, (10) the reactive oligomer has a number average molecular weight of 100 to 10,000, and the insulating film material (11), wherein the (11) copolymer has a reactive oligomer unit of 5 to 70. The insulating film material according to any one of items 1 to 10, wherein 1% by weight is introduced, (1
2) The insulating film material according to item 11, wherein the copolymer has 5 to 50% by weight of a reactive oligomer unit, and (13) the copolymer is a reactive oligomer unit 5
Insulating film material according to item 12, wherein (14) the material for insulating film according to any one of (1) to (13) is dissolved, or 15. A coating varnish for an insulating film, comprising the organic solvent capable of being dispersed, (15) the insulating film material according to any one of items 1 to 13 or the insulating film material according to claim 14. The coating varnish for an insulating film is composed of a resin layer having a main structure of polybenzoxazole obtained by subjecting the coating varnish to a heat treatment to cause a condensation reaction and a crosslinking reaction, and
An insulating film having fine holes, (16) an insulating film according to item 15, wherein the size of the fine holes of the insulating film is 1 μm or less, and (17) the size of the fine holes of the insulating film, 500
Insulating film according to item 16, which has a size of nm or less, (18) Insulating film according to item 17, which has a size of 100 nm or less, or (19) 20
The insulating film according to item 18, which has a porosity of 5 to 70%, and the insulating film according to any one of items 15 to 19, which has a porosity of 5 to 70%. The insulating film according to item 20, wherein the porosity is 5 to 50%, (22)
The insulating film according to item 21, wherein the insulating film has a porosity of 5 to 40%, (23) The insulating film according to any one of items 15 to 22, which is used as an interlayer insulating film for semiconductor multilayer wiring, (24) The insulating film according to any one of items 15 to 22 used as a semiconductor surface protective film, and (2
5) A semiconductor device comprising: an interlayer insulating film for multilayer wiring, which is formed of the insulating film according to item 23; and / or a surface protective layer, which is formed of the insulating film according to item 24.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The material for an insulating film of the present invention contains a copolymer obtained by reacting a polyamide and a reactive oligomer as a film-forming component, and the polyamide in the copolymer is used. In the main chain of the unit, a branched structure that previously functions as a crosslinked structure, and ethynyl that is crosslinked by heating,
Phenylethynyl, alkylethynyl, biphenylene,
And introducing at least one skeleton of internal acetylene,
A resin having high heat resistance is provided by converting the amide group into polybenzoxazole by a ring-closing reaction and by crosslinking the ethynyl, phenylethynyl, alkylethynyl, biphenylene, and internal acetylene skeletons into a three-dimensional resin structure. be able to. Then, the oligomer unit in the copolymer is thermally decomposed in the resin heating step and volatilized to form a fine pore in the resin film having a polybenzoxazole resin as a main structure to easily reduce the dielectric constant, The essence of the present invention is to obtain a porous insulating film having both heat resistance and electrical characteristics.

The polyamide constituting the polyamide unit in the copolymer in the insulating film material of the present invention has a structure represented by the above general formula (A). This polyamide comprises at least one bisaminophenol compound having any one of the tetravalent groups represented by the formula (B), the formula (C), the formula (D), the formula (E) and the formula (E). At least one dicarboxylic acid having any of the divalent groups represented by (F) is used or as the dicarboxylic acid, the dicarboxylic acid and the divalent group represented by the formula (G). In combination with a dicarboxylic acid having any of the above, it can be obtained by a conventional acid chloride method, an activated ester method, a condensation reaction in the presence of a dehydration condensation agent such as polyphosphoric acid or dicyclohexylcarbodiimide, etc. . Polyamide structures with branched structures obtained by reacting partially used bisaminophenols with polyfunctional carboxylic acids can also be used for conventional acid chloride method, activated ester method, dehydration condensation of polyphosphoric acid, dicyclohexylcarbodiimide, etc. It can be introduced by a method such as a condensation reaction in the presence of an agent. Further, at least one of ethynyl, phenylethynyl, alkylethynyl, biphenylene, and internal acetylene.
Similar heat resistance can also be obtained by combining a polyamide having a different skeleton with another type of polyamide that has not been used in the past (no crosslinking reaction) to form an interpenetrating network structure. It is possible to obtain a resin having a strong property. In this case, ethynyl, phenylethynyl,
The polyamide having no alkylethynyl, biphenylene, or internal acetylene skeleton has at least one bisaminophenol compound having any one of the tetravalent groups represented by the above formula (B), and a polyamide represented by the formula (G). It can be obtained by a similar method using at least one dicarboxylic acid having any of the divalent groups represented.

The bisaminophenol compound having a tetravalent group represented by the formula (B) used in the present invention is
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'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone,
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'-diamino-3,3'-dihydroxy-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-bis (trifluoro Methyl) 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 9,9-bis (4-
((4-amino-3-hydroxy) phenoxy) -3-
Phenyl-phenyl) -fluorene, 9,9-bis (4
-((3-amino-4-hydroxy) phenoxy) -3
-Phenyl-phenyl) -fluorene, 9,9-bis ((2-amino-3-hydroxy-4-phenyl) -phenyl) -fluorene, 9,9-bis ((2-hydroxy-3-amino-4-) Phenyl) -phenyl) -fluorene and the like. These may be used alone,
Moreover, you may use it in combination of 2 or more types.

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'-diethynyl-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'-diethynyl-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, 2,2-bis (4-
Carboxy-2-ethynylphenyl) hexafluoropropane, 4-ethynyl-1,3-dicarboxycyclopropane, 5-ethynyl-2,2-dicarboxycyclopropane, 1,3-bis (4-carboxy-phenoxy)
Structural isomers of 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,
Examples thereof include 2- (3-ethynyl-phenyl) -terephthalic acid, but are not limited thereto. These may be used alone or in combination of two or more. It is also possible to use two or more bisaminophenol compounds 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 and 2
-Phenylethynyl isophthalic acid, 4-phenylethynyl isophthalic acid, 5-phenylethynyl isophthalic 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, 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, structure of 1,3-bis (4-carboxy-phenyl) -5-phenylethynyl-benzene Isomer, 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 can be mentioned.

Further, a dicarboxylic acid having a structure represented by the formula (D), in which R is a biphenylethynyl group which is a biphenyl group among the monovalent groups represented by the formula (I), used in the present invention. Examples of 3-biphenylethynylphthalic acid, 4-biphenylethynylphthalic acid, 2-biphenylethynylisophthalic acid, 4-biphenylethynylisophthalic acid, 5-biphenylethynylisophthalic acid, 2-biphenylethynylterephthalic acid, 3-biphenyl Ethynyl terephthalic acid, 5-biphenylethynyl-terephthalic acid, 2-biphenylethynyl-1,5-naphthalenedicarboxylic acid, 3-biphenylethynyl-1,5-naphthalenedicarboxylic acid, 4-biphenylethynyl-1,5-naphthalenedicarboxylic acid , 1-biphenylethynyl-2,
6-naphthalenedicarboxylic acid, 3-biphenylethynyl-2,6-naphthalenedicarboxylic acid, 4-biphenylethynyl-2,6-naphthalenedicarboxylic acid, 2-biphenylethynyl-1,6-naphthalenedicarboxylic acid, 3-
Biphenylethynyl-1,6-naphthalenedicarboxylic acid, 4-biphenylethynyl-1,6-naphthalenedicarboxylic acid, 5-biphenylethynyl-1,6-naphthalenedicarboxylic acid, 7-biphenylethynyl-1,6-naphthalenedicarboxylic acid, 8-biphenylethynyl-1,
6-naphthalenedicarboxylic acid, 3,3'-dibiphenylethynyl-2,2'-biphenyldicarboxylic acid, 4,4'-dibiphenylethynyl-2,2'-biphenyldicarboxylic acid, 5,5'-dibiphenylethynyl -2,2'-biphenyldicarboxylic acid, 6,6'-dibiphenylethynyl-2,
2'-biphenyldicarboxylic acid, 2,2'-dibiphenylethynyl-3,3'-biphenyldicarboxylic acid, 4,4'-
Dibiphenylethynyl-3,3'-biphenyldicarboxylic acid, 5,5'-dibiphenylethynyl-3,3'-biphenyldicarboxylic acid, 6,6'-dibiphenylethynyl-3,
3'-biphenyldicarboxylic acid, 2,2'-dibiphenylethynyl-4,4'-biphenyldicarboxylic acid, 3,3'-
Dibiphenylethynyl-4,4′-biphenyldicarboxylic acid, 2,2-bis (2-carboxy-3-biphenylethynylphenyl) propane, 2,2-bis (2-carboxy-4-biphenylethynylphenyl) propane,
2,2-bis (2-carboxy-5-biphenylethynylphenyl) propane, 2,2-bis (2-carboxy-6-biphenylethynylphenyl) propane, 2,2
-Bis (3-carboxy-2-biphenylethynylphenyl) propane, 2,2-bis (3-carboxy-4-)
Biphenylethynylphenyl) propane, 2,2-bis (3-carboxy-5-biphenylethynylphenyl)
Propane, 2,2-bis (3-carboxy-6-biphenylethynylphenyl) propane, 2,2-bis (4-
Carboxy-2-biphenylethynylphenyl) propane, 2,2-bis (4-carboxy-3-biphenylethynylphenyl) propane, 2,2-bis (2-carboxy-4-biphenylethynylphenyl) hexafluoropropane, 2, 2-bis (3-carboxy-5-biphenylethynylphenyl) hexafluoropropane,
2,2-bis (4-carboxy-2-biphenylethynylphenyl) hexafluoropropane, 2,2-bis (4-carboxy-2-biphenylethynylphenyl)
Hexafluoropropane, 4-biphenylethynyl-
1,3-dicarboxycyclopropane, 5-biphenylethynyl-2,2-dicarboxycyclopropane, 1,3
Structural isomers of -bis (4-carboxy-phenoxy) -5-biphenylethynyl-benzene, 1,3-bis (4
-Carboxy-phenyl) -5-biphenylethynyl-
Structural isomers of benzene, 5- (3-biphenylethynyl-phenoxy) -isophthalic acid, 5- (1-biphenylethynyl-phenoxy) -isophthalic acid, 5- (2-biphenylethynyl-phenoxy) isophthalic acid, 2-
(1-biphenylethynyl-phenoxy) terephthalic acid, 2- (2-biphenylethynyl-phenoxy) terephthalic acid, 2- (3-biphenylethynyl-phenoxy) terephthalic acid, 5- (1-biphenylethynyl-phenyl) -isophthalic acid 5- (2-biphenylethynyl-phenyl) -isophthalic acid, 5- (3-biphenylethynyl-phenyl) -isophthalic acid, 2- (1-biphenylethynyl-phenyl) -terephthalic acid, 2- (2
-Biphenylethynyl-phenyl) -terephthalic acid, 2
Examples thereof include, but are not limited to,-(3-biphenylethynyl-phenyl) -terephthalic acid. These may be used alone or in combination of two or more. It is also possible to use two or more bisaminophenol compounds in combination.

Examples of R being an alkyl group include 3-hexynylphthalic acid, 4-hexynylphthalic acid, 2-hexynylisophthalic acid, 4-hexynylisophthalic acid, 5
-Hexynyl isophthalic acid, 2-hexynyl terephthalic acid, 3-hexynyl terephthalic 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'-di Xynyl-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-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, 1,3-bis (4-carboxy- Phenoxy) -5-hexynyl-benzene structural isomers, 1,
Structural isomers of 3-bis (4-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, 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, but not limited thereto. These may be used alone or in combination of two or more. It is also possible to use two or more bisaminophenol compounds in combination.

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 and 1,3-
Biphenylenedicarboxylic acid, 1,4-biphenylenedicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 1,6-
Biphenylenedicarboxylic acid, 1,7-biphenylenedicarboxylic acid, 1,8-biphenylenedicarboxylic acid, 2,3-
Examples thereof include biphenylenedicarboxylic acid, 2,6-biphenylenedicarboxylic acid, and 2,7-biphenylenedicarboxylic acid. From the performance of the resulting coating film, 2,6-biphenylenedicarboxylic acid and 2,7-biphenylenedicarboxylic acid are particularly preferable. . These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid having a divalent group represented by the formula (F) used in the present invention include 4,4'-transdicarboxylic acid, 3,4'-transdicarboxylic acid and 3,3 '. −
Transdicarboxylic acid, 2,4′-transdicarboxylic acid,
One or a mixture of 2,3′-transdicarboxylic acid and 2,2′-transdicarboxylic acid can be used.

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,
3,4'-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 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, 9,9-bis- (2-carboxy-phenyl) fluorene, 9,9
-Bis- (3-carboxy-phenyl) fluorene,
9,9-bis- (4-carboxy-phenyl) fluorene, bis-((2-carboxy-3-phenyl) -phenyl) -fluorene, bis-((4-carboxy-3-
Phenyl) -phenyl) -fluorene, bis-((5-
Carboxy-3-phenyl) -phenyl) -fluorene, bis-((6-carboxy-3-phenyl) -phenyl) -fluorene, 9,9-bis (4- (2-carboxy-phenoxy) -phenyl) -fluorene , 9,9
-Bis (4- (3-carboxy-phenoxy) -phenyl) -fluorene, 9,9-bis (4- (4-carboxy-phenoxy) -phenyl) -fluorene, 9,9-
Bis ((4- (2-carboxy-phenoxy) -3-phenyl) -phenyl) -fluorene, 9,9-bis ((4- (3-carboxy-phenoxy) -3-phenyl) -phenyl) -fluorene, 9,9-bis ((4-
(4-carboxy-phenoxy) -3-phenyl) -phenyl) -fluorene and the like can be mentioned, and these may be used alone or in combination of two or more kinds. The hydrogen atom on the benzene ring in the groups represented by formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) and formula (H) is It may be substituted with at least one group selected from an alkyl group having 1 to 4 carbon atoms, a fluorine atom and a trifluoromethyl group. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a t-butyl group.

As the polyfunctional carboxylic acid used in the present invention,
Preferably trimeric acid, trimesic acid, 1,3,5
-Cyclohexanetricarboxylic acid, 5,5'-bisisophthalic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, biphenylether-3,3', 5,5'-tetracarboxylic acid, 3,3 ' , 4,4 '-(1,1'-hexafluoroisopropylidenephenyl) tetracarboxylic acid, 1,2,3,4,5,6-benzenehexacarboxylic acid and the like. These may be used alone,
Moreover, you may use it in combination of 2 or more types. The amount of the polyfunctional carboxylic acid used is the dicarboxylic acid 1 used.
The amount is preferably 0.001 to 0.1 mol, and more preferably 0.005 to 0.08 mol. 0.00
If it is smaller than 1, the pore size may be non-uniform. On the other hand, if it is more than 0.1 mol, gelation may occur during the reaction to make it unusable. Further, the bisaminophenols used for the polyamide having a branched structure may be the same as the bisaminophenol compound having a tetravalent group represented by the formula (B).

In the polyamide of the present invention, with respect to m and n in the general formula (A), which is the number of repeating units having a crosslinkable skeleton and the number of repeating units having no crosslinkable skeleton, m and n are respectively m> 0, n ≧ 0, 2 ≦ m +
It is an integer that satisfies the relationship of n ≦ 1000 and 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 deteriorated and the mechanical strength of the resin film becomes insufficient. On the other hand, if it exceeds 1000, the molecular weight becomes too large and it becomes difficult to dissolve in a solvent, or even if it dissolves, it becomes a viscous varnish, which is not practical. m and n are 0.05 ≦ m / (m
It is essential that it is an integer that satisfies + n) ≦ 1, and more preferably 0.5 ≦ m / (m + n) ≦ 1. When 0.05> m / (m + n), it 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. Uneven fine pores are not preferable.

In the general formula (A), the repeating unit sequence may be block-like or random. For example, as a method for producing a block-like repeating unit, in the case of the acid chloride method, a bisaminophenol compound having a tetravalent group selected from the formula (B) and a divalent group selected from the formula (G) are included. After diluting with a chloride of dicarboxylic acid in advance to increase the molecular weight, a bisaminophenol compound having a tetravalent group selected from the formula (B) is reacted with a chloride of a polyfunctional carboxylic acid, and the formula (B ) To a bisaminophenol compound having a tetravalent group selected from the group consisting of divalent groups represented by formula (C), formula (D), formula (E) and formula (F). It can be obtained by reacting with a chloride of a dicarboxylic acid having a contributing structure. The order is not limited as long as it has a block-like structure.

In the case of a random repeating unit, a bisaminophenol compound having a tetravalent group selected from the formula (B), a chloride of a dicarboxylic acid having a divalent group selected from the formula (G) and a formula (C). ), A formula (D), a formula (E) and a formula (F), a dicarboxylic acid having a structure that contributes to crosslinking selected from divalent groups and a chloride of a polyfunctional carboxylic acid are simultaneously reacted. Can be obtained.

In the present invention, the reactive oligomer used in the reaction with the polyamide has in its structure a reactive substituent capable of reacting with the carboxyl group, amino group or hydroxyl group in the polyamide structure. As the reactive substituent, it is essential to have a carboxyl group, an amino group or a hydroxyl group, and it must be an oligomer that thermally decomposes at a temperature lower than the thermal decomposition temperature of polyamide and the decomposed product vaporizes. Specific examples include polyoxymethylene, polyoxyethylene, polyoxymethylene-oxyethylene copolymer, polyoxymethylene-oxypropylene copolymer, polyoxyethylene-oxypropylene copolymer, polyoxytetrahydrofuran and other polyoxymethylene. Alkylene, polymethylmethacrylate,
Suitable examples include polyurethane, poly α-methylstyrene, polystyrene, polyester, polyether ester, polycaprolactone and the like. These may be used alone or in combination of two or more. As this reactive oligomer, one having a reactive substituent introduced at one end or both ends of the side chain or main chain can be used. Industrially easily available,
It is a reactive oligomer in which the ends of the main chain are modified. More specifically, 4-aminobenzoic acid ester-terminated 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 has a number average molecular weight of 1
The range of 00-40,000 is preferable. More preferably, the number average molecular weight is 100 to 20,000,
More preferably, the number average molecular weight is 100 to 10,000.
It is in the range of. If the molecular weight is less than 100, the voids after decomposition and vaporization are small and easily crushed, so that it is difficult to achieve a reduction in the relative dielectric constant. On the other hand, if the molecular weight exceeds 40,000, the voids become too large and the mechanical properties of the insulating film are extremely deteriorated, which may cause a problem that it cannot be put to practical use. In the present invention, the amount of the reactive oligomer unit introduced into the copolymer is preferably 5 to 70% by weight. It is more preferably 5 to 50% by weight, and further preferably 5 to 40% by weight. If the amount introduced is less than 5% by weight, the porosity in the insulating film is small and it is insufficient to reduce the dielectric constant, and if it exceeds 70% by weight, the porosity in the film becomes large. The mechanical strength of No. 1 is extremely reduced, the voids are continuous and non-uniform, and the dielectric constant varies depending on the location, which is not preferable. Therefore, when reacting polyamide and reactive oligomer,
It is important to adjust the introduced amount of the reactive oligomer unit in the obtained copolymer to be in the above range.

In the present invention, examples of the method for producing the copolymer include a conventional acid chloride method, an activated ester method, a condensation reaction in the presence of a dehydrating condensation agent such as polyphosphoric acid and dicyclohexylcarbodiimide. Can be used. For example, in the acid chloride method, the dicarboxylic acid chloride and polyfunctional carboxylic acid chloride to be used are
In the presence of a solvent such as N-dimethylformamide, the dicarboxylic acid and an excess amount of thionyl chloride are mixed at room temperature to 130 ° C.
It can be obtained by reacting at about temperature, distilling off excess thionyl chloride by heating and reducing pressure, and recrystallizing the residue with a solvent such as hexane. When the dicarboxylic acid chloride and polyfunctional carboxylic acid chloride thus produced are used in combination with the other dicarboxylic acid, an acid chloride obtained in the same manner is used together with a bisaminophenol compound, usually N-methyl-2- Pyrrolidone, N, N
-Dissolved in a polar solvent such as dimethylacetamide, reacted in the presence of an acid acceptor such as pyridine and triethylamine at a temperature from room temperature to about -30 ° C to synthesize a polyamide. -Add the one dissolved in butyrolactone and react. Then, the reaction solution is added to a mixed solution of water and isopropyl alcohol, and the precipitate is collected and dried to obtain a copolymer in which the polyamide and the reactive oligomer are reacted. It is also possible to simultaneously react the acid chloride, the bisaminophenol compound and the reactive oligomer in a polar solvent to randomly synthesize a copolymer.

The charging molar ratio of the dicarboxylic acid and polyfunctional carboxylic acid chloride to the bisaminophenol compound is
It has a great influence on the molecular weight of the obtained polyamide and is important for controlling the end group structure of the polyamide. That is, in order to carry out the copolymerization reaction with the reactive oligomer, the end of the polyamide must be made reactive with the reactive group of the oligomer. That is, when the molar ratio of dicarboxylic acid and polyfunctional carboxylic acid chloride / bisaminophenol compound is less than 1, the end of the obtained polyamide has an amino group and a hydroxyl group and is copolymerized with an oligomer having a carboxyl group. Is possible. Further, when the molar ratio of acid chloride / bisaminophenol is larger than 1, the terminal of the obtained polyamide has a carboxyl group, and copolymerization with a reactive oligomer having an amino group or a hydroxyl group becomes possible. In this case, the terminal reactive group of the oligomer is more preferably an amino group having strong nucleophilicity. At this time, as an example of converting the terminal hydroxyl group of the oligomer to an amino group, a hydroxyl group-end reactive oligomer and 4-nitrobenzoic acid chloride are usually used in a solvent such as tetrahydrofuran in the presence of an acid acceptor such as pyridine at room temperature. A 4-nitrobenzoic acid ester-terminated oligomer can be obtained by reacting at a temperature of about -30 ° C. After that, this terminal oligomer is dissolved in a solvent such as tetrahydrofuran and reacted in the presence of a reducing catalyst such as palladium carbon in a hydrogen gas atmosphere,
After removing the catalyst from the reaction solution, the solvent is concentrated and removed to obtain a 4-aminobenzoic acid ester-terminated oligomer, which can be used as an amino group-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 a polyamide unit with a reactive oligomer having a carboxyl group or an isocyanate group. If there is, it is not particularly limited to these.

The insulating film material of the present invention may contain various additives in addition to the above-mentioned copolymer which is a film forming component depending on the purpose. Examples of various additives include a surfactant, a coupling agent typified by silanes, a radical initiator that generates oxygen radicals and sulfur radicals by heating, and a catalyst such as disulfides. Also,
The polyamide in the present invention is used as a positive photosensitive resin composition by using together with a naphthoquinonediazide compound as a photosensitizer, and at least one terminal of the hydroxyl group in the formula (A) has a methacryloyl group. When it is substituted with a group having such a photo-crosslinkable group, it can be used as a negative photosensitive resin composition by using a photoinitiator.

The insulating film material of the present invention can be used as a coating varnish by dissolving it in a suitable organic solvent or uniformly dispersing it. More specifically, the insulating film material is dissolved or uniformly dispersed in an organic solvent and applied on a suitable support such as glass, fiber, metal, silicon wafer, ceramic substrate and the like. Examples of the coating method include dipping, screen printing, spraying, spin coating, roll coating and the like. After coating, heating and drying can evaporate the solvent to form a tack-free coating film. Then, it is preferable to heat-treat and convert it into a crosslinked polybenzoxazole resin for use. Further, by selecting a dicarboxylic acid component, a bisaminophenol compound component and a reactive oligomer component, it can be used as a solvent-soluble polybenzoxazole resin.

The organic solvent for dissolving or dispersing the insulating film material of the present invention is preferably a solvent capable of completely dissolving solids, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethyl. Acetamide, 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-
Examples thereof include butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and tetrahydrofuran. These may be used alone or in combination of two or more. As the amount of solvent used when preparing a coating varnish,
There is no particular limitation as long as it is an amount capable of completely dissolving the material for the insulating film, and it can be appropriately adjusted according to its application. Generally, the solvent content in the varnish is 70 to 95.
About wt% is preferable.

In the insulating film material of the present invention, the coating film obtained as described above is subjected to heat treatment at a temperature of about 200 to 500 ° C. by evaporating the solvent at a temperature of usually 80 to 200 ° C. As a result, the polyamide unit in the insulating film material undergoes a cyclocondensation reaction and a crosslinking reaction to become a polybenzoxazole resin, and the oligomer unit in the insulating film material is thermally decomposed and decomposed at this time. Things vaporize
The insulating film of the present invention, which is a porous insulating film, can be obtained by volatilizing and forming fine pores in the resin layer having a polybenzoxazole main structure. The thermal history at this time is also important for forming fine pores. Usually, by using an oven or the like, heating is performed gradually and stepwise to form fine pores. According to the insulating film material of the present invention,
Good micropores can be obtained even when heated at once with a hot plate or the like. The heat treatment is preferably performed in an inert gas atmosphere or in vacuum. Examples of the inert gas include nitrogen gas and argon. At this time, the oxygen concentration in the system is preferably 100 ppm or less.

The size of the fine pores in the insulating film having the fine pores, which is composed of the resin layer containing polybenzoxazole as the main structure, depends on the use of the insulating film and the thickness of the film. , Generally 1 μm or less, preferably 500
nm or less, more preferably 100 nm or less, and preferably 20 n for applications such as interlayer insulating films for semiconductors.
m or less, and more preferably 5 nm or less. In the interlayer insulating film for semiconductor, the hole diameter is 20 nm.
If it is larger, the voids in the insulating film used between the wirings become non-uniform, and the electrical characteristics are not constant. In addition, the mechanical strength of the film is reduced, which causes a problem that the adhesiveness is adversely affected. However, 5 nm is not always necessary because there is an optimal film thickness and an optimal micropore size depending on the application of the film. The porosity of the insulating film is 5
˜70% is preferable, more preferably 5˜50%, further preferably 5˜40%. If the porosity is less than 5%, a sufficient decrease in the dielectric constant is difficult to be exhibited, and if it is more than 70%, the mechanical strength of the film is lowered, which may cause a problem such as adversely affecting the adhesiveness.

The thickness of the insulating film of the present invention varies depending on the purpose of use, but is usually 0.1 to 100 μm, preferably 0.1 to 50 μm, more preferably 0.1 to 20 μm.
The range is m. The insulating film material and insulating film of the present invention,
Inter-layer insulation film and protective film for semiconductors, Inter-layer insulation film for multilayer circuits,
It can be used for forming a cover coat of a flexible copper clad board, a solder resist film, a liquid crystal alignment film and the like.

As an example of using the insulating film of the present invention as an interlayer insulating film for a multilayer wiring of a semiconductor device, first, in the case of improving the adhesiveness, an adhesive coating agent is applied on a semiconductor substrate and then applied. Form a film. As a method of application,
Examples include spin coating with a spinner, spray coating with a spray coater, dipping, printing, and roll coating. Then, the adhesive coating film is formed by pre-baking at a temperature equal to or higher than the boiling point of the organic solvent to evaporate and dry the organic solvent. Next, a solution of the insulating film material of the present invention is applied onto the adhesive coating film so as to be laminated in the same manner as described above to form a coating film.
Then, the coating film is pre-baked under the above conditions to evaporate and dry the organic solvent, and further subjected to heat treatment to form a resin film having fine pores, and an interlayer insulating film can be formed. Similarly, a resin film can be formed to serve as a surface protective film.

[0033]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The relative dielectric constant, heat resistance, glass transition temperature, and water absorption of the films produced in Examples and Comparative Examples were measured by the following methods, and the cross sections of the films were observed. (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) Heat resistance TG / DTA620 manufactured by Seiko Instruments Inc.
0 was used to measure the temperature at a weight loss of 5% under the condition of a temperature rising rate of 10 ° C./min under a flow of 200 mL / min of nitrogen gas. (3) Glass transition temperature (Tg) Using DMS6100 manufactured by Seiko Instruments Inc. under a nitrogen gas flow of 300 mL / min, measurement frequency 1H
The glass transition temperature was defined as the peak top temperature of the loss tangent (tan δ), which was measured in the tensile mode under the conditions of z and temperature rising rate of 3 ° C./min. (4) Water absorption rate A test film having a 5 cm square and a thickness of 10 μm was immersed in pure water at 23 ° C. for 24 hours, and then the weight change rate was calculated. (5) Observation of film cross section Regarding the cross section of the film, a transmission electron microscope (TEM)
The presence and absence of fine pores and the diameter of the pores were observed using.

Production Example 1 10 g of styrene (96 mmol) was dissolved in 100 g of tetrahydrofuran dried under a dry nitrogen atmosphere to give -78.
After cooling to 0 ° C, 0.77 mL of a sec-butyllithium solution (solvent: cyclohexane) having a concentration of 1.3 mol / L as a reaction reagent was added thereto and stirred for 3 hours. Subsequently, 0.044 g (1.0 mmol) of ethylene epoxide was added and stirred for 3 hours, then 3 g of methanol was added, the solution was concentrated and the solvent was removed.
And was filtered. The filtrate obtained was concentrated under reduced pressure and dried to give a hydroxyl group at the end and a number average molecular weight of 9,600.
Of styrene oligomer was obtained. Obtained oligomer 93
g (9.68 mmol) was dissolved in 80 g of dry tetrahydrofuran under a dry nitrogen atmosphere to give 1.15 g of pyridine.
After dropping (14.52 mmol), 2.63 g of 4-nitrobenzoic acid chloride (1 g) in 20 g of tetrahydrofuran at 5 ° C. (1
What melt | dissolved 4.52 mmol) was dripped over 30 minutes. After completion of dropping, the mixture was returned to room temperature and stirred at room temperature for 24 hours. Then, the reaction solution was filtered to remove pyridine hydrochloride, and the solvent was concentrated and removed to obtain 4-nitrobenzoic acid ester of styrene oligomer. The 4-nitrobenzoic acid ester of this styrene oligomer was dissolved in 100 g of tetrahydrofuran, and then 0.5 g of 5 wt% palladium carbon was mixed under a hydrogen gas atmosphere, and the mixture was allowed to stand at room temperature for 24 hours.
Stir for hours. Then, the reaction solution was filtered through Celite, and the solvent was concentrated and removed to obtain a styrene oligomer having 4-aminobenzoic acid esterified terminal.

Production Example 2 10 g of styrene (96 mmol) was added to 49.9 g of styrene (4
Polystyrene having a hydroxyl group at the end and a number average molecular weight of 50,000 was obtained in the same manner as in Production Example 1 except that the amount was changed to 80 mmol. Tetrahydrofuran 100 obtained by drying 100 g (2 mmol) of the obtained polystyrene under a dry nitrogen atmosphere
Then, 1.15 g (14.52 mmol) of pyridine was added dropwise thereto, and then a solution of 2.63 g (14.52 mmol) of 4-nitrobenzoic acid chloride in 20 g of tetrahydrofuran was added dropwise at 5 ° C over 30 minutes. After completion of dropping, the mixture was returned to room temperature and stirred at room temperature for 24 hours. Then, the reaction solution was filtered to remove pyridine hydrochloride, and the solvent was concentrated and removed to obtain polystyrene 4-nitrobenzoate. The 4-nitrobenzoic acid ester of polystyrene was dissolved in 100 g of tetrahydrofuran, and 0.5 g of 5 wt% palladium carbon was mixed in a hydrogen gas atmosphere, and the mixture was stirred at room temperature for 24 hours. Then, the reaction solution was filtered through Celite, and the solvent was concentrated and removed to obtain 4-aminobenzoic acid ester-terminated polystyrene having 4-aminobenzoic acid esterified terminal.

Production Example 3 Production of 5-ethynylisophthalic acid dichloride (1) Synthesis of dimethyl 5-trifluoromethanesulfonyloxyisophthalate Thermometer, Dimlow condenser tube, calcium chloride tube, four-neck equipped with stirrer In a 5 L flask, dimethyl 5-hydroxyisophthalate (190.0 g, 0.904 mol), dehydrated toluene (3 L), dehydrated pyridine (214.7 g, 2.718 mo)
l) was charged and cooled to -30 ° C with stirring. 510.2 g of trifluoromethanesulfonic anhydride
(1.808 mol) was slowly added dropwise, taking care not to let the temperature rise above -25 ° C. in this case,
It took one hour to complete the dropping. After the completion of the dropping, the reaction temperature was raised to 0 ° C., the temperature was raised to 1 hour, and the temperature was further raised to room temperature to carry out the reaction for 5 hours. The reaction mixture obtained was poured into 4 L of ice water,
The aqueous layer and the organic layer were separated. Further, the aqueous layer was extracted twice with 500 mL of toluene, and this was combined with the previous organic layer. This organic layer was washed twice with 3 L of water, and anhydrous magnesium sulfate 10
The anhydrous magnesium sulfate was removed by drying at 0 g and filtration, toluene was distilled off with a rotary evaporator, and the residue was dried under reduced pressure to give dimethyl 5-trifluoromethanesulfonyloxyisophthalate as a pale yellow solid 294.
0 g was obtained (yield 95%). The crude product was recrystallized with hexane to give white needle crystals, which were used in the next reaction. (2) 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol synthesis thermometer, Dimroth condenser tube, nitrogen introduction tube, four ports equipped with stirrer In a 1-liter flask of No. 5 obtained in (1) above.
125 g (0.365 mol) of dimethyl trifluoromethanesulfonyloxyisophthalate, 1.1 g (0.00419 mol) of triphenylphosphine, 0.275 g of copper iodide
(0.00144 mol), 3-methyl-1-butyne-3-
A total of 33.73 g (0.401 mol) was charged and flushed with nitrogen. Dehydrated triethylamine (375 mL) and dehydrated pyridine (200 mL) were added and dissolved by stirring. After continuing the nitrogen flow for 1 hour, 0.3 g (0.00000427 mol) of dichlorobis (triphenylphosphine) palladium was quickly added, and the mixture was heated under reflux in an oil bath for 1 hour. Then, triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500 mL of water, the precipitated solid matter was collected by filtration, and further 500 mL of water and 5 mol / liter concentration of hydrochloric acid 5
Each was washed twice with 00 mL and 500 mL of water. This solid
By drying under reduced pressure at 50 ° C., 98.8 g of 4-
[3,5-bis (methoxycarbonyl) phenyl] -2
-Methyl-3-butyn-1-ol was obtained (yield 98
%)

(3) Synthesis of 5-ethynylisophthalic acid dipotassium salt In a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 3 L of n-butanol and potassium hydroxide (8
182 g (2.763 mol) of 5%) was charged and heated to reflux to dissolve. 4- [3,5 synthesized in (2) above
95 g (0.344 mol) of -bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol was added and the mixture was heated under reflux for 30 minutes. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. 2 L of this crystal with 1 L of ethanol
By washing twice and drying under reduced pressure at 60 ° C., 88.
87 g of 5-ethynylisophthalic acid dipotassium salt was obtained (yield 97%). (4) Synthesis of 5-ethynylisophthalic acid dichloride In a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 80 g of 5-ethynylisophthalic acid dipotassium salt obtained in the above (3) (0 (0.3 mol) and 400 L of chloroform were charged and cooled to 0 ° C. To this, 391 g (4.5 mol) of thionyl chloride was added dropwise at 5 ° C or lower over 1 hour. Then, 4 mL of dimethylformamide and 4 g of hydroquinone were added, and the mixture was stirred at 45 to 50 ° C for 3 hours. After cooling, the crystals were removed by filtration and the crystals were added to 150 mL of chloroform.
Washed with. The filtrate and washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the obtained residue was diluted with 200 mL of diethyl ether to 2 times.
It was extracted and filtered twice. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semi-solid crude product. This was washed with dried n-hexane and then recrystallized from diethyl ether to obtain 13 g of 5-ethynylisophthalic acid dichloride (yield 19%). Further, 5-ethynyl terephthalic acid dichloride and 4-ethynyl-2,6-naphthalenedicarboxylic acid dichloride were produced according to the above method.

Production Example 4 Production of 5-phenylethynyl isophthalic acid dichloride (1) Synthesis of 5-bromoisophthalic acid 5-aminoisophthalic acid 99.99 in a 4-necked 1 L flask equipped with a thermometer, a stirrer and a dropping funnel. 18g (0.55mo
l) and 165 mL of 48 wt% hydrobromic acid, 150 mL of distilled water
And stirred. The flask was cooled to 5 ° C or lower, and 39.4 g (0.57 mol) of sodium nitrite dissolved in 525 mL of distilled water was added dropwise thereto over 1 hour.
An aqueous diazonium salt solution was obtained. A 4-L 3 L flask equipped with a thermometer, a Dimroth condenser, a dropping funnel, and a stirrer was charged with 94.25 g (0.66 mol) of cuprous bromide and 45 mL of 48 wt% hydrobromic acid and stirred. . Flask at 0 ° C
After cooling below, the above diazonium salt aqueous solution was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes and then refluxed for 30 minutes. After allowing to cool, the precipitate was filtered off and washed twice with 2 L of distilled water, and the obtained white solid was dried at 50 ° C. for 2 times.
After drying under reduced pressure for a day, 117 g of a crude product was obtained. Used in the next reaction without purification. (2) Synthesis of dimethyl 5-bromoisophthalate In a 500 mL flask equipped with a stirrer and a Dimroth condenser, 5-bromoisophthalic acid 11 obtained in (1) above was added.
0 g, 500 mL of methanol and 10 g of concentrated sulfuric acid were added, and the mixture was refluxed for 6 hours. After allowing to cool, add dropwise to 1 L of distilled water and add 5
It was neutralized with an aqueous solution of sodium hydrogencarbonate in a weight percentage. The precipitate was separated by filtration, washed twice with 2 L of distilled water, and the obtained white solid was dried under reduced pressure at 50 ° C. for 2 days to obtain 109 g (0.4 mol) of dimethyl 5-bromoisophthalate (yield. 89
%). (3) Synthesis of 5-phenylethynyl isophthalic acid dichloride In Production Example 4 (2), 125 g (0.365 m) of dimethyl 5-trifluoromethanesulfonyloxyisophthalate was used.
ol) was 99.7 g (0.365 mol) of dimethyl 5-bromoisophthalate obtained in (2) above, and 80.8 g of 1- [3,5-bis (methoxycarbonyl) phenyl was similarly prepared. ] -2-Phenylethyne was obtained (yield 7
5%). Thereafter, in the same manner as in Production Example 3 (3) and (4), 5- (2-phenylethynyl) isophthalic acid dipotassium salt was obtained, and then 5- (2-phenylethynyl) isophthalic acid dichloride was obtained.

Production Example 5 Production of 4,4'-transdicarboxylic acid dichloride (1) Synthesis of methyl 4-ethynylbenzoate First, "J. Org. Chem." Vol. 57, No. 699.
4-Ethynylbenzoyl chloride was synthesized according to the method described on pages 8-6999 (1992). Next, in an ice bath, 24.7 g (0.15 mol) of 4-ethynylbenzoic acid chloride dissolved in 30 mL of tetrahydrofuran in 300 mL of methanol was added dropwise. End of dripping 2
Turbidity occurred after 0 minutes, and the mixture was stirred for 2 hours as it was. Then, the mixture is further stirred at room temperature for 2 hours, filtered, dried, and
g of methyl 4-ethynylbenzoate was obtained (yield 87
%). (2) Synthesis of dimethyl 4,4'-transdicarboxylate Methyl 4-ethynylbenzoate 1 obtained in the above (1)
6.0 g (0.1 mol), methyl-4-bromobenzoate 21.5 g (0.1 mol), triphenylphosphine 0.1.
288 g (0.0011 mol), cuprous iodide 0.07 g
(0.0037 mol), 250 mL of triethylamine, and 37.5 mL of pyridine were stirred, and the temperature was raised to 87 ° C. (reflux). After that, the mixture was cooled to a temperature at which no reflux occurred, and dichlorobis (triphenylphosphine) palladium was added.
098 g (0.0014 mol) was added and refluxed for 3 hours. The reaction solution was cooled, concentrated with an evaporator, the resulting precipitate was filtered, dried and washed twice with 500 mL of ethyl acetate. Then, the mixture was heated and stirred in tetrahydrofuran, hot filtered, and recrystallized from the filtrate to obtain 14.7 g of dimethyl 4,4′-transdicarboxylate (yield 50%). (3) Synthesis of 4,4′-transdicarboxylic acid dichloride 16.83 g (0.3 mol) of potassium hydroxide was dissolved in 450 mL of methanol, and dimethyl 4,4′-transdicarboxylic acid 8 obtained in the above (2) was used. After adding 0.22 g (0.033 mol), the temperature was raised and the mixture was refluxed for 18 hours. Then, it cooled, the precipitate was collect | recovered by filtration, and it melt | dissolved in 1 L of water. After removing the residue from this solution by filtration, the filtrate was gradually adjusted to pH 3 with hydrochloric acid having a concentration of 0.1 mol / liter,
4,4'-Transicarboxylic acid was precipitated, filtered and dried to obtain 6.7 g of 4,4'-transicarboxylic acid (yield 7
6%). Next, this 4,4'-transdicarboxylic acid 6.5
g (0.024 mol), 60 mL of 1,2-dichloroethane,
Benzyltriethylammonium chloride 10.013 g,
Thionyl chloride (3.9 mL) was mixed, the temperature was raised, and the mixture was refluxed for 10 hours. 40 mL of n-hexane was added to the reaction solution, and the mixture was recrystallized from the filtrate by hot filtration. Add this crystal to 1,2
Recrystallized from a mixed solvent of dichloroethane and hexane,
3 g of 4,4'-transdicarboxylic acid dichloride was obtained (41% yield).

Production Example 6 Production of 2,7-biphenylenedicarboxylic acid dichloride "J. Poly. Sci .: Polymer Lett"
ers Edition "Vol. 16, 653-656
According to the method described on page (1978),
2,7-biphenylenedicarboxylic acid dichloride was prepared.

Example 1 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane 35.9 g (0.098 mol)
Was dissolved in 330 mL of dried N-methyl-2-pyrrolidone, and 0.53 g of trimesic acid trichloride was added to this solution.
(0.002 mol), 2-ethynyl-2,6-naphthalenedicarboxylic acid dichloride 27.7 g (0.1 mol)
Was added at 10 ° C. under dry nitrogen. After addition, 1 at 10 ℃
The mixture was stirred for an hour and then at 20 ° C. for 1 hour. After the temperature was adjusted to 10 ° C., 22.3 g (0.22 mol) of triethylamine was added, and then, to 100 mL of γ-butyrolactone, 38.4 g (0.004 mol, number of 4-aminobenzoic acid ester-terminated styrene oligomer synthesized in Production Example 1). Average molecular weight 9,60
The solution in which 0) was dissolved 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, 80.9 g of polymer was obtained. The molecular weight of the obtained copolymer is GP manufactured by Tosoh Corporation.
When calculated in terms of polystyrene using C, the weight average molecular weight was 50,000 and the molecular weight distribution was 4.23. ¹ H
By NMR, the introduction ratio of the reactive oligomer component was 37% by weight. The obtained copolymer (5.00 g) was dissolved in N-methyl-2-pyrrolidone (20.00 g) and filtered through a 0.2 μm Teflon (R) filter to obtain a varnish. This varnish was applied onto a silicon wafer on which aluminum was vapor 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 about 5 μm. After coating, dry on a hot plate at 120 ° C for 240 seconds, and then introduce nitrogen to adjust the oxygen concentration to 1
A polybenzoxazole resin film having a terminal reacted with an oligomer was obtained by heating at 300 ° C. for 60 minutes using an oven controlled to 00 ppm or less. Furthermore, the oligomer unit was decomposed by heating at 400 ° C. for 60 minutes to obtain a film of polybenzoxazole resin having pores. Aluminum was vapor-deposited on the film and patterned to form an electrode having a predetermined size. 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 by oxygen plasma and the film thickness was measured by a surface roughness meter to determine the dielectric constant at a frequency of 1 MHz. The calculated value was 2.1. The cross section of this film is TE
When observed by M, the obtained voids were discontinuous with pores of 15 nm or less. The heat resistance, Tg and water absorption are also summarized in Table 1.

Example 2 9,9-bis (4-((4-amino-3-hydroxy))
Phenoxy) phenyl) fluorene 51.9 g (0.0
92 mol) to dry N-methyl-2-pyrrolidone 3
It was dissolved in 30 mL, and 1.212 g (0.003 mol) of 5,5'-bisisophthalic acid tetrachloride was added to this solution.
-Ethinyl terephthalic acid dichloride 22.7 g (0.1 mol
l) was added at 10 ° C. under dry nitrogen. After addition, 10 ℃
Stirred for 1 hour and then at 20 ° C. for 1 hour. After the temperature was adjusted to 10 ° C, 22.3 g (0.22 mol) of triethylamine was added, and then 64.0 g (0.016 mol, number) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co. was added to 100 mL of γ-butyrolactone. The solution in which the average molecular weight of 4000) was dissolved was dried at 10 ° C under nitrogen.
Added in. 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. Thus, 104 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 6,4000 and the molecular weight distribution was 4.20. The introduction rate of the reactive oligomer component was 46% by weight by ¹ H-NMR. Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

Example 3 41.1 g (0.19 mol) of 3,3'-diamino-4,4'-dihydroxybiphenyl was dissolved in 660 mL of dried N-methyl-2-pyrrolidone, and trimethic acid trichloride was added to this solution. 0.796 g (0.003 mol),
5-Phenylethynyl isophthalic acid dichloride 30.3
g (0.1mol), terephthalic acid dichloride 20.3g
(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 being brought to 10 ° C., 44.6 g of triethylamine
(0.44 mol) was added, followed by γ-butyrolactone 1
Aldrich poly (propylene glycol) bis (2-aminopropyl ether) 40 g (0.
01mol, a solution in which the number average molecular weight 4000) was dissolved,
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 washed with ion-exchanged water 6.6L and isopropanol 6.6.
The mixture was added dropwise to the mixed solution of L, and the precipitate was collected and dried to obtain 96 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 50,300 and the molecular weight distribution was 4.21. The introduction rate of the reactive oligomer component was 32% by weight by ¹ H-NMR. Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

EXAMPLE 4 29.4 g (0.127 mol) of 3,3'-diamino-4,4'-dihydroxy-biphenyl ether was dissolved in 400 mL of dried N-methyl-2-pyrrolidone, and trimeric acid was added to this solution. 0.706 g of trichloride (0.
(00266 mol), 5-phenylethynyl isophthalic acid 30.3 g (0.1 mol) and 5-ethynyl terephthalic acid 7.6 g (0.033 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 heating to 10 ° C, triethylamine 29.
6 g (0.29 mol) was added, and then 53.3 g of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich was added to 100 mL of γ-butyrolactone.
A solution of (0.0133 mol, number average molecular weight 4000) was added at 10 ° C. under dry nitrogen. After addition, 10 ℃
The mixture was stirred for 1 hour at 20 ° C. 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, 89.8 g of polymer was obtained. When the molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation, a weight average molecular weight of 48,
000 and the molecular weight distribution was 4.31. The introduction rate of the reactive oligomer component was 46% by weight by ¹ H-NMR. Using the obtained copolymer, in the same manner as in Example 1,
An evaluation sample was obtained and the measurement results are summarized in Table 1.

Example 5 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane 34.8 g (0.095 mol)
Was dissolved in 330 mL of dried N-methyl-2-pyrrolidone, and biphenyl ether-3,3 ', 5, was added to this solution.
0.42 g of 5'-tetracarboxylic acid tetrachloride
(0.001 mol) 2,7-biphenylene dicarboxylic acid dichloride 27.6 g (0.1 mol) was added at 10 ° C. under dry nitrogen.
Added in. 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 2
2.3 g (0.22 mol) was added, and 40 g of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich was added to 100 mL of γ-butyrolactone.
A solution in which (0.01 mol, number average molecular weight 4000) was dissolved was added at 10 ° C. under dry nitrogen. After addition, 1 at 10 ℃
The mixture was stirred for 20 hours and then at 20 ° C. for 20 hours. After the reaction,
The reaction liquid was filtered to remove triethylamine hydrochloride, and the filtered liquid was deionized water 6.6 L and isopropanol 6.
The mixture was added dropwise to 6 L of the mixed solution, and the precipitate was collected and dried to obtain 87.9 g of a copolymer. When the molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation, a weight average molecular weight of 54,300,
The molecular weight distribution was 4.23. The introduction rate of the reactive oligomer component was 37% by weight by ¹ H-NMR. Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

Example 6 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane 34.8 g (0.095 mol)
Was dissolved in 330 mL of dried N-methyl-2-pyrrolidone, and 0.543 g (0002 mol) of 1,3,5-cyclohexanetricarboxylic acid trichloride was added to this solution.
4'-Transicarboxylic acid dichloride 30.3 g (0.1 m
ol) was added at 10 ° C. under dry nitrogen. After addition, 10 ℃
Stirred for 1 hour and then at 20 ° C. for 1 hour. After the temperature was adjusted to 10 ° C, 22.3 g (0.22 mol) of triethylamine was added, and then 40 g (0.01 mol, number average molecular weight) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich Co. was added to 100 mL of γ-butyrolactone. A solution 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 is filtered to remove triethylamine hydrochloride, and the filtered solution is deionized water 6.
6 L and 6.6 L of isopropanol were added dropwise to a mixed solution,
Copolymer 90.8 was obtained by collecting and drying the precipitate.
g 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 52,100 and the molecular weight distribution was 4.10. The introduction ratio of the reactive oligomer component was 38% by weight by ¹ H-NMR. Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

Comparative Example 1 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane 34.8 g (0.095 mol)
Was dissolved in 330 mL of dried N-methyl-2-pyrrolidone, and 0.53 g of trimesic acid trichloride was added to this solution.
(0.002 mol), 7.7 g (0.1 mol) of 5-ethynyl-2,6-naphthalenedicarboxylic acid dichloride 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 the temperature was adjusted to 10 ° C, 22.3 g (0.22 mol) of triethylamine was added, and then 10 ° C.
The mixture was stirred for 1 hour at 20 ° C. 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 polymer. 53.5 g was obtained. When the molecular weight of the obtained polymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation, a weight average molecular weight of 44,
It had a molecular weight distribution of 600 and a molecular weight distribution of 4.11. Using the obtained polymer, a sample for evaluation was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

Comparative Example 2 2,2-bis (3-amino-4-hydroxyphenyl)
Hexafluoropropane 35.9 g (0.098 mol)
Was dissolved in 330 mL of dried N-methyl-2-pyrrolidone, and 0.53 g of trimesic acid trichloride was added to this solution.
(0.002 mol), 2-ethynyl-2,6-naphthalenedicarboxylic acid dichloride 27.7 g (0.002 mol)
l) was added at 10 ° C. under dry nitrogen. After addition, 10 ℃
Stirred for 1 hour and then at 20 ° C. for 1 hour. After the temperature was adjusted 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 obtained in Production Example 3.
A solution in which (0.001 mol, number average molecular weight 50,000) was dissolved was added at 10 ° C. under dry nitrogen. 10 after addition
The mixture was stirred at 0 ° 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, 82 g of polymer was obtained. The molecular weight of the obtained copolymer was calculated in terms of polystyrene using GPC manufactured by Tosoh Corporation, and the weight average molecular weight was 83.0
It was 0 and the molecular weight distribution was 4.3. The introduction rate of the reactive oligomer component was 45% by weight by ¹ H-NMR. Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

Comparative Example 3 30.3 g (0.14 mol) of 3,3'-diamino-4,4'-dihydroxybiphenyl was dissolved in 600 mL of dried N-methyl-2-pyrrolidone, and trimesic acid trichloride was added to this solution. 1.59 g (0.006 mol), 5
-Phenylethynyl isophthalic acid dichloride 30.3g
(0.1 mol), terephthalic acid dichloride 20.3 g
(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 being brought to 10 ° C., 44.6 g of triethylamine
(0.44 mol) was added, followed by γ-butyrolactone 2
240 g of Aldrich poly (propylene glycol) bis (2-aminopropyl ether) in 00 mL
A solution of (0.06 mol, number average molecular weight 4000) was added at 10 ° C. under dry nitrogen. After addition, 1 at 10 ℃
The mixture was stirred for 20 hours and then at 20 ° C. for 20 hours. After the reaction,
The reaction liquid was filtered to remove triethylamine hydrochloride, and the filtered liquid was deionized water 6.6 L and isopropanol 6.
The mixture was added dropwise to 6 L of the mixed solution, and the precipitate was collected and dried to obtain 245 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 40,300 and the molecular weight distribution was 4.25. The introduction rate of the reactive oligomer component was 77% by weight by ¹ H-NMR. Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

COMPARATIVE EXAMPLE 4 29.4 g (0.127 mol) of 3,3'-diamino-4,4'-dihydroxy-biphenyl ether was dissolved in 400 mL of dried N-methyl-2-pyrrolidone, and this solution was trimeric. Acid trichloride 0.706 g (0.
00266mol), terephthalic acid 20.3g (0.1mo
l), 6.70 g (0.033 mol) of isophthalic acid were added at 10 ° C. under dry nitrogen. 1 hour after addition,
Then, it stirred at 20 degreeC for 1 hour. After the temperature was adjusted to 10 ° C, 29.7 g (0.29 mol) of triethylamine was added, and then 53.3 g (0.0133 mol, number) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich was added to 100 mL of γ-butyrolactone. Average molecular weight 4
000) was dissolved 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 is filtered to remove triethylamine hydrochloride, and the filtered solution is used for deionized water 6.6.
L and isopropanol 6.6 L were added dropwise to the mixed solution, and the precipitate was collected and dried to give 85.8 g of the copolymer.
Got The molecular weight of the obtained copolymer was calculated in terms of polystyrene using GPC manufactured by Tosoh Corporation. As a result, the weight average molecular weight was 47,000 and the molecular weight distribution was 4.25. The introduction rate of the reactive oligomer component was found to be 49% by weight by ¹ H-NMR. Using the obtained copolymer, an evaluation sample was obtained in the same manner as in Example 1, and the measurement results are summarized in Table 1.

[0051]

[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 maintained excellent heat resistance and low water absorption. It can be seen that the low dielectric constant is possible. In addition, the porosity calculated from the logarithmic mixing equation using the measured dielectric constant and the reactive oligomer introduction ratio were almost the same.

[0053]

EFFECTS OF THE INVENTION According to the present invention, an insulating film material and a coating capable of forming an excellent insulating film capable of obtaining excellent micropores and excellent thermal characteristics, electrical characteristics, and water absorption. Varnish can be provided. The insulating film obtained by the present invention has an extremely low dielectric constant, and is an interlayer insulating film or protective film for semiconductors, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, a liquid crystal alignment film, etc. Can be suitably used for

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 179/04 C09D 179/04 B 5G305 H01B 3/30 H01B 3/30 C M H05K 3/28 H05K 3 / 28 C 3/46 3/46 T // C08L 79:04 C08L 79:04 B (72) Inventor Atsushi Izumi 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. F-term (reference) 4F074 AA56 AA71 CA11 DA03 DA47 4J038 CC032 CC082 CG142 CH032 DD002 DF022 DG002 DH021 DJ001 GA04 GA06 GA09 MA14 NA21 PB09 4J043 PA02 PA04 PA08 PA09 PA15 PA19 RA06 RA52 SA05 SA71 SB01 SB02 TA12 TA72 TB01 TB02 UA121 UA122 UA131 UA132 UA141 UA142 UA151 UB021 UB022 UB061 UB062 UB121 UB122 UB301 UB302 YA06 YB02 YB06 YB17 YB21 YB31 ZA46 ZB01 ZB03 5E314 AA36 BB02 BB06 BB11 CC01 GG08 5E346 AA12 BB01 CC10 DD 03 HH08 HH11 HH18 5G305 AA02 AA07 AA11 AB01 AB08 AB15 AB24 BA03 BA09 CA20 CA55 CB06 CB08 CB09

Claims (25)

[Claims] 1. A polyamide having a branched structure obtained by reacting a part of the polyamide structure represented by the general formula (A) with a bisaminophenol and a polyfunctional carboxylic acid, and a polyamide structure in the polyamide structure. A material for an insulating film, comprising a copolymer obtained by reacting a reactive oligomer having a substituent capable of reacting with a carboxyl group, an amino group or a hydroxyl group, as a film forming component. [Chemical 1] [Wherein R _{1 to} R ₄ are each independently a hydrogen atom or a monovalent organic group, and X represents a tetravalent group selected from the groups represented by the following formula (B), X may be the same or different, and Y is at least one divalent group selected from the groups represented by the following formula (C), formula (D), formula (E) and formula (F): , Z represents a divalent group selected from the groups represented by formula (G), and m and n are m> 0 and n ≧, respectively.
0, 2 ≦ m + n ≦ 1000 and 0.05 ≦ m / (m +
n) is an integer that satisfies the relationship of ≦ 1, and the arrangement of repeating units may be either block-like or random. ] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] [X _{1 in} Formula (B) and Formula (G) is the same as Formula (H): Represents a divalent group selected from the group represented by: R in the formula (D) is an alkyl group or a compound represented by the formula (I): A monovalent group selected from the groups represented by The hydrogen atom on the benzene ring in the groups represented by formula (B), formula (C), formula (D), formula (E), formula (F), formula (G) and formula (H) is a carbon atom. It may be substituted with at least one group selected from the alkyl groups of formulas 1 to 4, a fluorine atom and a trifluoromethyl group. ] 2. The polyfunctional carboxylic acid is trimeric acid, trimesic acid, 1,3,5-cyclohexanetricarboxylic acid, 5,5′-bisisophthalic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid. , Biphenyl ether-3,
3 ', 5,5'-tetracarboxylic acid, 3,3', 4,
4 '-(1,1'-hexafluoroisopropylidenebiphenyl) tetracarboxylic acid, 1,2,3,4,5,6
-The insulating film material according to claim 1, which is selected from benzenehexacarboxylic acid. 3. The polyamide according to claim 1, wherein Y in the general formula (A) has a divalent group selected from the groups represented by the formula (C). Insulating film material. 4. The polyamide according to claim 1, which has a divalent group selected from the groups represented by the formula (D) as Y in the general formula (A). Insulating film material. 5. The polyamide according to claim 1, wherein Y in the general formula (A) has a divalent group selected from the groups represented by the formula (E). Insulating film material. 6. The polyamide according to claim 1 or 2, wherein Y in the general formula (A) has a divalent group selected from the groups represented by the formula (F). Insulating film material. 7. The reactive oligomer is at least one selected from polyoxyalkylene, polymethylmethacrylate, polyα-methylstyrene, polystyrene, polyester, polyetherester, polycaprolactone and polyurethane. The insulating film material according to any one of 6 above. 8. The number average molecular weight of the reactive oligomer is 10
The insulating film material according to claim 1, which is 0 to 40,000. 9. The reactive oligomer has a number average molecular weight of 10.
The insulating film material according to claim 8, which is 0 to 20,000. 10. The reactive oligomer has a number average molecular weight of 1.
The insulating film material according to claim 9, which is from 00 to 10,000. 11. The insulating film material according to claim 1, wherein the copolymer has 5 to 70% by weight of a reactive oligomer unit introduced therein. 12. The insulating film material according to claim 11, wherein the copolymer has 5 to 50% by weight of a reactive oligomer unit introduced therein. 13. The insulating film material according to claim 12, wherein the copolymer has 5 to 40% by weight of a reactive oligomer unit introduced therein. 14. An insulating film coating varnish comprising the insulating film material according to claim 1 and an organic solvent capable of dissolving or dispersing the insulating film material. . 15. A polybenzo obtained by subjecting the insulating film material according to any one of claims 1 to 13 or the insulating film coating varnish according to claim 14 to heat treatment to cause a condensation reaction and a crosslinking reaction. An insulating film comprising a resin layer containing oxazole as a main structure and having fine pores. 16. The insulating film according to claim 15, wherein the size of the fine pores of the insulating film is 1 μm or less. 17. The size of the fine holes in the insulating film is 500 n.
The insulating film according to claim 16, which has a thickness of m or less. 18. The size of the fine holes in the insulating film is 100 n.
The insulating film according to claim 17, which has a thickness of m or less. 19. The size of the fine pores of the insulating film is 20 nm.
The insulating film according to claim 18, which is as follows. 20. The insulating film according to claim 15, wherein a porosity of the insulating film is 5 to 70%. 21. The insulating film according to claim 20, wherein the insulating film has a porosity of 5 to 50%. 22. The insulating film according to claim 21, wherein the insulating film has a porosity of 5 to 40%. 23. The insulating film according to claim 15, which is used as an interlayer insulating film for semiconductor multilayer wiring. 24. The insulating film according to claim 15, which is used as a surface protective film for a semiconductor. 25. A semiconductor device comprising an interlayer insulating film for multilayer wiring, which is formed of the insulating film according to claim 23, and / or a surface protective layer, which is formed of the insulating film according to claim 24.