JP2002141344A - Insulating film and resin composition therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating film which can have excellent heat, electrical and water-absorption characteristics, in particular, a heat resistance characteristic with a very low relative permittivity in semiconductor applications. SOLUTION: The resin composition for an insulating film contains, as essential components, a diaminophenol compound, a compound having an organic group of value 'd' (d being not smaller than 3 and not larger than 10) reactable with an amino group of the compound, polyamide and oligomer to react with dicarboxylic acid compound. The resin composition of the insulating film is made of a resin layer having a main structure of polybenzoxazole obtained by condensation and cross-linking reactions through heat treatment and having very fine holes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for an insulating film which becomes an insulating film material having excellent electrical, thermal and mechanical properties. It can be applied as an insulating film, a protective film, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, a liquid crystal alignment film, and the like.

[0002]

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

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

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

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

On the other hand, in the case of organic materials, techniques for obtaining submicrometer-order micropores are disclosed in Hedr.
U.S. Pat. No. 5,776,990 to ick et al. (199).
(July 7, 2008) discloses that a block copolymer is formed into a resin having fine pores on the order of sub-micrometer. It is known that block copolymers undergo phase separation on the order of sub-micrometer (T.
Hashimoto, M. Shibayama, M. Fujimura and H. Kawai, "M
icrophase Separation and the Polymer-polymer Inter
phase in Block Polymers "in" Block Copolymers-Sc
ience and Technology ", p.63, Ed.By DJMeier (Ac
ademic Pub., 1983), and it is generally well known in the field of polymer chemistry that polymers having a low ceiling temperature are easily decomposed. However, in order to obtain a resin composition having micropores while satisfying not only the relative permittivity but also the mechanical properties, electrical properties, water absorption resistance, and heat resistance, it is necessary to use a resin, a blocking technique, and a thermally decomposable component. Combinations are very limited in their choice, and none of them can satisfy all the characteristics.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition for an insulating film capable of maintaining excellent heat resistance and lowering the dielectric constant in a semiconductor application, and an insulating film using the same. It is in.

[0008]

The present inventors have conducted intensive studies in view of the above-mentioned conventional problems. As a result, a polyamide having a specific structure having a polyfunctional organic group and a tran skeleton has been found to be polyfunctional. Both the condensation reaction (dehydration ring closure reaction) with the organic group and the cross-linking reaction with the tran skeleton are three-dimensionalized, and the resulting structure has high heat resistance, and a polyamide having a specific structure having a polyfunctional organic group and a tran skeleton; The present inventors have found that a resin composition containing an oligomer as an essential component can satisfy the above problems, and have completed the present invention.

That is, the present invention relates to a diaminophenol compound (A) represented by the general formula (1) and a compound having a d-valent organic group capable of reacting with an amino group of the compound (d is 3 to 10). A) a polyamide (E) obtained by reacting (B) with a dicarboxylic acid compound (C) represented by the general formula (3) and a dicarboxylic acid compound (D) represented by the formula (5);
And an oligomer (F) as an essential component.

[0010]

Embedded image (However, X in the formula represents a group selected from the structure represented by the formula (2).)

[0011]

Embedded image

[0012]

Embedded image (However, Y in the formula represents a group selected from the structure represented by the formula (4).)

[0013]

Embedded image

[0014]

Embedded image

(However, Z in the formulas (2) and (4) is
A group selected from the structure represented by the formula (6) is shown. Also,
In the structures of the formulas (2), (4), (5) and (6),
Hydrogen atoms on the benzene ring are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t
It may be substituted with at least one group selected from the group consisting of -butyl, fluorine, and trifluoromethyl. )

[0016]

Embedded image

Further, the resin composition is a resin layer having a main structure of polybenzoxazole obtained by subjecting the resin composition to a heat treatment to cause a condensation reaction and a cross-linking reaction, and has fine pores. It is an insulating film characterized by the above.

[0018]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, polyamide (E)
Is branched by containing a compound having a d-valent organic group capable of reacting with an amino group of the diaminophenol compound (A) represented by the general formula (1) (d is 3 or more and 10 or less) (B). It has a structure, and the density of the insulating film of the present invention composed of a resin layer obtained from a resin composition containing this as an essential component can be reduced as compared with a layer composed of a resin having no branched structure. This is the result of an increase in the free volume inside the resin layer, and also reduces the dielectric constant of the entire resin layer.

In addition, a tran skeleton which is crosslinked by heating is introduced into the polyamide (E) structure, and the amide group is converted into polybenzoxazole by a ring-closing reaction, and the resin structure is made three-dimensional by the cross-linking reaction of the tran skeleton. By doing so, a resin having high heat resistance can be obtained.

Further, the oligomer (F), which is an essential component, is thermally decomposed during the heating of the resin and volatilized to form micropores in the resin layer having polybenzoxazole as a main structure. Further, the dielectric constant of the resin layer can be reduced. It is the gist of the present invention to obtain a porous insulating film having both heat resistance and electrical characteristics.

The bisaminophenol compound (A) represented by the general formula (1) 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) hexafluoropropane, 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 (trifluoromethyl) biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-bis (trifluoromethyl) biphenyl, 3,3 '-Diamino-4,4'-dihydroxy-6,6'
-Bis (trifluoromethyl) biphenyl, 4,4'-diamino-3,3'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl, 1,1'-binaphthyl-3,
3′-diamino-2,2′-diol, bis (2-((4
-Amino-3-hydroxy) phenoxy))-1,1'-
And binaphthyl and bis (2-((3-amino-4-hydroxy) phenoxy))-1,1′-binaphthyl. These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound (C) represented by the general formula (3) 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, , 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-
Examples thereof include trifluoromethyl isophthalic acid and the like, and these may be used alone or in combination of two or more.

Examples of the dicarboxylic acid compound (D) having a tran skeleton represented by the formula (5) used in the present invention include 4,4′-trandicarboxylic acid, 3,4′-trandicarboxylic acid, , 3'-Tandicarboxylic acid, 2,4'-Tandicarboxylic acid, 2,3'-Tandicarboxylic acid, 2,2 '
-Transdicarboxylic acid and the like. These may be used alone or in combination of two or more. Various transdicarboxylic acids of the present invention include, for example, a method of preparing a stilbene from a benzoate derivative and then preparing and synthesizing a tran skeleton, or a method of preparing a stilbene from a benzoate derivative and a phenylethynyl derivative using a Heck reaction. It can be obtained by a method of synthesis by introducing a skeleton.

In the present invention, when the polyamide (E) is obtained by the reaction, the ratio of the total amount of the dicarboxylic acid compound (C) and the dicarboxylic acid compound (D) is 50 to 99 relative to the diaminophenol compound (A). The reaction is preferably performed in the range of mol%. When it is more than 99 mol%, as a result, the compound having a d-valent organic group (d is 3
(10 or less)) The content of (B) in the polyamide (E) is low, the number of branched structures is small, the density is low,
That is, a decrease in the dielectric constant does not occur. If it is less than 50 mol%, the molecular weight of the obtained polymer does not increase, and the unreacted diaminophenol compound (A) remains, causing a problem in the formation of the organic insulating film or forming a brittle organic insulating film. This is because there is a case that

Further, as the dicarboxylic acid compound, a compound represented by the formula (3) having a group selected from the structure represented by the formula (4):
At least one dicarboxylic acid compound (C) represented by
Or 1 of the dicarboxylic acid compound (D) represented by the formula (5)
Although more than one kind is used, the ratio of the dicarboxylic acid compound (D) is preferably 5 to 100 mol% based on the total of the dicarboxylic acid compound (C) and the dicarboxylic acid compound (D).

This is at least one dicarboxylic acid compound (D) having a group selected from the structure represented by the formula (5).
However, since it has a tran skeleton that is cross-linked by heating, the resin structure is converted into a polybenzoxazole by a ring-closing reaction of the amide group, and the resin structure is formed by a cross-linking reaction of the tran skeleton.
This is because a resin having high heat resistance can be obtained by dimensioning. The proportion of one or more dicarboxylic acid compounds (D) having a group selected from the structure represented by the formula (5) is more than 5 mol% based on the total amount of the dicarboxylic acid compound (C) and the dicarboxylic acid compound (D). When the amount is small, the tran skeleton is small, and the resin structure is 3
In some cases, the dimensioning effect is small, and the degree of improvement in heat resistance is small.

Similarly, the polyamide (E) having a tran skeleton is combined with another polyamide of a type which does not undergo a cross-linking reaction to form an interpenetrating network structure. Can be obtained. In this case, the polyamide having no tolan skeleton comprises at least one of the bisaminophenol compound (A) and at least one of the dicarboxylic acid compounds having any of the structures represented by the formula (3). And can be obtained by a similar method.

The compound having a d-valent organic group capable of reacting with the amino group of the diaminophenol compound (A) (d is 3 or more and 10 or less) (B) used in the present invention is represented by the general formula (1). Any compound that reacts with the amino group of the diaminophenol compound (A) may be used. For example, the compound is trimesic acid, trimeric acid, 1,3,5-cyclohexanetricarboxylic acid, 5,5′-bisisophthalic acid, 3,
3 ′, 4,4′-biphenyltetracarboxylic anhydride,
3,3 ′, 4,4 ′-(1,1′-hexafluoroisopropylidene) biphenyltetracarboxylic anhydride,
1,2,3,4,5,6-benzenehexacarboxylic acid,
Biphenyl ether-3,3 ', 5,5'-tetracarboxylic acid, biphenyl ether-3,3', 4,4'-tetracarboxylic anhydride and the like can be mentioned. Among them, trimesic acid, trimeric acid, 1,3,5-cyclohexanetricarboxylic acid, and 5,5′-bisisophthalic acid are preferred. These may be used alone or in combination of two or more.

The ratio of the compound having a d-valent organic group capable of reacting with the amino group of the diaminophenol compound (A) (d is 3 or more and 10 or less) (B) used in the present invention is the same as that of the diaminophenol compound (A). On the other hand, it is preferably 2 / d to 100 / d mol%. When the proportion of the compound (B) having an organic group having a d valence or more is less than 2 / d mol%, the amount of the compound having an organic group having a d valency that reacts with an amino group is reduced, and the branched structure is reduced. In some cases, the effect of reducing the dielectric constant of the entire resin layer is small.
If it is more than 100 / d mol%, the polyamide (E)
In some cases, a cross-linking reaction may proceed. At that time, the solvent becomes insoluble, and a uniform varnish cannot be obtained, which may have an adverse effect on the formation of an insulating film.

Polyamide (E) which is an essential component of the present invention
Is produced by reacting a diaminophenol compound (A), a compound having a d-valent organic group capable of reacting with an amino group (d is 3 or more and 10 or less) (B), and a dicarboxylic acid compound (C) or (D). Any method may be used, but methods such as a conventional acid chloride method, an activated ester method, and a condensation reaction in the presence of a dehydrating condensing agent such as polyphosphoric acid or dicyclohexylcarbodiimide can be suitably used.

When the dicarboxylic acid compounds (C) and (D) are reacted as an acid chloride, the compound having a d-valent organic group (d is 3 or more and 10 or less) (B) is also an acid chloride compound. Dicarboxylic acid compounds (C) and (D)
Is reacted as an active ester compound, a compound having a d-valent organic group (d is 3 or more and 10 or less) (B)
Is also preferably an active ester compound. A compound having a d-valent organic group (d is 3 or more and 10 or less) (B) is a compound which is converted into a chloride or an active ester.
Obtained in a general manner.

Among the polyamide production methods, for example, the acid chloride method is described below. The acid chloride used is
Compound having a d-valent organic group (d is 3 or more and 10 or less) in the presence of a catalyst such as N, N-dimethylformamide (B)
Alternatively, the dicarboxylic acid compound (C) or the dicarboxylic acid compound (D) and an excess amount of thionyl chloride are reacted at room temperature to 130
The reaction can be carried out at 0 ° C., excess thionyl chloride is distilled off by heating and reduced pressure, and the residue can be obtained by recrystallization with a solvent such as hexane. Compound having a d-valent organic group synthesized as described above (d is 3 or more and 10 or less) (B)
And the acid chloride compound of the dicarboxylic acid compound (C) and the acid chloride compound of the dicarboxylic acid compound (D) together with the bisaminophenol compound (A) are usually combined with N-methyl-2-pyrrolidone, N, N -Polyamide (E) is obtained by dissolving in a polar solvent such as dimethylacetamide and reacting at room temperature to -30 ° C in the presence of an acid acceptor such as pyridine. In order to prevent partial gelation during the reaction, a bisaminophenol compound (A) and an acid chloride compound of a compound having a d-valent organic group (d is 3 or more and 10 or less) (B) are mixed in a polar solvent. Reacts well in advance, and then dicarboxylic acid compound (C)
It is also preferable to additionally add an acid chloride compound of the formula (1) and an acid chloride compound of the dicarboxylic acid compound (D).

In the present invention, the oligomer (F), which is another essential component, may be any oligomer as long as it is an oligomer which is thermally decomposed at a temperature lower than the thermal decomposition temperature of the polyamide and a decomposition product is vaporized. . Specific examples include polyoxymethylene, polyoxyethylene, polyoxypropylene, polyoxymethylene-oxyethylene copolymer, polyoxymethylene-oxypropylene copolymer, and polyoxyethylene-oxypropylene copolymer. Preferable examples include oxyalkylene, polymethyl methacrylate, polyurethane, poly α-methylstyrene, and polystyrene. If necessary, hydroxyl group, amino group, nitro group, carboxy group, cyano group,
Those in which a functional group such as a methacryl group is introduced at one end or both ends can be used. It is also possible to react with a carboxy group, an amino group, a hydroxyl group or a hydroxyl group in the main chain structure of the terminal of the polyamide resin or the polybenzoxazole resin and use it as a copolymer. These organic compounds may be used alone or in combination of two or more.

The oligomer (F) has a number average molecular weight of 1
Those having a range of from 00 to 10,000 are preferred. Molecular weight 1
If it is less than 00, the gap after being decomposed and vaporized is small and easily crushed, so that the relative dielectric constant cannot be reduced. On the other hand, if the molecular weight exceeds 10,000, the voids become too large, and the mechanical properties of the insulating film are extremely reduced, which causes a problem that the insulating film cannot be put to practical use.

With respect to the blending amount of the oligomer (F),
It is preferable to use 5 to 40 parts by weight based on 100 parts by weight of the polyamide (E). If the amount is less than 5 parts by weight, the porosity in the insulating film is small, and it is insufficient to reduce the dielectric constant. If the amount exceeds 40 parts by weight, the porosity in the film increases and the mechanical strength of the film decreases. It is not preferable because it extremely decreases or the gap becomes continuous and non-uniform, and the dielectric constant varies from place to place.

The resin composition for an insulating film of the present invention is obtained by mixing the polyamide and the oligomer. In addition, as necessary, various additives such as a surfactant, a coupling agent represented by a silane group, a radical initiator that generates oxygen radicals and sulfur radicals by heating, and the like are added, and an interlayer insulating film for a semiconductor, a protective film, It can be used for forming 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, and the like. Further, the polyamide in the present invention can be used as a photosensitive resin composition by being used together with a naphthoquinonediazide compound as a photosensitive agent.

As a method of using the resin composition for an insulating film of the present invention, it is possible to dissolve it in a suitable organic solvent and use it as a varnish. Specifically, the resin composition is dissolved in an organic solvent, and a suitable support, for example,
Apply to glass, fiber, metal, silicon wafer, ceramic substrate, etc. Examples of the application method include dipping, screen printing, spraying, spin coating, roll coating, and the like. After application, the coating is heated and dried to volatilize the solvent, and a tack-free coating film can be obtained.

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

The polyamide (E) in the resin composition of the present invention is obtained by coating the coating film obtained as described above at 300 ° C.
Further heating at a temperature of preferably 350 ° C. or more causes a cyclization condensation reaction and a crosslinking reaction, and the oligomer (F) is thermally decomposed at this time, and the decomposed product is vaporized.
The porous insulating film can be obtained by volatilizing and forming micropores in a resin layer having polybenzoxazole as a main structure.

In the insulating film having the main structure of polybenzoxazole of the present invention and having fine holes, the size of the fine holes is at least 20 nm or less, preferably 5 nm or less when used for an interlayer insulating film for semiconductors. Desirably. If the pore size is larger than 20 nm, the porosity of the insulating film used between the wirings will be non-uniform, and the electrical characteristics will not be constant. In addition, problems such as a decrease in mechanical strength of the film and an adverse effect on adhesiveness occur.

[0041]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.

Using the films prepared in Examples and Comparative Examples, the dielectric constant, heat resistance, and glass transition temperature were measured by the following methods for evaluating characteristics. These results are summarized in Table 1. 1. Relative permittivity According to JIS-K6911, at a frequency of 100 KHz,
Hewlett-Packard HP-4284A Pre
The measurement was performed using a cision LCR meter. 2. Heat resistance TG / DTA220 manufactured by Seiko Instruments Inc.
, The temperature at a weight loss of 5% was measured under a flow rate of nitrogen gas of 200 mL / min and a temperature rising rate of 10 ° C./min. 3. Glass transition temperature (Tg) Using DMS6100 manufactured by Seiko Instruments Inc., under a flow of nitrogen gas at 300 mL / min, measurement frequency 1
The measurement was performed in a tensile mode under the conditions of Hz and a heating rate of 3 ° C./min, and the peak top temperature of the loss tangent (tan δ) was defined as the glass transition temperature. 4. A 5 cm square test film having a thickness of 10 μm and a water absorption of 10 μm were immersed in pure water at 23 ° C. for 24 hours to calculate a weight change rate. 5. Confirmation of Presence and Existence of Micropores The cross section of the film was observed using a transmission electron microscope H-8000 manufactured by Hitachi, Ltd. to confirm the presence or absence of micropores. The pore size was also measured.

(Synthesis Example 1) 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
6.6 g (0.1 mol) of dried N-methyl-2
Dissolved in 200 g of pyrrolidone and 19.8 g of pyridine
After adding (0.25 mol), 1.4 g of trimesic acid trichloride (0.0 g) was added to 20 g of γ-butyrolactone.
053 mol) was dissolved at -15 ° C under dry nitrogen.
For 10 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and stirred at room temperature for 2 hours. Then the reaction solution is cooled,
A solution prepared by dissolving 9.1 g (0.045 mol) of isophthalic acid chloride and 13.6 g (0.045 mol) of 4,4′-trandicarboxylic acid chloride in 35 g of γ-butyrolactone was obtained at -15 ° C. under dry nitrogen at 30 ° C. Dropped over minutes. After completion of the dropwise addition, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped into 5 liters of ion-exchanged water, and the precipitate was collected and dried to obtain 51 g of polyamide. The number average molecular weight (M
n) was 20,000 when determined in terms of polystyrene using GPC manufactured by Tosoh Corporation.

Synthesis Example 2 In Synthesis Example 1, 2,2-
Instead of bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-((4
-Amino-3-hydroxy) phenoxy) phenyl) fluorene (56.5 g, 0.1 mol) and isophthalic acid chloride in an amount of 1.0 g (0.005 mol),
Instead of 4'-trandicarboxylic acid chloride, 3,
23.6 g of 4'-trandicarboxylic acid chloride (0.0
78 mol) and the amount of trimesic acid trichloride in 2.
Except having changed to 7 g (0.01 mol), 74 g of polyamide was obtained in the same manner as in Synthesis Example 1. The number average molecular weight (Mn) of the obtained polyamide was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation.
000.

(Synthesis Example 3) In Synthesis Example 1, 2,2-
Instead of bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-((4
-Amino-3-hydroxy) phenoxy) phenyl) fluorene (56.5 g, 0.1 mol) was replaced with 3,4'-trandicarboxylic acid chloride in place of isophthalic chloride and 4,4'-transdicarboxylic acid chloride.
74 g of polyamide was obtained in the same manner as in Synthesis Example 1 except that 1 g (0.086 mol) was changed to 2.1 g (0.008 mol) of trimesic acid trichloride. The number average molecular weight (Mn) of the obtained polyamide was determined to be 21,000 in terms of polystyrene using GPC manufactured by Tosoh Corporation.

(Synthesis Example 4) In Synthesis Example 1, the amounts of isophthalic chloride and 4,4'-trandicarboxylic acid chloride were changed to 9.9 g (0.049 mol) and 1 respectively.
52 g of polyamide was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 4.9 g (0.049 mol) and the amount of trimesic acid trichloride was omitted. The number average molecular weight (Mn) of the obtained polyamide was determined by GP manufactured by Tosoh Corporation.
When calculated in terms of polystyrene using C, 2200
It was 0.

(Example 1) Polyamide 1 obtained in Synthesis Example 1
00 parts by weight together with 5 parts by weight of polymethyl methacrylate (manufactured by Aldrich, number average molecular weight 5000) and N-
Dissolved in 195 parts by weight of methyl-2-pyrrolidone;
A varnish was obtained by filtration through a μm Teflon (registered trademark) filter. This varnish was applied on a glass plate using a doctor knife. Then, at 70 ° C / 1 in an oven
Time, 150 ° C / 30 minutes, 300 ° C / 2 hours, 420 ° C
/ 1 hour to obtain a film having a thickness of 10 µm.

Example 2 Polyamide 1 obtained in Synthesis Example 1
00 parts by weight together with 35 parts by weight of polymethyl methacrylate (manufactured by Aldrich, number average molecular weight 5000) and N
-Methyl-2-pyrrolidone was dissolved in 165 parts by weight, and a film was obtained in the same manner as in Example 1 below.

(Example 3) Polyamide 1 obtained in Synthesis Example 2
00 parts by weight were dissolved in 190 parts by weight of N-methyl-2-pyrrolidone together with 10 parts by weight of polyoxypropylene (manufactured by Aldrich, number average molecular weight 7500), and a film was obtained in the same manner as in Example 1 below. .

Example 4 Polyamide 1 obtained in Synthesis Example 2
00 parts by weight of a polyoxyethylene-oxypropylene copolymer (manufactured by Aldrich, number average molecular weight 3500)
N-methyl-2-pyrrolidone 185 with 15 parts by weight
It was dissolved in parts by weight, and a film was obtained in the same manner as in Example 1 below.

Example 5 Polyamide 1 obtained in Synthesis Example 2
00 parts by weight together with 15 parts by weight of polystyrene (manufactured by Aldrich, number average molecular weight 2000) and N-methyl-2.
-Dissolved in 185 parts by weight of pyrrolidone to obtain a film in the same manner as in Example 1 below.

(Example 6) Polyamide 1 obtained in Synthesis Example 3
00 parts by weight were dissolved in 190 parts by weight of N-methyl-2-pyrrolidone together with 10 parts by weight of polyoxypropylene (manufactured by Aldrich, number average molecular weight 7500), and a film was obtained in the same manner as in Example 1 below. .

(Example 7) Polyamide 1 obtained in Synthesis Example 3
00 parts by weight of a polyoxyethylene-oxypropylene copolymer (manufactured by Aldrich, number average molecular weight 3500)
N-methyl-2-pyrrolidone 185 with 15 parts by weight
It was dissolved in parts by weight, and a film was obtained in the same manner as in Example 1 below.

Example 8 Polyamide 1 obtained in Synthesis Example 3
00 parts by weight together with 15 parts by weight of polystyrene (manufactured by Aldrich, number average molecular weight 2000) and N-methyl-2.
-Dissolved in 185 parts by weight of pyrrolidone to obtain a film in the same manner as in Example 1 below.

Comparative Example 1 Polyamide 1 obtained in Synthesis Example 2
00 parts by weight were dissolved in 200 parts by weight of N-methyl-2-pyrrolidone, and a film was obtained in the same manner as in Example 1 below.

Comparative Example 2 Polyamide 1 Obtained in Synthesis Example 3
00 parts by weight were dissolved in 200 parts by weight of N-methyl-2-pyrrolidone, and a film was obtained in the same manner as in Example 1 below.

(Comparative Example 3) Polyamide 1 obtained in Synthesis Example 1
00 parts by weight together with 10 parts by weight of polymethyl methacrylate (number average molecular weight: 30000) and N-methyl-2-
It was dissolved in 190 parts by weight of pyrrolidone, and a film was obtained in the same manner as in Example 1 below.

(Comparative Example 4) Polyamide 1 obtained in Synthesis Example 1
00 parts by weight of polyoxypropylene (number average molecular weight:
7500) was dissolved in 150 parts by weight of N-methyl-2-pyrrolidone together with 50 parts by weight, and a film was obtained in the same manner as in Example 1 below.

Comparative Example 5 Polyamide 1 Obtained in Synthesis Example 1
00 parts by weight of ethylene carbonate 20 having a molecular weight of 88.
It was dissolved in 180 parts by weight of N-methyl-2-pyrrolidone together with parts by weight, and a film was obtained in the same manner as in Example 1 below.

(Comparative Example 6) Polyamide 1 obtained in Synthesis Example 4
00 parts by weight were dissolved in 195 parts by weight of N-methyl-2-pyrrolidone together with 5 parts by weight of polymethyl methacrylate (number average molecular weight 5000), and a film was obtained in the same manner as in Example 1.

[0061]

[Table 1]

From the evaluation results of Examples and Comparative Examples summarized in Table 1, the resin composition of the present invention is capable of lowering the dielectric constant while maintaining excellent heat resistance and low water absorption. Understand.

[0063]

Industrial Applicability The resin composition for an insulating film of the present invention and the insulating film using the same can achieve excellent thermal characteristics, electric characteristics, and water absorption. In particular, an insulating film having an extremely low dielectric constant can be obtained. It is possible to form an interlayer insulating film for semiconductors,
It can be suitably used for applications such as a protective film, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, and a liquid crystal alignment film.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 3/30 H01B 3/30 N H01L 21/768 H01L 21/90 SF Term (Reference) 4J002 AA012 BG062 CM041 4J043 PA04 PA08 QB15 QB32. 5F033 RR21 SS21 XX24 5F058 AA10 AC10 AH02 5G305 AA11 AB10 AB24 BA09 BA18 CA20 CA33 CA35 CA54 CA60

Claims (10)

[Claims] 1. A diaminophenol compound (A) represented by the general formula (1) and a compound having a d-valent organic group capable of reacting with an amino group of the compound (d is 3 or more and 10 or less)
(B), a dicarboxylic acid compound (C) represented by the general formula (3), and a dicarboxylic acid compound (D) represented by the formula (5)
And a polyamide (E) and an oligomer (F) which are reacted with each other. Embedded image (However, X in the formula represents a group selected from the structure represented by the formula (2).) Embedded image (However, Y in the formula represents a group selected from the structure represented by the formula (4).) Embedded image (However, Z in the formulas (2) and (4) represents a group selected from the structure represented by the formula (6). In addition, the formulas (2), (4), (5) and (5)) In the structure of (6), the hydrogen atom on the benzene ring is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group,
It may be substituted with at least one group selected from the group consisting of a fluorine atom and a trifluoromethyl group. ) 2. The dicarboxylic acid compound (C) and the dicarboxylic acid compound (D) are reacted in a total amount of 50 to 99 mol% with respect to the diaminophenol compound (A). 2. The resin composition for an insulating film according to 1. 3. The method according to claim 1, wherein the dicarboxylic acid compound (D) is reacted at a ratio of 5 to 100 mol% based on the total amount of the dicarboxylic acid compound (C) and the dicarboxylic acid (D). 3. The resin composition for an insulating film according to 2. 4. A compound having a d-valent organic group (d is 3 or more and 10 or less) (B) was reacted with the diaminophenol compound (A) at a ratio of 2 / d to 100 / d mol%. The resin composition for an insulating film according to claim 1, wherein: 5. A compound having a d-valent organic group (d is 3 or more and 10 or less) (B) is selected from trimesic acid, trimeric acid, 1,3,5-cyclohexanetricarboxylic acid, and 5,5′-bisisophthalic acid. The resin composition for an insulating film according to claim 1, wherein the resin composition is selected from the group consisting of an acid. 6. The oligomer (F) has at least one type of repeating unit selected from the group consisting of oxyalkylene, methyl methacrylate, urethane, α-methylstyrene, and styrene. 6. The resin composition for an insulating film according to any one of items 5 to 5. 7. The oligomer (F) is used in an amount of 100 to 1000.
7. The resin composition for an insulating film according to claim 6, having a number average molecular weight of 0. 8. The oligomer (F) is a polyamide (E)
8. The resin composition for an insulating film according to claim 6, wherein 5 to 40 parts by weight is blended with respect to 100 parts by weight. 9. A resin layer having a main structure of polybenzoxazole obtained by subjecting the resin composition for an insulating film according to claim 1 to a heat treatment to cause a condensation reaction and a cross-linking reaction. An insulating film characterized by having a fine hole. 10. The size of a fine hole in an insulating film is 20 nm.
The insulating film according to claim 9, wherein: