JP2002008446A - Resin composite for insulating material and insulating material using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating material which has excellent heat and electrical characteristics for semiconductor application. SOLUTION: A resin composite for an insulating material and an insulating material using it which requires, as its indispensable constituent, an organic chemical compound (A) and a heat resistant resin or its precursor (B), glass transition temperature of which is higher than that of the heat decomposition or the heat sublimation of (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material, and more particularly, to a resin composition for an insulating material having excellent characteristics for use in electric / electronic devices, circuit board materials, and semiconductor devices. It relates to the used insulating material.

[0002]

2. Description of the Related Art Among the characteristics required for materials for electric / electronic devices, circuit board materials and semiconductor devices, electric characteristics and heat resistance are the most important characteristics. In particular, with miniaturization of circuits and speeding up of signals, an insulating material having a low dielectric constant is required. An insulating material using a heat-resistant resin is expected as a material for achieving both of these two characteristics. For example, conventionally used insulating materials of inorganic materials such as silicon dioxide show high heat resistance, but in the current situation where the dielectric constant is high and the required characteristics are becoming more severe, it is difficult to achieve compatibility with the above-mentioned characteristics. It is becoming.

A heat-resistant resin typified by a polyimide resin has excellent electrical characteristics and heat resistance, and can make the above two characteristics compatible with each other, and is actually used for a coverlay of a printed circuit or a passivation film of a semiconductor device. It is used for such purposes.

[0004] However, with the recent enhancement of the functions and performance of semiconductors, it has become necessary to further improve electrical characteristics and heat resistance. In particular, with respect to the dielectric constant, a material having a low dielectric constant of 2.5 or less is desired, and the required properties have not been achieved with a conventional insulating material.

[0005] One of the solutions is an insulating material having fine voids, which has been actively studied.
The dielectric constant of the insulating material can be further reduced by filling the inside of the gap with air having a dielectric constant of 1. Specifically, a high heat-resistant resin is used as a matrix, and a thermally decomposable resin is added thereto. Then, in the heating step, the thermally decomposable resin is decomposed and volatilized to form voids.
Until now, for example, adding a thermally decomposable resin other than polyimide to a resin composition composed of polyimide and a solvent, and decomposing this thermally decomposable resin in a heating step to form voids, thereby reducing the dielectric constant of the insulating material Attempts have been made to let them. However, when the heat-resistant resin such as polyimide and the thermally decomposable resin are compatible with each other, the glass transition temperature of the entire composition is lowered. The effect of reducing the rate may not be exhibited. On the other hand, when a thermally decomposable resin that is incompatible with a heat-resistant resin such as polyimide is used, even if a phase-separated structure can be formed, the insulating resin composition becomes non-uniform during storage and is used. There is a problem that can not be
A large amount of labor is required for the heating step and the like when decomposing the thermally decomposable resin.

[0006]

SUMMARY OF THE INVENTION In view of the above-mentioned current situation of low dielectric constant insulating materials, the present invention provides a novel dielectric material having an extremely low dielectric constant and good insulating properties, and also having excellent heat resistance and water absorption. An object is to provide a resin composition for an insulating material and an insulating material using the same.

[0007]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned conventional problems, and as a result, completed the present invention by the following means.

That is, the present invention provides the resin composition for an insulating material according to any one of Items 1 to 4, and the insulating material according to Item 5. 1. In a resin composition for an insulating material containing an organic compound (A) and a heat-resistant resin or a precursor thereof (B) as essential components, the heat-resistant resin or a precursor thereof (B) has a heat resistance of the organic compound (A). A resin composition for an insulating material having a glass transition temperature higher than a decomposition temperature or a sublimation temperature.

[0009] 2. 2. The resin composition for an insulating material according to claim 1, wherein the organic compound (A) preferably has a melting point higher than the onset temperature of the ring closure temperature of the precursor (B).

[0010] 3. Heat-resistant resin or its precursor (B)
The resin composition for an insulating material according to the above item 1 or 2, which is preferably a polyimide resin or a polyimide precursor.

4. Heat-resistant resin or its precursor (B)
The resin composition for an insulating material according to the above item 1 or 2, which is preferably a polybenzoxazole resin or a polybenzoxazole precursor.

5. It is obtained from the heat-resistant resin or its precursor (B) at a temperature higher than the thermal decomposition temperature of the organic compound (A) using the resin composition for an insulating material according to any one of claims 1 to 4. An insulating material manufactured by a method including a step of performing a heat treatment at a temperature equal to or lower than a glass transition temperature of a resin.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for insulating material of the present invention comprises:
An essential component is an organic compound (A) and a heat-resistant resin having a glass transition temperature of the resin higher than a thermal decomposition temperature or a sublimation temperature of the organic compound (A) or a precursor (B) for producing the heat-resistant resin. Things. As a method for producing a heat-resistant resin from the precursor, any of a reaction by heating and a chemical ring closure reaction may be used. A solvent can be used as a component other than the organic compound (A) and the heat-resistant resin or its precursor (B).

The resin composition for an insulating material of the present invention is usually dissolved in a solvent, applied as a varnish on a substrate or the like, and then heated and heated.
An insulating material can be obtained by forming a film or impregnating a glass cloth or the like and heating. In this heating step, the organic compound (A) is first dried by heating.
Is precipitated from a homogeneous state of a composition containing a solvent, and phase-separates with the heat-resistant resin or its precursor (B), thereby producing an original high glass transition of the heat-resistant resin or its precursor (B). Temperature develops. Next, the resin is cured at a temperature lower than the melting point of the organic compound (A) to form a phase separation structure. When a resin is formed by heating using a heat-resistant resin precursor, the resin is cured from the precursor (B) at a temperature lower than that of the organic compound (A), whereby the resin is cured and the phase separation structure is formed. Is preferably formed. Further, the heating temperature is increased to a temperature higher than the temperature at which the organic compound (A) is thermally decomposed and lower than the glass transition temperature of the heat-resistant resin or the resin obtained from its precursor (B). Before reaching the glass transition temperature of the conductive resin or the resin obtained from the precursor (B), the organic compound (A) is thermally decomposed or sublimated and volatilized to form fine voids, thereby obtaining a low dielectric constant. Can be obtained.

Examples of the organic compound (A) used in the present invention include 1- (4-nitrophenylazo) -2-naphthol, 2- (4-imidazolyl) ethylamine, nepsilon-acetyl-L-lysine, α -Cyano-4-hydroxycinnamic acid, 2,2-dihydroxy-1,3-indandione, tetrachlorophthalonitrile, trichloroisocyanuric acid, 2,4,6-trihydroxypyrimidine, N- (p-methoxyphenyl) -P-phenylenediamine, DL-3-fluorophenylalanine, 3-hydroxy-4-methoxybenzoic acid, 3-hydroxy-2
-Naphthoic anilide, ethylenediaminetetraacetic acid, 2-
Carboxy-3-carboxymethyl-4-isopropenylpyrrolidine, (+)-3 ′, 5′-o- (1,1,
3,3-tetraisopropyl-1,3-disiloxanediyl) cytidine, 2,5-bis (4-aminophenyl)
-1,3,4-oxadiazole, 1,9-dimethyl-
Methylene blue, nepsilon- (tert-butoxycarbonyl) -L-lysine, 1- (4- (trans-4
-Butylcyclohexyl) phenyl) -2- (tran
s-4- (4-Isothiocyanatophenyl) cyclohexyl) ethane, coumarin 337, 2,2′-bis (3
-Hydroxy-1,4-naphthoquinone), 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-ter
t-butyl-4-hydroxybenzyl) benzene, 7-
Nitro-4-fluorenecarboxylic acid, 4-amino-5
(4-pyridyl) -4H-1,2,4-triazole-
3-thiol, 5- (4- (2-pyridylsulfamoyl) phenylazo) salicylic acid, (indane-1,3-
Diylidene) dimalanonitrile, 2,4-difluorophenylboronic acid, 6-hydroxy-2-naphthoic acid, octakis (dimethylsilyloxy) silsesquioxane, 5-bromoisatin, 4- (phenylazo) benzoic acid, ethyl-2-thiouracil -5-carboxylate, 12β-hydroxydigitoxin, L-aspartyl-L-phenylalanine methyl ester, 1-methyl-DL-tryptophan, 3,4-dehydro-L-proline, acenaphthoquinone, 4-chlorocinnamic acid, 5 -Formylsalicylic acid, 9- (β-d-ribofuranosyl) guanine, 4-hydroxy-9-fluorenone, 3-hydroxy-1H-indazole, 6-nitro-3,4-benzocoumarin, 1,4-phenylene diacetate, 2,6-pyridinedicarboxylic acid, 2 , 4,6-Triaminopyrimidine, 4 ', 5,7-trihydroxyflavanone, 6-fluoro-DL-tryptophan, 1,2-dihydroxyanthraquinone, 3-fluoro-DL-tyrosine, 2,
9-dimethyl-4,7-diphenyl-1,10-phenanthroline, dithiouracil, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,4′-biphenol, 3-quinolinecarboxylic acid, L -Ethionine,
5,6-dihydrouracil, hexamethylenetetramine, 4,5-imidazoledicarboxylic acid, 2-aminopurine, 7-hydroxy-3,4,8-trimethylcoumarin, 1,3-dihydroxy-9-acridinecarboxylic acid, 7 -Amino-4-methyl-2 (1H) -quinolinone, 2,3-naphthalenedicarboxamide, perylene, 4,4'-bis ((4-chlorophenyl) sulfonyl) -1,1'-biphenyl, D-asparagine , 1-
Hydride-3,5,7,9,11,13,15-heptacyclopentylpentacyclo (9.5.1.13,9.
15, 15.17, 13) octasiloxane, (R)-
(-)-2- (2,5-dihydrophenyl) glycine,
5-fluorouracil, 5-aminosalicylic acid, lanthionine, DL-methionine, L-tryptophan, 3-
(3-hydroxyphenyl) -DL-alanine, 3-
(3,4-dihydroxyphenyl) -DL-alanine,
DL-alanine, L-histidine, L-isoleucine,
3- (3,4-dihydroxyphenyl) -L-alanine, D-alanine, DL-2-aminobutyric acid, DL-
Valine, DL-leucine, hydroxyethyl cellulose, 1,2,4,5-benzenetetracarboxylic acid, 2,
4-diamino-6-hydroxypyrimidine, 18β-glycyrrhetinic acid, 2-piperidinecarboxylic acid, 2-phenylglycine, L-valine, 2-aminonicotinic acid, 6
-Amino-1,3-dimethyluracil, fumaramide,
3,6-dimethyl-2,5-piperazinedione, DL-
Valine, DL-leucine, 1,2-dihydro-6-methyl-2-oxo-3-pyridinecarbonitrile, anthraquinone, 2,4-dihydroxypyrimidine-5-carboxylic acid, DL-aspartic acid, terephthalic acid, 1,
1,4,5-benzenetetracarboxylic dianhydride, 2,
4-dihydroxy-5,6-dimethylpyrimidine, 2,
5-diaminobenzenesulfonic acid, fumaric acid, 2- (4
-Thiazolyl) benzimidazole, 3,5,7,9,
11,13,15-heptacyclopentylpentacyclo (9.5.1.13, 9.15, 15.17,13) octasiloxane-1-butyronitrile, 3,5,7,
9,11,13,15-heptacyclopentylpentacyclo (9.5.1.13, 9.15, 15.17, 1
3) octasiloxane-1-ol, 6-chloro-1,
2-dihydro-4H-3,1-benzoxazine-2,
4-dione, DL-5-hydroxytryptophan,
1,8-naphthalimide, L-valine, 2,4-dihydroxy-5-methylpyrimidine, 3,3 ′, 4,4′-
Biphenyltetracarboxylic dianhydride, 4-nitroimidazole, 2,6-pyridinedicarboxamide, 3-
(4-hydroxyphenyl) -DL-alanine, 2-
(3-sulfobenzoyl) pyridine-2-pyridylhydrazone, (2-hydroxyethyl) trimethylammonium chloride, 4-hydroxyaniline, silatran glycol, 4-tert-butylcalix (4) arene, L-alanine, triethylmethylammonium Bromide, 1-amino-1-cyclopentanecarboxylic acid, 4
-Tert-butylcalix (6) arene, 2,5-
Dichloro-3,6-dihydroxy-1,4-benzoquinone, 2,6-dihydroxy-4-methyl-3-pyridinecarbonitrile, 4-chlorobenzohydrazine hydrochloride, 2-aminoterephthalic acid, 2,4-dihydroxy- 6-methylpyrimidine, 4,4'-sulfonylbis (2,6-dimethylphenol), 3,6-dihydroxypyridazine, isonicotinic acid, 4-azatricyclo (4.3.1.13,8) undecane-5- On, isophthalic acid, 6,11-dihydroxy-5,12-naphthacenedione, 2-mercaptobenzimidazole, 3-
Cyano-7-hydroxy-4-methylcoumarin, (R)
-(-)-2-phenylglycine, 5- (4-pyridyl) -1H-1,2,4-triazole-3-thiol, octaphenylcyclotetrasilane, DL-tyrosine and the like, but are not limited thereto is not. Among these, DL-valine, DL-leucine, 18β-glycyrrhetinic acid, 2-piperidinecarboxylic acid, 2-phenylglycine, L-valine, DL-valine, DL-leucine, anthraquinone, DL-aspartic acid, terephthalic acid, 1,1,4,5-benzenetetracarboxylic dianhydride, fumaric acid, L-valine, 2,6-pyridinedicarboxamide, 2- (3-sulfobenzoyl) pyridine-2-pyridylhydrazone, silatran glycol , L
-Alanine, 1-amino-1-cyclopentanecarboxylic acid, 2,6-dihydroxy-4-methyl-3-pyridinecarbonitrile, 2-aminoterephthalic acid, 2,4-dihydroxy-6-methylpyrimidine, isonicotinic acid ,
Isophthalic acid, (R)-(-)-2-phenylglycine, octaphenylcyclotetrasilane, and DL-tyrosine are preferred in terms of thermal decomposition behavior. Further, only one of these may be used, or two or more thereof may be used in combination.

Examples of the heat-resistant resin or heat-resistant resin precursor (B) used in the present invention include polyimide, polyamic acid, polyamic acid ester, polyisoimide, polyamideimide, polyamide, bismaleimide, polybenzoxazole, and polyhydroxy. Examples thereof include, but are not limited to, amides and polybenzothiazoles. Among them, polyimide resins and polyimide precursors such as polyamic acid, polyamic acid ester and polyisoimide, and polybenzoxazole resins and polybenzoxazole precursors such as polyhydroxyamide are preferable because of high heat resistance.

As the organic solvent used when the resin composition for an insulating material of the present invention is used as a varnish, a solvent that completely dissolves the organic compound (A) and the heat-resistant resin or its precursor (B) is preferable. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, cellosolve, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, cellosolve acetate, butyl cellosolve acetate , Propylene glycol monomethyl ether acetate, 1,3-butylene glycol acetate, ethyl lactate, butyl lactate, methyl pyruvate, ethyl pyruvate, methyl Ethyl ketone, methyl isobutyl ketone, cyclohexanone, do not cyclopentanone, although tetrahydroxyfuran like as being limited thereto. Further, only one of these may be used, or two or more thereof may be used in combination. Further, a small amount of a surfactant may be added in order to improve applicability and impregnation.

The minute voids formed to reduce the dielectric constant of the insulating material of the present invention are discontinuous closed cells,
Its diameter is 50 nm or less, preferably 10 nm.
nm or less. In addition, the ratio of the minute voids is preferably 5 to 60 vol.
1%, more preferably 10 to 50 vol%. If the addition amount is less than 5 vol%, the effect of reducing the dielectric constant due to the addition of the organic compound (A) cannot be sufficiently exhibited. On the other hand, if the addition amount exceeds 60 vol%, the mechanical properties and adhesion of the resin are significantly reduced, which is not preferable.

The resin composition for an insulating material of the present invention is obtained by mixing each component within a range where the above-mentioned voids are formed, and uniformly mixing and dissolving them. The mixing ratio is such that the weight ratio (A / B) of the component (A) to the component (B) is from 5/95 to 60/4.
0, more preferably 10/90 to 50/50.
At this time, as the combination of the component (A) and the component (B), the component (B) having a higher glass transition temperature of the resin than the thermal decomposition temperature or the sublimation temperature of the component (A) is selected. B)
Is a precursor, it is further preferable that the component (A) has a melting point higher than the ring-closing start temperature of the precursor. At this time, for example, a polybenzoxazole precursor having a ring closure start temperature of about 250 ° C. as a heat-resistant resin (A) component,
When used, the phase separation structure between the heat-resistant resin (A) and the organic compound (B) can be obtained by using the organic compound (B) having a melting point higher than 250 ° C.

Examples of the method for producing an insulating material of the present invention include:
10 to 30 wt% of the resin composition in the organic solvent
It is dissolved and applied to a suitable support, for example, glass, fiber, metal, silicon wafer, ceramic substrate or the like.
The coating method includes dipping, screen printing, spray coating, spin coating, roll coating, and the like. After the coating, the solvent is removed by heating and drying to form a tack-free coating film. Thereafter, in the case of heat curing, the heat-resistant resin or its precursor (B) component is preferably cured at a temperature equal to or lower than the melting point of the organic compound (A), or cured by a chemical ring closure reaction, A desired insulating film in which the heat-resistant resin component and the organic compound component are phase-separated can be formed. Depending on the intended use, it is also possible to perform only a volatilization removal of the solvent, perform a predetermined process, and then cure by heating or a chemical ring closure reaction. Further, a prepreg can be obtained by impregnating and drying a substrate such as glass fiber cloth, other cloth, or paper.
The impregnation method can use brushing, spraying, dipping, etc.
A partially cured product can be obtained. further,
At a temperature higher than the thermal decomposition temperature of the organic compound (A),
In addition, by performing heat treatment at a temperature equal to or lower than the glass transition temperature of the heat-resistant resin or the resin obtained from the precursor (B), the organic compound (A) in the film is vaporized and volatilized to obtain the insulating material of the present invention. it can. Note that the heat curing is preferably performed by a heating device capable of exhausting the volatilized components. The thus obtained insulating material of the present invention can be used, for example, as an interlayer insulating film for a semiconductor, an interlayer insulating film of a multilayer circuit, or the like.

[0021]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 (1) Synthesis of polyimide resin 2,2-bis (4- (4,4'-aminophenoxy)) was placed in a separable flask equipped with a stirrer, a nitrogen inlet tube, and a raw material inlet. Phenyl) hexafluoropropane 5.18
g (0.01 mol) and 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 9.60 g
(0.03 mol) is dissolved in 200 g of dried N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). The solution was cooled to 10 ° C. under dry nitrogen, and 2.94 g (0.01 mol) of biphenyltetracarboxylic dianhydride and 13.32 g of hexafluoroisopropylidene-2,2′-bis (phthalic anhydride) ( 0.03 mol) was added. Five hours after the addition, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 2 hours to obtain a solution of polyamic acid as a polyimide precursor. After 50 g of pyridine was added to this polyamic acid solution, 5.1 g (0.05 mol) of acetic anhydride was added dropwise, and an imidization reaction was carried out for 7 hours while maintaining the temperature of the system at 70 ° C. This solution was dropped into a 20-fold amount of water to collect a precipitate, followed by vacuum drying at 60 ° C. for 72 hours to obtain a solid polyimide resin as a heat-resistant resin. The polyimide resin has a number average molecular weight of 26,000 and a weight average molecular weight of 5400.
It was 0.

(2) Measurement of Glass Transition Temperature of Heat Resistant Resin 5.0 g of the polyimide resin synthesized above was added to NMP1
After dissolving in 5.0 g and applying on a release-treated glass substrate, the film was held in an oven at 120 ° C. for 30 minutes, and then held at 230 ° C. for 90 minutes to form a film. It was heated at 400 ° C. for 90 minutes to obtain a polyimide resin film. The glass transition temperature of the polyimide resin measured by a differential scanning calorimeter was 335 ° C.

(3) Measurement of melting point and thermal decomposition temperature of organic compound (A) The melting point and thermal decomposition temperature of 2-aminoterephthalic acid were measured by thermogravimetric analysis under a nitrogen atmosphere.
4 ° C (decomposition).

(4) Preparation of Resin Composition for Insulating Material and Production of Insulating Material 10.0 g of the polyimide resin synthesized as described above was added to NM.
After dissolving in 50.0 g of P, 2.0 g of the above 2-aminoterephthalic acid was added and stirred to obtain a resin composition for an insulating material. This resin composition for an insulating material was spin-coated on a silicon wafer on which a 200-nm-thick tantalum film was formed, and then heated and cured in an oven in a nitrogen atmosphere. The heat treatment is performed at 120 ° C. for 30 minutes, 230 ° C. for 120 minutes, and 31 minutes.
After holding at 5 ° C. for 180 minutes, the temperature was further raised to 335 ° C., and then lowered to 200 ° C. for 15 minutes.
The temperature was returned to room temperature for another 60 minutes. Thus, an 800 nm-thick insulating material film was obtained. An aluminum electrode having an area of 0.1 cm ² was formed on the insulating film by vapor deposition, and the capacitance between the electrode and tantalum on the substrate was measured by an LCR meter. The dielectric constant of the insulating material calculated from the film thickness, the electrode area, and the capacitance was 2.4. The density of the insulating material was determined to be 1.10. The density when no 2-aminoterephthalic acid was added and there were no voids was 1.41, so the porosity was calculated to be 22.0% from this. Further, when the cross section of the insulating material film was observed with a TEM, it was found that voids having an average pore diameter of 9 nm were uniformly and discontinuously dispersed.

Example 2 (1) Synthesis of Polyimide Precursor The 2,2-bis (4- (4,4'-aminophenoxy)) used in the synthesis of the polyimide precursor in the synthesis of the polyimide resin of Example 1 8.18 g (0.01 mol) of phenyl) hexafluoropropane and 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl
60 g (0.03 mol) and 4,01′-diaminodiphenyl ether (8.01 g, 0.04 mol) and biphenyltetracarboxylic dianhydride 2.94 g (0.01
mol) and hexafluoroisopropylidene-2,2 '
13.32 g of bis (phthalic anhydride) (0.03 mol
l) and 8.72 g (0.04 g) of pyromellitic dianhydride
mol), a solution of polyamic acid as a polyimide precursor was obtained in the same manner as in Example 1. This solution was dropped into 20 times the volume of water to collect a precipitate.
Vacuum drying was performed for 2 hours to obtain a solid of polyamic acid, which is a precursor of polyimide as a heat-resistant resin. The number average molecular weight of the obtained polyamic acid was 27,000, and the weight average molecular weight was 55,000.

(2) Measurement of Ring Closing Start Temperature of Polyimide Precursor The ring closing start temperature of the polyamic acid synthesized as described above was measured by a differential scanning calorimeter and found to be 120 ° C.

(3) Measurement of Glass Transition Temperature of Heat-Resistant Resin 5.0 g of the polyamic acid synthesized as described above was added to NMP2
After dissolving in 0.0 g and applying on a release-treated glass substrate, the film was held in an oven at 100 ° C. for 30 minutes, then held at 250 ° C. for 90 minutes to form a film, and the film was peeled off from the substrate. Heating was performed at 450 ° C. for 90 minutes to obtain a polyimide resin film as a heat-resistant resin. When the glass transition temperature of this polyimide resin was measured by a differential scanning calorimeter, it was 41
9 ° C.

(4) Measurement of melting point and thermal decomposition temperature of organic compound (A) The melting point and thermal decomposition temperature of 2,6-pyridinedicarboxamide were measured by thermogravimetric analysis under a nitrogen atmosphere. The thermal decomposition temperature was 373 ° C.

(5) Preparation of Resin Composition for Insulating Material and Production of Insulating Material 10.0 g of the polyamic acid synthesized as described above was added to NMP5
After dissolving in 0.0 g, 2.0 g of high-purity 2,6-pyridinedicarboxamide was added and stirred to obtain a resin composition for an insulating material. This resin composition for an insulating material was spin-coated on a silicon wafer on which a 200-nm-thick tantalum film was formed, and then heated and cured in an oven in a nitrogen atmosphere. The heat treatment is carried out in the order of 30 minutes at 120 ° C., 120 minutes at 260 ° C., and then 90 minutes at 400 ° C., then the temperature is lowered to 200 ° C. in 20 minutes, and the temperature is lowered to room temperature in 40 minutes. I went back. Thus, a 700-nm-thick insulating film was obtained. The dielectric constant of this heat-resistant resin was measured in the same manner as in Example 1 and found to be 2.4. Moreover, the density of the insulating material was determined to be 1.13 using a density gradient tube. The density in the case where 2,6-pyridinedicarboxamide was not added and there were no voids was 1.43.
It was calculated to be 0%. Further, when the cross section of the insulating material film was observed with a TEM, it was found that voids having an average pore diameter of 8 nm were uniformly and discontinuously dispersed.

Example 3 (1) Synthesis of polybenzoxazole resin 25 g of 4,4'-hexafluoroisopropylidenediphenyl-1,1'-dicarboxylic acid, 45 m of thionyl chloride
l and 0.5 ml of dry dimethylformamide were placed in a reaction vessel and reacted at 60 ° C. for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off by heating and reduced pressure. The residue was recrystallized from hexane to obtain 15 g of 4,4'-hexafluoroisopropylidenediphenyl-1,1'dicarboxylic acid chloride. Stirrer, nitrogen inlet tube,
In a separable flask equipped with a dropping funnel, 7.32 g (0.02 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 100 g of dried dimethylacetamide, and pyridine.
After adding 96 g (0.05 mol), under dry nitrogen introduction,
8.55 g of 4,4′-hexafluoroisopropylidenediphenyl-1,1′-dicarboxylic acid chloride synthesized above was added to 50 g of dimethylacetamide at −15 ° C.
(0.02 mol) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped into 1000 ml of water, and the precipitate was collected and vacuum-dried at 40 ° C. for 48 hours to obtain a solid substance of polyhydroxyamide, a polybenzoxazole precursor. This polyhydroxyamide is NM
After adding 50 g of pyridine to a solution dissolved in 200 g of P, 3.1 g (0.03 mol) of acetic anhydride was added dropwise, and the oxazole-forming reaction was carried out for 7 hours while maintaining the temperature of the system at 70 ° C. This solution was dropped into 20 times the volume of water to collect the precipitate, and vacuum-dried at 60 ° C. for 72 hours to obtain a solid substance of a polybenzoxazole resin as a heat-resistant resin. The number average molecular weight of the obtained polybenzoxazole resin is 2,000
0, the weight average molecular weight was 40,000.

(2) Measurement of glass transition temperature of heat-resistant resin Polybenzoxazole resin 5.0 synthesized as described above
g of NMP in a mixed solvent of 8.0 g of NMP and 12.0 g of tetrahydrofuran, coated on a release-treated glass substrate, kept in an oven at 120 ° C. for 30 minutes, and then heated at 240 ° C. for 9 minutes.
Hold for 0 minutes to form a film, and after removing the film from the substrate,
Heating was performed at 00 ° C. for 90 minutes to obtain a film of a polybenzoxazole resin as a heat-resistant resin. The glass transition temperature of this polybenzoxazole resin measured by a differential scanning calorimeter was 362 ° C.

(3) Measurement of melting point and thermal decomposition temperature of organic compound (A) The melting point and thermal decomposition temperature of 2-phenylglycine were measured by thermogravimetric analysis under a nitrogen atmosphere.
° C and a thermal decomposition temperature of 321 ° C.

(4) Preparation of resin composition for insulating material and production of insulating material Polybenzoxazole resin synthesized as described above
0 g of NMP 16.0 g and tetrahydrofuran 24.0
g of 2-phenylglycine.
0 g was added and stirred to obtain a resin composition for an insulating material. This resin composition for an insulating material was spin-coated on a silicon wafer on which a 200-nm-thick tantalum film was formed, and then heat-cured in an oven in a nitrogen atmosphere. Heat treatment is 1
After holding at 20 ° C. for 30 minutes and then at 260 ° C. for 120 minutes, the temperature was further held at 350 ° C. for 90 minutes, the temperature was lowered to 200 ° C. in 15 minutes, and the temperature was returned to room temperature in 40 minutes. . Thus, a 700-nm-thick insulating film was obtained. Thereafter, the dielectric constant of this heat-resistant resin was measured in the same manner as in Example 1, and it was 2.1. Also, when the density of the insulating material was determined using a density gradient tube,
1.11. Without adding 2-phenylglycine,
Since the density without any voids was 1.45, the porosity was calculated to be 23.4% from this. Further TEM
Observation of the cross section of the insulating material film with a mean pore diameter of 6n
It was found that the m voids were uniformly and discontinuously dispersed.

Example 4 (1) Synthesis of polyhydroxyamide 2,2'-bis (trifluoromethyl) biphenyl-
4,4'-dicarboxylic acid 22g, thionyl chloride 45ml
And 0.5 ml of dry dimethylformamide was put into a reaction vessel and reacted at 60 ° C. for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off by heating and reduced pressure. The residue was recrystallized using hexane to obtain 2,2′-bis (trifluoromethyl) biphenyl-4,4′-dicarboxylic acid chloride. In a separable flask equipped with a stirrer, a nitrogen inlet tube, and a dropping funnel, 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane7.
32 g (0.02 mol) was dissolved in 100 g of dried dimethylacetamide, and 3.96 g (0.0%) of pyridine was dissolved.
5 mol) was added, and under dry nitrogen introduction, dimethylacetamide (50 g) was added to dimethylacetamide (50 g) at -15 ° C.
2'-bis (trifluoromethyl) biphenyl-4,
8.30 g of 4'-dicarboxylic acid chloride (0.02 mol
The solution of l) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped into 1,000 ml of water, and the precipitate was collected and vacuum-dried at 40 ° C. for 48 hours to obtain a solid substance of polyhydroxyamide, which is a polybenzoxazole precursor which is a heat-resistant resin. The number average molecular weight of the obtained polyhydroxyamide was 20,000, and the weight average molecular weight was 40,000.

(2) Measurement of Ring Closing Start Temperature of Polyhydroxyamide The ring closure start temperature of the polyhydroxyamide synthesized as described above was 220 ° C. as measured by a differential scanning calorimeter.

(3) Measurement of Glass Transition Temperature of Heat-Resistant Resin
After dissolving in 20.0 g of MP and applying it on a glass substrate subjected to a mold release treatment, it was kept in an oven at 120 ° C. for 30 minutes, and then 24
The film was formed by holding the film at 0 ° C. for 90 minutes, and after peeling the film from the substrate, the film was further heated at 400 ° C. for 90 minutes to obtain a polybenzoxazole film as a heat-resistant resin. The glass transition temperature of this polybenzoxazole was measured by a differential scanning calorimeter, and was 410 ° C.

(4) Measurement of Melting Point and Thermal Decomposition Temperature of Organic Compound (A) The melting point and thermal decomposition temperature of isonicotinic acid were measured by thermogravimetric analysis under a nitrogen atmosphere, and the melting point was 315 ° C. (sublimation). .

(5) Preparation of Resin Composition for Insulating Material and Production of Insulating Material 10.0 g of the polyhydroxyamide synthesized as described above was dissolved in 50.0 g of NMP, and 2.0 g of isonicotinic acid was dissolved.
g was added and stirred to obtain a resin composition for an insulating material. Thickness 2
The resin composition for an insulating material was spin-coated on a silicon wafer on which a 00 nm tantalum film was formed, and then heat-cured in an oven in a nitrogen atmosphere. Heat treatment is 120 ° C
For 30 minutes at 260 ° C. for 120 minutes,
After holding at 400 ° C. for 90 minutes, 200 minutes
C., and the temperature was returned to room temperature for another 40 minutes. Thus, a 700-nm-thick insulating film was obtained. Thereafter, the dielectric constant of this heat-resistant resin insulating material was measured in the same manner as in Example 1, and it was 2.1.
Moreover, the density of the heat-resistant resin insulating material was determined to be 1.15 using a density gradient tube. Since the density in the case where no isonicotinic acid was added and there were no voids was 1.42, the porosity was calculated to be 19.0% from this. Further, when the cross section of the insulating material film was observed with a TEM, it was found that voids having an average pore size of 5 nm were uniformly and discontinuously dispersed.

Comparative Example 1 The 2-aminoterephthalic acid 2.0 used in the preparation of the resin composition for an insulating material of Example 1 was used.
Except not adding g, adjustment of the resin composition for insulating materials and manufacture of insulating materials were performed in the same manner as in Example 1. The dielectric constant of the obtained heat-resistant resin insulating material was 2.9, and the density was 1.
41. By observing the cross section of the insulating film by TEM,
No voids were observed.

Comparative Example 2 The same procedure as in Example 2 was repeated except that 2.0 g of 2,6-pyridinedicarboxamide used in the preparation of the resin composition for insulating material of Example 2 was not added. Of a resin composition for use and manufacture of an insulating material. The obtained heat-resistant resin had a dielectric constant of 3.0 and a density of 1.43. No void was observed in the cross section of the insulating film by TEM.

Comparative Example 3 2.0 g of 2-phenylglycine used in preparing the resin composition for an insulating material of Example 3
The preparation of the resin composition for the insulating material and the manufacture of the insulating material were carried out in the same manner as in Example 3 except that no was added. The dielectric constant of the obtained heat-resistant resin was 2.6, and the density was 1.45. No void was observed in the cross section of the insulating film by TEM.

Comparative Example 4 The same procedure as in Example 4 was carried out except that 2.0 g of isonicotinic acid used in the preparation of the resin composition for insulating material of Example 4 was not added. Adjustment and manufacture of insulation. The dielectric constant of the obtained heat-resistant resin was 2.6, and the density was 1.42.
No void was observed in the cross section of the insulating film by TEM.

Comparative Example 5 In preparing the resin composition for an insulating material of Example 4, the melting point was 212 ° C. instead of isonicotinic acid.
Except for adding adamantane, the preparation of the insulating resin composition and the production of the insulating material were carried out in the same manner as in Example 4. The dielectric constant of the obtained heat-resistant resin was 2.6, and the density was 1.41. No void was observed in the cross section of the insulating film by TEM.

In Examples 1 to 4, the dielectric constant was 2.1.
A very low heat-resistant insulating material of about 2.4 was obtained. In Comparative Examples 1 to 4, the organic compound (A) was not contained,
The dielectric constant could not be reduced because there was no void in the insulating material. In Comparative Example 5, since the organic compound (A) was added, the organic compound (A) was thermally decomposed before the heat-resistant resin or the precursor (B) was thermally cured, and no void was formed in the insulating material. Dielectric constant could not be reduced.

[0046]

Industrial Applicability The resin composition for insulating material of the present invention and the insulating material using the same are excellent in electrical properties, particularly dielectric properties and heat resistance, and are used in various fields where these properties are required. For example, it is a synthetic resin useful as an interlayer insulating film for semiconductors, an interlayer insulating film for multilayer circuits, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 79:04 C08L 79:04 (72) Inventor Masanori Fujimoto 2-5 Higashishinagawa, Shinagawa-ku, Tokyo No. 8 Sumitomo Bakelite Co., Ltd. F-term (reference) 4F074 AA74 AA97 AD09 AD13 BA01 BA20 CA11 CC04X CC04Y CC04Z CC32X CC32Y CC42 DA47 5F058 AA10 AC04 AF04 AG01 AH02 5G305 AA06 AA07 AA11 AB10 AB24 BA09 BA14 CA32 CA32

Claims (5)

[Claims] An insulating resin composition comprising an organic compound (A) and a heat-resistant resin or its precursor (B) as essential components, wherein the heat-resistant resin or its precursor (B) is an organic compound. A resin composition for an insulating material having a glass transition temperature higher than the thermal decomposition temperature or sublimation temperature of (A). 2. The resin composition for an insulating material according to claim 1, wherein the organic compound (A) has a melting point higher than the onset temperature of the ring closure temperature of the precursor (B). 3. The heat-resistant resin or a precursor (B) thereof,
2. A polyimide resin or a polyimide precursor.
Or the resin composition for an insulating material according to 2. 4. The heat-resistant resin or a precursor (B) thereof,
3. The resin composition for an insulating material according to claim 1, which is a polybenzoxazole resin or a polybenzoxazole precursor. 5. A heat-resistant resin or a precursor thereof at a temperature higher than the thermal decomposition temperature of the organic compound (A), using the resin composition for an insulating material according to claim 1. B. An insulating material produced by a method having a step of heat-treating the resin obtained at or below the glass transition temperature of the resin obtained.