JP2001283638A - Resin composition for insulating material and insulating material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating material having superior thermal and electric characteristics for use in a semiconductor. SOLUTION: The resin composition for the insulating material has as essential components a multi-branching polymer (A) having a size of one molecule of 1-100 nm and a heat resistant resin or its precursor (B). The glass transition temperature of the (B) is higher than the thermal decomposition temperature of the (A). The (A) is, for example, a dendrimer or a hyper-branch polymer. The (B) is, for example, a polyimide resin or a polyimide precursor, a benzene zooxazole resin or a benzene zooxazole precursor. The insulating material uses the resin composition for the insulating material.

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 material and an insulating material, and more particularly, to a resin composition for an insulating material having excellent properties for use in electric / electronic devices and semiconductor devices. And an insulating material using the same.

[0002]

2. Description of the Related Art Among the characteristics required for materials for electric / electronic devices and semiconductor devices, electric characteristics and heat resistance are the most important characteristics. In particular, in recent years, with miniaturization of circuits and speeding up of signals, an insulating material having a low dielectric constant has been required. An insulating material using a heat-resistant resin is expected as a material for achieving both of these characteristics. For example,
Conventionally, inorganic insulating materials such as silicon dioxide have high heat resistance, but have a high dielectric constant and the required characteristics are now sophisticated. A heat-resistant resin typified by a polyimide resin has excellent electrical characteristics and heat resistance, and can achieve both of the two characteristics, and is actually used for a coverlay of a printed circuit, a passivation film of a semiconductor device, and the like.

[0003] However, with recent advances in the functions and performance of semiconductor devices, remarkable improvements in electrical characteristics and heat resistance have been required, so that even higher performance resins have been required. ing. In particular, a low dielectric constant material having a dielectric constant of less than 2.5 is expected, and a conventional insulating material does not reach required characteristics. In contrast, heretofore, for example, to a resin composition comprising polyimide and a solvent, a heat-decomposable resin other than polyimide is added, and a heating step is performed to decompose the heat-decomposable resin to form voids. Thus, attempts have been made to reduce the dielectric constant of the insulating material. However, when the heat-resistant resin such as polyimide and the heat-decomposable resin are compatible with each other, the glass transition point is lowered. Few. Further, when a thermally decomposable resin that is incompatible with a heat-resistant resin such as polyimide is used, there is a problem that the resin composition for an insulating material becomes non-uniform during storage and cannot be used.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition for an insulating material which exhibits an extremely low dielectric constant and good insulating properties, and also has excellent heat resistance and an insulating material using the same. Aim.

[0005]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned conventional problems, and as a result, heat-treated a multi-branched polymer having a specific size in a resin composition for an insulating material. It has been found out that a high dielectric constant can be obtained by volatilization by the formation of fine pores in the insulating material, thereby completing the present invention.

That is, the present invention provides: (1) a hyperbranched polymer (A) having a molecular size of 0.1 to 100 nm; and a resin having a glass transition temperature of component (A).
A resin composition for an insulating material comprising a heat-resistant resin or a precursor thereof (B) higher than the thermal decomposition temperature of

(2) The size of one molecule is 0.1 to 100 n
m, wherein the multibranched polymer (A) is a dendrimer;

(3) The size of one molecule is 0.1 to 100 n
m, wherein the multibranched polymer (A) is a hyperbranched polymer;

(4) Heat-resistant resin or its precursor (B)
Is a polyimide resin or a polyimide precursor, the resin composition for an insulating material according to any one of the items (1) to (3),

(5) Heat-resistant resin or its precursor (B)
Is a polybenzoxazole resin or a polybenzoxazole precursor, the resin composition for an insulating material according to any one of the items (1) to (3),

(6) Using the resin composition for an insulating material according to any one of (1) to (5), the component (A)
Characterized in that the insulation is produced by a method having a step of performing a heat treatment at a temperature higher than the thermal decomposition temperature of the resin and at a temperature equal to or lower than the glass transition temperature of the heat-resistant resin of component (B) or the resin obtained by ring-closing the precursor thereof. Material.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for insulating material of the present invention comprises:
A hyperbranched polymer (A) having a molecular size of 0.1 to 100 nm, a heat-resistant resin having a glass transition temperature higher than the thermal decomposition temperature of the component (A), or a reaction or chemical ring closure by heating And a heat-resistant resin precursor (B) that forms the heat-resistant resin by a reaction.

The resin composition for an insulating material of the present invention can be applied to a substrate or the like and heated and formed into a film, or impregnated in a glass cloth or the like and heated to form an insulating material. A hyperbranched polymer (A) having a size of one molecule of 0.1 to 100 nm is converted into a heat-resistant resin or its precursor (B).
Can be combined or chemically bonded to form a composition. The component (A) is uniformly dispersed in the heat-resistant resin or its precursor (B) and causes phase separation, thereby reducing the original high glass transition temperature of the heat-resistant resin or the resin obtained by ring-closing the precursor. Express. Further, by increasing the heating temperature to a temperature higher than the temperature at which the component (A) thermally decomposes and a temperature equal to or lower than the glass transition temperature of the resin of the component (B), the glass transition temperature of the resin of the component (B) is increased. Before reaching (1), the component (A) is thermally decomposed and volatilized to form fine voids of 0.1 to 100 nm. The voids formed are each discontinuous,
Thus, an insulating material having a low dielectric constant can be obtained.

The size of one molecule used in the present invention is from 0.1 to
As an example of the hyperbranched polymer (A) having a thickness of 100 nm,
1st generation polyamidoamine dendrimer, 2nd generation polyamidoamine dendrimer, 3rd generation polyamidoamine dendrimer, 4th generation polyamidoamine dendrimer, 5th generation polyamidoamine dendrimer, 1st generation polytrimethyleneimine dendrimer, 2nd generation polytrimethylene Imine dendrimer, 3rd generation polytrimethyleneimine dendrimer, 4th generation polytrimethyleneimine dendrimer, 5th generation polytrimethyleneimine dendrimer, polyamide dendrimer, polyamine dendrimer, polyether dendrimer, polyester dendrimer, polyphenylacetylene Dendrimer, polyamide hyperbranched polymer, polyamine hyperbranched polymer, polyether hyperbranched poly Chromatography, polyester hyperbranched polymer, there is a polyphenyl acetylene hyperbranched polymers. The terminal groups of these dendrimers and hyperbranched polymers include amino groups, imino groups, ester groups, carboxyl groups, hydroxyl groups, cyano groups,
Those having a phenyl group or the like are used, but are not limited thereto. Among these, polyamidoamine dendrimers, polytrimethyleneimine dendrimers, and amine-based hyperbranched polymers are particularly preferred. In some cases, it is also possible to perform surface modification by chemically modifying the terminal functional groups of the dendrimer and the hyperbranched polymer. Further, only one of these may be used, or two or more thereof may be used in combination. The size of one molecule is selected by the thickness of the insulating material, and must be at least smaller than the thickness of the insulating material. More preferably, the insulating material has a size of 1/10 or less of the thickness of the insulating material.

Examples of the heat-resistant resin or its precursor (B) used in the present invention include polyimide, polyamic acid,
Examples include, but are not limited to, polyamic acid esters, polyisoimides, polyamideimides, polyamides, bismaleimides, polybenzoxazoles, polyhydroxyamides, polybenzothiazoles, and the like. Among these, a polyimide resin, a polyamic acid, a polyimide precursor such as a polyamic acid ester and a polyisoimide,
A polybenzoxazole resin and a polybenzoxazole precursor such as polyhydroxyamide are preferable because of high heat resistance, and a combination with these components is also preferable for obtaining an insulating material having a dielectric constant of less than 2.5. Also,
These may be used alone, or may be mixed or copolymerized.

Solvents other than those described above can be used as components of the resin composition for insulating materials of the present invention. In such a case, preferred examples include N, N-dimethylacetamide and N-methyl-2- Pyrrolidone, tetrahydrofuran,
Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, γ-butyrolactone,
1,1,2,2-tetrachloroethane and the like, but not limited thereto. Further, two or more of these may be used simultaneously. Further, an additive such as a surfactant may be used in order to improve applicability and impregnation.

The resin composition for an insulating material of the present invention is obtained by blending the components so that the porosity of the insulating material is 1 to 70% by volume, and uniformly mixing or chemically bonding them. . The mixing ratio of the component (A) and the component (B) is such that the weight ratio (A) / (B) is 5/95 to 90/1.
0, more preferably 10/90 to 70/30.
If it is smaller than the lower limit, there is no effect of reducing the dielectric constant, and if it is larger than the upper limit, the mechanical strength of the insulating material is reduced.

Examples of the method for producing an insulating material of the present invention include:
The resin composition for an insulating material of the present invention is dissolved in the above-mentioned solvent to form a varnish, and then applied to an appropriate support, for example, glass, metal, a silicon wafer or a ceramic substrate to form a coating film. Specific coating methods include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, when a precursor of a heat-resistant resin is used as the component (B), the precursor is heat-treated at a temperature lower than the thermal decomposition temperature of the component (A) and higher than the ring-closure reaction temperature of the precursor, and is converted into a resin. And cure the resin. Finally, the coating film is heat-treated at a temperature higher than the thermal decomposition temperature of the component (A) and lower than the glass transition temperature of the heat-resistant resin of the component (B) or the resin obtained by ring-closing the precursor thereof. By volatilization, an insulating material having fine voids and a low dielectric constant can be formed. These heat treatments are preferably performed with a heating device capable of exhausting the volatilized components.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention.

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 molecular weight of the polyimide resin is number average molecular weight 26,000, weight average molecular weight 54,
000.

(2) Measurement of Glass Transition Temperature of Heat Resistant Resin 5.0 g of the polyimide resin synthesized above was added to NMP1.
After melt | dissolving in 5.0 g and apply | coating on the glass substrate which carried out the release processing, it hold | maintained at 120 degreeC for 4 minutes and 300 degreeC for 60 minutes in an oven, and formed a film.
Heating was performed at 00 ° C. for 60 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) The size of one molecule is 0.1 to 100 n
Measurement of Thermal Decomposition Temperature of Multi-branched Polymer Component of m Third-generation polyamidoamine dendrimer having a diameter of about 7 nm per molecule (Starburs manufactured by Aldrich)
t (PAMAM-OH), Gen3)
When measured by thermogravimetry under a nitrogen atmosphere, 30
It was 0 ° C.

(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 NMP
After dissolution in 50.0 g, the third generation polyamidoamine dendrimer (Starburs manufactured by Aldrich) was used.
4.0 g of t (PAMAM-OH), Gen3) was added, stirred, and uniformly mixed 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. At the time of heat curing, after holding at 120 ° C. for 4 minutes,
Hold for minutes. Thus, a 0.8 μm thick insulating film was obtained. On this insulating material film, an area of 0.1 c
An m2 aluminum electrode was formed 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. Further TEM
Observation of the cross section of the insulating material film showed that the obtained voids were discontinuous with an average pore diameter of 7 nm.

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 was used. 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 a 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, which was then vacuum-dried at 25 ° C. for 72 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 Glass Transition Temperature of Heat-Resistant Resin 5.0 g of the polyamic acid synthesized above was added to NMP2
After dissolving it in 0.0 g and applying it on a release-treated glass substrate, a film was formed by holding it in an oven at 120 ° C. for 4 minutes and at 300 ° C. for 60 minutes.
Heating was performed at 00 ° C. for 60 minutes to obtain a polyimide resin film which is a heat-resistant resin. When the glass transition temperature of this polyimide resin was measured by a differential scanning calorimeter, it was 419.
° C.

(3) The size of one molecule is 0.1 to 100 n
Measurement of the Thermal Decomposition Temperature of the Hyperbranched Polymer Component of m 4th Generation Polyamidoamine Dendrimer (Aldrich Starburs) with a diameter of about 9 nm per molecule
t (PAMAM-OH), Gen4)
When measured by thermogravimetry under a nitrogen atmosphere, 33
It was 0 ° C.

(4) 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, the fourth-generation polyamidoamine dendrimer (Starburst manufactured by Aldrich) was used.
(PAMAM-OH), Gen4) (4.0 g) was added, stirred, and uniformly mixed 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. In the case of heat curing, the film was held at 120 ° C. for 4 minutes, at 300 ° C. for 60 minutes, and then at 400 ° C. for 60 minutes. Thus, a 0.9 μm-thick insulating material film was obtained. Thereafter, the dielectric constant of this heat-resistant resin was measured in the same manner as in Example 1, and was 2.3. Further, when the cross section of the insulating material film was observed with a TEM, the obtained voids were discontinuous with an average pore diameter of 9 nm.

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 using hexane to obtain 4,4′-hexafluoroisopropylidenediphenyl-1,1′-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) hexafluoropropane (7.32 g, 0.02 mol) was dissolved in dry dimethylacetamide (100 g), and pyridine (3.96 g) was dissolved.
g (0.05 mol), and then dry nitrogen was introduced.
8.55 g of 4,4'-hexafluoroisopropylidenediphenyl-1,1'-dicarboxylic acid chloride synthesized above was added to 50 g of dimethylacetamide at 5 ° 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 a 20-fold amount of water to collect a precipitate, followed by vacuum drying 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 20,
000 and 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 was dissolved in a mixed solvent of 8.0 g of NMP and 12.0 g of tetrahydrofuran, and applied on a release-treated glass substrate, and then held in an oven at 120 ° C. for 4 minutes and at 300 ° C. for 60 minutes to form a film. After removing the film from
Heating was performed at 00 ° C. for 60 minutes to obtain a film of a polybenzoxazole resin which is a heat-resistant resin. The glass transition temperature of this polybenzoxazole resin measured by a differential scanning calorimeter was 360 ° C.

(3) The size of one molecule is 0.1 to 100 n
Measurement of the Thermal Decomposition Temperature of the Multibranched Polymer Component of m The fourth generation polytrimethylene imine dendrimer (Aldrich DAB (A
M) 32, Gen4.0) was 340 ° C. as measured by thermogravimetric analysis under a nitrogen atmosphere.

(4) Preparation of Resin Composition for Insulating Material and Production of Insulating Material Polybenzoxazole resin 5.0 synthesized as described above.
g was dissolved in a mixed solvent of 8.0 g of NMP and 12.0 g of tetrahydrofuran, and then the fourth-generation polytrimethyleneimine dendrimer (DAB (A
2.0 g of M) 32, Gen4.0) was added, stirred, and uniformly mixed to obtain a resin composition for insulating materials. Thickness 200
This resin composition for an insulating material was spin-coated on a silicon wafer on which a tantalum film having a thickness of nm was formed, and then cured by heating in an oven in a nitrogen atmosphere. 120 ° C for heat curing
And then kept at 350 ° C. for 60 minutes. Thus, a coating of an insulating material having a thickness of 0.7 μm was obtained.
Thereafter, the dielectric constant of this heat-resistant resin was measured in the same manner as in Example 1, and was found to be 2.2. Further, when the cross section of the insulating material film was observed by TEM, the obtained voids were discontinuous with an average pore diameter of 2 nm.

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, 7.32 g (0.02 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 100 g of dried dimethylacetamide. Dissolved and 3.96 g of pyridine
(0.05 mol), and then -15 under dry nitrogen introduction.
At 50 ° C., 50 g of dimethylacetamide was added to 2,2′-bis (trifluoromethyl) biphenyl-
8.30 g of 4,4'-dicarboxylic acid chloride (0.02
mol) was dropped 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 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, the film was formed by holding it in an oven at 120 ° C. for 4 minutes and at 300 ° C. for 60 minutes. For 60 minutes to obtain a film of polybenzoxazole, which is a heat-resistant resin. The glass transition temperature of this polybenzoxazole was measured by a differential scanning calorimeter, and was 410 ° C.

(3) The size of one molecule is 0.1 to 100 n
Measurement of the Thermal Decomposition Temperature of the Hyperbranched Polymer Component of m The fifth generation polytrimethylene imine dendrimer (Aldrich DAB (A
M) 64, Gen5.0) was found to have a thermal decomposition temperature of 370 ° C. by thermogravimetric analysis under a nitrogen atmosphere.

(4) Preparation of Resin Composition for Insulating Material and Production of Insulating Material After dissolving 10.0 g of the polyhydroxyamide synthesized as above in 50.0 g of NMP, the fifth-generation polytrimethyleneimine dendrimer (Aldrich) DA
B (AM) 64, Gen5.0) (2.0 g) was added, stirred, and uniformly mixed to obtain a resin composition for an insulating material. On a silicon wafer with a 200 nm thick tantalum film,
After spin-coating this resin composition for an insulating material, it was heated and cured in an oven in a nitrogen atmosphere. In the case of heat curing, 1
After holding at 20 ° C. for 4 minutes and at 300 ° C. for 60 minutes, 40
Hold at 0 ° C. for 60 minutes. Thus, a thickness of 0.8
A μm coating of insulating material 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. Further, when the cross section of the insulating material film was observed with a TEM, the obtained voids were discontinuous with an average pore diameter of 3 nm.

Comparative Example 1 In the preparation of the insulating resin composition of Example 1, the third generation polyamidoamine dendrimer (Starburst manufactured by Aldrich) was used.
(PAMAM), Gen4) Except not adding 4.0 g, adjustment of the resin composition for insulating materials and production 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 3.0, and no void was observed in the cross-section of the insulating film by TEM.

Comparative Example 2 A fourth-generation polyamidoamine dendrimer (Starburst manufactured by Aldrich) used in the preparation of the resin composition for insulating material of Example 2.
(PAMAM-OH), Gen4) Preparation of insulating resin composition and production of insulating material were performed in the same manner as in Example 2 except that 2.0 g of polystyrene having a molecular weight of 20,000 was added instead of 2.0 g. went. This largely separated the phase and did not result in a uniform film.

Comparative Example 3 In the preparation of the resin composition for insulating material of Example 3, the fourth-generation polytrimethyleneimine dendrimer (DAB (AM) manufactured by Aldrich) was used.
32, Gen 4.0) molecular weight 100 instead of 2.0 g
Except that 2.0 g of polyethyleneimine was added.
Preparation of an insulating resin composition and production of an insulating material were performed in the same manner as in Example 3. The dielectric constant of the obtained heat-resistant resin was 2.7, and no void was observed in the cross-section of the insulating film by TEM.

Comparative Example 4 In preparing the insulating resin composition of Example 4, the fifth-generation polytrimethyleneimine dendrimer (DAB (AM) manufactured by Aldrich) was used.
64, Gen 5.0) 2.0 g instead of 100
Preparation of an insulating resin composition and production of an insulating material were performed in the same manner as in Example 4 except that 2.0 g of polymethyl methacrylate of No. 00 was added. The dielectric constant of the obtained heat-resistant resin was 2.7, and 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 resin of ~ 2.4 was obtained.

In Comparative Example 1, the size of one molecule is 0.1 to
Since the multi-branched polymer component (A) having a thickness of 100 nm was not contained in the composition component, the dielectric constant could not be reduced.

In Comparative Example 2, since the added polystyrene was not a hyperbranched polymer, the dielectric constant could not be reduced.

In Comparative Example 3, the dielectric constant could not be reduced because the added polyethyleneimine was not a hyperbranched polymer.

In Comparative Example 4, the dielectric constant could not be reduced because the added polymethyl methacrylate was not a hyperbranched polymer.

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 79/04 C08L 79/04 101/00 101/00 F term (reference) 4F073 AA23 BA29 BA31 BA34 GA01 HA04 4J002 AA03W BC01W BG02W BH02X BJ00W BM00W CF00W CH05W CL00X CL09W CM01W CM03X CM04W CM04X CN06X FD310 GH00 GQ01 HA05 5G305 AA06 AA07 AA11 AB01 AB24 BA09 CA21 CA32 DA22

Claims (6)

[Claims] 1. A hyperbranched polymer (A) having a molecular size of 0.1 to 100 nm, a heat-resistant resin having a glass transition temperature higher than the thermal decomposition temperature of the component (A) or a precursor thereof. A resin composition for an insulating material, comprising a body (B) as an essential component. 2. The hyperbranched polymer (A) having a size of one molecule of 0.1 to 100 nm is a dendrimer.
The resin composition for an insulating material as described in the above. 3. The resin composition for an insulating material according to claim 1, wherein the hyperbranched polymer (A) having a size of one molecule of 0.1 to 100 nm is a hyperbranched polymer. 4. The heat-resistant resin or its precursor (B) is a polyimide resin or a polyimide precursor.
4. The resin composition for an insulating material according to any one of 3. 5. The resin composition for an insulating material according to claim 1, wherein the heat-resistant resin or its precursor (B) is a polybenzoxazole resin or a polybenzoxazole precursor. 6. A heat-resistant resin having a temperature higher than the thermal decomposition temperature of the component (A) and the component (B), using the resin composition for an insulating material according to any one of claims 1 to 5. Alternatively, an insulating material manufactured by a method having a step of performing a heat treatment at a temperature equal to or lower than a glass transition temperature of a resin obtained by ring-closing a precursor thereof.