JPH0565342A - Polyimide precursor and cured polyimide resin - Google Patents

Abstract

(57) [Summary] [Object] The present invention provides a polyimide having a low dielectric constant, a low thermal expansion coefficient, a high heat resistance, a high glass transition temperature, and high mechanical properties, a precursor thereof, and a method for producing the same. is there. [Structure] And (I); 30 to 80%, (II); 70 to 20
% Of a repeating unit, a cured product thereof, and a method for producing the same.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide precursor having a low dielectric constant and excellent heat resistance, a cured polyimide, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, polyimide has been known as a resin having excellent heat resistance. Polyimide is generally obtained by a method in which a diamine component and a tetracarboxylic dianhydride component are polymerized in an organic solvent to produce a polyamic acid, which is dehydrated and ring-closed. As examples of these, for example, (a) general formula (Formula 12) or general formula (Formula 13)

[0003]

[Chemical formula 12]

[0004]

[Chemical 13]

(In the formula, R'represents a divalent hydrocarbon group.)
There are known novel polyimides containing the structural unit shown by and their precursors, polyamic acid or polyamic acid ester (JP-A-62-265327, JP-A-63-10629).

(B) General formula (Chem. 14)

[0007]

[Chemical 14]

Polyimides in which a repeating unit is represented by (wherein R "is a tetravalent aliphatic group or aromatic group and n is 1 or 2) are known (Japanese Patent Laid-Open No. 57-114258).
JP-A-57-188883, JP-A-60-250
031, JP-A-60-212426).

Further, (c) general formula (formula 15)

[0010]

[Chemical 15]

(In the formula, Y is --C (CH ₃ ) _3-, --C (CF ₃ ).
₃ -, - SO ₂ - it is. ) Is known to have a repeating unit represented by JP-A-62-231935.
No. 62-231936, 62-231.
937).

(D) Polyimides excellent in low dielectric constant include 2,2-bis (3,4-dicarboxyphenyl) propanoic acid dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexa Fluoropropanoic acid dianhydride and 4,4 '
-Bis (4-aminophenoxy) biphenyl, 4,4 '
Polyimides obtained from aromatic diamines such as -bis (4-amino-2-trifluoromethylphenoxy) biphenyl are known (Japanese Patent Laid-Open No. 60934/1990), and (e) 2,2-bis ( Obtained from a mixed acid dianhydride consisting of 4-aminophenyl) hexafluoropropane and 2,2-bis (3-aminophenyl) hexafluoropropane and pyromellitic dianhydride and an acid dianhydride having a diaryl nucleus Polyimide (JP-A-2-67320), 2,
From 2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride and 2,2-bis (4-aminophenyl) hexafluoropropane and 2,2-bis (3-aminophenyl) hexafluoropropane The obtained polyimide (Japanese Patent Laid-Open No. 2-86624) is known.

However, the above (a), (b), (c),
Various properties such as high heat resistance, low dielectric constant, low thermal expansion coefficient, high mechanical properties (especially flexibility), and high glass transition temperature are not taken into consideration in the polyimides of (d) and (e) at the same time. ..

[0014]

[Problems to be Solved by the Invention]
Polyimides (b), (c), (d), and (e) have various properties such as high heat resistance, low dielectric constant, low coefficient of thermal expansion, high mechanical properties (especially flexibility), and high glass transition temperature. Are not considered at the same time. (A), (b), (c) have high heat resistance,
It excels in low coefficient of thermal expansion and high glass transition temperature, but it has a high dielectric constant and is not flexible. It has a relatively large number of imide rings in the polymer, and

[0015]

[Chemical 16]

Heat resistance due to containing the structural unit represented by
Although it has a high glass transition temperature and a low coefficient of thermal expansion, it is considered that it has a high dielectric constant and is not flexible. Also (d), (e)
Then, in either the acid dianhydride component or the diamine component, -C
Since a compound containing F ₃ or a compound having a —O— bond is used, the dielectric constant is low and the flexibility is excellent, but the heat resistance and the glass transition temperature are low, and the thermal expansion coefficient is high.

The inventors of the present invention have achieved various properties that could not be achieved by these conventional techniques, namely, high heat resistance, low dielectric constant, low thermal expansion coefficient, high mechanical properties (particularly flexibility), and high glass transition. The present invention has been accomplished as a result of extensive studies aimed at finding a polyimide having various properties such as temperature and high alkali resistance.

[0018]

In the present invention, the general formula (Formula 9) is used.

[0019]

[Chemical 9]

(Wherein R ¹ is

[0021]

[Chemical 3]

It is In the tetracarboxylic dianhydride component represented by the formula (1), the diamine component and the aminosiloxane compound are represented by 1) the general formula:

[0023]

[Chemical 10]

Is 30 to 80, and 2) the general formula, H ₂ N--R ³ --NH ₂ is 70 to 20 (wherein
R ² is

[0025]

[Chemical 4]

R ³ is (formula 5)

[0027]

[Chemical 5]

A diamine component represented by (using at least one or more of the diamines represented by) and 3) if necessary, a compound represented by the general formula (Chem. 11)

[0029]

[Chemical 11]

(In the formula, R ⁴ and R ⁷ are a hydrocarbon group having 1 to 9 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁶ is an ether group if necessary. One or more groups selected from an alkyl group having 1 to 5 carbon atoms or a trialkylsilyl group,
R ⁸ and R ⁹ are alkyl groups having 1 to 3 carbon atoms, aryl groups having 1 to 9 carbon atoms, n is 0, 1 or 2, and f is a positive integer. ) A monoaminosiloxane compound or diaminosiloxane component represented by the formula (1), wherein the proportion of the monoaminosiloxane compound or siloxanediamine component used is in the range of 0.5 to 10% of the total amount of the diamine component; Polymerized in a solvent, further heated to adjust the viscosity of the varnish, obtained by the general formula (Formula 1)
(Chemical formula 2)

[0031]

[Chemical 1]

[0032]

[Chemical 2]

(In the formula, R ¹ is

[0034]

[Chemical 3]

R ² is

[0036]

[Chemical 4]

The main component of R ³ is

[0038]

[Chemical 5]

A divalent group selected from the group consisting of two or more kinds, and a sub-component thereof, in the case where -R ³ -is a terminal of the polymer or a main chain of the polymer, respectively, are generally used. Formula (Formula 17)

[0040]

[Chemical 17]

A hydrocarbon group containing a silicon atom represented by: R ⁴ is a hydrocarbon group having 1 to 9 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁶ is an optional hydrocarbon group. It is one or more groups selected from an alkyl group having 1 to 5 carbon atoms including an ether group or a trialkylsilyl group. n is 0 to 3
, And f is a positive integer. A polyimide having a reduced viscosity of at least 0.5 dl / g (solvent N-methyl-2-pyrrolidone, concentration 0.1 g / 100 ml, temperature 25 ° C.) or more and comprising a repeating unit represented by the formula A polyimide cured film obtained by thermosetting a precursor at a temperature of 100 ° C. or higher has various properties such as high heat resistance, low dielectric constant, low thermal expansion coefficient, high mechanical properties (especially flexibility), and high glass transition temperature. I found that I have a combination.

The present invention will be described in detail below.

The tetracarboxylic acid dianhydride used in the present invention is paraterphenyl-3,3 ", 4.
4 ″ -tetracarboxylic dianhydride and meta-terphenyl-3,3 ″, 4,4 ″ -tetracarboxylic dianhydride can be used.

The diamine component used in the present invention includes 4,4 "-diamino-paraterphenyl, 4,
4 "-diamino-paraquaterphenyl, 9,10
-Another diamine component which is diaminoanthracene and contains at least two or more aromatic rings is, for example,

[0045]

Embedded image and the like. It is possible to use at least one or more of these monomers.

It can be done.

In addition, other diamines have high heat resistance, low dielectric constant,
It may be used when adjusting a low coefficient of thermal expansion, a high glass transition temperature, a high mechanical strength, flexibility and the like. For example,
8)

[0048]

[Chemical 18]

And the like.

In addition, the general formula (Formula 19)

[0051]

[Chemical 19]

(In the formula, R ⁴ is a hydrocarbon group having 1 to 9 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁶ is a hydrocarbon group having 1 to 5 carbon atoms and optionally an ether group. A monoaminosilane compound represented by 1 or 2 or more groups selected from an alkyl group or a trialkylsilyl group, n is 0, 1 or 2, for example, 3-aminopropyltrimethylsilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminopropyldimethylpropoxysilane, 3-aminopropylmethyldipropoxysilane, 3-aminopropyl 3-aminopropyldialkylalkoxysilane, 3-aminopropylalkyldialkoxysilane, 3-amino such as rutripropoxysilane, 3-aminopropyldimethylbutoxysilane, 3-aminopropylmethyldibutoxysilane, and 3-aminopropyltributoxysilane. Propyltrialkoxysilane,
3- (4-aminophenoxy) propyldialkylalkoxysilane, 3- (4-aminophenoxy) propyldialkylalkoxysilane, 3- (4-aminophenoxy) propylalkyldialkoxysilane, 3- (4
-Aminophenoxy) propyltrialkoxysilane,
3- (3-aminophenoxy) propyldialkylalkoxysilane, 3- (3-aminophenoxy) propylalkyldialkoxysilane, 3- (3-aminophenoxy) propyltrialkoxysilane, 4-aminobutyldimethylethoxysilane, 4- 4-aminobutyldialkylalkoxysilanes such as aminobutylmethyldiethoxysilane and 4-aminobutyltriethoxysilane, 4
-Aminobutylalkyldialkoxysilane, 4-alkylalkoxysilane, 4-aminobutylalkyldialkoxysilane, 4-aminominotrialkoxysilane, 3-aminopropyltris (trimethylsiloxy)
Silane, meta-aminophenyldimethylmethoxysilane, meta-aminophenylmethyldimethoxysilane, meta-aminophenyltrimethoxysilane, meta-aminophenyldimethylethoxysilane, meta-aminophenylmethyldiethoxysilane, meta-aminophenyltriethoxysilane, meta-amino Meta-aminophenyldialkylalkoxysilanes such as phenyldimethylpropoxysilane, meta-aminophenylmethyldipropoxysilane, meta-aminophenyltripropoxysilane,
Metaminophenylalkyldialkoxysilane, meta-aminophenyltrialkoxysilane, para-aminophenyldimethylmethoxysilane, para-aminophenylmethyldimethoxysilane, para-aminophenyltrimethoxysilane, para-aminophenyldimethylethoxysilane, para-aminophenylmethyldiethoxysilane Silane, para-aminophenyltriethoxysilane, para-aminophenyldimethylpropoxysilane, para-aminophenylmethyldipropoxysilane, para-aminophenyltripropoxysilane and other para-aminophenyldialkylalkoxysilanes, para-aminophenylalkyldialkoxysilanes, para-aminophenyl Trialkoxysilane, meta-aminobenzyldimethylethoxysilane, Tar aminobenzyl methyl diethoxy silane, meta - aminobenzyl triethoxysilane silane, meta-aminobenzyl dimethyl propoxysilane,
Meta-aminobenzyldialkylalkoxysilanes such as meta-aminobenzylmethyldipropoxysilane, meta-aminobenzyltripropoxysilane, meta-aminobenzyldimethylpropoxysilane, meta-aminobenzylmethyldipropoxysilane, meta-aminobenzyltripropoxysilane, meta-aminobenzyl Alkyldialkoxysilane, meta-aminobenzyltrialkoxysilane, para-aminobenzyldimethylpropoxysilane, para-aminobenzylmethyldipropoxysilane, para-aminobenzyldialkylalkoxysilane such as para-aminobenzyltripropoxysilane, para-aminobenzylalkyldialkoxysilane, Para-aminobenzyltrialkoxysilane, para-aminophenethyl dimethyl Toxisilane, para-aminophenethylmethyldimethoxysilane, para-aminophenethyldialkylalkoxysilane such as para-aminophenethyltrimethoxysilane, para-aminophenethylalkyldialkoxysilane, para-aminophenethyltrialkoxysilane, or the above meta- or para-benzyl, phenethyl Examples include hydrogenated compounds.

As the siloxane diamine component used in the present invention, a compound represented by the general formula (formula 20)

[0054]

[Chemical 20]

(In the formula, R ⁷ is a divalent hydrocarbon group having 1 to 9 carbon atoms, R ⁸ and R ⁹ are each an alkyl group having 1 to 3 carbon atoms, and an aryl group having 1 to 9 carbon atoms. A diaminosiloxane compound represented by the following formula: n is an integer of 0 to 3, and f is a positive integer of 1 or more.

[0056]

[Chemical 21]

And the like. The above-mentioned monoaminosiloxane compound or diaminesiloxane component is used in the range of the monoaminosiloxane component or diaminosiloxane component for the purpose of improving the adhesiveness.
When set to 00%, 0.5 to 10 of the total amount of diamine components
%, Preferably 0.5 to 5%. When the content of the monoaminosiloxane component is 0.5% or less, the effect of adhesiveness is small, and 1
If it is 0% or more, heat resistance and mechanical properties are adversely affected.

The solvent used in producing the polyimide precursor and the polyimide of the present invention is, for example, N 2.
-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, para-chlorophenol, para-bromophenol and the like, and at least 1 of them More than one species can be used.

In carrying out the present invention, in the case of a polyimide precursor, the diamine component is first dissolved in the aprotic polar solvent and then terphenyl-3,3 ", 4,4.
Add 4 "-tetracarboxylic dianhydride and adjust temperature to 0-3
Stir for 2-6 hours, keeping at 0 ° C. As a result, the reaction gradually progresses, the viscosity of the varnish increases, and the polyimide precursor is produced. Further, the viscosity of the varnish is adjusted by stirring while maintaining the temperature at 50 to 80 ° C. However, when an aminosiloxane compound is used as the diamine component, the temperature is 0 to 30 ° C.
The mixture is stirred for 1 to 4 hours while maintaining the temperature at 50 ° C. and then stirred at 50 to 80 ° C. to adjust the viscosity of the varnish.

Further, the polyimide cured product passing through the above polyimide precursor is cured by heating at a temperature of 100 ° C. or higher, and the following general formulas (Formula 22) and (Formula 23) are obtained.

[0061]

[Chemical formula 22]

[0062]

[Chemical formula 23]

(Wherein R ¹ is

[0064]

[Chemical 3]

R ² is (formula 4)

[0066]

[Chemical 4]

R ³ is the following (formula 5)

[0068]

[Chemical 5]

When a single or two or more kinds of divalent groups selected from the group, and optionally R ³ moiety is the end of the polymer or the main chain of the polymer, each has the general formula (Formula 17).

[0070]

[Chemical 17]

A hydrocarbon group containing a silicon atom represented by R ⁴ , R ^{7 of which} is a hydrocarbon group having 1 to 9 carbon atoms, a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, and R ⁵
Is a hydrocarbon group having 1 to 3 carbon atoms, R ⁶ is an alkyl group having 1 to 5 carbon atoms or a trialkylsilyl group optionally containing an ether bond, and R ⁸ and R ⁹ are alkyl groups having 1 to 3 carbon atoms , 1 selected from aryl groups having 1 to 9 carbon atoms
It is a group of species or more. n is an integer of 0 to 3, and f is a positive integer of 1 or more. ), A repeating unit having a structure represented by

[0072]

[Chemical 6]

A diamine component represented by the formula (Formula 23)
When the total amount of the other aromatic diamine components represented by -R ³ -of is 100,

[0074]

[Chemical 6]

The diamine component represented by
The other aromatic diamine component represented by —R ³ — is 70 to 2
It is considered that the use range of the diamine component and / or aminosilane compound or siloxanediamine having a range of 0 becomes a polyimide cured product having a range of 0.5 to 10 of the total amount of the diamine component.

[Formula 6] of Formula (Formula 22) in the cured polyimide

[0077]

[Chemical 6]

The diamine component represented by the formula
When the total amount of the other aromatic diamine components represented by —R ³ — of 100 is 100, the composition ratio thereof is represented by the formula (6) in the formula (22).

[0079]

[Chemical 6]

The diamine component represented by is 80 to 3
0, preferably 80 to 50 from the viewpoint of process reliability when applied to a semiconductor device or the like,
Examples of the other aromatic diamine component represented by -R ^3- include
20 to 70, and preferably 20 to 50 from the viewpoint of process reliability when applied to a semiconductor device or the like.
(Chemical formula 22)

[0081]

[Chemical 6]

When the amount of the diamine component represented by is 80 or more, the produced polyimide film lacks flexibility, and
Below, the glass transition temperature Tg is low and the thermal expansion coefficient is high. Further, when the other aromatic diamine component represented by -R ^3-in (Chemical Formula 23) is 50 or more, the glass transition temperature Tg is low and the thermal expansion coefficient is high, and when it is 20 or less, the polyimide film formed is flexible. Run out.

[0083]

As described above, according to the present invention, para (or meta) -ta-phenyltetracarboxylic dianhydride and a diamine having a rigid (linear) structure throughout the molecule as a diamine component. By using a diamine having a flexible (flexible) structure in the molecule, low dielectric constant, low thermal expansion coefficient,
It was possible to find a polyimide and its precursor that have a high degree of heat resistance, a high glass transition temperature, and high mechanical properties (flexibility). This is because the polyimide according to the present invention contains many linearly bonded aromatic rings and relatively few imide rings that cause an increase in the dielectric constant, resulting in a low dielectric constant and a low coefficient of thermal expansion. It is considered that a polyimide having high heat resistance and high glass transition temperature was achieved at the same time. Further, by using a diamine having a flexible (flexible) structure as a part of the diamine component, the polyimide according to the present invention can also have high mechanical properties (flexibility).

[0084]

The present invention will be described below with reference to examples. The polyimide according to the present invention is excellent in all characteristics. Therefore, in order to compare the comprehensive evaluation with the comparative example, the ideal evaluation standard of the characteristic value when polyimide is used as an insulating film of a multilayer wiring structure is shown below.

Dielectric constant ε ≦ 2.7, thermal decomposition temperature Td ≧ 48
0 ° C., glass transition temperature Tg ≧ 350 ° C., thermal expansion coefficient α ≦
25 ppm / ° C., the tensile strength ≧ 15Kg / mm ^2, the Young's modulus ≦ 700Kg / mm ^2, elongation ≧ 10%.

Example 1 2,2-bis [4- (p-aminophenoxy) phenyl] hexafluoropropane 3.49 at room temperature under a stream of nitrogen
4 g (6.740 mmol, 50% molar ratio in the diamine component) and 4,4 "-diamino-p-terphenyl 1.7
55 g (6.740 mmol, molar ratio of 50% in diamine component) was added to N, N-dimethylacetamide (DMA).
c) and N-methyl-2-pyrrolidone (NMP) 1: 1
50.0 g of a mixed solvent (solid concentration 17%) was dissolved with stirring. Then p-terphenyl-3,3 ", 4,
4 "-tetracarboxylic dianhydride (TPDA) 4.99
2 g (13.48 mmol) was dissolved in the above solution with stirring under a nitrogen stream. At this time, the temperature of the solution rose to around 30 degrees and its viscosity became 120 poise. Further, this solution was heated at 60 to 70 ° C. for about 5 hours to adjust its viscosity to 50 poise to obtain a polyamic acid varnish.
This varnish was diluted with N-methyl-2-pyrrolidone (concentration 0.1 g / 100 ml) and diluted with an Uberode-viscometer to 25
When the reduced viscosity was determined by measuring the viscosity at ℃, 1.66dl
/ G.

The above-mentioned polyamic acid varnish was spin-coated on a silicon wafer or a glass substrate, and was applied in a nitrogen stream for 20 minutes.
When cured at 0 ° C. for 30 minutes and at 350 ° C. for 30 minutes and peeled from the substrate, a film having good flexibility was obtained.

Next, various characteristic values of this film were evaluated by the following test methods. The composition of the polymer is shown in Table 1, and the evaluation results are shown in Table 2. The infrared absorption spectrum of this polyimide film is shown in FIG.

(1) Dielectric constant ε Within 24 hours after the film was formed, it was measured by LCHP meter 4277A manufactured by YHP (Yokogawa Hulet Packer). Measurement conditions: humidity in measurement room 60% or less, frequency 1
0 KHz, temperature 25 ° C, electrode is Al-Al or Cr
-Al.

(2) Pyrolysis temperature Td Using 50 mg of the above film, a high-speed differential calorimeter TGD-5000 manufactured by ULVAC, Inc. was used under a nitrogen stream under a temperature rising rate of 5.
It was measured at ° C / min. The temperature when the weight loss rate was 3% was defined as the thermal decomposition temperature Td.

(3) Glass Transition Temperature Tg The film was used as a strip-shaped test piece of 5 mm × 25 mm, and its elongation was measured under a nitrogen stream by a thermomechanical measuring device TM-3000 manufactured by ULVAC. The temperature at which the elongation rate sharply increases was defined as the glass transition temperature Tg.

(4) Thermal Expansion Coefficient α The above film was used as a strip test piece of 5 mm × 25 mm, its elongation was measured under a nitrogen stream by a thermomechanical measuring device TM-3000 manufactured by ULVAC, and the thermal expansion coefficient α was measured. I asked.

(5) Tensile Strength, Young's Modulus, and Elongation The above film was used as a 5 mm × 45 mm strip-shaped test piece (film thickness 8 μm), and it was determined from elongation and stress using an Instron tensile tester.

(6) Infrared absorption spectrum A polyimide having a film thickness of 1.2 to 1.8 μm was formed on a silicon wafer by the above method, and it was kept at room temperature without peeling.
It was measured with a Nicolet 170SX Fourier transform infrared spectrophotometer.

Examples 2 to 3 Polyimide films were prepared in the same manner as in Example 1 using the components shown in Table 1, and various characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2. The obtained polyimide film had excellent flexibility and was a good film over all properties.

Example 4 2,2-bis [4- (p-aminophenoxy) phenyl] hexafluoropropane 2.32 at room temperature under a nitrogen stream
3 g (4.4800 mmol, 40% molar ratio in diamine component) and 4,4 "-diamino-p-terphenyl 1.
633 g (6.272 mmol, 56% in diamine component)
Molar ratio) and 3-aminopropylmethyldimethoxysilane 0.171 g (0.896 mmol, diamine ratio 4)
% Molar ratio), N, N-dimethylacetamide (DM
Ac) and N-methyl-2-pyrrolidone (NMP) 1:
It was dissolved in 40.0 g of mixed solvent of 1 (solid content concentration 17.1%) with stirring. Then p-terphenyl-3,3 ",
4,4 "-tetracarboxylic dianhydride (TPDA) 4.
148 g (11.20 mmol) was dissolved in the above solution with stirring under a nitrogen stream. At this time, the temperature of the solution rose to around 30 degrees and its viscosity became 80 poise. Further, this solution was heated at 60 to 70 ° C. for about 5 hours to adjust its viscosity to 38.3 poise to obtain a polyamic acid varnish.

The above polyamic acid varnish was spin-coated on a silicon wafer, and the mixture was kept at 200 ° C. for 30 minutes in a nitrogen stream for 3 minutes.
It was cured at 50 ° C. for 30 minutes. Next, an attempt was made to peel the polyimide film from this wafer, but it was difficult to remove it easily, and it was found that the adhesiveness was extremely excellent. In addition, a polyimide film was formed in the same manner as in Example 1, and
Various characteristic values were evaluated by the same method as. The results are shown in Table 2.

[0098]

[Table 1]

[0099]

[Table 2]

Comparative Examples 1 to 4 Polyimide films were prepared in the same manner as in Example 1 using the components shown in Table 3, and various properties were evaluated in the same manner as in Example 1. The results are shown in Table 4. The obtained polyimide film is a good film with excellent flexibility, but since it has a large coefficient of thermal expansion and a low glass transition temperature, it has a problem in reliability when used in a multilayer wiring structure etc. it is conceivable that.

Comparative Example 5 Using the components shown in Table 3, a polyimide film was prepared in the same manner as in Example 1, and various properties were evaluated in the same manner as in Example 1. The results are shown in Table 4. The obtained polyimide film was very poor in flexibility and could not be formed as a film. Therefore, it was not possible to measure various characteristic values such as thermal expansion coefficient, tensile strength and elongation.

Comparative Example 6 As another comparative example, PIQ (Hitachi Chemical Industry Co., Ltd.)
(Registered trademark). Example 1 of various characteristic values of PIQ
Evaluation was carried out in the same manner as in, and shown in Table 4. Among the various characteristic values of PIQ, the various characteristic values other than Young's modulus and elongation did not satisfy the evaluation criteria of the above characteristic values.

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

INDUSTRIAL APPLICABILITY As described in the above Examples and Comparative Examples, the polyimide obtained from the novel polyamic acid according to the present invention has all the characteristics as compared with the polyimide obtained from the conventionally known polyamic acid. In particular, since it is excellent in low dielectric constant, low thermal expansion coefficient, and high heat resistance and is expected to have high reliability, it is extremely useful in all industrial applications including multilayer wiring structures.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of Example 1.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Fumio Kataoka Inventor Fumio Kataoka 292 Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Stock Manufacturing Research Institute, Hitachi, Ltd. Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (7)

[Claims] 1. A general formula (Formula 1) (Formula 2) [Chemical 2] (In the formula, R ¹ is (Chemical Formula 3), R ² is (Chemical formula 4) R ³ is (Chemical Formula 5) Of at least one monomer of the diamine represented by the formula), and the constitution ratio thereof is represented by the formula (6) When the total amount of the diamine component represented by and the aromatic diamine component represented by —R ³ — in formula (Formula 2) is 100, (Formula 6) The diamine component represented by 30 to 80 and the aromatic diamine component represented by -R ³ -are in the range of 70 to 20, and the reduced viscosity thereof is at least 0.5 dl / g (solvent N
-Methyl-2-pyrrolidone, concentration 0.1g / 100m
1, a temperature of 25 ° C.) or higher. 2. General formulas (formula 1) (formula 2) (formula 7) [Chemical 2] [Chemical 7] (In the formula, R ¹ is (Chemical Formula 3), R ² is (Chemical formula 4) R ³ is (Chemical Formula 5) At least one monomer of these diamines represented by the following formula is used, and R ⁴ is represented by the following general formula (Chemical Formula 8) when the portion is the end of the polymer or the main chain of the polymer. ] A hydrocarbon group containing a silicon atom represented by R ⁵ ,
R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms, a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, R ⁶ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁷ is an ether bond if necessary. At least one group selected from an alkyl group having 1 to 5 carbon atoms or a trialkylsilyl group, wherein R ⁹ and R ¹⁰ are an alkyl group having 1 to 3 carbon atoms, or an ant having 1 to 9 carbon atoms; Group, n is an integer of 0 to 3, and f is a positive integer. ), And the composition ratio thereof is represented by the formula (formula 1) (formula 6) When the total amount of the diamine component represented by the formula, the aromatic diamine component represented by —R ³ — of the formula (Formula 2) and the aromatic diamine component represented by —R ⁴ — of the formula (Chemical Formula 7) is 100, 6) [Chemical 6] The diamine component represented by 30 to 80, the aromatic diamine component represented by —R ³ — is 70 to 20, and the aromatic diamine component represented by —R ⁴ — is 0.5 to 10; A reduced viscosity of at least 0.5 dl / g (solvent N
-Methyl-2-pyrrolidone, concentration 0.1g / 100m
1, a temperature of 25 ° C.) or higher. 3. A polyimide precursor, wherein the diamine component constituting them comprises a diamine having a linear structure and a diamine having a bent structure. 4. A general formula (formula 1) (formula 2) [Chemical 2] (In the formula, R ¹ is (Chemical Formula 3)) R ² is (Chemical formula 4) R ³ is (Chemical Formula 5) Of at least one of these diamines represented by the formula (1), and the composition ratio thereof is represented by the formula (6) When the total amount of the diamine component represented by and the aromatic diamine component represented by —R ³ — in formula (Formula 2) is 100, (Formula 6) The diamine component represented by 30 to 80 and the aromatic diamine component represented by -R ³ -are in the range of 70 to 20, and the reduced viscosity thereof is at least 0.5 dl / g (solvent N
-Methyl-2-pyrrolidone, concentration 0.1g / 100m
1, the temperature is 25 ° C.)
A cured polyimide product, which is heat-cured by heating at 00 ° C. or higher. 5. A general formula (formula 1) (formula 2) (formula 7) [Chemical 2] [Chemical 7] (In the formula, R ¹ is (Chemical Formula 3)) R ² is (Chemical formula 4) R ³ is (Chemical Formula 5) At least one monomer of these diamines represented by the following formula is used, and R ⁴ is represented by the following general formula (Chemical Formula 8) when the portion is the end of the polymer or the main chain of the polymer. ] A hydrocarbon group containing a silicon atom represented by R ⁵ ,
R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms, a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, R ⁶ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁷ is an ether bond if necessary. One or more groups selected from an alkyl group having 1 to 5 carbon atoms or a trialkylsilyl group, wherein R ⁹ and R ¹⁰ are alkyl groups having 1 to 3 carbon atoms, or an aryl group having 1 to 9 carbon atoms , N is an integer of 0 to 3, and f is a positive integer. ), And the composition ratio thereof is represented by the formula (formula 1) (formula 6) When the total amount of the diamine component represented by the formula, the aromatic diamine component represented by —R ³ — of the formula (Formula 2) and the aromatic diamine component represented by —R ⁴ — of the formula (Formula 7) is 100, ( Chemical formula 6) The diamine component represented by 30 to 80, the aromatic diamine component represented by —R ³ — is 70 to 20, and the aromatic diamine component represented by —R ⁴ — is 0.5 to 10; A reduced viscosity of at least 0.5 dl / g (solvent N
-Methyl-2-pyrrolidone, concentration 0.1g / 100m
1, the temperature is 25 ° C.)
A cured polyimide product, which is heat-cured by heating at 00 ° C. or higher. 6. A cured polyimide product, which comprises a diamine having a linear structure and a diamine having a bent structure in the cured diamine component. 7. In the production of a polyimide precursor obtained from a diamine component and a tetracarboxylic dianhydride, a compound represented by the general formula: (In the formula, R ₁ is (Chemical Formula 3) Is. In the case where the total amount of the tetracarboxylic dianhydride component represented by) and the diamine component used is 100, 1) the general formula (Formula 10) Is 30 to 80 and 2) the general formula H ₂ N—R ³ —NH ₂ is 70 to 20 (wherein R is
² is (Chemical 4), [Chemical 4] R ³ is (Chemical formula 5) A diamine component represented by (using at least one or more monomers among the diamines represented by the following formula) and, if necessary, 3) the general formula: (Formula 11) (In the formula, R ⁴ and R ⁷ are a hydrocarbon group having 1 to 9 carbon atoms, a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, R ⁵
Is a hydrocarbon group having 1 to 3 carbon atoms, R ⁶ is at least one group selected from an alkyl group having 1 to 5 carbon atoms or a trialkylsilyl group containing an ether bond, if necessary, R ⁸ ,
R ⁹ is an alkyl group having 1 to 3 carbon atoms or an aryl group having 1 to 9 carbon atoms, and n is an integer of 0 to 3. f is a positive integer. The ratio of the aminosilane compound or siloxane diamine represented by) is 0.5 based on the total amount of the diamine component.
A polyimide precursor characterized by polymerizing a diamine component in the range of 10 to 10 at a temperature of 0 to 30 ° C. in an aprotic polar solvent, and further heating at 50 to 80 ° C. with stirring to adjust the varnish viscosity. Manufacturing method.