JPH05112642A - Polyimide precursor, its cured material and their producion - Google Patents

Abstract

PURPOSE:To obtain a polyimide precursor providing a polyimide having high heat resistance, low dielectric constant, low coefficient of thermal expansion, high mechanical characteristics, flexibility, etc., having a repeating unit containing terphenyl and oligophenylene structure in a molecular chain. CONSTITUTION:The objective polyimide precursor comprising a molecular chain consisting of a repeating unit of formula I and a repeating unit of formula II (R<1> is tetrafu7nctional organic) group of formula III or formula IV; R<2> is bifunctional organic group of formula V, formula VI or formula VII; R<3> is bifunctional organic group containing two or more aromatic rings and having flexible structure). The objective precursor is thermally cured at >=100 deg.C into a cured material of polyimide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide precursor and a polyimide cured product which are excellent in low dielectric constant, low thermal expansion coefficient and heat resistance, and a method for producing them.

[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. Examples of these include, for example, (a) general formula (formula 13) or general formula (formula 14)

[0003]

[Chemical 13]

[0004]

[Chemical 14]

(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).

Further, (b) the general formula (Formula 15)

[0007]

[Chemical 15]

Polyimides in which a repeating unit is represented by the formula (wherein R is a tetravalent aliphatic group or aromatic group, and n is 1 or 2) are known (JP-A-57-114258).
JP-A-57-188883, JP-A-60-250
031, JP-A-60-212426).

Further, (c) general formula (formula 16)

[0010]

[Chemical 16]

(In the formula, Y is --C (CH ₃ ) _3-, --C (C
_{F 3) 3 -, - SO} 2 - it is. ), A polyimide represented by repeating units is known (Japanese Patent Laid-Open No. 62-2319).
35, JP-A-62-231936, JP-A-62-2
31937).

Further, (2) 2,2-bis (3,4-dicarboxyphenyl) as a polyimide having an excellent low dielectric constant
Propanic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride and 4,4′-bis (4-aminophenoxy) biphenyl,
A polyimide obtained from an aromatic diamine such as 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl is known (Japanese Patent Laid-Open No. 60934/1990).
issue).

Further, (e) 2,2-bis (4-aminophenyl) hexafluoropropane and 2,2-bis (3-
A polyimide obtained from a mixed acid dianhydride consisting of (aminophenyl) hexafluoropropane, pyromellitic dianhydride, and an acid dianhydride having a diaryl nucleus (Japanese Patent Laid-Open No. HEI-2)
-67320), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride and 2,2
Polyimide obtained from -bis (4-aminophenyl) hexafluoropropane and 2,2-bis (3-aminophenyl) hexafluoropropane (JP-A-2-866)
24) is known.

However, the above (a), (b), (c),
For the polyimides (d) and (e), various properties such as high heat resistance, low dielectric constant, low thermal expansion coefficient, high mechanical properties (especially flexibility), and high glass transition temperature should be considered at the same time. In addition, since the above-mentioned polyimides (d) and (e) have a trifluoromethyl group, they have low resistance to an alkaline liquid such as an electroless plating liquid.

[0015]

[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 has excellent low coefficient of thermal expansion and high glass transition temperature, but has high dielectric constant and is not flexible. It has a relatively large number of imide rings in the polymer, and

[0016]

[Chemical 17]

Heat resistance due to containing a 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)
Contains —CF ₃ (trifluoromethyl group), and —O
- in order to have a bond, it is excellent in flexibility low dielectric constant, low heat resistance and glass transition temperature, high thermal expansion coefficient, even -C (CF _{3) 2} - alkali for bonding It is considered that the solution is easily hydrolyzed by C—F bond and has low resistance to alkali solution.

The inventors of the present invention have various properties which cannot 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 temperature. The present invention has been made as a result of extensive studies for the purpose of finding a polyimide having various properties such as high alkali resistance.

[0019]

According to the present invention, a molecular chain is composed of a repeating unit represented by the following general formula (Formula 1) and a repeating unit represented by the following general formula (Formula 2). The present invention relates to a characteristic polyimide precursor.

General formula (Formula 1)

[0021]

[Chemical 1]

General formula (Formula 2)

[0023]

[Chemical 2]

(Wherein R ¹ is

[0025]

[Chemical 3]

[0026] From at least one tetravalent organic group selected, R ² is (of 4)

[0027]

[Chemical 4]

At least one linear divalent organic group selected from the group consisting of R ³ and R ³ is a divalent organic group containing at least two aromatic rings and having a bent structure. )
In the above polyimide precursor, the number of divalent organic groups having a linear structure represented by —R ² — in the general formula (Formula 1) and the number of —R ³ — in the general formula (Formula 2) are represented. When the total number of divalent organic groups having a bent structure is 100, -R ²
- The number of the organic group represented by is 30 to 80, -R ³ - number of organic group represented by is preferably a proportion ranging from 70 to 20. The ratio of the number of organic groups represented by —R ² — is 80.
As described above, when the ratio of the number of organic groups represented by —R ³ — is 20 or less, the polyimide film produced from this polyimide precursor lacks flexibility, and the organic group represented by —R ² — When the ratio of the number of R is 30 or less and the ratio of the number of the organic groups represented by -R ^3- is 70 or more, the glass transition temperature Tg is low and the thermal expansion coefficient is high. Further, when applied to a multilayer wiring structure requiring a lower coefficient of thermal expansion, the ratio of the number of organic groups represented by —R ² — is 80 to 50, and the organic group represented by —R ³ —. More preferably, the ratio of the groups is in the range of 20-50.

In the present invention, the molecular chain has a repeating unit represented by the following general formula (Formula 1), and the following general formula (Formula 2)
And a repeating unit represented by the following general formula (Formula 5).

General formula (Formula 1)

[0031]

[Chemical 1]

General formula (Formula 1)

[0033]

[Chemical 2]

General formula (Formula 5)

[0035]

[Chemical 5]

(Wherein R ¹ is

[0037]

[Chemical 3]

[0038] From at least one tetravalent organic group selected, R ² is (of 4)

[0039]

[Chemical 4]

R ³ is at least one divalent organic group having a linear structure, R ³ is a divalent organic group having at least two aromatic rings and having a bent structure, and R 3
⁴ is a general formula (Chemical Formula 6) when the part is the end of the polymer or the main chain of the polymer.

[0041]

[Chemical formula 6],

General formula (Formula 7)

[0043]

[Chemical 7]

A hydrocarbon group containing a silicon atom represented by the following formulas, wherein R ⁵ and R ⁸ are a hydrocarbon group having 1 to 9 carbon atoms or 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, R ⁷ is at least one group selected from an alkyl group having 1 to 5 carbon atoms or an trialkylsilyl group containing an ether bond as necessary,
R ⁹ and R ¹⁰ are alkyl groups having 1 to 3 carbon atoms or 1 carbon atom
One or more groups selected from the aryl groups 9 to 9;
Is an integer from 0 to 3, and f is a positive integer. ) In the polyimide precursor, -R ² in the general formula (Formula 1) - Number of divalent organic group with a linear structure represented by the general formula (Formula 2)
When the total number of divalent organic groups having a bent structure represented by —R ³ — and the number of silicon-containing hydrocarbon groups represented by —R ⁴ — is 100, then —R ² The number of organic groups represented by − is 30 to 80, the number of organic groups represented by —R ³ — is 70 to 20, and the number of silicon-containing hydrocarbon groups represented by —R ⁴ — is 0. It is preferably in the range of 1-10.
The desirable range of the ratio of the number of organic groups represented by —R ² — and the ratio of the number of organic groups represented by —R ³ — is the same as in the case of the above-mentioned polyimide precursor. Further, the introduction of the number of silicon-containing hydrocarbon groups represented by —R ⁴ — is for improving the adhesiveness, and the effect of the adhesiveness is small at 0.1% or less and the heat resistance at 10% or more. And adversely affect the mechanical properties. More preferably, it is in the range of 0.5 to 5%.

The above polyimide precursor can be manufactured as follows.

That is, tetracarboxylic dianhydride and 2
In the method for producing a polyimide precursor from one or more diamine components, a compound represented by the general formula:

[0047]

[Chemical 10]

(In the formula, R ¹ is (Chemical Formula 3),

[0049]

[Chemical 3]

It is at least one tetravalent organic group selected from When the total of the molar ratios of the tetracarboxylic dianhydride component represented by the formula (4) and each diamine component used is 100, 1) the general formula H ₂ N—R ² —NH ₂ (wherein R ² Is (Chemical 4),

[0051]

[Chemical 4]

It is at least one divalent organic group having a linear structure selected from the group consisting of: The molar ratio of the diamine component represented by) is 30 to 80, and 2) the general formula H ₂ N—R ³ —NH ₂ (In the formula, R ³ has at least two or more aromatic rings and has a bent structure. The diamine component represented by the formula (1) has a molar ratio of 70 to 20, and 3) if necessary, the compound represented by the general formula (Formula 11)

[0053]

[Chemical 11]

Or (Chemical formula 12)

[0055]

[Chemical 12]

(In the formula, R ⁵ and R ⁸ are hydrocarbon groups having 1 to 9 carbon atoms, saturated alkyl groups having 1 to 7 carbon atoms containing an ether bond, and R ⁶ is hydrocarbon groups having 1 to 3 carbon atoms. R ⁷ , R ⁷ is one or more groups selected from an alkyl group having 1 to 5 carbon atoms or a trialkylsilyl group containing an ether bond as necessary, and R ⁹ and R ¹⁰ are carbon atoms having 1 to 5 carbon atoms. 3 alkyl group, one or more kinds of groups selected from aryl groups having 1 to 9 carbon atoms, n is an integer of 0 to 3, and f is a positive integer. A polyimide precursor is obtained by polymerizing a diamine component having a molar ratio of siloxane diamine in the range of 0.1 to 10 in an aprotic polar solvent at a temperature of 0 to 30 ° C., and further heating at 50 to 80 ° C. with stirring. Is obtained.

A polyimide cured product is obtained by heating and curing the above polyimide precursor at a temperature of 100 ° C. or higher.

According to the experiments of the present inventor, when the polyimide cured product obtained according to the present invention is formed into a polyimide cured film, it has high heat resistance, low dielectric constant, low thermal expansion coefficient and high mechanical properties (especially good flexibility). And various properties such as high glass transition temperature).

The present invention will be described in detail below.

Examples of the tetracarboxylic dianhydride used in the present invention include para-phenyl-3,3 ", 4.
4 "-tetracarboxylic dianhydride and meta-ta-phenyl-3,3", 4,4 "-tetracarboxylic dianhydride can be used.

The general formula used in the present invention H ₂ N—R ² —
The diamine component represented by NH ₂ includes 4,4 ″ -diamino-para-ta-phenyl, 4,4 ″ -diamino-para-quater-phenyl and 9,10-bis (4-diaminophenyl). Is anthracene and has the general formula H ₂ N-
Examples of the diamine component represented by R ³ —NH ₂ are (Chemical formula 8), (Chemical formula 9), (Chemical formula 18)

[0062]

[Chemical 8]

[0063]

[Chemical 9]

[0064]

[Chemical 18]

And at least one of these compounds can be used.

Other diamines may be used for adjusting heat resistance, dielectric constant, thermal expansion coefficient, glass transition temperature, mechanical strength and flexibility. For example, the general formula H ₂ N—R ¹¹
In the formula of the diamine represented by —NH ₂ , R ¹¹ is

[0067]

[Chemical 19]

And the like.

The aminosilane compound used in the present invention has the general formula (Chem. 11)

[0070]

[Chemical 11]

(Wherein R ⁵ is a hydrocarbon group having 1 to 9 carbon atoms or 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, R ⁷ is one or more kinds of groups selected from an alkyl group having 1 to 5 carbon atoms or a trialkylsilyl group containing an ether bond as necessary, and n is an integer of 0 to 3. ) Monoaminosilane compound represented by, for example, 3-aminopropyltrimethylsilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane. , 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylpropoxysilane, 3-amido 3-aminopropyldialkylalkoxysilanes such as nopropylmethyldipropoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropyldimethylbutoxysilane, 3-aminopropylmethyldibutoxysilane, 3-aminopropyltributoxysilane, 3 -Aminopropylalkyldialkoxysilane, 3-aminopropyltrialkoxysilane,
3- (4-aminophenoxy) propyldialkylalkoxysilane, 3- (4-aminophenoxy) propylalkyldialkoxysilane, 3- (4-aminophenoxy) propyltrialkoxysilane, 3- (3-aminophenoxy) propyldialkyl Alkoxysilane,
3- (3-aminophenoxy) propylalkyldialkoxysilane, 3- (3-aminophenoxy) propyltrialkoxysilane, 4-aminobutyldimethylethoxysilane, 4-aminobutylmethyldiethoxysilane, 4-aminobutyltriethoxy 4-aminobutyldialkylalkoxysilane such as silane, 4-aminobutylalkyldialkoxysilane, 4-aminobutyltrialkoxysilane, 3-aminopropyltris (trimethylsiloxy) silane, meta-aminophenyldimethylmethoxysilane, meta-amino Phenylmethyldimethoxysilane, meta-aminophenyltrimethoxysilane,
Meta-aminophenyldimethylethoxysilane, meta-
Aminophenylmethyldiethoxysilane, meta-aminophenyltriethoxysilane, meta-aminophenyldimethylpropoxysilane, meta-aminophenylmethyldipropoxysilane, meta-aminophenyltripropoxysilane, and other meta-aminophenyldialkylalkoxysilanes, meta -Aminophenylalkyldialkoxysilane, meta-aminophenyltrialkoxysilane, para-aminophenyldimethylmethoxysilane, para-aminophenylmethyldimethoxysilane, para-aminophenyltrimethoxysilane, para-aminophenyldimethylethoxysilane, para- Aminophenylmethyldiethoxysilane, para-aminophenyltriethoxysilane, para-aminophenyldimethylpropoxysilane, para-amino E methylpropenylmethyl dipropoxy silane, para - aminophenyl dialkyl alkoxysilane, para - - Para such aminophenyl tripropoxysilane aminophenyl alkyl dialkoxy silane, para -
Aminophenyltrialkoxysilane, meta-aminobenzyldimethylethoxysilane, meta-aminobenzylmethyldiethoxysilane, meta-aminobenzyltriethoxysisilane, meta-aminobenzyldimethylpropoxysilane, meta-aminobenzylmethyldipropoxysilane, Meta-aminobenzyltripropoxysilane, meta-aminobenzyldimethylpropoxysilane,
Meta-aminobenzylmethyldipropoxysilane, meta-aminobenzyldialkylalkoxysilane such as meta-aminobenzyltripropoxysilane, meta-aminobenzylalkyldialkoxysilane, meta-aminobenzyltrialkoxysilane, para-aminobenzyldimethylpropoxysilane , Para-aminobenzylmethyldipropoxysilane, para-aminobenzyldipropoxysilane, para-aminobenzyldialkylalkoxysilane, para-aminobenzylalkyldialkoxysilane, para-aminobenzyltrialkoxysilane, para-aminophenethyldimethylmethoxy. Silane,
Para-aminophenethylmethyldimethoxysilane, para-aminophenethyldialkylalkoxysilane such as para-aminophenethyltrimethoxysilane, para-aminophenethylalkyldialkoxysilane, para-aminophenethyltrialkoxysilane, or the above meta-, para- Examples thereof include hydrogenated benzyl and phenethyl compounds of the body.

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

[0073]

[Chemical 12]

(In the formula, R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms, R ⁹ and R ¹⁰ are 1 selected from an alkyl group having 1 to 3 carbon atoms or an aryl group having 1 to 9 carbon atoms. A diaminosiloxane compound represented by one or more groups, and f is a positive integer.

[0075]

[Chemical 20]

The above-mentioned aminosilane compound or diaminosiloxane component is added for the purpose of improving adhesiveness, and the range of use of the monoaminosiloxane component or diaminosiloxane component is 100% of all diamine components. When it is set to 0.1 of the total amount of diamine components
It is -10%, preferably 0.5-5%. If it is 0.1% or less, the effect of adhesiveness is small, and if it is 10% or more, heat resistance and mechanical properties are adversely affected.

The solvent used in producing the polyimide precursor and 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, At least one of these can be used.

In the practice of the present invention, in the case of a polyimide precursor, the diamine component is first dissolved in the above aprotic polar solvent, and then ta-phenyl-3,3 ", 4.
Add 4 "-tetracarboxylic dianhydride and adjust temperature to 0-3
Stir for about 6 hours while maintaining 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 further adding an aminosilane compound or a diaminosiloxane component, after stirring for about 1 hour while maintaining the temperature at 0 to 30 ° C, 50
The viscosity of the varnish is adjusted by stirring while maintaining at -80 ° C.

The reduced viscosity of the polyimide precursor is, for example, the solvent N-methyl-2-pyrrolidone, concentration 0.1 g /
At 100 ml and a temperature of 25 ° C., it is desirable that the amount be 0.5 dl / g or more.

When the polyimide cured product passing through the above polyimide precursor is heat-cured at a temperature of 100 ° C. or higher, the molecular chain has a repeating unit represented by the following general formula (Formula 21) and the following general formula (Formula 22). In the case where a polyimide cured product comprising a repeating unit represented by the formula (1) or an aminosilane compound or a diaminosiloxane component is further added, the repeating unit whose molecular chain is represented by the following general formula (Formula 21), The polyimide cured product has a repeating unit represented by the general formula (Formula 22) and a repeating unit represented by the following general formula (Formula 23).

[0081]

[Chemical 21]

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

In (Chemical formula 21), (Chemical formula 22) and (Chemical formula 23), R ¹ is (Chemical formula 3),

[0085]

[Chemical 3]

Is at least one tetravalent organic group selected from: and R ² is

[0087]

[Chemical 4]

R ³ is a divalent organic group having at least one linear structure selected from the group R ³ is a divalent organic group having at least two aromatic rings and having a bent structure, and R 3
⁴ is a general formula (Chemical Formula 6) when the part is the end of the polymer or the main chain of the polymer.

[0089]

[Chemical formula 6],

General formula (Formula 7)

[0091]

[Chemical 7]

A hydrocarbon group containing a silicon atom represented by R ⁵ and R ⁸ are hydrocarbon groups having 1 to 9 carbon atoms or saturated alkyl groups having 1 to 7 carbon atoms containing an ether bond, R
⁶ is a hydrocarbon group having 1 to 3 carbon atoms, R ⁷ is at least one group selected from an alkyl group having 1 to 5 carbon atoms or an trialkylsilyl group containing an ether bond as necessary,
R ⁹ and R ¹⁰ are alkyl groups having 1 to 3 carbon atoms or 1 carbon atom
One or more groups selected from the aryl groups 9 to 9;
Is an integer from 0 to 3, and f is a positive integer. ) In the above-mentioned polyimide cured product, the number of divalent organic groups having a linear structure represented by —R ² — in the general formula (Formula 21), the general formula (Formula 2)
2) in the number of divalent organic groups having a bending structure represented by —R ³ — and the number of silicon atom-containing hydrocarbon groups represented by —R ⁴ — in the general formula (Formula 23). The composition ratio corresponds to the composition ratio in the polyimide precursor before curing. That is, the polyimide precursor is a silicon atom represented by —R ⁴ — and the number of organic groups represented by —R ² — and the number of organic groups represented by —R ³ — and optionally introduced. When the total number of hydrocarbon groups containing
² - The number of organic groups represented is 30 to 80, -R ³ in - the number of organic groups represented by the 70 to 20 and -R ⁴ - The number of hydrocarbon groups containing a silicon atom represented is When it is formed with a desirable composition ratio of 0.1 to 10, the same applies to the cured product.

[0093]

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).

[0094]

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%.

In each of the examples, various characteristic values of the film were evaluated by the following test methods.

(1) Permittivity ε Within 24 hours after film formation, it was measured by LCZ meter 4277A manufactured by YHP (Yokogawa Hulett Packard). Measurement conditions: humidity in measurement room 60% or less, frequency 1
0 KHz, temperature 25 ° C, electrode is Al-Al or Cr
-Al.

(2) Thermal decomposition temperature Td Using 50 mg of the above film, a high speed differential thermal analyzer TGD-5000 manufactured by ULVAC Co., Ltd. was used in 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 above film was used as a strip test piece of 5 mm × 25 mm, and its elongation rate 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 same method as in Example 1, and was allowed to stand at room temperature.
It was measured with a Nicolet 170SX Fourier transform infrared spectrophotometer.

Example 1 2.842 g (7.393 mmol, 50% molar ratio in diamine component) of bis [4- (4-aminophenoxy) phenyl] ether at room temperature under a nitrogen stream and 4,4 " -Diamino-p-ta-phenyl (1.924 g, 7.393 mmol, molar ratio of 50% in diamine component) was added to N, N-
Dimethylacetamide (DMAc) and N-methyl-2-
53.6 g of 1: 1 mixed solvent of pyrrolidone (NMP)
It was dissolved with stirring (solid content concentration 16%). Then p-
5.475 g (14.78 mmol) of ta-phenyl-3,3 ", 4,4" -tetracarboxylic dianhydride (TPDA) was dissolved in the above solution under a nitrogen stream while stirring. At this time, the temperature of the solution rises to around 30 degrees and its viscosity is 15
It became 0 poise. Add 60-70 ° C to this solution.
Then, heat was applied for about 5 hours to adjust its viscosity to 56 poise to obtain a polyamic acid varnish. This varnish was diluted with N-methyl-2-pyrrolidone (concentration 0.1 g / 100 m
l) The reduced viscosity was determined by measuring the viscosity at 25 ° C. with an Ubbelohde viscometer and found to be 1.78 dl / g.

The above-mentioned polyamic acid varnish was spin-coated on a silicon wafer or a glass substrate, and the solution was kept 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.

The constitution of the polymer is shown in Table 1, and the evaluation results are shown in Table 2.
Shown in. The infrared absorption spectrum of this polyimide film is shown in FIG. From FIG. 1, 1720 cm- ¹ and 1780
Absorption of imide groups was observed at cm- ¹ and formation of polyimide was confirmed.

Examples 2 to 9 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. The infrared absorption spectra of the polyimide films of Examples 2 and 5 are shown in FIGS. 2 and 3, respectively. 2 and 3, 1720 cm- ¹ and 1
Absorption of an imide group was observed at 780 cm to ¹ , confirming the formation of polyimide.

Example 10 1.64 g of bis [4- (4-aminophenoxy) phenyl] ether (4.321 mmol, 40% molar ratio in the diamine component) and 4,4 "at room temperature under a nitrogen stream. 1.575 g of -diamino-p-ta-phenyl (6.048 mmol, 56% molar ratio in diamine component) and 0.165 g of 3-aminopropylmethyldimethoxysilane (0.
864 mmol, molar ratio of diamine ratio 4%), N, N
-Dimethylacetamide (DMAc) and N-methyl-2
36.2 g of 1: 1 mixed solvent of pyrrolidone (NMP)
It dissolved in (solid content concentration 17%) while stirring. Then p-
Ta-phenyl-3,3 ", 4,4" -tetracarboxylic dianhydride (TPDA) 4.0 g (10.80 mmol)
Was dissolved in the above solution with stirring under a nitrogen stream. At this time, the temperature of the solution rises to around 30 degrees and its viscosity is 88 p.
It became oise. Further, the solution was heated at 60 to 70 ° C. for about 5 hours to adjust its viscosity to 38 poise to obtain a polyamic acid varnish.

The above-mentioned polyamic acid varnish was spin-coated on a silicon wafer, and the mixture was kept under a nitrogen stream at 200 ° C. for 30 minutes 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. The infrared absorption spectrum of this polyimide film is shown in FIG. From FIG. 4, 1720 cm to ¹ and 1780 cm
Absorption of imide groups was observed in ~ ¹ , confirming the formation of polyimide.

Example 11 In the case of Example 2, p-ta-phenyl-3,3 ″,
Example 1 was carried out using m-ta-phenyl-3,3 ", 4,4" -tetracarboxylic dianhydride (m-TPDA) instead of 4,4 "-tetracarboxylic dianhydride (TPDA).
A polyimide film was prepared in the same manner as in, and various characteristics of the polyimide film were evaluated. The results are shown in Table 2. The obtained polyimide film was excellent in all properties.

Example 12 4,4 "-Diamino-p-ter in the case of Example 2
Using 9,10-bis (4-aminophenyl) anthracene in place of phenyl, a polyimide film was prepared in the same manner as in Example 1, and its various properties were evaluated. The results are shown in Table 2. The obtained polyimide film was excellent in all properties.

[0111]

[Table 1]

[0112]

[Table 1]

[0113]

[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 characteristics 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 characteristics 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 Constitution of polymer shown in Table 3, ie, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride (BPDA) as acid dianhydride and 4,4 as diamine. '
A polyimide film was prepared in the same manner as in Example 1 using diaminodiphenyl ether, and the dielectric constant and glass transition temperature were measured. As a result, the dielectric constant was as high as 3.0 and the glass transition temperature was as low as 290 ° C.

Comparative Example 7 As another comparative example, PIQ (Hitachi Chemical 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 for the above characteristic values.

[0118]

[Table 3]

[0119]

[Table 4]

[0120]

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

[Brief description of drawings]

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

FIG. 2 is an infrared absorption spectrum diagram of Example 2.

FIG. 3 is an infrared absorption spectrum diagram of Example 5.

FIG. 4 is an infrared absorption spectrum diagram of Example 10.

Front page continuation (72) Fumio Kataoka Inventor Fumio Kataoka 292 Yoshida-cho, Totsuka-ku, Yokohama, Kanagawa, Ltd. Production Engineering Research Laboratory, Hitachi, Ltd. Kasei Industry Co., Ltd. Yamazaki Factory

Claims (15)

[Claims] 1. A polyimide precursor having a molecular chain composed of a repeating unit represented by the following general formula (Formula 1) and a repeating unit represented by the following general formula (Formula 2). General formula (Formula 1) General formula (Formula 2) (In the formula, R ¹ is (Chemical Formula 3), R is at least one tetravalent organic group selected from
² is (Chemical 4), [Chemical 4] Is a divalent organic group having at least one linear structure selected from R ³ and R ³ is a divalent organic group having at least two aromatic rings and having a bent structure. ) 2. The polyimide precursor according to claim 1, wherein the number of divalent organic groups having a linear structure represented by —R ² — in the general formula (Formula 1) and the general formula (Formula 2) The total number of divalent organic groups having a bending structure represented by —R ³ — is 100.
And the number of organic groups represented by —R ² — is 30 to
80, The number of the organic groups represented by -R < ³ >-is the range of 70-20, The polyimide precursor characterized by the above-mentioned. 3. A repeating unit represented by the following general formula (formula 1), a repeating unit represented by the following general formula (formula 2), and a repeating unit represented by the following general formula (formula 5). And a polyimide precursor. General formula (Formula 1) General formula (Formula 1) [Formula 2] General formula (Formula 5) (In the formula, R ¹ is (Chemical Formula 3), R is at least one tetravalent organic group selected from
² is (Chemical 4), [Chemical 4] Is a divalent organic group having at least one linear structure selected from among R ³ , R ³ is a divalent organic group having at least two aromatic rings and having a bent structure, and R ⁴ is a polymer having a portion thereof. At the end of or the main chain of the polymer, respectively, in the general formula (Chemical formula 6) General formula (Formula 7) A hydrocarbon group containing a silicon atom represented by R ⁵ ,
R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, and R ⁶ is 1 carbon atom
3 hydrocarbon group having, R ⁷ is optionally et - one or more groups selected from among alkyl group or a trialkylsilyl group having 1 to 5 carbon atoms including ether bond, R ^9, R ¹⁰ Is one or more groups selected from an alkyl group 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. ) 4. The polyimide precursor according to claim 3, wherein the number of divalent organic groups having a linear structure represented by —R ² — in the general formula (formula 1), When the total number of divalent organic groups having a bent structure represented by —R ³ — and the number of silicon-containing hydrocarbon groups represented by —R ⁴ — is 100, then —R ² — Number of organic groups represented is 30 to 8
0, the number of organic groups represented by —R ³ — is 70 to 20, and —R ⁴
The number of silicon-containing hydrocarbon groups represented by-is 0.1 to 1.
A polyimide precursor having a range of 0. 5. A polyimide precursor comprising a structural unit having a linear structure containing three or more aromatic rings and a structural unit having a bent structure. 6. The divalent organic group having a bending structure represented by —R ³ — in the general formula (Formula 2) according to claim 1, claim 2, claim 3 or claim 4, (Chemical formula 8) (Chemical formula 9) [Chemical 9] A polyimide precursor which is one or more kinds of divalent organic groups selected from the structural formulas represented by: 7. A polyimide precursor having a molecular chain consisting of a repeating unit represented by the following general formula (Formula 1) and a repeating unit represented by the following general formula (Formula 2) is heated at a temperature of 100 ° C. or higher. And cured by heat to cure the polyimide. General formula (Formula 1) General formula (Formula 2) (In the formula, R ¹ is (Chemical Formula 3), R is at least one tetravalent organic group selected from
² is (Chemical 4), [Chemical 4] Is a divalent organic group having at least one linear structure selected from R ³ and R ³ is a divalent organic group having at least two aromatic rings and having a bent structure. ) 8. The cured polyimide product according to claim 7, wherein the number of divalent organic groups having a linear structure represented by —R ² — in the general formula (Formula 1) and the general formula (Formula 2). The total number of divalent organic groups having a bending structure represented by —R ³ — is 100.
And the number of organic groups represented by —R ² — is 30 to
80, The number of the organic groups represented by -R < ³ >-is the range of 70-20, The polyimide hardened | cured material characterized by the above-mentioned. 9. A molecular chain having a repeating unit represented by the following general formula (Formula 1), a repeating unit represented by the following general formula (Formula 2) and a repeating unit represented by the following general formula (Formula 5). A polyimide cured product obtained by heat-curing a polyimide precursor composed of and heated at a temperature of 100 ° C. or higher. General formula (Formula 1) General formula (Formula 2) General formula (Formula 5) (In the formula, R ¹ is (Chemical Formula 3), R is at least one tetravalent organic group selected from
² is (Chemical 4), [Chemical 4] Is a divalent organic group having at least one linear structure selected from among R ³ , R ³ is a divalent organic group having at least two aromatic rings and having a bent structure, and R ⁴ is a polymer having a portion thereof. At the end of or the main chain of the polymer, respectively, in the general formula (Chemical formula 6) General formula (Formula 7) A hydrocarbon group containing a silicon atom represented by R ⁵ ,
R ⁸ is a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, and R ⁶ is 1 carbon atom
To R 3 are hydrocarbon groups, R ⁷ is one or more groups selected from an alkyl group having 1 to 5 carbon atoms or an trialkylsilyl group containing an ether bond as necessary, R ⁹ , R ¹⁰ Is one or more groups selected from an alkyl group 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. ) 10. The polyimide cured product according to claim 9, wherein the number of divalent organic groups having a linear structure represented by —R ² — in the general formula (Formula 1), When the total number of divalent organic groups having a bent structure represented by —R ³ — and the number of silicon-containing hydrocarbon groups represented by —R ⁴ — is 100, then —R ² — Number of organic groups represented is 30 to 8
0, the number of organic groups represented by —R ³ — is 70 to 20, and —R ⁴
The number of silicon-containing hydrocarbon groups represented by-is 0.1 to 1.
A polyimide cured product characterized by being in the range of 0. 11. A cured polyimide composition comprising a structural unit having a linear structure containing three or more aromatic rings and a structural unit having a bent structure. 12. The cured polyimide product according to claim 7, 8, 9 or 10, wherein the divalent organic group having a bending structure represented by —R ³ — in the general formula (Formula 2) is 8)
(Chemical formula 9) [Chemical formula 8] [Chemical 9] A cured product of polyimide, which is one or more kinds of divalent organic groups selected from the structural formulas represented by: 13. A method for producing a polyimide precursor from a tetracarboxylic dianhydride and two or more kinds of diamine components, wherein the compound represented by the general formula (Chemical Formula 10): (In the formula, R ¹ is (Chemical Formula 3), It is at least one tetravalent organic group selected from )
When the total of the molar ratios of the tetracarboxylic dianhydride component represented by and the respective diamine components used is 100: 1) General formula H ₂ N—R ² —NH ₂ (In the formula, R ² is (Chemical formula 4), [Chemical formula 4] It is at least one divalent organic group having a linear structure selected from ) The molar ratio of the diamine component represented by
0, and 2) the general formula _{^{H 2 N-R 3 -NH 2}} ( wherein, R ³ is represented by a divalent organic group having a bent structure comprises at least two or more aromatic rings.) And a diamine component having a molar ratio of the diamine component of 70 to 20 are polymerized in an aprotic polar solvent at a temperature of 0 to 30 ° C., and further heated at 50 to 80 ° C. with stirring. Body manufacturing method. 14. A method for producing a polyimide precursor from a tetracarboxylic dianhydride and two or more kinds of diamine components, wherein a compound represented by the general formula (Chemical Formula 10): (In the formula, R ¹ is (Chemical Formula 3), It is at least one tetravalent organic group selected from )
When the total of the molar ratios of the tetracarboxylic dianhydride component represented by and the respective diamine components used is 100: 1) General formula H ₂ N—R ² —NH ₂ (In the formula, R ² is (Chemical formula 4), [Chemical formula 4] It is at least one divalent organic group having a linear structure selected from ) The molar ratio of the diamine component represented by
0, 2) represented by the general formula H ₂ N—R ³ —NH ₂ (wherein R ³ is a divalent organic group having at least two aromatic rings and having a bent structure). The molar ratio of the diamine component is 70 to 20, and 3) the general formula (Formula 11) Or (Chemical formula 12) (In the formula, R ⁵ and R ⁸ are a hydrocarbon group having 1 to 9 carbon atoms or a saturated alkyl group having 1 to 7 carbon atoms containing an ether bond, R 5
⁶ is a hydrocarbon group having 1 to 3 carbon atoms, R ⁷ is at least one group selected from an alkyl group having 1 to 5 carbon atoms or an trialkylsilyl group containing an ether bond as necessary,
R ⁹ and R ¹⁰ are alkyl groups having 1 to 3 carbon atoms or 1 carbon atom
One or more groups selected from the aryl groups 9 to 9;
Is an integer of 0 to 3, and f is a positive integer. ) Aminosilane compound or siloxanediamine having a molar ratio of 0.1 to 10 is polymerized with a diamine component in an aprotic polar solvent at a temperature of 0 to 30 ° C., and further stirred at 50 to 80 ° C. A method for producing a polyimide precursor, which comprises heating. 15. The method for producing a polyimide precursor according to claim 13 or 14, wherein the general formula H ₂ N—R ³ —NH is used.
₂ (in the formula, R ³ is a divalent organic group having at least two or more aromatic rings and having a bent structure), and a divalent group represented by —R ³ — in the diamine component represented by The organic groups of
(Chemical formula 8), (Chemical formula 9) [Chemical 9] A method for producing a polyimide precursor, which comprises one or more divalent groups selected from the structural formulas represented by: