JP3537907B2 - Polyimide precursor, polyimide precursor composition, polyimide resin and electronic component - Google Patents

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 bismaleimide-based cured resin precursor suitably used for forming various insulating members, and a polyimide resin or bismaleimide-based cured resin produced from these precursors. The present invention relates to an electronic component including a resin as an insulating film or an insulating substrate.

[0002]

2. Description of the Related Art In recent years, as a material for an interlayer insulating film of a semiconductor device, a polyimide resin having excellent heat resistance, which can withstand a high-temperature heat treatment at 400 ° C. or higher, has been used. As such a polyimide resin, Kapton (a registered trademark of DuPont) comprising a condensation product of pyromellitic dianhydride and 4,4'-oxydianiline is known. In addition, with the increase in capacity, miniaturization, lightness, high reliability, and high density of electronic components, materials for multilayer wiring boards include high heat resistance, through-hole bonding reliability, dimensional stability, electrical characteristics, and flexibility. There is a demand for an organic polymer material having excellent properties.
Conventionally, a bismaleimide-based cured resin has been used as a material for a multilayer wiring board. Such a bismaleimide-based cured resin is obtained by curing a reaction product of bis (4-maleimidophenyl) methane and methylene-4,4'-dianiline (for example, Japanese Patent Publication No. 46-23250).
It has been known.

Meanwhile, as semiconductor devices become more highly integrated and the line and space widths of wiring patterns approach quarter-micron levels, the delay time and power consumption of semiconductor devices increase. Is becoming a serious problem. That is, the signal transmission speed V _s is given by V _s = c × ε _r ^−0.5 (c: light speed, ε
_r : dielectric constant of a dielectric). As is apparent from this equation, it is important to lower the dielectric constant of the interlayer insulating film to increase the signal transmission speed. Conventionally, S commonly used as an interlayer insulating film of a semiconductor device
It is desired that the dielectric constant of iO ₂ is as high as about 3.5, and the dielectric constant of the material used instead is sufficiently lower than this value. Similarly, in a multilayer wiring board, it is an essential task to lower the dielectric constant of the board.

[0004] From such a background, an organic polymer film capable of realizing a low dielectric constant of 3.0 or less has been demanded as an insulating member of an electronic component. However, both the conventional polyimide resin and the bismaleimide-based cured resin have a dielectric constant of about 3.4, which is not so low. In this regard, fluororesins are attracting attention because of their low dielectric constant of about 2.5. However, fluororesins have poor workability and are extremely dimensionally stable, especially under high-temperature conditions in the multilayering process when fabricating multilayer substrates. There is a disadvantage that it is inferior in nature.

[0005] Insulating members used for semiconductor devices and the like, besides having a low dielectric constant, can improve the flatness of the surface of the semiconductor device, have low hygroscopicity, and are difficult to chemically decompose. Characteristics are required.

For example, the flatness will be described. Since the conventional polyimide precursor has a high molecular weight before curing and its solution (varnish) has a high viscosity, it is obtained when an insulating film is formed on an uneven surface using this polyimide precursor varnish. Flatness is impaired on the surface of the film. In particular, a width of 0.1 to 0.5 μm formed on the surface of the semiconductor substrate
It is difficult to completely fill the inside of the trench with the polyimide resin. Therefore, the step of the underlying wiring is about 1 μm.
A polyimide film having a thickness of 3 to 4 μm with respect to m is formed, and etched back by reactive ion etching (RIE) to flatten the surface. However, it is difficult to detect the end point by RIE, and there is a problem that the inside of the device is contaminated by an etching product. For this reason, it is desirable that the amount of etch-back be as small as possible. From this point, it is also required that the insulating film has good flatness. In addition, in order to fill the trench with a polyimide resin, a varnish having a low concentration must be used. When a low-concentration varnish is used, the amount of the solvent to be volatilized increases. As described above, the conventional polyimide precursor has a high molecular weight before curing, and thus loses fluidity at a stage where the amount of the remaining solvent is large. As a result, volatilization of the solvent is suppressed, and local contraction of the polyimide resin is caused, so that voids are easily generated.

Further, conventional polyimide resins and bismaleimide-based cured resins have a considerably high moisture absorption rate, and when left in the air, part of the resin is decomposed by humidification and decomposition.
There are also problems with environmental stability, such as release of toluene components.

[0008] In addition, the insulating member used for a specific electronic component may be required to have characteristics specific to the electronic component in addition to the characteristics described above. For example, a polyimide resin used as a liquid crystal alignment film of a liquid crystal display element will be described. In a liquid crystal display device, an STN (super twisted nematic) method is frequently used in order to increase a viewing angle. In the STN type liquid crystal display element,
Since the major axis direction of the liquid crystal molecules is twisted by 270 ° in the cell, a liquid crystal alignment film capable of giving a high pretilt angle to the liquid crystal is required to achieve this purpose. Also,
In a high-definition color liquid crystal display device, a TFT (thin film transistor) is provided for each pixel, and a color filter is used. In this case, since the heat resistance of the color filter is low, a liquid crystal alignment film that can be formed at a low curing temperature of 200 ° C. or less is required.

As a liquid crystal alignment film giving a high pretilt angle, Japanese Patent Application Laid-Open No. Sho 62-174725 discloses a polyimide resin having a fluoroalkyl group bonded to a chain carbon. However, this polyimide resin has disadvantages that a stable pretilt angle cannot be obtained and a voltage holding ratio is small. In addition, as an alignment film with a low curing temperature,
Soluble polyimides are known as disclosed in the 9th Polymer Electronics Workshop, Lecture Abstracts, page 32. However, this soluble polyimide has a problem that a high pretilt angle cannot be obtained. A polyimide liquid crystal alignment film that can provide such a high pretilt angle and has a large voltage holding ratio has not been realized.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to form a film having excellent flatness on a substrate having fine irregularities,
Moreover, it is an object of the present invention to provide a precursor of a polyimide resin or a bismaleimide-based cured resin which has a low dielectric constant, a low hygroscopicity, and excellent environmental stability. Another object of the present invention is to provide a highly reliable electronic component which includes the above-described resin as an insulating member, can realize high-speed operation and power saving.

[0011]

The first polyimide precursor of the present invention has the following general formula (DA1):

[0012]

Embedded image (X ¹ may be the same or different,
Divalent oxy, thio, sulfonyl group, a carbonyl group, peralkyl polysiloxanolate Sani alkylene group, an unsubstituted or aliphatic substituted with fluoro hydrocarbon group or a single bond, R ¹ is a respectively identical May represent a fluoro group, an unsubstituted or substituted aliphatic hydrocarbon group with a fluoro group,
An integer of 4, i is an integer of 1 to 6, j is an integer of 0 to 6, and k is 0 or 1. A) a diamine component containing at least 0.40 molar equivalent of an aromatic diamine compound represented by the formula:
~ 1.03 molar equivalents and the following general formula (DAH1)

[0013]

Embedded image (Y represents a tetravalent organic group.) A tetracarboxylic acid dianhydride represented by (1-n _1/2) molar equivalents, and at least 1 selected from maleic anhydride and maleic acid derivatives anhydride Seed n ₁ molar equivalent (n ₁ is 0.02 to 0.
And a structure obtained by polymerizing an acid anhydride component containing (40).

The second polyimide precursor of the present invention has the following general formula (DA2)

[0015]

Embedded image (X ² represents a perfluoroalkylene group, perfluoroalkylidene group, a sulfonyl group or a single bond,, R ⁰
May be the same or different, each represents a fluoro group, or an unsubstituted or substituted with a fluoro group, an aliphatic hydrocarbon group; R ² may be the same or different, and Group, an unsubstituted or substituted with a fluoro group, an aliphatic hydrocarbon group or a hydrogen atom, at least one of which is a fluoro group or an aliphatic hydrocarbon group substituted with a fluoro group;
It is an integer of 3. An amine component containing at least 0.10 molar equivalents of the fluorinated aromatic diamine compound represented by
The following general formula (DAH1)

[0016]

Embedded image (Y represents a tetravalent organic group), characterized by having a structure obtained by polymerizing an acid anhydride component containing at least 0.80 molar equivalent of a tetracarboxylic dianhydride represented by the formula: is there.

The second polyimide precursor of the present invention is more specifically a diamine compound 0.97 containing at least 0.10 molar equivalents of the fluorinated aromatic diamine compound represented by the general formula (DA2). and ～1.03 molar equivalents, the general formula (DAH1) tetracarboxylic acid dianhydride represented by (1-n _2/2) molar equivalents and dicarboxylic anhydrides n
₂ molar equivalents (n ₂ is 0 to 0.4) were polymerized and structure,
Or the general formula (DA2) containing more fluorine-containing aromatic diamine compound 0.10 molar equivalents represented by the diamine compound (1-n _3/2) molar equivalents and monoamine compound n ₃ molar equivalents (n ₃ is 0 To 0.4) and the tetracarboxylic dianhydride represented by the general formula (DAH1).
It has a structure in which 97 to 1.03 molar equivalents are polymerized.

When a photosensitive agent is further added to the first and second polyimide precursors, a photosensitive polyimide precursor can be obtained.

Still another polyimide precursor of the present invention has photosensitivity and has the following general formula (PA11):

[0020]

Embedded image (Y is a tetravalent organic group, L is a divalent organic group consisting of the residue of the diamine compound represented by the above general formula (DA1), and D ¹ may be the same or different. Wherein at least one is a photosensitive organic group.) And a photopolymerization initiator.

The fluorine-containing aromatic diamine compound of the present invention has the following general formulas (DA3) and (DA4)

Embedded image (Wherein, X ³ is a perfluoroalkylene group or a perfluoroalkylidene group, R ⁰ may be the same or different, and each represents a fluoro group or an unsubstituted or substituted aliphatic hydrocarbon group with a fluoro group. And R
² may be the same or different and each represents a fluoro group, an unsubstituted or substituted aliphatic hydrocarbon group or a hydrogen atom, and at least one is substituted with a fluoro group or a fluoro group It is an aliphatic hydrocarbon group, and a and b are integers of 0-3. ). The bismaleimide-based cured resin precursor of the present invention has the following general formula (DM1)

[0022]

Embedded image (X ³¹ is a divalent oxy group, thio group, sulfonyl group, carbonyl group, peralkyl polysiloxanylene group, 1,3
A phenylenedioxy group, a 1,4-phenylenedioxy group, an unsubstituted or substituted with a fluoro group, an aliphatic hydrocarbon group, or a single bond; R ³¹ may be the same or different, and Or an aliphatic hydrocarbon group which is unsubstituted or substituted with a fluoro group, at least one of which is a fluoro group or an aliphatic hydrocarbon group substituted with a fluoro group, and R ³² may be the same or different , A halogen group, an aliphatic hydrocarbon group unsubstituted or substituted with a fluoro group, or a hydrogen atom, and a and b are integers of 1 to 4. ) And 1 molar equivalent of a bismaleimide compound represented by the following general formula (DA1)
1) a diamine compound represented by the following general formula (DP)
Dihydric phenol compound represented by 1)

[0023]

Embedded image (X ³² in the general formula (DA11) represents a divalent organic group, X ³³ in the general formula (DP1) represents a divalent organic group, and Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group. , N is 0 or 1.) at least one compound selected from the group consisting of 0.01 to 2 molar equivalents.

The polyimide resin of the present invention is obtained by curing each of the above-mentioned polyimide precursors.

The bismaleimide-based cured resin of the present invention is obtained by curing the above-described bismaleimide-based cured resin precursor.

The electronic component of the present invention is characterized in that it contains a polyimide resin obtained by curing each of the above-mentioned polyimide precursors as an insulating member.

Another electronic component according to the present invention is characterized in that it contains a bismaleimide-based cured resin obtained by curing the above-described bismaleimide-based cured resin precursor as an insulating member.

Hereinafter, the present invention will be described in more detail.

The polyimide precursor of the present invention (polyamic acid) is generally a diamine component from 0.97 to 1.03 molar equivalents, tetracarboxylic dianhydride (1-n _2/2) molar equivalents and dicarboxylic acid anhydride things n ₂ molar equivalents (n ₂ is 0 to 0.4) formulating and or diamine component (1
And -n _3/2) molar equivalents and monoamine compound n ₃ molar equivalents (n ₃ is 0 to 0.4), blended with a tetracarboxylic acid dianhydride from 0.97 to 1.03 molar equivalents, of the polymerization It has the structure made to be.

First, the first polyimide precursor (polyamic acid) according to the present invention will be described. The polyimide precursor comprises: (a) a diamine component having a specific molecular structure represented by the general formula (DA1) of 0.97 to 10.3 mole equivalent containing at least 0.40 mole equivalent of an aromatic diamine compound; (b) the general formula (DAH1) tetracarboxylic acid dianhydride represented by (1-n _1/2), as well as maleic anhydride and at least one n ₁ molar equivalent selected from maleic anhydride derivatives thereof ( n ₁ is 0.02 to 0.40)
And an acid anhydride component containing the same.

The aromatic diamine compound represented by the general formula (DA1) is (a1) an aromatic diamine compound having one benzene ring and two amino groups bonded to the benzene ring at a meta position to each other. A diamine compound, and (a
2) Aroma having two or more benzene rings and a structure in which two amino groups are each bonded to a terminal benzene ring at a meta position as viewed from a bonding site of the terminal benzene ring to another benzene ring. Including an aromatic diamine compound.

The following are examples of the aromatic diamine compound represented by the general formula (DA1). For example, 1,3-phenylenediamine, 3,3′-diaminobiphenyl, 1,3-phenylene-3,3′-dianiline, 1,4-phenylene-3,3′-dianiline, oxy-3,3′- Dianiline, thio-3,3'-dianiline, sulfonyl-3,3'-dianiline, methylene-
3,3′-dianiline, 1,2-ethylene-3,3′-
Dianiline, 1,3-trimethylene-3,3′-dianiline, 2,2-propylidene-3,3′-dianiline,
1,4-tetramethylene-3,3′-dianiline, 1,
5-pentamethylene-3,3'-dianiline, 1,1,
1,3,3,3-hexafluoro-2,2-propylidene-3,3′-dianiline, difluoromethylene-3,
3'-dianiline, 1,1,2,2-tetrafluoro-
1,2-ethylene-3,3'-dianiline, 1,1,
2,2,3,3-hexafluoro-1,3-trimethylene-3,3′-dianiline, 1,3-bis (3-aminophenyl) -1,1,3,3, -tetramethyldisiloxane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenylthio) benzene, 1,3-bis (3-aminophenylsulfonyl) benzene, 1,3-bis [2- ( 3-aminophenyl)-
2-propyl] benzene, 1,3-bis [2- (3-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,4-bis (3- Aminophenoxy) benzene, 1,4-bis (3-aminophenylthio) benzene, 1,4-bis (3-aminophenylsulfonyl) benzene, 1,4-bis [2- (3
-Aminophenyl) -2-propyl] benzene, 1,4
-Bis [2- (3-aminophenyl) -1,1,1,
3,3,3-hexafluoro-2-propyl] benzene, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 5- Fluoro-1,3-phenylenediamine,
2,4,5,6-hexafluoro-1,3-phenylenediamine, 3,3′-diamino-5,5′-difluorobiphenyl, 3,3′-diamino-2,2 ′, 4
4 ', 5,5', 6,6'-octafluorobiphenyl, oxy-5,5'-bis (3-fluoroaniline), sulfonyl-5,5'-bis (3-fluoroaniline), 1,3 -Bis (3-aminophenoxy) -5-
Fluorobenzene, 1,3-bis (3-amino-5-fluorophenoxy) benzene, 1,3-bis (3-amino-5-fluorophenoxy) -5-fluorobenzene, 5-trifluoromethyl-1,3 -Phenylenediamine, oxy-5,5'-bis (3-trifluoromethylaniline), sulfonyl-5,5'-bis (3-trifluoromethylaniline), 1,3-bis (3-aminophenoxy)- 5-trifluoromethylbenzene, 1,
3-bis (3-amino-5-trifluoromethylphenoxy) benzene, 1,3-bis (3-amino-5-trifluoromethylphenoxy) -5-trifluoromethylbenzene, 3,3′-bis (tri Fluoromethyl)-
5,5′-diaminobiphenyl, 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis [3-amino-4-methylphenyl] -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] -1,1,1
1,3,3,3-hexafluoropropane, 3 ″,
3 ′ ″-diamino-p-quaterphenyl, 4,4′-
Bis (3-aminophenoxy) biphenyl, bis [4-
(3-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ether, bis {4- [4- (2- (3-aminophenyl) propylidenephenoxy)] phenyl ｝ Sulfone,
2,2-bis [4- (3-aminophenoxy) phenyl] propane and the like. These may be used alone or as a mixture of two or more.

The polyimide precursor containing an aromatic diamine compound having an amino group at the meta position of a benzene ring represented by the general formula (DA1) is, for example, an aromatic diamine having an amino group at a para position of a benzene ring. Compared with those contained, polyimide resin that has excellent heat resistance, generates very little gas (toluene, xylene, etc.) as a humidified decomposition product even when left in the air, and has excellent environmental stability It is preferable in that it can be obtained. In particular, a polyimide precursor containing an aromatic diamine compound having a plurality of benzene rings as in (a2) is hardly hydrolyzed and has excellent environmental stability.

In the present invention, the aromatic diamine compound represented by the general formula (DA1) is compounded in an amount of 0.40 mole equivalent or more of all the diamine components, and may be further added in an amount of 0.70 mole equivalent or more. preferable. The reason for this is that if the amount of the aromatic diamine compound represented by the general formula (DA1) is too small, a polyimide resin which is hardly hydrolyzed and has excellent environmental stability cannot be obtained.

From the viewpoints of heat resistance, environmental stability and low dielectric constant characteristics of the polyimide resin, particularly preferred aromatic diamine compounds among the aromatic diamines represented by the general formula (DA1) are as follows. Can be For example,
1,3-phenylenediamine, 3,3′-diaminobiphenyl, 1,3-phenylene-3,3′-dianiline,
1,4-phenylene-3,3'-dianiline, oxy-
3,3′-dianiline, sulfonyl-3,3′-dianiline, 1,1,1,3,3,3-hexafluoro-2,
2-propylidene-3,3'-dianiline, difluoromethylene-3,3'-dianiline, 1,1,2,2-tetrafluoro-1,2-ethylene-3,3'-dianiline, 1,1,2 , 2,3,3-hexafluoro-1,3
-Trimethylene-3,3'-dianiline, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3
-Aminophenoxy) benzene, 5-fluoro-1,3
-Phenylenediamine, 3,3'-diamino-5,5 '
-Difluorobiphenyl, 5-trifluoromethyl-
1,3-phenylenediamine, oxy-5,5'-bis (3-trifluoromethylaniline), sulfonyl-
5,5′-bis (3-trifluoromethylaniline),
1,3-bis (3-aminophenoxy) -5-trifluoromethylbenzene, 1,3-bis (3-amino-5-
(Trifluoromethylphenoxy) benzene, 1,3-bis (3-amino-5-trifluoromethylphenoxy)
-5-trifluoromethylbenzene, 2,2-bis (3
-Amino-4-methylphenyl) -1,1,1,3,
3,3-hexafluoropropane, 2,2-bis (3-
Amino-4-hydroxyphenyl) -1,1,1,3
3,3-hexafluoropropane, 3,3′-bis (trifluoromethyl) -5,5′-diaminobiphenyl,
2,2-bis [3-amino-5- (trifluoromethyl) phenyl) -1,1,1,3,3,3-hexafluoropropane.

In the first polyimide precursor of the present invention, a diamine component is used together with an aromatic diamine compound represented by the general formula (DA1) and a compound represented by the following general formula (DA6):
Or a bis (aminoalkyl) peralkylpolysiloxane compound represented by the formula (1).

[0037]

Embedded image (R ³ may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, m and n are integers of 1 to 10, and p is a positive integer.) General formula (DA6) Examples of the bis (aminoalkyl) peralkylpolysiloxane compound represented by the following are given below. For example, 1,3-bis (aminomethyl) -1,1,1,
3,3-tetramethyldisiloxane, 1,3-bis (2
-Aminoethyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,
1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (5-aminopentyl)-
1,1,3,3-tetramethyldisiloxane, 1,3-
Bis (6-aminohexyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (7-aminoheptyl) -1,1,3,3-tetramethyldisiloxane,
1,3-bis (8-aminooctyl) -1,1,3,3
-Tetramethyldisiloxane, 1,3-bis (10-aminodecyl) -1,1,3,3-tetramethyldisiloxane, 1,5-bis (3-aminopropyl) -1,1,1
3,3,5,5-hexamethyltrisiloxane, 1,7
-Bis (3-aminopropyl) -1,1,3,3,5
5,7,7-octamethyltetrasiloxane, 1,11
-Bis (3-aminopropyl) -1,1,3,3,5
5,7,7,9,9,11,11-dodecamethylhexasiloxane, 1,15-bis (3-aminopropyl)-
1,1,3,3,5,5,7,7,9,9,11,1
1,13,13,15,15-hexadecamethyloctasiloxane, 1,19-bis (3-aminopropyl)-
1,1,3,3,5,5,7,7,9,9,11,1
1,13,13,15,15,17,17,19,19
-Eicosamethyldecasiloxane.

The bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) has a function of improving the adhesion and adhesion of the polyimide resin to, for example, a semiconductor substrate. These compounds are preferably used in an amount of 0.02 to 0.1 molar equivalent of all the diamine components. This is because, although the adhesion and adhesion of the polyimide resin obtained by blending such a compound to, for example, a semiconductor substrate are improved, excessive blending may cause a decrease in the heat resistance of the polyimide resin. is there.

In the present invention, as long as the physical properties of the finally obtained polyimide resin are not impaired, the general formula (DA)
In addition to the aromatic diamine compound represented by 1), other diamine compounds can be used in combination. Examples of such other diamine compounds include an aromatic diamine compound in which an amino group is bonded to, for example, a para position instead of a meta position of a benzene ring, and an aliphatic diamine compound. The following are mentioned as such a diamine compound. For example, 1,2-phenylenediamine, 1,4-phenylenediamine, 3,4′-diaminobiphenyl,
4,4'-diaminobiphenyl, 1,3-phenylene-
4,4'-dianiline, 1,4-phenylene-4,4 '
-Dianiline, oxy-4,4'-dianiline, thio-
4,4'-dianiline, sulfonyl-4,4'-dianiline, methylene-4,4'-dianiline, 1,2-ethylene-4,4'-dianiline, 1,3-trimethylene-
4,4'-dianiline, 2,2-propylidene-4,
4'-dianiline, 1,4-tetramethylene-4,4 '
-Dianiline, 1,5-pentamethylene-4,4'-dianiline, 1,1,1,3,3,3-hexafluoro-
2,2-propylidene-4,4'-dianiline, difluoromethylene-4,4'-dianiline, 1,1,2,2
-Tetrafluoro-1,2-ethylene-4,4'-dianiline, 1,1,2,2,3,3-hexafluoro-
1,3-trimethylene-4,4′-dianiline, 1,3
-Bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenylthio) benzene, 1,3-bis (4-aminophenylsulfonyl) benzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4-aminophenyl)- 1,1,1,3,3
3, -Hexafluoro-2-propyl] benzene, 1,
4-bis (4-aminophenoxy) benzene, 1,4-
Bis (4-aminophenylthio) benzene, 1,4-bis (4-aminophenylsulfonyl) benzene, 1,4
-Bis [2- (4-aminophenyl) -2-propyl]
Benzene, 1,4-bis [2- (4-aminophenyl)
-1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3 -Hexafluoropropane, 2-fluoro-1,4-phenylenediamine, 2,, 6,6'-octafluorobiphenyl, oxy-4,4'-bis (2-fluoroaniline), oxy-4,4'- Bis (3-fluoroaniline), sulfonyl-4,4'-bis (2-fluoroaniline), sulfonyl-4,4'-bis (3-fluoroaniline), 2-trifluoromethyl-1,4-phenylenediamine , 2,5-bis (trifluoromethyl)-
1,4-phenylenediamine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,
3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, oxy-4,4'-bis (2-trifluoromethylaniline), oxy-4,4'-bis (3-
Trifluoromethylaniline), sulfonyl-4,4 '
-Bis (2-trifluoromethylaniline), sulfonyl-4,4'-bis (3-trifluoromethylaniline), bis (4-aminophenoxy) dimethylsilane,
1,3-bis (4-aminophenyl) -1,1,3,3
-Tetramethyldisiloxane, methanediamine, 1,2
-Ethanediamine, 1,3-propanediamine, 1,4
-Butanediamine, 1,5-pentanediamine, 1,6
-Hexanediamine, 1,7-heptanediamine, 1,
8-octanediamine, 1,9-nonanediamine, 1,
10-decanediamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-diaminocyclohexane,
1,4-diaminocyclohexane, bis (3-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1,2-bis (3-aminocyclohexyl) ethane, 1,2-bis (4-aminocyclohexyl) ethane , 2,2-bis (3-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-aminocyclohexyl) ether, bis (4-aminocyclohexyl) ether, bis (3-amino Cyclohexyl) sulfone, bis (4-
Aminocyclohexyl) sulfone, 2,2-bis (3-
Aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 3-xylylenediamine, 1,4-xylylenediamine, 1,8-diaminonaphthalene, 2,
7-diaminonaphthalene, 2,6-diaminonaphthalene, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyrazine, and 2,4-diamino-s-triazine.

From the viewpoint of the heat resistance, environmental stability and low dielectric constant characteristics of the polyimide resin, the above-mentioned general formula (DA1)
Among other diamine compounds that can be used in combination with the aromatic diamine compound represented by the following formula, it is particularly preferable to use the following diamine compounds. For example, 1,4-phenylenediamine, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 1,3-phenylene-4,4′-dianiline, 1,4-phenylene-4,4′-dianiline , Oxy-4,4'-dianiline, thio-4,4'-
Dianiline, sulfonyl-4,4'-dianiline, methylene-4,4'-dianiline, 2,2-propylidene-
4,4′-dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-dianiline, 1,3-bis (4-aminophenoxy) benzene, 4-bis (4-aminophenoxy) benzene,
1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2-bis [4-
(4-aminophenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 2-fluoro-
1,4-phenylenediamine, 2,5-difluoro-
1,4-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,4′-diamino-2,2′-difluorobiphenyl, 4,4′-
Diamino-3,3'-difluorobiphenyl, 4,4 '
-Diamino-2,2'3,3 ', 5,5', 6,6'-
Octafluorobiphenyl, oxy-4,4'-bis (2-fluoroaniline), oxy-4,4'-bis (3-fluoroaniline), sulfonyl-4,4'-bis (2-fluoroaniline), sulfonyl -4,4'-
Bis (3-fluoroaniline), 2-trifluoromethyl-1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 2,
2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl)
-4,4'-diaminobiphenyl, oxy-4,4'-
Bis (2-trifluoromethylaniline), oxy-
4,4′-bis (3-trifluoromethylaniline),
Sulfonyl-4,4'-bis (2-trifluoromethylaniline), sulfonyl-4,4'-bis (3-trifluoromethylaniline), 1,8-diaminonaphthalene, 2,7-diaminonaphthalene, 2, 6-diaminonaphthalene and the like.

In the first polyimide precursor of the present invention, as the tetracarboxylic dianhydride represented by the general formula (DAH1), Y in the general formula (DAH1) has 1 carbon atom.
To 30 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or heterocyclic groups, and aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or heterocyclic groups; A compound that is a tetravalent organic group selected from the group consisting of polycyclic compound groups connected to each other directly or by a crosslinking group can be used. The following are mentioned as these tetracarboxylic dianhydrides. For example, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride,
3-trifluoromethylpyromellitic dianhydride, 3,6
-Bis (trifluoromethyl) pyromellitic dianhydride,
1,2,3,4-benzenetetracarboxylic dianhydride,
3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 3,3 ", 4,4" -p-
Terphenyltetracarboxylic dianhydride, 3,3 ′ ″,
4,4 ′ ″-p-quaterphenyltetracarboxylic dianhydride, 3,3 ″ ″, 4,4 ″ ″-p-quinkphenyltetracarboxylic dianhydride, 2,2 ′ , 3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4 '
-Diphthalic dianhydride, 1,1-ethylidene-4,4 '
-Diphthalic dianhydride, 2,2-propylidene-4,
4'-diphthalic dianhydride, 1,2-ethylene-4,
4'-diphthalic dianhydride, 1,3-trimethylene-
4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,1 , 1,
3,3,3-hexafluoro-2,2-propylidene-
4,4'-diphthalic dianhydride, difluoromethylene-
4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3 -Hexafluoro-
1,3-trimethylene-4,4′-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4′-diphthalic acid Dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4'-diphthalic dianhydride, oxy-4,4 '-Diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,
4-dicarboxyphenyl) -1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 3,3′-bis (3 4-dicarboxyphenyl) biphenyl dianhydride, 1,3-bis (3,4-dicarboxyphenoxy)
Benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2-
(3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride,
1,3-bis (3,4-dicarboxyphenylsulfonyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenylsulfonyl) benzene dianhydride, bis [3- (3,4-di Carboxyphenoxy) phenyl]
Methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl]
Propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride,
2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis [4- (3 4-
Dicarboxyphenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) -1,1,3,3 3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetra Carboxylic dianhydride, 2,3,6,7-phenanthrenetetracarboxylic dianhydride, 2,3,8,9-naphthacenetetracarboxylic dianhydride, 1,3-bis (3,
4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetra Carboxylic anhydride, cyclohexane-1,2,3
4-tetracarboxylic dianhydride, cyclohexane-1,
2,4,5-tetracarboxylic dianhydride, 3,3 ′,
4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis (cyclohexane-
1,2-dicarboxylic acid) dianhydride, methylene-4,4 '
-Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4, 4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,
4'-bis (cyclohexane-1,2-dicarboxylic acid)
Dianhydride, 1,1,1,3,3,3-hexafluoro-
2,2-propylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,
4'-bis (cyclohexane-1,2-dicarboxylic acid)
Dianhydride, thio-4,4'-bis (cyclohexane-
1,2-dicarboxylic acid) dianhydride, sulfonyl-4,
4'-bis (cyclohexane-1,2-dicarboxylic acid)
Dianhydride, 2,2'-difluoro-3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, 5,5'-difluoro-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 6,6'-difluoro-3,3',
4,4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 5,5', 6,6'-hexafluoro-3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis (trifluoromethyl) -3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-bis (trifluoromethyl) -3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-bis (trifluoromethyl) -3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride 2,2 ′, 6,6′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoro Methyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5
5 ', 6,6'-Hexakis (trifluoromethyl)-
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3'-difluorooxy-4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'
-Diphthalic dianhydride, 6,6'-difluorooxy-
4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′,
6,6'-hexafluorooxy-4,4'-diphthalic dianhydride, 3,3'-bis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 5,5'-bis (Trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 6,6′-bis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5
5'-tetrakis (trifluoromethyl) oxy-4,
4'-diphthalic dianhydride, 3,3 ', 6,6'-tetrakis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 5,5', 6,6'-tetrakis ( Trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride 3,3′-difluorosulfonyl-4,4′-diphthalic dianhydride, 5,5′-difluorosulfonyl-
4,4′-diphthalic dianhydride, 6,6′-difluorosulfonyl-4,4′-diphthalic dianhydride, 3,
3 ′, 5,5 ′, 6,6′-hexafluorosulfonyl-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride 5,5′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 6,6′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) sulfonyl-4,4 '-Diphthalic dianhydride, 5,5', 6,6'-tetrakis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride,
3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) sulfonyl-4,4′-diphthalic anhydride, 3,3′-difluoro-2,2-perfluoropropylidene- 4,4′-diphthalic dianhydride, 5,5′-
Difluoro-2,2-perfluoropropylidene-4,
4'-diphthalic dianhydride, 6,6'-difluoro-
2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexafluoro-2,2-perfluoropropylidene-4,
4'-diphthalic dianhydride, 3,3'-bis (trifluoromethyl) -2,2-perfluoropropylidene-
4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 6,6′-bis ( (Trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5
5′-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) -2,2 -Perfluoropropylidene-4,4 '
Diphthalic anhydride, 5,5 ′, 6,6′-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic anhydride, 3,3 ′,
5,5 ', 6,6'-Hexakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-
Diphthalic dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3 6,7-tetracarboxylic dianhydride and bicyclo [2,2,2] oct-7-ene-
2,3,5,6-tetracarboxylic dianhydride and the like. These tetracarboxylic dianhydrides may be used alone or in combination of two or more. Tetracarboxylic dianhydride is 0.80% of the total anhydride component.
0.99 molar equivalents, preferably 0.90 to 0.98 molar equivalents are used. The reason for this is that if the blending amount of the tetracarboxylic dianhydride is too small, the heat resistance of the obtained polyimide resin decreases, and conversely, if the blending amount of the tetracarboxylic dianhydride is too large, as the acid anhydride component The amount of maleic anhydride or maleic acid derivative anhydride is reduced, and the intrinsic viscosity of the polyimide precursor solution increases,
This is because, for example, it becomes difficult to fill minute irregularities on the substrate surface without gaps.

From the viewpoint of obtaining a high heat-resistant polyimide resin having a high glass transition point and a high decomposition temperature, the general formula (DAH)
Among the tetracarboxylic dianhydrides represented by 1), it is particularly preferable to use aromatic tetracarboxylic dianhydrides represented by the following general formulas (DAH2) to (DAH4).

[0043]

Embedded image (R ¹¹ may be the same or different, and each represents a fluoro group or an unsubstituted or substituted with a fluorine atom an aliphatic hydrocarbon group, φ represents an aromatic hydrocarbon group,
a is an integer of 0 to 10. )

[0044]

Embedded image (X ¹¹ is a divalent oxy group, a thio group, a sulfonyl group, a carbonyl group, a peralkyl polysiloxanylene group, an unsubstituted or substituted with a fluorine atom, an aliphatic hydrocarbon group,
A 1,4-phenylene group, a biphenyl-4,4′-diyl group, or a single bond, wherein R ¹² may be the same or different and each represents a fluoro group, or an unsubstituted or substituted aliphatic atom A hydrocarbon group; b and c are integers from 0 to 4; )

[0045]

Embedded image (R ¹³ may be the same or different and each represents a fluoro group or an unsubstituted or substituted aliphatic hydrocarbon group with a fluorine atom, and d and e are integers of 0 to 4.) Examples of the aromatic tetracarboxylic dianhydride represented by DAH2) include the following. For example, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride,
3-trifluoromethylpyromellitic dianhydride, 3,6
-Bis (trifluoromethyl) pyromellitic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 2,3 6,7-phenanthrenetetracarboxylic dianhydride, 2,3,8,9-naphthacenetetracarboxylic dianhydride and the like.

The following are examples of the aromatic tetracarboxylic dianhydride represented by the general formula (DAH3). For example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″
-P-terphenyltetracarboxylic dianhydride, 3,
3 ′ ″, 4,4 ′ ″-p-quaterphenyltetracarboxylic dianhydride, methylene-4,4′-diphthalic dianhydride, 1,1-ethylidene-4,4′-diphthalic acid Dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic Acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,1,1,3,3 , 3-Hexafluoro-2,2-propylidene-4,4'-diphthalic dianhydride, difluoromethylene-4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1, 2-ethylene-4,4'-diphthalic dianhydride, 1,1,2,2
2,3,3-hexafluoro-1,3-trimethylene-
4,4'-diphthalic dianhydride, 1,1,2,2,3
3,4,4-octafluoro-1,4-tetramethylene-4,4′-diphthalic dianhydride, 1,1,2,2
3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4′-diphthalic dianhydride, oxy-
4,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl ) -1,1,3,3-Tetramethylsiloxane dianhydride, 2,2′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-difluoro-3 , 3 ', 4,4'-biphenyltetracarboxylic dianhydride, 6,6'-difluoro-3,3', 4,4 '
-Biphenyltetracarboxylic dianhydride, 2,2 ',
5,5 ', 6,6'-hexafluoro-3,3', 4
4'-biphenyltetracarboxylic dianhydride, 2,2 '
-Bis (trifluoromethyl) -3,3 ', 4,4'-
Biphenyltetracarboxylic dianhydride, 5,5'-bis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 6,6'-bis (trifluoromethyl)- 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride Anhydrous, 2,2 ', 6
6'-tetrakis (trifluoromethyl) -3,3 ',
4,4′-biphenyltetracarboxylic dianhydride, 5,
5 ', 6,6'-tetrakis (trifluoromethyl)-
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) -3,3 ′, 4,4′- Biphenyltetracarboxylic dianhydride, 3,3'-difluorooxy-4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'-diphthalic dianhydride, 6,6 '
-Difluorooxy-4,4'-diphthalic dianhydride,
3,3 ′, 5,5 ′, 6,6′-hexafluorooxy-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) oxy-4,4′-diphthalic acid Dianhydride, 5,5'-bis (trifluoromethyl) oxy-
4,4′-diphthalic dianhydride, 6,6′-bis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl ) Oxy-4,4′-diphthalic dianhydride, 3,
3 ′, 6,6′-tetrakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 5,5 ′, 6
6'-tetrakis (trifluoromethyl) oxy-4,
4'-diphthalic dianhydride, 3,3 ', 5,5', 6
6'-hexakis (trifluoromethyl) oxy-4,
4′-diphthalic dianhydride, 3,3′-difluorosulfonyl-4,4′-diphthalic dianhydride, 5,5′-difluorosulfonyl-4,4′-diphthalic dianhydride,
6,6′-difluorosulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexafluorosulfonyl-4,4′-diphthalic dianhydride,
3,3'-bis (trifluoromethyl) sulfonyl-
4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 6,6′-bis (trifluoromethyl) sulfonyl-4, 4'-diphthalic dianhydride, 3,3 ', 5
5'-tetrakis (trifluoromethyl) sulfonyl-
4,4'-diphthalic dianhydride, 3,3 ', 6,6'-
Tetrakis (trifluoromethyl) sulfonyl-4,
4'-diphthalic dianhydride, 5,5 ', 6,6'-tetrakis (trifluoromethyl) sulfonyl-4,4'-
Diphthalic dianhydride, 3,3 ', 5,5', 6,6'-
Hexakis (trifluoromethyl) sulfonyl-4,
4'-diphthalic dianhydride, 3,3'-difluoro-
2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 5,5′-difluoro-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride,
6,6′-difluoro-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5
5 ', 6,6'-hexafluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,
3′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride,
5,5'-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-bis (trifluoromethyl) -2,2-
Perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,
4′-diphthalic anhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic anhydride, 5,
5 ', 6,6'-tetrakis (trifluoromethyl)-
2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3 ', 5,5', 6,6'-hexakis (trifluoromethyl) -2,2-perfluoropropylidene -4,4'-diphthalic dianhydride and the like.

Examples of the aromatic tetracarboxylic dianhydride represented by the general formula (DAH4) include the following. For example, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3,6,7- And tetracarboxylic dianhydride.

From the viewpoints of the heat resistance, environmental stability and low dielectric constant of the polyimide resin, the general formulas (DAH2) to (DAH2)
Among the aromatic tetracarboxylic dianhydrides represented by H4), it is particularly preferable to use the following ones. For example, pyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2
Propylidene-4,4'-diphthalic dianhydride, oxy-4,4'-diphthalic dianhydride, sulfonyl-4,
4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 9-phenyl-9- (trifluoromethyl ) Xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl)
Xanthene-2,3,6,7-tetracarboxylic dianhydride and the like.

The maleic anhydride or maleic acid derivative anhydride used in the first polyimide precursor of the present invention is represented by the following general formula (MA1).

[0050]

Embedded image (R ²¹ may be the same or different and each represents a halogen group, an unsubstituted or substituted aliphatic hydrocarbon group or a hydrogen atom, or a hydrogen atom.) These maleic anhydrides or maleic acid derivative anhydrides Examples include the following. For example,
Maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, ethyl maleic anhydride, diethyl maleic anhydride, propyl maleic anhydride, butyl maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride Bromomaleic anhydride, dibromomaleic anhydride, fluoromaleic anhydride, difluoromaleic anhydride, trifluoromethylmaleic anhydride, bis (trifluoromethyl) maleic anhydride and the like. These maleic anhydrides or maleic acid derivative anhydrides may be used alone or in combination of two or more.

These maleic anhydrides or maleic acid derivative anhydrides have the effect of lowering the molecular weight of the polyamic acid, which is a polyimide precursor, to lower the viscosity of the solution. Further, the maleimide skeleton introduced at the terminal of the polyamic acid is crosslinked at the time of curing directly or via an excess of a diamine component. Maleic anhydride or maleic acid derivative anhydride is 0.02-0.02% of the total anhydride component.
It is used in an amount of 0.40 molar equivalent, preferably 0.05 to 0.20 molar equivalent. The reason for this is that if the amount of maleic anhydride or maleic acid derivative anhydride is too small, the intrinsic viscosity of the polyimide precursor solution exceeds 0.7 dL / g, and fine irregularities on the substrate surface, especially width 0.1 This is because it is difficult to fill the trench with a thickness of about 0.5 μm with the polyimide resin without any gap. Conversely, if the amount is too large, the heat resistance of the polyimide resin decreases.

The method for synthesizing the polyamic acid as the first polyimide precursor of the present invention is not particularly limited, but a diamine component containing an aromatic diamine compound represented by the general formula (DA1) in an organic solvent may be used. A method of reacting a tetracarboxylic dianhydride represented by (DAH1) with an acid anhydride component containing maleic anhydride or a maleic acid derivative anhydride is preferable. Examples of the organic solvent used in this reaction include the following. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N
-Dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidin, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis ( 2-
Methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran,
1,3-dioxane, 1,4-dioxane, pyrroline,
Picoline, dimethyl sulfoxide, sulfolane, phenol, cresol, anisole, γ-butyrolactone,
Propylene carbonate, acetylacetone, acetonylacetone and the like. These solvents may be used alone,
Two or more kinds may be used as a mixture. The reaction temperature is usually 25
The temperature is 0 ° C or less, preferably 200 ° C or less. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. The reaction time varies depending on the type of tetracarboxylic dianhydride and the type of reaction solvent, but usually 4 to 24 hours is sufficient. The polyamic acid obtained at this time has an inherent viscosity at 30 ° C. of a 0.5 wt% N-methyl-2-pyrrolidone solution of 0.2 to 0.2%.
The polymerization degree is preferably 0.7 dL / g, and more preferably 0.3 to 0.6 dL / g. The reason for this is
If the intrinsic viscosity of the polyamic acid is too low, that is, if the degree of polymerization is too low, a polyimide resin having sufficient heat resistance may not be able to be obtained thereafter, and conversely, the intrinsic viscosity is too high, that is, the degree of polymerization is too high This is because it becomes difficult to fill the fine irregularities on the substrate surface with the polyimide resin without any gap.

In order to produce a polyimide resin from polyamic acid, which is the first polyimide precursor of the present invention, a heat treatment method of heating polyamic acid to 100 to 450 ° C. to imidize the polyamic acid is performed by irradiating the polyamic acid with light. A light irradiation method of imidizing the polyamic acid or a chemical treatment method of chemically imidizing the polyamic acid using an imidizing agent such as acetic anhydride is used. The polyimide resin obtained by these methods can be formed as a film with excellent flatness even on a substrate having fine irregularities due to the low viscosity of the solution containing the polyamic acid as a precursor thereof, and furthermore, the dielectric constant and hygroscopicity And has excellent thermal stability and environmental stability. In addition, even if the viscosity of the solution is relatively low molecular weight, the polyimide precursor has a maleimide skeleton at the end, so that the maleimide skeleton is crosslinked directly or via an excess diamine component during curing to a polyimide resin. As a result, it is possible to obtain a polyimide resin having excellent heat resistance.

Next, the second polyimide precursor (polyamic acid) according to the present invention will be described. This polyimide precursor comprises an amine component containing at least 0.10 molar equivalents of the fluorinated aromatic diamine compound represented by the general formula (DA2) and a tetracarboxylic dianhydride represented by the general formula (DAH1). Characterized by having a structure obtained by polymerizing an acid anhydride component containing at least 0.80 molar equivalents of the compound. More specifically, the polyimide precursor is (a) 0.97 to 1.03 mol of a diamine compound containing 0.10 mol equivalent or more of the fluorine-containing aromatic diamine compound represented by the general formula (DA2). equivalents, (b) the general formula (DAH1) tetracarboxylic acid dianhydride represented by (1-n _2/2) molar equivalents and dicarboxylic anhydrides n ₂ molar equivalents (n ₂ is 0 to 0.4 ) and was polymerized structure or (a ') the general formula (DA2) containing more fluorine-containing aromatic diamine compound 0.10 molar equivalents represented by the diamine compound (1-n _3/2) molar equivalents, And monoamine compound n ₃ molar equivalent (n ₃ is 0 to 0.4)
And (b ') 0.97 to 1.03 molar equivalents of the tetracarboxylic dianhydride represented by the general formula (DAH1). This polyimide precursor is different from the first polyimide precursor according to the present invention,
It is not necessary to include maleic anhydride or maleic acid derivative anhydride as a raw material.

The aromatic diamine compound represented by the general formula (DA2) is more specifically represented by the following general formula (DA3)
(DA5).

[0056]

Embedded image (X ³ in the general formula (DA3) represents a perfluoroalkylene group or a perfluoroalkylidene group, R ⁰ , R ² , a
And b have the same meaning as defined in formula (DA2). The following are mentioned as an aromatic diamine compound represented by General formula (DA3). For example, 2,2-
Bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3-amino-5- (pentafluoroethyl) phenyl ] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3-amino-5-
(Heptafluoropropyl) phenyl] -1,1,1,
3,3,3-hexafluoropropane, 2,2-bis [3-amino-5- (nonafluorobutyl) phenyl]
-1,1,1,3,3,3-hexafluoropropane,
2,2-bis (3-amino-5-fluorophenyl]-
1,1,1,3,3,3-hexafluoropropane, bis [3-amino-5- (trifluoromethyl) phenyl] difluoromethane, 1,2-bis [3-amino-5
-(Trifluoromethyl) phenyl] -1,1,2,2
-Tetrafluoroethane, 1,3-bis [3-amino-
5- (trifluoromethyl) phenyl] -1,1,2,2
2,3,3-hexafluoropropane, 2,2-bis [3-amino-5- (trifluoromethyl) phenyl]
-1,1,1,3,3,4,4,4-octafluorobutane, 1,4-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,2,2,3 , 3,4,4
-Octafluorobutane and the like.

The following are examples of the aromatic diamine compound represented by the general formula (DA4). For example, 3,3′-diamino-5,5′-difluorobiphenyl, 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl, 3,3′-diamino-5-fluorobiphenyl, , 3'-diamino-5- (trifluoromethyl) biphenyl and the like.

The following are examples of the aromatic diamine compound represented by the general formula (DA5). For example, 3,3'-diamino-5,5'-difluorodiphenylsulfone, 3,3'-diamino-5,5'-bis (trifluoromethyl) diphenylsulfone, 3,3 '
-Diamino-5-fluorodiphenylsulfone, 3,
3′-diamino-5- (trifluoromethyl) diphenyl sulfone and the like.

These aromatic diamine compounds are used alone,
Alternatively, two or more kinds can be used in combination.

The aromatic diamine compound represented by the general formula (DA3) can be synthesized by the following method. (1) First, a compound represented by the general formula (DZ1) and a compound represented by R ² -X are heated in an autoclave without a solvent or in an organic solvent in the presence of a copper powder catalyst, A compound represented by the general formula (DR1) is obtained. (2) Next, the compound represented by the general formula (DR1) is nitrated with fuming nitric acid in a concentrated sulfuric acid or fuming sulfuric acid solution to obtain a dinitro compound represented by the general formula (DN1). (3) Finally, the aromatic diamine compound represented by the general formula (DA3) can be synthesized by reducing the nitro group of the dinitro compound represented by the general formula (DN1). Examples of the organic solvent that can be used in the step (1) include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, nitrobenzene, benzene, and naphthalene. . Examples of the reducing agent used for reducing the nitro group to the amino group in the step (3) include a palladium catalyst, a Raney nickel catalyst, an iron chloride catalyst, a tin chloride catalyst, ammonium sulfide, and hydrazine.

[0061]

Embedded image (Z represents an iodine group, a bromo group or a chloro group, and X ³
And R ² are as defined in the formula (DA3). The aromatic diamine compound represented by the general formula (DA4) can be synthesized by the following method. That is, the nitrobenzene compound represented by the general formula (NZ1) is heated in the absence of a solvent or in an organic solvent in the presence of a copper powder catalyst to cause a coupling reaction, and the fluorine-containing compound represented by the general formula (DN2) 3 A 3′-dinitrobiphenyl compound is synthesized. Next, the nitro group of the fluorine-containing 3,3'-dinitrobiphenyl compound represented by the general formula (DN2) is reduced to thereby reduce the fluorine-containing 3,3'-diaminobiphenyl represented by the general formula (DA4). Compounds can be synthesized.

The nitrobenzene compound represented by the general formula (NZ1) includes 3-chloro-5-fluoronitrobenzene, 3-bromo-5-fluoronitrobenzene,
-Iodo-5-fluoronitrobenzene, 3-chloro-
5-nitrobenzofluoride, 3-bromo-5-nitrobenzofluoride, 3-iodo-5-nitrobenzofluoride and the like. Examples of the organic solvent used in the coupling reaction and the reducing agent used in reducing the nitro group to an amino group include those similar to those listed in the description of the synthesis method of formula (DA3).

[0063]

Embedded image (Z represents iodo, bromo group or chloro group, R ²
Is synonymous with the definition of formula (DA3). In the second polyimide precursor (polyamic acid) of the present invention, the fluorinated aromatic diamine compound represented by the general formula (DA2) has an effect of improving the thermal stability of the polyimide resin. From the viewpoint of sufficiently improving the thermal stability of the polyimide resin, the fluorinated aromatic diamine compound represented by the general formula (DA2) contains 0.1% of all amine components.
It is used in an amount of at least 10 molar equivalents, preferably at least 0.20 molar equivalents.

In the second polyimide precursor of the present invention, as in the case of the first polyimide precursor of the present invention, as long as the physical properties of the finally obtained polyimide resin are not impaired,
A diamine compound represented by the general formula (DA6) or another diamine compound can be used in combination.

In the second polyimide precursor of the present invention, the tetracarboxylic dianhydride represented by the general formula (DAH1) is the same as that used in the first polyimide precursor of the present invention. Used. The tetracarboxylic dianhydride represented by the general formula (DAH1) is
0.80 molar equivalent or more, preferably 0.90 molar equivalent or more of all the acid anhydride components is used. The reason is the same as in the case of the first polyimide precursor of the present invention. Further, from the viewpoint of obtaining a highly heat-resistant polyimide resin having a high glass transition point and a high decomposition temperature, among the tetracarboxylic dianhydrides represented by the general formula (DAH1), particularly, the above-mentioned general formulas (DAH2) to (DAH4) It is preferred to use the aromatic tetracarboxylic dianhydride represented by the formula (1).

In the second polyimide precursor of the present invention, a dicarboxylic anhydride or a monoamine compound is used as necessary.

Examples of the dicarboxylic anhydride include the following. For example, maleic anhydride, citraconic anhydride, dimethylmaleic anhydride, ethylmaleic anhydride, diethylmaleic anhydride, propylmaleic anhydride, butylmaleic anhydride, chloromaleic anhydride, dichloromaleic Acid anhydride, bromomaleic anhydride, dibromomaleic anhydride, fluoromaleic anhydride, difluoromaleic anhydride, trifluoromethylmaleic anhydride, bis (trifluoromethyl) maleic anhydride, cyclobutanedicarboxylic acid Anhydride, cyclopentanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, tetrahydrophthalic acid, endmethylenetetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendmethylenetetrahydrophthalic acid, phthalic anhydride, no methylphthalic acid Anhydride, ethylphthalic anhydride, dimethylphthalic anhydride, fluorophthalic anhydride, difluorophthalic anhydride, chlorophthalic anhydride, dichlorophthalic anhydride, bromophthalic anhydride, dibromophthalic anhydride, nitrophthalic anhydride Product, 2,3-benzophenone dicarboxylic anhydride, 3,
4-benzophenone dicarboxylic anhydride, 2,3-dicarboxydiphenyl ether anhydride, 3,4-dicarboxydiphenyl ether anhydride, 2,3-dicarboxydiphenylsulfone anhydride, 3,4-dicarboxydiphenylsulfone anhydride, 2,3-dicarboxybiphenyl anhydride, 3,4-dicarboxybiphenyl anhydride,
1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, 1,9
-Anthracene dicarboxylic anhydride, 2,3-pyridine dicarboxylic anhydride, 3,4-pyridine dicarboxylic anhydride and the like.

The following are examples of the monoamine compound. For example, methylamine, ethylamine, propylamine, butylamine, pentylamine,
Hexylamine, heptylamine, octylamine, 1
-(3-aminopropyl) -1,1,3,3,3-pentamethyldisiloxane, vinylamine, allylamine,
Glycine, alanine, aminobutyric acid, valine, norvaline, isovaline, leucine, norleucine, isoleucine, glutamine, glutamic acid, tryptophan, aminocrotonic acid, aminoacetonitrile, aminopropionitrile, aminocrotononitrile, cyclopropylamine, cyclobutylamine, cyclopentyl Amine, cyclohexylamine, cycloheptylamine, cyclooctylamine, aminoadamantane, aminobenzocyclobutane, aminocaprolactam, aniline, chloroaniline, dichloroaniline, bromoaniline, dibromoaniline, fluoroaniline, difluoroaniline, nitroaniline, dinitroaniline, toluidine , Xylidine, ethylaniline, anisidine, phenetidine, aminoacetanilide Aminoacetophenone, aminobenzoic acid, aminobenzaldehyde, aminobenzonitrile, aminophthalonitrile, aminobenzotrifluoride, aminostyrene, aminostilbene, aminoazobenzene, aminodiphenyl ether, aminodiphenylsulfone, aminobenzenesulfonamide, aminophenylmaleimide, aminophenyl Phthalimide, aminobiphenyl, aminoterphenyl, aminonaphthalene,
Aminoacridine, aminoanthraquinone, aminofluorene, aminofluorenone, aminopyrrolidine, aminopiperazine, aminopiperidine, aminohomopiperidine, aminomorpholine, aminobenzooxyl, aminobenzodioxane, aminopyridine, aminopyridazine, aminopyrimidine, aminopyrazine, amino Quinoline, aminocinnoline, aminophthalazine, aminoquinazoline, aminoquinoxaline, aminopyrrole, aminoimidazole, aminopyrazole, aminotriazole, aminooxazole, aminoisoxazole, aminothiazole, aminoisothiazole, aminoindole, aminobenzimidazole, amino Indazole, aminobenzoxazole, aminobenzothiazole, benzylamine, Enechiruamin, phenylpropylamine, a phenyl butyl amine, benzhydrylamine, aminoethyl-1,3-dioxolane, aminoethyl pyrrolidine, aminoethylpiperazine, amino ethyl piperidine, aminoethyl morpholine, aminopropylimidazole, aminopropyl cyclohexane.

As a method for synthesizing the second polyimide precursor of the present invention, a diamine component containing a fluorine-containing aromatic diamine compound represented by the general formula (DA2) in an organic solvent and a diamine component represented by the general formula (DAH1) are used. A preferred method is to react with an acid anhydride component containing a tetracarboxylic dianhydride. The organic solvent used during this reaction, and the temperature,
Reaction conditions such as pressure and time are the same as in the case of the first polyimide precursor of the present invention. The obtained polyamic acid preferably has a polymerization degree at which the intrinsic viscosity at 30 ° C. of a 0.5 wt% N-methyl-2-pyrrolidone solution is within a range of 0.5 dL / g or more. If the degree of polymerization of the polyamic acid is too low, a polyimide resin having sufficient heat resistance may not be obtained thereafter. on the other hand,
The upper limit is not particularly limited, but if the degree of polymerization is too high, it becomes difficult to fill the fine irregularities with the polyimide resin without gaps on the substrate surface, so that the flatness on the substrate having the fine irregularities is improved. In the case where an excellent film is formed, the intrinsic viscosity is preferably 0.8 dL / g or less.

The method for obtaining a polyimide resin from the second polyimide precursor of the present invention is the same as that of the first polyamic acid of the present invention. The polyimide resin obtained from the second polyimide precursor of the present invention has low dielectric constant and low hygroscopicity, and is excellent in thermal stability and environmental stability.
In particular, a polyimide precursor using an aromatic diamine compound represented by the general formula (DA3) is preferable in that a polyimide resin having a low dielectric constant can be obtained. In addition, the general formula (DA4)
Alternatively, a polyimide precursor using an aromatic diamine compound represented by (DA5) is preferable because a polyimide resin having a low glass transition point and a low decomposition temperature and excellent in heat resistance can be obtained.

Next, the photosensitive polyimide precursor according to the present invention will be described.

The first photosensitive polyimide precursor of the present invention comprises (a) the first polyimide precursor or the second polyimide precursor of the present invention.
And (b) a photosensitive agent.

In the first photosensitive polyimide precursor of the present invention, as a sensitizer, an amine compound having a double bond as shown below, preferably a tertiary amine compound having a double bond, or an azide group is used. Compounds. For example, 2-N, N-dimethylaminoethyl acrylate, 2-N, N-dimethylaminoethyl methacrylate, 2-N, N-diethylaminoethyl acrylate, 2-N, N-diethylaminoethyl methacrylate, 3-N, N- Dimethylaminopropyl acrylate, 3-N, N-dimethylaminopropyl methacrylate, 2-allylpyridine, 4-allylpyridine, 3-
N, N-dimethylaminopropylacrylamide, acroylmorpholine, 2-aminoethyl acrylate,
—N, N-dimethylaminobutyl acrylate, 2-N, N-dimethylaminoethyl cinnamate and the like. Further, a compound represented by the following chemical formula can also be used as the photosensitive agent.

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image

[0080]

Embedded image As the photosensitizer, at least one selected from the group consisting of the above compounds is used. The amount of the photosensitizer to be added is preferably 0.1 to 120 parts by weight, more preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the polyimide precursor. The reason is as follows. That is, if the amount of the photosensitive agent is less than 0.1 part by weight,
The sensitivity of the photosensitive polyimide precursor to exposure becomes insufficient, and no difference is observed in the dissolution rate of the exposed part and the unexposed part in the developing solution. Conversely, when the amount of the photosensitive agent added is 12
If the amount exceeds 0 parts by weight, a residue of a photosensitive agent component after development becomes a problem.

The first photosensitive polyimide precursor of the present invention may optionally contain a sensitizer. Examples of the sensitizer include the following. For example, benzophenone, anthraquinone, benzoquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 1,2-
Benzanthraquinone, Michler's ketone, 4,4'-dimethylbenzophenone, 5-nitroacenaphthene, benzoyl ether, 4,4'-bis (diethylamino) benzophenone, 2,6-bis (4-dimethylaminobenzylidene) cyclohexanone, 4-t -Butyl-2,6
-Bis (4-dimethylaminobenzylidene) cyclohexanone, 3,3'-carbonylbis (7-diethylaminocoumarin), 3- (2-benzimidazoyl) -7-
Diethylaminocoumarin, N-phenylglycine, 2-
(Dimethylamino) ethyl benzoate, ethyl (4-
Dimethylamino) benzoate, diethylthioxanthene, isopropylthioxanthene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethylketal, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone , 1
-Hydroxycyclohexylphenyl ketone, anthrone, acridine, methyl 4-dimethylaminobenzoate and the like. As the sensitizer, at least one selected from the group consisting of the above compounds is used. The amount of the sensitizer is 0.5 to 50 parts by weight based on 100 parts by weight of the photosensitizer.
Preferably it is in the range of 1 to 30 parts by weight. Addition of a sensitizer can further improve the photosensitive characteristics of the first photosensitive polyimide precursor of the present invention.

The first photosensitive polyimide precursor of the present invention is prepared by dissolving a sensitizer and a sensitizer used as needed in a solution of a predetermined polyimide precursor synthesized in an organic solvent as described above. By doing so, it is prepared in the form of a varnish. The concentration of the polyimide precursor in the varnish is preferably 5 to 30 parts by weight. In preparing the varnish, another solvent may be used in addition to the above organic solvent for the purpose of adjusting the viscosity and improving the applicability to the substrate. Such solvents include isopropanol, methanol, ethylene glycol, butyl acetate, cellosolve, butyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether,
Examples thereof include ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, and xylene. Further, in the first photosensitive polyimide precursor of the present invention, a surfactant, a silane coupling agent and the like may be blended according to the purpose of use.

A method for forming a pattern of an insulating film of a semiconductor device using the first photosensitive polyimide precursor of the present invention will be described. First, after filtering the varnish of the photosensitive polyimide precursor to remove fine insolubles,
It is applied on a semiconductor substrate by a method such as spin coating or dipping. This is dried at 60 to 100 ° C. to form a photosensitive polyimide precursor layer. A mask having a predetermined pattern is provided on the layer of the photosensitive polyimide precursor, and energy rays such as X-rays, visible light, infrared rays, ultraviolet rays, and electron beams are irradiated through the mask to perform exposure. At the time of this exposure, the photosensitizer reacts, and the polymer chain of the resin component is crosslinked in the exposed portion. The reaction at this time differs depending on whether the photosensitizer used is (1) an azide compound or (2) a compound having a double bond such as acrylate. (1) When an azide compound is used as a photosensitizer, the azide compound (AZ) changes to a nitrene radical (NR) in the exposed area. When the generated nitrene radical is used in combination with an amine compound having a double bond, a compound having a double bond introduced by an ionic bond into the polyimide precursor, for example, 2-N, N-dimethylaminoethyl acrylate A cross-linking reaction for a double bond, a hydrogen abstraction reaction, and the like occur to cross-link the polymer chain in the exposed area. (2) When an amine compound having a double bond such as acrylate is used as a photosensitizer, biradicals are generated at the double bond site of these compounds by irradiation with energy rays, and recombination of radicals proceeds in a chain. I do. These acrylates are introduced into the polyimide precursor by ionic bonding simply by blending with the polyimide precursor in the varnish, and the polymer chain is crosslinked at this portion. The layer of the photosensitive polyimide precursor after the exposure may be subjected to heat treatment at 80 to 200 ° C. for 5 seconds to 60 minutes as needed. When the heat treatment is performed in this manner, the crosslinked state of the polymer chains of the resin component becomes even stronger.

[0084]

Embedded image Next, the photosensitive polyimide precursor layer is subjected to a developing treatment using a developer by a method such as an immersion method, a spray method, or a paddle method. At this time, since the polymer chains are not crosslinked in the unexposed portions, they are dissolved in the developer. On the other hand, in the exposed area, the polymer chains are cross-linked, and are insoluble in the developer. As the developer, for example, the organic solvent used for producing the polyimide precursor can be used. Further, for the purpose of smoothly performing the development processing, together with such an organic solvent, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, acetone, cellosolve,
Methyl cellosolve, butyl cellosolve, ethylene glycol monoethyl ether acetate, toluene, xylene, water and the like may be used in combination. Further, after the development processing, a rinsing processing using water, alcohol, acetone, or the like may be performed, and a processing such as baking may be subsequently performed in order to remove a developer residue or the like.

Finally, the developed photosensitive polyimide precursor having a predetermined relief pattern is heated under predetermined conditions. By this heat treatment, the photosensitizing agent cross-linking the polymer chain of the polyimide precursor is removed, the solvent remaining in the pattern is volatilized, and the amide acid is closed to form a polyimide film pattern. In this step, the final heating temperature is from 150 to 450 ° C.
It is desirable to gradually raise the temperature until heating. When the final heating temperature is lower than 150 ° C., some polyimide precursors remain without being imidized and may hinder thermal stability. Conversely, if the final heating temperature exceeds 450 ° C,
The imidized polymer may be decomposed and the thermal stability may be impaired.

Next, the second photosensitive polyimide precursor of the present invention will be described. The second photosensitive polyimide precursor of the present invention contains (a) a polyamic acid derivative having a repeating unit represented by the general formula (PA11), and (b) a photopolymerization initiator. In order to obtain sufficient photosensitive characteristics, the general formula (PA1
It is preferable that the repeating unit represented by 1) be contained in an amount of 25% or more.

In the general formula (PA11), Y is a tetravalent organic group derived from tetracarboxylic dianhydride;
Is a residue of the diamine compound represented by the general formula (DA1). D ¹ is a photosensitive organic group or OH, and at least one of D ¹ is a photosensitive organic group. Examples of D ¹ include those represented by the following chemical formula.

[0088]

Embedded image The method for synthesizing the polyamic acid derivative represented by the general formula (PA11) is not limited. For example, R. Rubner
Et al., Photograph. Sci. Eng. , 23
(5), p. 303 (1979). Specifically, 2-hydroxyethyl methacrylate is reacted with tetracarboxylic dianhydride to synthesize a dicarboxylic diester in which a photosensitive organic group is introduced into tetracarboxylic dianhydride. Next, the obtained dicarboxylic acid diester is reacted with thionyl chloride to convert a carboxyl group into a carboxylic acid chloride. Finally, a predetermined diamine compound is reacted to form a compound of the general formula (PA
The polyamic acid derivative represented by 11) is obtained. When synthesizing this polyamic acid derivative, it is preferable to carry out the reaction in an organic solvent. As the organic solvent, the same organic solvent as used in synthesizing the first and second polyimide precursors of the present invention can be used.

In the second photosensitive polyimide precursor of the present invention, as the photopolymerization initiator, an azide compound of the photosensitive agent described for the first photosensitive polyimide precursor of the present invention and, if necessary, At least one sensitizer can be used. The amount of the photopolymerization initiator is in the range of 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyamic acid derivative represented by the general formula (PA11).

The method of forming an insulating film pattern using the second photosensitive polyimide precursor of the present invention is the same as that of the first photosensitive polyimide precursor of the present invention.

Next, the precursor of the bismaleimide-based cured resin according to the present invention will be described. This bismaleimide-based cured resin precursor comprises (a) a bismaleimide compound represented by the general formula (DM1), and (b) a bismaleimide compound (DA1
Diamine compound represented by 1) and general formula (DP1)
At least one compound selected from the group consisting of dihydric phenol compounds represented by the formula is blended, and these are reacted to some extent to have a molecular structure. In the general formula (DM1), the fluoro group or the aliphatic hydrocarbon group (R ³¹ ) substituted with the fluoro group is located at the meta position when viewed from the bonding site of the benzene ring to the maleimide ring and other benzene rings. Preferably, they have been introduced.

The bismaleimide compound represented by the general formula (DM1), which is the component (a) of the bismaleimide-based cured resin precursor of the present invention, includes the following. For example, 3,3′-dimaleimide-5,5′-bis (trifluoromethyl) biphenyl, bis [3-maleimido-5- (trifluoromethyl) phenyl] ether, bis [3-maleimido-5- (trifluoro Methyl) phenyl] sulfide, bis [3-maleimido-5
-(Trifluoromethyl) phenyl] sulfone, 3,
3′-dimaleimide-5,5′-bis (trifluoromethyl) benzophenone, 1,3-bis [3-maleimido-5- (trifluoromethyl) phenyl] -1,1,1
3,3-tetramethyldisiloxane, 2,2-bis [3
-Maleimido-5- (trifluoromethyl) phenyl]
-1,1,1,3,3,3-hexafluoropropane,
1,3-bis [3-maleimido-5- (trifluoromethyl) phenoxy] benzene, 1,4-bis [3-maleimido-5- (trifluoromethyl) phenoxy] benzene, 3,5-bis [3- Maleimidophenoxy] benzotrifluoride, 3,5-bis [3-maleimido-5
-(Trifluoromethyl) phenoxy] benzotrifluoride, 3,3'-difluoro-5,5'-dimaleimidebiphenyl, bis (3-fluoro-5-maleimidophenyl) ether, bis (3-fluoro-5-maleimide Phenyl) sulfide, bis (3-fluoro-5-maleimidophenyl) sulfone, 3,3′-difluoro-
5,5′-dimaleimidobenzophenone, 1,3-bis (3-fluoro-5-maleimidophenyl) -1,1,1
3,3-tetramethyldisiloxane, 2,2-bis (3
-Fluoro-5-maleimidophenyl) -1,1,1,
3,3,3-hexafluoropropane, 1,3-bis (3-fluoro-5-maleimidophenoxy) benzene, 1,4-bis (3-fluoro-5-maleimidophenoxy) benzene, 1,3-bis ( 3-fluorophenoxy) -5-fluorobenzene, 1,3-bis (3-fluoro-5-maleimidophenoxy) -5-fluorobenzene, and the like.

The method for synthesizing the bismaleimide compound represented by the general formula (DM1) is not particularly limited, but the following method is generally used. (1) First, 1 mole equivalent of an aromatic diamine compound represented by the general formula (DA31) and 2 mole equivalents of a maleimidic anhydride or a maleimidic acid derivative anhydride represented by the general formula (MA1) in an organic solvent. By reacting, a bismaleamic acid compound represented by the following general formula (DMA1) is synthesized. (2) Next, acetic anhydride 2 to 2 mole equivalents of the bismaleamic acid compound represented by the general formula (DMA1) is used as a dehydrating agent in an organic solvent.
4 molar equivalents are added, and the bismaleimide compound represented by the general formula (DM1) is synthesized by dehydration cyclization in the presence of 0.05 to 2 molar equivalents of a base and 0.0005 to 0.2 molar equivalents of a catalyst. .

[0094]

Embedded image (X ³¹ , R ³¹ , R ³² , a and b represent the general formula (DM1)
Is synonymous with the definition. Examples of the aromatic diamine compound represented by the general formula (DA31) include the following. For example, 3,
3'-diamino-5,5'-bis (trifluoromethyl) biphenyl, bis [3-amino-5- (trifluoromethyl) phenyl] ether, bis [3-amino-5
-(Trifluoromethyl) phenyl] sulfide, bis [3-amino-5- (trifluoromethyl) phenyl]
Sulfone, 3,3′-diamino-5,5′-bis (trifluoromethyl) benzophenone, 1,3-bis [3-
Amino-5- (trifluoromethyl) phenyl] -1,
1,3,3-tetramethyldisiloxane, 2,2-bis [3-amino-5- (trifluoromethyl) phenyl]
-1,1,1,3,3,3-hexafluoropropane,
1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] benzene, 1,4-bis [3-amino-5- (trifluoromethyl) phenoxy] benzene,
3,5-bis (3-aminophenoxy) benzotrifluoride, 3,5-bis [3-amino-5- (trifluoromethyl) phenoxy] benzotrifluoride, 3,
3′-diamino-5,5′-difluorobiphenyl, bis (3-amino-5-fluorophenyl) ether, bis (3-amino-5-fluorophenyl) sulfide,
Bis (3-amino-5-fluorophenyl) sulfone,
3,3′-diamino-5,5′-difluorobenzophenone, 1,3-bis (3-amino-5-fluorophenyl) -1,1,3,3-tetramethyldisiloxane,
2,2-bis (3-amino-5-fluorophenyl)-
1,1,1,3,3,3-hexafluoropropane,
1,3-bis (3-amino-5-fluorophenoxy)
Benzene, 1,4-bis (3-amino-5-fluorophenoxy) benzene, 1,3-bis (3-amino-5-
Fluorophenoxy) -5-fluorobenzene and the like.

Specific examples of the maleimidic anhydride or maleimidic acid derivative anhydride represented by the general formula (MA1) are as described above.

The following are examples of the organic solvent used in the reaction (1). For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclohexanone, chloroform, methylene chloride, dichloroethane, trichloroethylene, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N
-Dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, diethyl ether, dipropyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane,
1,4-dioxane, pyrroline, picoline, dimethyl sulfoxide, sulfolane and the like. These organic solvents may be used alone or as a mixture of two or more. The reaction temperature is 100 ° C or lower, preferably 30 ° C or lower. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. The reaction time varies depending on the type of the aromatic diamine compound and the solvent, but 0.5 to 24 hours is sufficient.

The base used in the reaction (2) includes an alkali metal acetate or a tertiary amine. For example, sodium acetate, potassium acetate, trimethylamine, triethylamine, tributylamine, etc.

As the catalyst used in the reaction (2), an oxide of an alkaline earth metal, or iron (II), iron (III), nickel (II), magnesium (I
I), manganese (III), copper (I), copper (II), cobalt (II) or cobalt (III) carbonate;
Sulfate, phosphate, acetate and the like can be mentioned. These catalysts may be used alone or in combination of two or more. Particularly preferred catalysts are nickel (II) acetate,
Cobalt (III) acetate or magnesium oxide.

As the organic solvent used in the reaction (2), the same organic solvents as those used in the reaction (1) can be used. Therefore, in this reaction, (1)
It is not necessary to isolate the bismaleamic acid compound which is the reaction product of the above. The reaction temperature is 200 ° C. or less, preferably 20 ° C.
~ 120 ° C. The reaction pressure is not particularly limited,
It can be carried out at normal pressure. The reaction time varies depending on the type of the bismaleamic acid compound and the solvent, but is 0.5 to 24.
Time is enough. After completion of the reaction, the precipitated bismaleimide compound can be obtained by filtering the precipitated crystals or putting them in water or methanol.

As the diamine compound represented by the general formula (DA11) among the component (b) of the bismaleimide-based cured resin precursor of the present invention, the following compounds may be mentioned.
For example, 1,3-phenylenediamine, 1,2-phenylenediamine, 1,4-phenylenediamine, 3-aminobenzylamine, 4-aminobenzylamine, 4,
4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis (3-aminophenyl) sulfide,
(3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4- Aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-
Aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3′-diaminobenzophenone,
3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobiphenyl,
3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 1,3-phenylene-4,4′-dianiline, 1,4-phenylene-4,4′-dianiline,
3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylethane, 3,4'-
Diaminodiphenylethane, 4,4′-diaminodiphenylethane, 3,3′-diaminodiphenylpropane,
3,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylpropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy)
Benzene, 2,2-bis (3-aminophenyl) -1,
1,1,3,3,3-hexafluoropropane, 2,2
-Bis (4-aminophenyl) -1,1,1,3,3
3-hexafluoropropane, 1,3-bis [2- (4
-Aminophenyl) -2-propyl] benzene, 1,4
-Bis [2- (4-aminophenyl) -2-propyl]
Benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane, bis [3-amino-5- (trifluoromethyl) phenyl] ether, bis [4-amino-2
-(Trifluoromethyl) phenyl] ether, bis [3-amino-5- (trifluoromethyl) phenyl]
Sulfone, bis [4-amino-2- (trifluoromethyl) phenyl] sulfone, 4,4′-diamino-2,
2'-bis (trifluoromethyl) biphenyl, 3,
3′-diamino-5,5′-bis (trifluoromethyl) biphenyl, 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1,3,3
3-hexafluoropropane, 1,8-diaminonaphthalene, 2,7-diaminonaphthalene, 2,6-diaminonaphthalene, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,6-diamino-4- ( Trifluoromethyl) pyridine, 2,5-diaminopyrazine, 2,4
-Diamino-s-triazine, methanediamine, 1,2
-Ethanediamine, 1,3-propanediamine, 1,4
-Butanediamine, 1,5-pentanediamine, 1,6
-Hexanediamine, 1,7-heptanediamine, 1,
8-octanediamine, 1,9-nonanediamine, 1,
10-decanediamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-diaminocyclohexane,
1,4-diaminocyclohexane, bis (3-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1,2-bis (3-aminocyclohexyl) ethane, 1,2-bis (4-aminocyclohexyl) ethane , 2,2-bis (3-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-aminocyclohexyl) ether, bis (4-aminocyclohexyl) ether, bis (3-amino Cyclohexyl) sulfone, bis (4-
Aminocyclohexyl) sulfone, 2,2-bis (3-
Aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 3-xylylenediamine, 1,4-xylylenediamine and the like. These diamine compounds may be used alone or as a mixture of two or more.

From the viewpoints of heat resistance and environmental stability of the bismaleimide-based cured resin, it is preferable to use a diamine compound having an aromatic ring as shown below among the diamine compounds represented by the general formula (DA11). . For example, 1,
2-phenylenediamine, 1,4-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,3 ′
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,
3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone,
3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 1,3-phenylene-4,4′-dianiline, 1,4-phenylene-4,4′-dianiline, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,
4'-diaminodiphenylmethane, 3,3'-diaminodiphenylethane, 3,4'-diaminodiphenylethane, 4,4'-diaminodiphenylethane, 3,3'-
Diaminodiphenylpropane, 3,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylpropane, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,4-
Bis (4-aminophenoxy) benzene, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1 , 1,1,3,3,3-hexafluoropropane, 1,3-bis [2- (4-aminophenyl) -2
-Propyl] benzene, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1
1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, bis [3-amino-5- (trifluoromethyl) phenyl]
Ether, bis [4-amino-2- (trifluoromethyl) phenyl] ether, bis [3-amino-5- (trifluoromethyl) phenyl] sulfone, bis [4-amino-2- (trifluoromethyl) phenyl Sulfone, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-5,5 '
-Bis (trifluoromethyl) biphenyl, 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,8-diamino Naphthalene, 2,7-diaminonaphthalene, 2,6-diaminonaphthalene, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,6-diamino-4- (trifluoromethyl) pyridine, 2,5
-Diaminopyrazine, 2,4-diamino-s-triazine and the like.

Further, together with these diamine compounds,
The bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) described above may be used in combination. The bis (aminoalkyl) peralkylpolysiloxane compound has an effect of improving the adhesion and adhesion of the bismaleimide-based cured resin to, for example, a glass substrate or a silicon substrate. These compounds are preferably used in an amount of 0.02 to 0.2 molar equivalent of all the diamine components. This is because although the bismaleimide-based cured resin obtained by blending such a compound improves the adhesion and adhesion to the substrate, excessive blending may cause a decrease in the heat resistance of the bismaleimide-based cured resin. Because there is.

Among the components (b) of the bismaleimide-based cured resin precursor of the present invention, the following are examples of the dihydric phenol compound represented by the general formula (DP1). For example, resorcinol, pyrocatechol, hydroquinone, 4,4'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 3,
4'-dihydroxydiphenyl ether, bis (3-hydroxyphenyl) sulfide, (3-hydroxyphenyl) (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide, bis (3-hydroxyphenyl) sulfoxide, (3- Hydroxyphenyl) (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfoxide, bis (3
-Hydroxyphenyl) sulfone, (3-hydroxyphenyl) (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 3,3'-dihydroxybenzophenone, 3,4'-dihydroxybenzophenone, 4,4'- Dihydroxybenzophenone,
3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl, 1,3-phenylene-4,4′-diphenol,
1,4-phenylene-4,4′-diphenol, 3,
3'-dihydroxydiphenylmethane, 3,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylethane, 3,4'-dihydroxydiphenylethane, 4,
4'-dihydroxydiphenylethane, 3,3'-dihydroxydiphenylpropane, 3,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylpropane, 1,3-bis (3-hydroxyphenoxy) benzene, 1,4 -Bis (3-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) benzene, 1,4-bis (4-hydroxyphenoxy) benzene, 2,2-bis (3-hydroxyphenyl) -1, 1,1,3,3,3-hexafluoropropane, 2,2-bis (4-hydroxyphenyl) -1,
1,1,3,3,3-hexafluoropropane, 1,3
-Bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,4-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 2,2-bis [4
-(4-hydroxyphenoxy) phenyl] -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-hydroxyphenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane, bis [3-hydroxy-5- (trifluoromethyl) phenyl] ether, bis [4-hydroxy-2- (trifluoromethyl) phenyl] ether, Bis [3-hydroxy-5- (trifluoromethyl) phenyl] sulfone, bis [4-hydroxy-2- (trifluoromethyl) phenyl] sulfone, 4,4′-dihydroxy-
2,2′-bis (trifluoromethyl) biphenyl,
3,3′-dihydroxy-5,5′-bis (trifluoromethyl) biphenyl, 2,2-bis [3-hydroxy-5- (trifluoromethyl) phenyl] -1,1,1
1,3,3,3-hexafluoropropane, 1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,5-dihydroxypyridine, 2,6-dihydroxypyridine, 2,
6-dihydroxy-4- (trifluoromethyl) pyridine, 2,5-dihydroxypyrazine, 2,4-dihydroxy-s-triazine, 1,3-bis [3- (4-hydroxyphenyl) propyl] -1,1 , 3,3-Tetramethyldisiloxane, 1,3-bis [4- (4-hydroxyphenyl) butyl] -1,1,3,3-tetramethyldisiloxane, 1,3-bis [3- (4 -Hydroxyphenyl) propyl] -1,1,3,3-tetraphenyl, 1,5-bis [3- (4-hydroxyphenyl) propyl] -1,1,3,3,5,5-hexamethyltri Siloxane, 1,7-bis [3- (4-hydroxyphenyl) propyl] -1,1,3,3,5,5,7,7-
Octamethyltetrasiloxane, 1,9-bis [3-
(4-hydroxyphenyl) propyl] -1,1,3,
3,5,5,7,7,9,9-decamethylpentasiloxane and the like. These dihydric phenol compounds may be used alone or in combination of two or more.

In the bismaleimide-based cured resin precursor of the present invention, at least one compound selected from the group consisting of a diamine compound and a dihydric phenol compound as the component (b) (curing agent component) is (a) It is used in an amount of 0.01 to 2 molar equivalents per 1 molar equivalent of the bismaleimide compound as a component. Furthermore, in the case of a diamine compound, 0.2 to 1 mole equivalent of a bismaleimide compound is used.
0.8 molar equivalent, 0.1 in case of dihydric phenol compound.
It is preferable to mix 7 to 1.3 molar equivalents. The reason is that if the amount of the curing agent component (b) is too small, the degree of progress of the curing reaction is insufficient, and the heat resistance of the cured resin formed using the precursor may be reduced. . In this case, since the bismaleimide compound (a) is added in an excessive amount, the maleimide molecules react with each other during the curing reaction, and the flexibility of the obtained cured resin is impaired. Conversely, if the amount of the curing agent component (b) is too large, an excessive amount of the curing agent component may remain in the cured resin, and the heat resistance and moisture resistance of the cured resin may be insufficient. In particular, when about 0.5 molar equivalent of a diamine compound or about 1 molar equivalent of a dihydric phenol compound is blended as a curing agent component with respect to 1 molar equivalent of a bismaleimide compound, the curing reaction of the composition proceeds most efficiently. .

The bismaleimide-based cured resin precursor of the present invention may optionally contain a curing catalyst for the purpose of accelerating the curing reaction. Examples of the curing catalyst include a boron tetrafluoride complex, an aluminum complex / phenol catalyst, and an aluminum complex / silicon catalyst. By appropriately selecting and using these curing catalysts, the curing reaction can be adjusted to produce a high molecular weight cured resin having various two-dimensional or three-dimensional structures. Also,
In the bismaleimide-based cured resin precursor of the present invention,
In addition to the above components, various additives such as polyamic acid, epoxy resin, isocyanate compound, triazine resin, phenol resin, and acrylic compound may be blended.

The bismaleimide-based cured resin precursor of the present invention is prepared in the form of a varnish by dissolving the above-mentioned components in an organic solvent. As the organic solvent used here,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2
-Methoxyethyl) ether, bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethylsulfoxide, And sulfolane. These organic solvents may be used alone or as a mixture of two or more.

Further, the varnish obtained is usually used in an A-stage before being used as an interlayer insulating film of an electronic component.
Is performed. That is, at 50 to 150 ° C. for 5 minutes to 5
Heating for some time causes the addition reaction of the diamine or dihydric phenol compound to the bismaleimide compound to proceed somewhat to increase the viscosity of the varnish so that it is convenient to apply the varnish.

A method for forming an insulating film of, for example, an electronic component using the bismaleimide-based cured resin precursor of the present invention will be described. First, a varnish of an A-staged bismaleimide-based cured resin precursor is applied on an arbitrary substrate to form a film. The film is heated at 50-150 ° C. for 5-10 minutes to evaporate the solvent. Further, this film is heated at a predetermined temperature in a vacuum oven or an oven purged with nitrogen to cure the bismaleimide-based cured resin precursor. The heating temperature varies depending on the structure of the bismaleimide compound used, but is usually set in the range of 100 to 450 ° C. Thus, an insulating film made of a bismaleimide-based cured resin is formed.

As a result, the obtained bismaleimide-based cured resin is not only excellent in heat resistance but also compared with a conventional bismaleimide-based cured resin even when left in the air for a long period of time. It produces very little gas, such as xylene, and has excellent environmental stability, and has a low dielectric constant and low moisture absorption.

Next, the electronic component of the present invention will be described. The electronic component of the present invention is a bismaleimide-based cured resin obtained by curing a polyimide resin or a bismaleimide-based cured resin precursor obtained by curing the above-described polyimide precursor,
It is provided as an insulating member such as an insulating film or an insulating substrate. Such an electronic component can realize high-speed operation and power saving because the polyimide resin or the bismaleimide-based cured resin constituting the insulating member has a low relative dielectric constant, and furthermore, the insulating member has low moisture absorption and thermal stability. High reliability due to excellent environmental stability.

More specifically, the polyimide resin or bismaleimide-based cured resin according to the present invention can be used as an insulating film such as an interlayer insulating film, a moisture-resistant protective film, an α-ray blocking film, a carrier film, a flat cable, a flexible film, etc. of a semiconductor device. It is useful as an insulating member for electronic components such as a printed board, a film insulating coil, an interlayer insulating film of a thin-film magnetic head or a magnetic bubble memory element, and a glass cloth laminate. Further, the polyimide resin according to the present invention is also very suitable for a liquid crystal alignment film of a liquid crystal display device. Hereinafter, examples of these electronic components will be described with reference to the drawings. In the following description, an example in which the insulating member is made of a polyimide resin will be described.
In most cases, a bismaleimide-based cured resin may be used in place of the polyimide resin.

FIG. 1 is a sectional view showing an example in which a polyimide resin produced from the precursor according to the present invention is applied to an interlayer insulating film of a semiconductor device. In FIG. 1, on a surface of a silicon substrate 11, a field oxide film 12, a diffusion layer 13, a thermal oxide film 14, a CVD oxide film 15, and the like are formed.
A contact hole is formed in the thermal oxide film 14 on the diffusion layer 13, and the first layer Al electrode 1 connected to the diffusion layer 13 is formed.
6 are formed. Further, an interlayer insulating film 17 made of a polyimide resin is formed on the entire surface. A contact hole is formed in the interlayer insulating film 17 to form a second layer Al electrode 18 connected to the first layer Al electrode 16. Further, a passivation film 19 made of a polyimide resin is formed on the entire surface.

FIG. 2 is a cross-sectional view of a package obtained by resin molding a semiconductor chip having a surface formed with a passivation film made of a polyimide resin as shown in FIG. In FIG. 2, a semiconductor chip 20 having a surface on which a passivation film 19 made of a polyimide resin is formed is mounted on a bed 21. The bonding pads exposed from the passivation film 19 on the surface of the semiconductor chip 20 and the leads 22 are bonded by wires 23. Further, these members are molded with the sealing resin 24, and a part of the lead 23 protrudes from the sealing resin 24.

FIG. 3 is a sectional view showing an example in which a polyimide resin produced from the precursor according to the present invention is applied to an interlayer insulating film of a thin-film magnetic head. 3, a lower alumina 32, a lower magnetic body 33, and a gap alumina 34 are sequentially formed on the surface of a substrate 31. A first conductor coil 36 and a second conductor coil 37 are formed on the gap alumina 34 so as to be embedded in an interlayer insulating film 35 made of a polyimide resin. Further, an upper magnetic body 38 is formed on the interlayer insulating film 35, and the lower magnetic body 33 and the upper magnetic body 38 face each other with the gap alumina 34 interposed therebetween at the tip of the magnetic head.

FIG. 4 is a sectional view showing an example in which a polyimide resin produced from the precursor according to the present invention is applied to an interlayer insulating film of a high-density wiring board. In FIG. 4, the silicon substrate 4
On the substrate 1, a thermal oxide film 42 and a first layer copper wiring 43 are sequentially formed. An interlayer insulating film 44 made of a polyimide resin is formed over the entire surface. This interlayer insulating film 4
4, a contact hole is opened, and the first layer copper electrode 43 is formed.
And a second-layer copper electrode 45 connected thereto. Further, a passivation film 46 made of a polyimide resin is formed on the entire surface. This passivation film 46
A barrier metal 47 and a Pb / Sm bump 48 are formed so as to be connected to the copper wiring 45 of the second layer.

FIG. 5 is a sectional view showing an example in which a polyimide resin produced from the precursor according to the present invention is applied to an interlayer insulating film of a magnetic bubble memory element. In FIG. 5, a conductor 52 is formed on a garnet substrate 51, and an interlayer insulating film 53 made of a polyimide resin is formed on the entire surface. Further, a permalloy 54 is formed on the interlayer insulating film 53.

FIG. 6 is a sectional view showing an example in which a polyimide resin produced from the precursor according to the present invention is applied to a heat-resistant transparent resin layer of a solar cell. In FIG. 6, the glass substrate 6
A heat-resistant transparent resin layer 62 made of a polyimide resin is formed on the entire surface of the substrate 1. On this heat-resistant transparent resin layer 62, a transparent electrode 63, amorphous Si 64 and a metal electrode 65 are formed in a predetermined pattern.

As shown in FIG. 1 to FIG. 6, if an insulating member is formed using the polyimide precursor of the present invention in any electronic component, the level difference of the wiring is greatly reduced to obtain a flat wiring structure. And the reliability of electronic components can be improved. In addition, as described above, the insulating member obtained by curing the polyimide precursor of the present invention can realize high-speed operation and power saving because of its low dielectric constant, and is excellent in heat absorption and environmental stability with low moisture absorption. ing.

FIG. 7 is a sectional view of a liquid crystal display element having a liquid crystal alignment film made of a polyimide resin produced from the precursor according to the present invention. In FIG. 7, a pixel electrode 72 and a thin film transistor (not shown) are formed on a glass substrate 71, and a liquid crystal alignment film 73 made of polyimide resin is coated on the entire surface. On the other hand, the glass substrate 74
A common electrode 75 is formed thereon, and the entire surface is covered with a liquid crystal alignment film 76 made of polyimide resin.
These glass substrates 71 and 74 serve as liquid crystal alignment films 73 and 76.
Are placed in parallel with each other with a predetermined gap therebetween, and a liquid crystal 77 is sealed between the two. Note that a substrate provided with a color filter may be used for colorizing a liquid crystal display element.

As the substrate, in addition to glass, a transparent film such as polycarbonate, polyetheretherketone, polyethersulfone, and polyethylene terephthalate may be used. As the electrodes, ITO (Indi
um Tin Oxide) and a transparent oxide such as indium oxide are used. The thickness of the liquid crystal alignment film is 5 to 10
00 nm, preferably in the range of 20 to 200 nm. The polyimide resin constituting the liquid crystal alignment film is obtained by applying a varnish of polyamic acid, which is a precursor thereof, to a substrate on which electrodes are formed, and preliminarily drying at 90 to 120 ° C.
It is formed by performing a heat treatment at ~ 350 ° C. Next, this polyimide resin is rubbed to form a liquid crystal alignment film. The liquid crystal alignment films on the two substrates are rubbed according to the purpose so that the rubbing directions of the cells are the same, 90 ° twisted, or 200 to 290 ° twisted when the cells are assembled. You. In order to stabilize the orientation of the liquid crystal, the liquid crystal display element may be annealed after sealing the liquid crystal.

The liquid crystal alignment film made of the polyimide resin produced from the polyimide precursor of the present invention can give a large pretilt angle to the liquid crystal in addition to the effects described above.
In addition, there is an effect that the voltage holding ratio is high.

[0122]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Examples 1-1 to 1-45 and Comparative Examples 1 to
5 (1) Synthesis of Polyimide Precursor (Polyamic Acid) Using the raw materials shown in Tables 1 to 7 at a predetermined blending ratio (expressed in molar equivalent), polyamic acid was synthesized as follows. First, 50 mL of N-methyl-2-pyrrolidone was placed in a separable flask cooled to −5 to 0 ° C. with a refrigerant under a nitrogen gas atmosphere, and an acid anhydride component represented by the general formula (DA)
A predetermined amount of the tetracarboxylic dianhydride represented by H1) was added and dissolved with stirring. In this solution, a predetermined amount of an aromatic diamine compound represented by the general formula (DA1) and a bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) are added as N-methyl-2 as diamine components. -A solution dissolved in 50 mL of pyrrolidone was slowly dropped from a dropping funnel equipped with a pressure balance tube. After stirring for 2 hours, a predetermined amount of maleic anhydride was added to N
-A solution dissolved in 50 mL of methyl-2-pyrrolidone,
The solution was slowly dropped from a dropping funnel equipped with a pressure balance tube. After further stirring for 4 hours, a varnish containing the desired polyamic acid was obtained.

Abbreviations used in Tables 1 to 7 will be described. (Tetracarboxylic dianhydride) 6FDPA: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride PMA: pyromellitic dianhydride BPTA: 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride ODPA: oxy-4,4'-diphthalic dianhydride 6FXTA: 9,9-bis (trifluoromethyl) xanthene-2,3,6 , 7-tetracarboxylic dianhydride (maleic anhydride) MLA: maleic anhydride (diamine compound) mSNDA: sulfonyl-3,3'-dianiline mPODA: 1,3-bis (3-aminophenoxy) benzene mODA : Oxy-3,3'-dianiline 6FmODA: Oxy-5,5'-bis [3- (trifluoromethyl) aniline] 3FmPODA: 3,5-bis (3 Aminophenoxy) benzotrifluoride 6FmPODA: 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] benzene 9FmPODA: 3,5-bis [3-amino-5- (trifluoromethyl) phenoxy) benzo Trifluoride 3FmPDA: 5- (trifluoromethyl) -1,3-
Phenylenediamine 6FmSNDA: 1,1′-bis [3-amino-5
(Trifluoromethyl) phenyl] sulfone 6FmBPDA: 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl 6FpBPDA: 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl m6FDA: 1,1,1,3,3,3- hexafluoro-2,2-propylidene - 3,3 '- dianiline MPDA: 1,3-phenylenediamine mBPDA: 3,3'- diaminobiphenyl pBPDA: 4, 4'-diaminobiphenyl pODA: oxy-4,4'-dianiline p6FDA: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-dianiline TSL9306: 1,3- Bis (3-aminopropyl)
Comparative Example 1 is a commercially available polyamic acid (manufactured by Sumitomo Bakelite Co., Ltd., CRC-6061), and includes PMA (pyromellitic dianhydride) and CBDPA (3,5). 3 ', 4,4'-
Benzophenone tetracarboxylic dianhydride) and pO
DA (oxy-4,4'-dianiline) as a main raw material. Comparative Examples 2 to 5 use an aromatic diamine compound not included in the general formula (DA1).

The 0.1% of each of the synthesized polyamic acids.
The intrinsic viscosity of the 5 wt% N-methyl-2-pyrrolidone solution was measured at 30 ° C. Tables 1 to 7 show these results. From Tables 1 to 7, it was confirmed that a polyamic acid having a low intrinsic viscosity of 0.5 or less can be synthesized by using maleic anhydride.

(2) Measurement of physical properties of polyimide film Tables 1 to 7 show the results of measurement of the following physical properties of the polyimide film.

(A) Decomposition start temperature A varnish of polyamic acid was added to a 1 mm × 130 mm × 150 mm
75 mm on a glass plate with a bar coater.
After coating to a thickness of μm, it was prebaked at 110 ° C. for 1 hour. The obtained film was peeled off from the glass plate and fixed to a brass frame having an inner size of 100 mm × 100 mm.
This is heated from room temperature to 150 ° C., 250 ° C., and 350 ° C. for 1 hour in a dryer in which nitrogen gas is introduced, and finally heated at 400 ° C. for 30 minutes. Then, a polyimide film was formed. In addition, the heating time between each temperature was set to 1 hour. The obtained polyimide film was subjected to thermogravimetric analysis / differential thermal analysis (TG / DTA) in a nitrogen stream, the temperature at which a weight loss of 0.5 wt% occurred was measured, and the decomposition start temperature of the polyimide film was determined. As a result, it was confirmed that the polyimide films of Examples 1-1 to 45 had heat resistance equivalent to that of the comparative example.

(B) Adhesion to Silicon Substrate A varnish of polyamic acid was spin-coated on a 4-inch diameter silicon substrate so that the film thickness after curing was 5 to 10 μm. This was heated from room temperature in a drier into which nitrogen gas was introduced, and then heated to 150 ° C., 250 ° C., and 350 ° C.
, And finally heated at 400 ° C. for 30 minutes to form a polyimide film. The heating time between each temperature was 30 minutes. The silicon substrate on which the polyimide film was formed was allowed to stand in a pressure cooker under an atmosphere of water vapor at 120 ° C. and 2 atm for 24 hours. Then, put a cellophane tape on the surface of the polyimide film, and examine the percentage of the film that peels off from the substrate when it is peeled off under certain conditions.
A value indicating the adhesion was used. As a result, Examples 1-1 to 45
It was confirmed that the polyimide film of Example 1 had better adhesion to the silicon substrate than those of Comparative Examples 1 to 5.

(C) Filling the Trench A varnish of polyamic acid was coated on a 4-inch silicon substrate having a trench having a width of 0.3 μm and a depth of 1.0 μm formed on the silicon substrate having a cured thickness of 5 μm. It was spin-coated so as to have a thickness of 10 to 10 μm, and cured under the same conditions as in (b) to form a polyimide film. Thereafter, the cross section of the trench was observed with a scanning electron microscope (SEM), and the filling property of the trench was examined. As a result, Examples 1-1 to 45
The trench was completely filled with polyimide without gaps. On the other hand, in Comparative Examples 1 to 5, it was confirmed that the trench was not completely filled with polyimide, and a large gap remained.

(D) Dielectric constant Polyamic acid varnish was prepared as follows: 1 mm × 100 mm × 100
film thickness after curing on an aluminum plate
Spin coating was performed 2 to 4 times so that the thickness became 0 to 60 μm.
This is heated from room temperature to 150 ° C., 250 ° C., and 350 ° C. for 1 hour in a dryer in which nitrogen gas is introduced, and finally heated at 400 ° C. for 30 minutes. Then, a polyimide film was formed. The heating time between each temperature was 30 minutes. The dielectric constant at 10 kHz of the obtained polyimide film was measured. As a result, it was confirmed that the polyimide films of Examples 1-1 to 45 had a dielectric constant of 3.0 or less, which was much lower than that of Comparative Example 1, and were excellent in dielectric properties.

(E) A polyimide film was formed on a silicon substrate in the same manner as in (b) of the amount of humidified decomposition gas generated. This was left at 20 ° C. under saturated steam for one week. Thereafter, the polyimide film was introduced into pyrofoil, heated at 358 ° C. for 3 seconds with a Curie pyrolyzer, and the generated gas components were analyzed by GC-MASS. The amount of toluene generated as a humidified decomposition gas was evaluated by a value obtained by converting the integrated value of the toluene signal in the ion chromatograph into 1 mg of the sample. As a result, it was confirmed that the polyimide films of Examples 1-1 to 45 generated very little toluene gas and had excellent environmental stability.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

[Table 6]

[0138]

[Table 7] Examples 2-1 to 2-11 (1) Synthesis of fluorinated aromatic diamine compound [Synthesis Example 2A] 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1 , 3,3
Synthesis of 3-hexafluoropropane (6Fm6FDA) (a) Synthesis of 2,2-bis [3- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane (compound 2Aa) In a 500 mL autoclave, 44.5 g (80.0 mmol) of 2,2-bis (3-iodophenyl) -1,1,1,3,3,3-hexafluoropropane and 40.0 g of trifluoromethyl iodide ( 204 mmol), 150 mL of dry N, N-dimethylformamide, and copper powder as a catalyst were added, and the mixture was heated with stirring at 150 ° C. for 24 hours. After cooling, the copper powder was filtered off from the reaction solution, and the filtrate was fractionally distilled under reduced pressure to obtain the target compound 2Aa.

Molecular formula: C ₁₇ H ₈ F ₁₂ Molecular weight: 440.227 Yield: 28.5 g (64.7 mmol) Yield: 81% (B) Synthesis of 2,2-bis [3-nitro-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane (compound 2Ab) obtained in (a). Compound 2Aa 26.5 g (60.2 g)
mmol) was dissolved in 60 mL of 95% concentrated sulfuric acid, and 20 mL of 90% fuming nitric acid was slowly added with a dropping funnel.
For 5 hours. After completion of the reaction, the reaction solution was poured into ice water, and the product was extracted with 300 mL of methylene chloride.
The extract was separated by a separating funnel and washed twice with 300 mL of a 5% aqueous sodium hydroxide solution and once with 300 mL of water. After dehydration with anhydrous sodium sulfate, the extract was concentrated under reduced pressure, and the residue was recrystallized from a hot ethanol solution to obtain the target compound 2Ab.

Molecular formula: C ₁₇ H ₆ F ₁₂ N ₂ O ₄ Molecular weight:
530.221 Yield: 28.0 g (52.8 mmol) Yield: 88% Elemental analysis: Carbon Hydrogen Fluorine Nitrogen Calculated 38.5% 1.1% 43.0% 5.3% Analyzed 38.8% 1 0.2% 42.8% 5.3% (c) 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane ( 6Fm6FDA) 26.5 g (50.0 g) of compound 2Ab obtained in synthesis (b)
mmol), 50 mL of isopropyl alcohol and 5
1.5 g of a% -Pd / C reducing agent (50% water-containing product) was placed in a reducing device, and reacted at 80 ° C. for 4 hours under a hydrogen atmosphere.
After completion of the reaction, insolubles were removed by suction filtration, and the reaction solution was concentrated under reduced pressure. The precipitated crude crystals were recrystallized from a hot ethanol solution to obtain the desired 6Fm6FDA.

Molecular formula: C ₁₇ H ₁₀ F ₁₂ N ₂ Molecular weight: 470.257 Yield: 21.5 g (45.7 mmol) Yield: 91% Elemental analysis: Carbon hydrogen Fluorine Nitrogen Calculated 43.4% 2.1% 48.5% 6.0% Analytical value 43.6% 2.2% 48.3% 5.9% Infrared absorption spectrum (KBr method): 3480 cm ^-1 NH antisymmetric stretching vibration (primary amine) ) 3390 cm ^-1 N-H symmetric stretching vibration (primary amine) 1600 cm ^-1 N-H plane bending (scissors) vibration (aromatic primary amine) 1320,1250,1220,1190,1140C
m ^-1 CF stretching vibration and bending vibration (CF ₃ group) [Synthesis Example 2B] 3,3'-diamino-5,5'-bis (trifluoromethyl) biphenyl (6FmBPDA)
Synthesis of 3-iodo-5-nitrobenzotrifluoride 15.9
g (50.2 mmol) was dissolved in 50 mL of N, N'-dimethylformamide, and 20 g of copper powder was added thereto.
The mixture was refluxed for 2 hours. After cooling, insolubles were removed by suction filtration, and the filtrate was concentrated under reduced pressure and dried under vacuum. The obtained residue was dissolved in 50 mL of isopropyl alcohol, and 1.5 g of a 5% -Pd / C reducing agent (50% water-containing product) was added thereto, followed by a reaction at 80 ° C. for 4 hours under a hydrogen atmosphere. After completion of the reaction, insolubles were removed by suction filtration, and the reaction solution was concentrated under reduced pressure to precipitate crude crystals. Recrystallization from the hot ethanol solution gave the target compound (6FmBPDA).

Molecular formula: C ₁₄ H ₁₀ F ₆ N ₂ Molecular weight: 320.236 Yield: 10.9 g (34.0 mmol) Yield: 68% Elemental analysis: Calculated hydrogen hydrogen fluorine nitrogen 52.5% 3.1% 35.6% 8.7% Analytical value 52.6% 3.0% 35.6% 8.8% Infrared absorption spectrum (KBr method): 3500 cm ^-1 NH inverse symmetric stretching vibration (primary amine ) 3400 cm ^-1 N-H symmetric stretching vibration (primary amine) 1600 cm ^-1 N-H plane bending (scissors) vibration (aromatic primary amine) 1320 cm ^-1 CF ₃ symmetric deformation vibration 1200 cm ^-1 CN stretching vibration (primary amine) 1140 cm ^-1 CF ₃ anti-symmetric bending vibration [Synthesis example 2C]
Synthesis of 3,3′-diamino-5,5′-bisfluorobiphenyl (2FmBPDA) 13.4 g of 3-fluoro-5-iodonitrobenzene
(50.2 mmol) and the target compound (2FmBPDA) was obtained in the same manner as in Synthesis Example 2B.

Molecular formula: C ₁₂ H ₁₀ F ₂ N ₂ Molecular weight: 220.222 Yield: 7.1 g (32.2 mmol) Yield: 64% Elemental analysis: Carbon hydrogen Fluorine Nitrogen Calculated 65.4% 4.6% 17.3% 12.7% Analytical value 65.7% 4.6% 17.1% 12.6% Infrared absorption spectrum (KBr method) 3520 cm ^-1 NH inverse symmetric stretching vibration (primary amine) 3420cm ^-1 N-H symmetric stretching vibration (primary amine) 1605 cm ^-1 N-H plane bending (scissors) vibration (aromatic primary amine) 1240 cm ^-1 C-F stretching vibration (fluorobenzene) 1205Cm ^-1 CN stretching vibration (primary amine) (2) Synthesis of polyimide precursor (polyamic acid) The raw materials shown in Tables 8 and 9 were used at a predetermined blending ratio (expressed in molar equivalents). To synthesize polyamic acid did. First, 50 mL of N-methyl-2-pyrrolidone was placed in a separable flask cooled to −5 to 0 ° C. with a refrigerant under a nitrogen gas atmosphere, and an acid anhydride component represented by the general formula (DA)
A predetermined amount of tetracarboxylic dianhydride represented by H2) was added and dissolved with stirring. In this solution, a general formula (DA2) synthesized as described above as a diamine component
A predetermined amount of the fluorinated aromatic diamine compound represented by the formula and the bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) is added to N-methyl-2-
The solution dissolved in pyrrolidone was slowly dropped from a dropping funnel equipped with a pressure balance tube. After stirring for 6 hours, a varnish containing the desired polyamic acid was obtained.

The abbreviations used in Tables 8 and 9 will be described. (Tetracarboxylic dianhydride) PMA: pyromellitic dianhydride BPTA: 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride ODPA: oxy-4,4'-diphthalic dianhydride 6FDPA: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-diphthalic dianhydride 6FXTA: 9,9-bis (trifluoromethyl) xanthene-2,3,6 , 7-Tetracarboxylic dianhydride SNDPA: sulfonyl-4,4'-diphthalic dianhydride (diamine compound) 6Fm6FDA: 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1 , 1,1,3,3
3-hexafluoropropane 6FmBPDA: 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl 2FmBPDA: 3,3′-diamino-5,5′-fluorobiphenyl TSL9306: 1,3-bis ( 3-aminopropyl)
-1,1,3,3-tetramethyldisiloxane (3) Measurement of various physical properties In the same manner as in Example 1, the intrinsic viscosity of the polyamic acid solution was measured.
Tables 8 and 9 show the results of measuring the decomposition start temperature, dielectric constant, and moisture absorption of the polyimide film. As a result, it was confirmed that the polyimide films of Examples 2-1 to 2-11 had the same heat resistance as that of Comparative Example 1, and had a very low dielectric constant.

[0145]

[Table 8]

[0146]

[Table 9] Examples 3-1 to 3-8 (1) Synthesis of Polyimide Precursor (Polyamide Acid) Polyamide acid was synthesized as follows by using the raw materials shown in Table 10 at a predetermined mixing ratio (expressed in molar equivalent). . First, N-methyl-2-pyrrolidone 5 was placed in a separable flask cooled to −5 to 0 ° C. with a refrigerant under a nitrogen gas atmosphere.
Add 0 mL, and as an acid anhydride component, formula (DAH1)
A predetermined amount of tetracarboxylic dianhydride represented by the formula was added and dissolved with stirring. In this solution, a predetermined amount of a fluorinated aromatic diamine compound represented by the general formula (DA5) and a bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) are added as N-methyl-diamine components. The solution dissolved in 2-pyrrolidone was slowly dropped from a dropping funnel equipped with a pressure balance tube. After stirring for 6 hours, a varnish containing the desired polyamic acid was obtained.

Abbreviations used in Table 10 will be described. (Tetracarboxylic dianhydride) PMA: pyromellitic dianhydride BPTA: 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride ODPA: oxy-4,4'-diphthalic dianhydride SNDPA: Sulfonyl-4,4'-diphthalic dianhydride CBDPA: carbonyl-4,4'-diphthalic dianhydride 6FDPA: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4 , 4'-Diphthalic dianhydride SXDPA: 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride PODPA: 1,3-bis (3 , 4-Dicarboxyphenoxy) benzene dianhydride (diamine compound) 6FmSNDA: 1,1'-bis [3-amino-5
(Trifluoromethyl) phenyl] sulfone (2) Measurement of Various Physical Properties In the same manner as in Example 1, the intrinsic viscosity of the polyamic acid solution,
Table 10 shows the results of measuring the decomposition start temperature, dielectric constant, and moisture absorption of the polyimide film. as a result,
It was confirmed that the polyimide films of Examples 3-1 to 3-8 had sufficient heat resistance and had a very low dielectric constant.

[0148]

[Table 10] Examples 4-1 to 4-15 (1) Synthesis of Polyimide Precursor (Polyamic Acid) The raw materials shown in Tables 11 and 12 were used at a predetermined mixing ratio (expressed in molar equivalent), and the polyamic acid was prepared as follows. Was synthesized. First, in a nitrogen gas atmosphere, −5 to 0
50 mL of N-methyl-2-pyrrolidone was placed in a separable flask cooled to ° C., a predetermined amount of a tetracarboxylic dianhydride represented by the general formula (DAH1) was added as an acid anhydride component, and the mixture was dissolved with stirring. . In this solution, a predetermined amount of an aromatic diamine compound represented by the general formula (DA1) and a bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) are added as N-methyl-2 as diamine components. -A solution dissolved in 50 mL of pyrrolidone was slowly dropped from a dropping funnel equipped with a pressure balance tube. After stirring for 6 hours, a varnish containing the desired polyamic acid was obtained.

The abbreviations used in Tables 11 and 12 will be described. (Tetracarboxylic dianhydride) 6FDPA: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-diphthalic dianhydride PMA: pyromellitic dianhydride ODPA: Oxy-4,4'-diphthalic dianhydride SNDPA: sulfonyl-4,4'-diphthalic dianhydride (maleic anhydride) MLA: maleic anhydride (diamine compound) mSNDA: sulfonyl-3,3 ' -Dianiline mPODA: 1,3-bis (3-aminophenoxy) benzene mODA: oxy-3,3'-dianiline 6FmODA: oxy-5,5'-bis [3- (trifluoromethyl) aniline] 3FmPODA: 3 5-bis (3-aminophenoxy) benzotrifluoride 6FmPODA: 1,3-bis [3-amino-5- (trifluoromethyl) phenyl [Enoxy] benzene 9FmPODA: 3,5-bis [3-amino-5- (trifluoromethyl) phenoxy) benzotrifluoride 3FmPDA: 5- (trifluoromethyl) -1,3-
Phenylenediamine 6FmSNDA: 1,1′-bis [3-amino-5
(Trifluoromethyl) phenyl] sulfone 2FmBPDA: 3,3′-diamino-5,5′-difluorobiphenyl 6FmBPDA: 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl 6FpBPDA: 4,4 '-Diamino-2,2'-bis (trifluoromethyl) biphenyl pODA: oxy-4,4'-dianiline TSL9306: 1,3-bis (3-aminopropyl)
-1,1,3,3-tetramethyldisiloxane 0.5 wt% N- of each synthesized polyamic acid
The intrinsic viscosity of the methyl-2-pyrrolidone solution was measured at 30C. Table 4 shows the results. From Table 4, it was confirmed that when maleic anhydride was used, a polyamic acid having a low intrinsic viscosity of 0.5 or less could be synthesized.

[0150]

[Table 11]

[0151]

[Table 12] (2) Preparation of photosensitive polyimide precursor Example 4-1 16% by weight of polyamic acid (4-1) N-methyl-2-
To 20 g of the pyrrolidone solution was added 1.57 g (0.07 g) of 2-N, N-dimethylaminoethyl methacrylate as a photosensitizer.
1 mol) and 2,6-di (4-azidobenzal) -4
-Hydroxycyclohexanone 0.37 g (0.001
Mol) was dissolved to form a homogeneous solution, which was filtered through a filter having a pore size of 0.5 μm to prepare a photosensitive polyimide precursor.

Examples 4-2 to 4-15 As shown in Tables 13 and 14, 16
Weight% N-methyl-2-pyrrolidone solution and photosensitizer,
In addition, a photosensitive polyimide precursor was prepared in the same manner as in Example 4-1 using a sensitizer at a predetermined compounding ratio (indicated by weight) as necessary.

The abbreviations used in Tables 13 and 14 will be described. (Photosensitizer) DMAEA: 2-N, N-dimethylaminoethyl acrylate DMAEM: 2-N, N-dimethylaminoethyl methacrylate DMABM: 4-N, N-dimethylaminobutyl methacrylate DABMCH: 2,6-di (4- Azidobenzar) -4
-Methylcyclohexanone DABHCH: 2,6-di (4-azidobenzal) -4
-Hydroxycyclohexanone (sensitizer) BDKM: benzyldimethyl ketal

[0154]

[Table 13]

[0155]

[Table 14] (3) Evaluation of photosensitive characteristics The photosensitive characteristics of each of the obtained photosensitive polyimide precursors were evaluated according to the following method. First, a photosensitive polyimide precursor was spin-coated on a silicon substrate,
It was dried by heating at 0 ° C. for 6 minutes to form a coating film having a thickness of 4 to 6 μm. Next, an exposure apparatus (PLA-500, manufactured by Canon Inc.)
Using F), ultraviolet rays were irradiated through a mask provided on the coating film. Subsequently, the film was developed with a developing solution consisting of 4 parts by volume of N-methyl-2-pyrrolidone and 1 part by volume of isopropyl alcohol, and further rinsed with ethanol to form a relief pattern. The cross section of the thus formed relief pattern was observed with a scanning electron microscope. Table 15 shows the initial film thickness, light irradiation amount, development time, residual film ratio, and resolution.

As shown in Table 15, the minimum line width was 4 μm.
Was obtained. Even when each silicon substrate on which the relief pattern was formed was heated at 400 ° C. for 90 minutes, no deformation of the relief pattern was observed.

[0157]

[Table 15] (4) Filling into trenches Aluminum is deposited on the surface of a silicon substrate having a diameter of 6 inches and patterned to form a line-and-space 0.3.
A trench having a depth of 1.2 μm and a depth of 1.2 μm was formed. Spin coating each photosensitive polyimide precursor, at 90 ° C. for 1 hour,
Heat treatment was performed at 150 ° C. for 30 minutes, 250 ° C. for 30 minutes, and 400 ° C. for 1 hour to form a polyimide film. After that, the cross section of the trench was observed with a scanning electron microscope,
The filling property for the trench was examined. As a result, in Examples 4-1 to 15-15, the trench was completely filled with polyimide without any gap. On the other hand, in Comparative Examples 6 and 7, it was confirmed that the trench was not completely filled with the polyimide and a large gap remained. Thus, it was found that there was a large difference in the fluidity and the castability of the photosensitive polyimide precursor solution depending on the molecular structure of the polyimide. Example 5 In a 100 mL four-necked flask having a nitrogen inlet tube, 1,
1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-diphthalic dianhydride (6FDPA)
8.88 g (0.02 mol) and 5.2 g (0.04 mol) of 2-hydroxyethyl methacrylate were added.
The solution was stirred at room temperature for 6 days to give the diester of 6FDPA. The solution was kept at -15 ° C and thionyl chloride was added slowly. Thereafter, while continuing stirring, the temperature of the reaction solution was gradually increased and kept at 5 ° C., and the reaction was performed for 4 hours. To this solution, 7.04 g of 1,3-bis (3-amino-5-trifluoromethylphenoxy) benzene (0.
02 mol) and 4.4 g (0.04
(4 mol) in 25 g of N-methyl-2-pyrrolidone was slowly added. This solution is placed in a nitrogen atmosphere for 5
C., and the mixture was stirred for 8 hours, and then filtered under reduced pressure to remove the generated precipitate. The filtrate was decanted into water to precipitate a polyamic acid derivative.

3.0 g of this polyamic acid derivative was dissolved in 12 g of N-methyl-2-pyrrolidone, and 0.05 g of 4,4'-bis (diethylamino) benzophenone and 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropanone-10.
01 g, filtered through a 0.5 μm filter,
A photosensitive polyimide precursor was obtained.

This photosensitive polyimide precursor was spin-coated on a silicon substrate and dried by heating at 90 ° C. for 5 minutes. Next, an exposure apparatus (PLA-500, manufactured by Canon Inc.)
Using F), exposure was performed by irradiating ultraviolet rays for 60 seconds through a mask provided on the coating film. Then, N-methyl-2-
It was developed with a developing solution consisting of 7 parts by volume of pyrrolidone and 3 parts by volume of methanol, and rinsed with water. Further, a heat treatment was performed at 150 ° C. for 30 minutes, at 250 ° C. for 30 minutes, and at 350 ° C. for 60 minutes to obtain a film having a thickness of 5 μm and a line and space
A μm relief pattern was obtained.

Even when the silicon substrate on which the relief pattern was formed was heated at 400 ° C. for 90 minutes, no deformation of the relief pattern was observed.

Further, as in the case of the fourth embodiment (4),
Using a silicon substrate provided with an aluminum pattern having an AND space of 0.3 μm and a depth of 12 μm, the filling property of the photosensitive polyimide precursor into the trench was examined. As a result, the trench was completely filled with polyimide, and the flatness of the trench surface was good.

Examples 6-1 to 6-3 and Comparative Example 6 (Liquid Crystal Display Device) (1) Preparation of Liquid Crystal Cell Example 6-1 N-methyl-2 of polyamic acid synthesized in Example 1-3
-The pyrrolidone solution was diluted with butyl cellosolve acetate to prepare a solution having a concentration of 8% by weight. This solution was filtered through a filter having a pore size of 0.2 μm to remove insolubles such as dust, and then applied by screen printing onto a glass substrate on which an ITO electrode had been formed. This glass substrate is
5 minutes at 150 ° C, 30 minutes at 150 ° C, 3 minutes at 250 ° C.
Heat treatment was performed for 0 minutes to form a 60-nm polyimide film. Next, using a rubbing machine having a roll wound with a nylon cloth, the number of rotations of the roll was 4
The polyimide film was subjected to a rubbing treatment at 50 RPM at a stage moving speed of 1 cm / sec to form a liquid crystal alignment film. In this way, a pair of glass substrates having a rubbed liquid crystal alignment film was prepared. The peripheral portions of these glass substrates were adhered to each other by heating and curing an epoxy-based adhesive containing beads as spacers at 180 ° C. to produce a cell having a cell gap of 10 μm. Finally, a nematic liquid crystal (manufactured by Merck, ZLI-1565) was injected from a liquid crystal injection port, and the injection port was sealed with a photocurable epoxy resin to produce a test liquid crystal cell.

Examples 6-2 and 6-3 Instead of the polyamic acid of Example 1-3, Examples 1-3
A test liquid crystal cell was produced in exactly the same manner as in Example 6-1 except that the polyamic acid synthesized in Example 9 or Example 3-9 was used.

Comparative Example 6 In a four-necked flask equipped with a stirring rod, a thermometer, and a nitrogen inlet tube, 10.921 g (0.05%) of pyromellitic dianhydride was placed.
Mol) and 60 g of N-methyl-2-pyrrolidone, and stirred while flowing dehydrated nitrogen to form a suspension.
This suspension was kept at 5 ° C., and 1,1,1,3,3,3-
Hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane 24.892 g (0.04
8 mol) and 1,3-bis (3-aminopropyl)-
1,1,3,3-tetramethyldisiloxane 0.495
g (0.002 mol) of N-methyl-2-pyrrolidone 1
A solution dissolved in 20 g was slowly added. Then 5 ℃
The stirring was continued for 6 hours at room temperature to synthesize a polyamic acid.
35 g of N-methyl-2-pyrrolidone was added to 50 g of this solution.
And 25 g of butyl cellosolve acetate, and add 8 g
A weight percent polyamic acid solution was prepared. Using this solution, a test liquid crystal cell was produced in the same manner as in Example 6-1.

(2) Evaluation of Alignment Characteristics The alignment characteristics of these liquid crystal cells were evaluated by measuring the pretilt angle and the voltage holding ratio.

Here, the pretilt angle is set in the Journal of Applied Physics, Vol. 10,
It was measured by the method described on pages 2013 to 4 (1980).

The voltage holding ratio is a ratio at which the writing voltage applied to the electrodes of the liquid crystal cell is held until the next writing (frame period 16 msec). This voltage holding ratio was measured as follows using a measurement circuit shown in FIG. That is, as shown in FIG.
As shown in (b), the pulse width is 65 μs and the frequency is 60H.
z, a rectangular wave Vs having a wave height of ± 5 V is applied, and a drain voltage V
_D was monitored. As shown in FIG. 8C, V _D attenuates until the next pulse voltage is applied. Then, in FIG. 8C, the area between the broken line and V = 0 (the voltage integral value when V _D is not attenuated) is
The ratio of the area of the hatched portion between the monitored V _D and V = 0 (the integral value of the voltage actually applied to the electrode) is defined as the voltage holding ratio. The voltage holding ratio was measured at 90 ° C.

Table 16 shows the measurement results. Table 16
Therefore, the liquid crystal cell using the liquid crystal alignment film made of polyimide according to Examples 6-1 to 3 has a desirable pretilt angle and a high voltage holding ratio. This indicates that a liquid crystal display device having excellent contrast and visibility can be realized, and is suitable for increasing the size and color.

[0169]

[Table 16] Examples 7-1 to 7-16 and Comparative Examples 7-1 to 7-4 (1) Synthesis of bismaleimide compound [Synthesis Example 7A] 3,3′-dimaleimide-5,5′-
Bis (trifluoromethyl) biphenyl (6FmBPD
50 mL of dimethylformamide was placed in the synthesis flask of M), and 10.8 g (110 mmol) of maleic anhydride was stirred with stirring.
Was dissolved. At room temperature, 3,3′-diamino-
5,5'-bis (trifluoromethyl) biphenyl (6
A solution of 16.0 g (50.0 mmol) of FmBPDA dissolved in 50 mL of dimethylformamide was slowly dropped from the dropping funnel. After stirring for 3 hours, triethylamine 2.4 g, magnesium oxide (100 mg),
And 10 mg of cobalt (II) acetate tetrahydrate were added, and 13 g of acetic anhydride was added dropwise at room temperature from a dropping funnel over 30 minutes. The mixture was further stirred for 3 hours, 1 L of water was added little by little to the reaction solution, and the precipitated crude crystals were collected by filtration. The obtained crude crystals were dissolved in a small amount of dimethylformamide, and the solution was decanted into 1 L of water to precipitate crystals. This operation was repeated once, and the purified crystals were collected by filtration. The crystals were dried under vacuum to obtain the target compound (6FmBPDM).

Molecular formula: C ₂₂ H ₁₀ F ₆ N ₂ O ₄ Molecular weight:
480.320 Yield: 23.3 g (48.5 mmol) Yield: 97% Elemental analysis: Carbon hydrogen Fluorine Nitrogen Calculated 55.0% 2.1% 23.7% 5.8% Analytical value 55.0% 2 0.1% 23.8% 5.8% Infrared absorption spectrum: 1780, 1720 cm ^-1 C = O stretching vibration (cyclic imide) 1320, 1140 cm ^-1 CF symmetric bending vibration (CF
₃ group) Synthesis Example 7B] bis instead of synthetic 6FmBPDA of [3- maleimido-5- (trifluoromethyl) phenyl] ether (6FmODM), oxy-5,5'-bis (3-trifluoromethyl aniline) (6FmODA)
Using 16.8 g (50.0 mmol), a target compound (6FmODM) was obtained in the same manner as in Synthesis Example 7A.

Molecular formula: C ₂₂ H ₁₀ F ₆ N ₂ O ₅ Molecular weight:
496.319 Yield: 23.6 g (47.6 mmol) Yield: 95% Elemental analysis: Carbon hydrogen Fluorine Nitrogen Calculated 53.2% 2.0% 23.0% 5.6% Analytical value 53.3% 2 0.0% 22.9% 5.7% Infrared absorption spectrum: 1780, 1720 cm ^-1 C = O stretching vibration (cyclic imide) 1320 cm ^-1 CF symmetric bending vibration (CF ₃ group) 1245 cm ^-1 C- OC antisymmetric stretching vibration (aromatic ether) 1140 cm ^-1 CF symmetric bending vibration (CF ₃ group) [Synthesis example 7C] Bis [3-maleimido-5- (trifluoromethyl) phenyl] sulfone (6FmSNDM )
In place of 6FmBPDA, 1,1′-bis [3- (trifluoromethyl) phenyl] sulfone (6FmSND
A) Synthesis Example 7 using 19.2 g (50.0 mmol)
In the same manner as in A, the desired compound (6FmSND
M) was obtained.

Molecular formula: C ₂₂ H ₁₀ F ₆ N ₂ O ₆ S Molecular weight: 544.378 Yield: 25.6 g (47.0 mmol) Yield: 94% Elemental analysis: Carbon hydrogen Fluorine Nitrogen Sulfur Calculated 48.5% 1.9% 20.9% 5.2% 5.9% Analytical value 48.6% 1.8% 21.0% 5.1% 5.9% Infrared absorption spectrum: 1780, 1720 cm ^-1 C = O stretching vibration (cyclic imide) 1320 cm ^-1 CF symmetric bending vibration (CF ₃ group) 1310 cm ^-1 S = O inverse symmetric stretching vibration (sulfone) 1160 cm ^-1 S = O symmetric bending vibration (sulfone) 1140 cm ^{− 1} CF symmetric bending vibration (CF ₃ group) [Synthesis Example 7D] 2,2-bis [3-maleimido-5-
(Trifluoromethyl) phenyl] -1,1,1,3,
Synthesis of 3,3-hexafluoropropane (6Fm6FDM) Instead of 6FmBPDA, 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1
1,3,3,3-hexafluoropropane (6Fm6F
DA) using 23.5 g (50.0 mmol) of the desired compound (6Fm6FD) in the same manner as in Synthesis Example 7A.
M) was obtained.

Molecular formula: C ₂₅ H ₁₀ F ₁₂ N ₂ O ₄ Molecular weight:
630.341 Yield: 29.0 g (46.0 mmol) Yield: 92% Elemental analysis: Carbon hydrogen Fluorine Nitrogen Calculated 47.6% 1.6% 36.2% 4.4% Analytical value 47.7% 1 3.6% 36.1% 4.5% Infrared absorption spectrum: 1780, 1720 cm ^-1 C = O stretching vibration (cyclic imide) 1320, 1250, 1220, 1190, 1140c
m ^-1 CF stretching vibration and bending vibration (CF ₃ group) (2) Preparation of bismaleimide resin varnish As shown in Tables 17 to 19, bismaleimide compound and aromatic diamine compound or dihydric phenol compound Is dissolved in N, N-dimethylacetamide at a prescribed mixing ratio (expressed in molar equivalent), and 50 wt% of the resin composition
A solution was prepared. The solution was heated at 80 ° C. for about 1 hour to cause some reaction between the bismaleimide compound and the diamine compound or dihydric phenol compound (A-sta).
Ge)), until the viscosity of the solution becomes about 1 poise,
N-dimethylacetamide was added to prepare a varnish of a bismaleimide-based resin.

Abbreviations used in Tables 17 to 19 are described below. (Bismaleimide compound) 6FmBPDM: 3,3'-dimaleimide-5,5'-
Bis (trifluoromethyl) biphenyl 6FmODM: bis [3-maleimido-5- (trifluoromethyl) phenyl] ether 6FmSNDM: bis [3-maleimido-5- (trifluoromethyl) phenyl] sulfone 6Fm6FDM: 2,2-bis [3-maleimido-5-
(Trifluoromethyl) phenyl] -1,1,1,3,
3,3-hexafluoropropane pMDM: bis (4-maleimidophenyl) methane p6FDM: 2,2-bis (4-maleimidophenyl)
-1,1,1,3,3,3-hexafluoropropane (aromatic diamine compound) pODA: oxy-4,4'-dianiline m6FDA: 1,1,1,3,3,3-hexafluoro-2 , 2-Propyridene-3,3'-dianiline 6FpBPDA: 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl pMDA: methylene-4,4'-dianiline p6FDA: 1,1,1,1 3,3,3-hexafluoro-2,2-propylidene-4,4'-dianiline (dihydric phenol compound) p6FDP: 1,1,1,3,3,3-hexafluoro-2,2-propylidene- 4,4'-diphenol Comparative Examples 8-1 and 8-2 use bismaleimide compounds not included in the general formula (DM1).

(3) Measurement of Physical Properties of Bismaleimide-Based Cured Resin Film (a) Decomposition Start Temperature Varnish of bismaleimide-based resin was
After coating on a glass plate of 1 mm x 130 mm x 150 mm to a thickness of 75 m with a bar coater,
Prebaked at 110 ° C for 1 hour. This was heated from room temperature to 150 ° C.
Heated at 50 ° C. and 350 ° C. for 1 hour,
Finally, by heating at 400 ° C. for 30 minutes, a bismaleimide-based cured resin film was formed. In addition, the heating time between each temperature was set to 1 hour. The obtained bismaleimide-based cured resin film was subjected to thermogravimetric analysis / differential thermal analysis (TG / DTA) in a nitrogen stream to obtain 0.5 wt%.
Was measured to determine the decomposition start temperature of the bismaleimide-based cured resin film. as a result,
It was confirmed that the bismaleimide-based cured resin films of Examples 8-1 to 16 had heat resistance equal to or higher than that of the comparative example.

(B) A varnish of a dielectric constant bismaleimide-based resin was
Spin coating was performed 2 to 4 times on an aluminum plate having a size of × 100 mm so that the film thickness after curing was 40 to 60 μm. This is heated from room temperature to 150 ° C., 250 ° C., and 350 ° C. for 1 hour in a dryer in which nitrogen gas is introduced, and finally heated at 400 ° C. for 30 minutes. And a bismaleimide-based cured resin film was formed. The heating time between each temperature was 30 minutes. The resulting bismaleimide-based cured resin film was measured for a dielectric constant at 100 kHz. As a result, the bismaleimide-based cured resin films of Examples 8-1 to 16 have a low dielectric constant of 3.0 or less, and have superior dielectric properties as compared with those of Comparative Example 1 which is generally used. Was confirmed.

(C) Generated amount of humidified decomposition gas A varnish of bismaleimide resin was spin-coated on a 4-inch diameter silicon substrate so that the cured film thickness was 5 to 10 μm. This was heated from room temperature to 150 ° C., 250 ° C., and 350 ° C. for one hour in a drier into which nitrogen gas was introduced, and finally heated at 400 ° C.
For 30 minutes to form a bismaleimide-based cured resin film. The heating time between each temperature was 30 minutes. The silicon substrate on which the bismaleimide-based cured resin film was formed was left at 20 ° C. under saturated steam for one week. Thereafter, the bismaleimide-based cured resin film was introduced into pyrofoil and heated at 358 ° C. for 3 seconds with a Curie pyrolyzer, and the generated gas component was subjected to G
Analyzed by C-MASS. The amount of aniline generated as the humidified decomposition gas was evaluated based on the value obtained by converting the integrated value of the aniline signal in the ion chromatograph into 1 mg of the sample. As a result, it was confirmed that the bismaleimide-based cured resin films of Examples 8-1 to 16-16 produced very little aniline gas and were excellent in environmental stability as compared with those of the comparative examples.

[0178]

[Table 17]

[0179]

[Table 18]

[0180]

[Table 19]

[0181]

As described above in detail, according to the present invention, a film having excellent flatness can be formed on a substrate having fine irregularities, and has a low dielectric constant, low moisture absorption, and environmental stability. It is possible to provide a precursor of a polyimide resin or a bismaleimide-based cured resin having excellent properties. Furthermore, by providing the above-mentioned resin as an insulating member, a high-speed operation and power saving can be realized, and a highly reliable electronic component can be provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a semiconductor device having an interlayer insulating film made of a polyimide resin manufactured from a precursor according to the present invention;

FIG. 2 is a cross-sectional view of a resin molded package of a semiconductor chip having a passivation film made of a polyimide resin manufactured from a precursor according to the present invention;

FIG. 3 is a cross-sectional view of a thin-film magnetic head having an interlayer insulating film made of a polyimide resin manufactured from a precursor according to the present invention,

FIG. 4 is a cross-sectional view of a high-density wiring board having an interlayer insulating film made of a polyimide resin manufactured from the precursor according to the present invention;

FIG. 5 is a cross-sectional view of a magnetic bubble memory device having an interlayer insulating film made of a polyimide resin manufactured from a precursor according to the present invention;

FIG. 6 is a cross-sectional view of a solar cell having a heat-resistant transparent resin layer made of a polyimide resin manufactured from the precursor according to the present invention,

FIG. 7 is a cross-sectional view of a liquid crystal display device having a liquid crystal alignment film made of a polyimide resin manufactured from the precursor according to the present invention,

FIG. 8 is a circuit diagram of a circuit used to measure a pretilt angle and a voltage holding ratio of a liquid crystal display element, and waveform diagrams of V _S and V _D.

[Explanation of symbols]

11 silicon substrate, 12 field oxide film, 13
Diffusion layer, 14: thermal oxide film, 15: CVD oxide film, 16 ...
1st layer Al electrode, 17 ... interlayer insulating film, 18 ... second layer Al electrode, 19 ... passivation film, 20 ... semiconductor chip, 21 ... bed, 22 ... lead, 23 ... wire, 2
4: sealing resin, 31: substrate, 32: lower alumina, 33
... Lower magnetic material, 34 gap alumina, 35 interlayer insulating film, 36 first conductor coil, 37 second conductor coil
38: Upper magnetic body, 41: Silicon substrate, 42: Thermal oxide film, 43: First layer copper wiring, 44: Interlayer insulating film, 45 ...
Copper electrode of second layer, 46: passivation film, 47: barrier metal, 48: Pb / Sm bump, 51: garnet substrate, 52: conductor, 53: interlayer insulating film, 54:
Permalloy, 61: glass substrate, 62: heat-resistant transparent resin layer, 63: transparent electrode, 64: amorphous Si, 65 ...
Metal electrode, 71: glass substrate, 72: pixel electrode, 73 ...
Liquid crystal alignment film, 74: glass substrate, 75: common electrode, 76
... liquid crystal alignment film, 77 ... liquid crystal.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shigeru Matake 1 Toshiba-cho, Komukai-shi, Kawasaki-shi, Kanagawa Prefecture Inside the R & D Center of Toshiba Corporation (72) Inventor Shuji Hayase Toshiba-cho, Koyuki-ku, Kawasaki-shi, Kanagawa No. 1 Toshiba R & D Center Co., Ltd. (72) Inventor Satoshi Mikoshiba No. 1, Komukai Toshiba-cho, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture Toshiba R & D Center Co., Ltd. (56) References JP-A-61-287938 (JP, A (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-79/08 G03F 7/00-7 / 42 CAPLUS (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. A compound represented by the following general formula (DA1) (X ¹ may be the same or different,
Divalent oxy, thio, sulfonyl group, a carbonyl group, peralkyl polysiloxanolate Sani alkylene group, an unsubstituted or aliphatic substituted with fluoro hydrocarbon group or a single bond, R ¹ is a respectively identical May represent a fluoro group, an unsubstituted or substituted aliphatic hydrocarbon group with a fluoro group,
An integer of 4, i is an integer of 1 to 6, j is an integer of 0 to 6, and k is 0 or 1. ) , Sulfonyl-3,3 ′
-Dianiline, 1,3-bis (3-aminophenoxy)
Benzene, oxy-3,3'-dianiline, oxy-
5,5'-bis [3- (trifluoromethyl) anily
], 3,5-bis (3-aminophenoxy) benzoto
Fluoride, 1,3-bis [3-amino-5- (tri
Fluoromethyl) phenoxy] benzene, 3,5-bis
[3-Amino-5- (trifluoromethyl) phenoxy
B) benzotrifluoride, 5- (trifluoromethyl)
L) -1,3-phenylenediamine, 1,1′-bis
[3-Amino-5- (trifluoromethyl) phenyl]
Sulfone, 3,3′-diamino-5,5′-bis (tri
Fluoromethyl) biphenyl, 1,1,1,3,3,3
-Hexafluoro-2,2-propylidene-3,3'-
Dianiline, 1,3-phenylenediamine, and 3,
0.97 to 1.03 molar equivalents of a diamine component containing 0.40 molar equivalents or more of an aromatic diamine compound selected from the group consisting of 3′-diaminobiphenyl ; , 3,3-hexafluoro-2,2-p
Ropiriden 4,4' diphthalic dianhydride (1-n ₁
/ 2) molar equivalents, and at least one n ₁ molar equivalent of maleic anhydride and selected from maleic anhydride derivative thereof (n ₁ polymerization and the acid anhydride component containing 0.02 to 0.40) Characterized by having a
Liimide precursor. 2. A polyimide precursor composition comprising the polyimide precursor according to claim 1 and a photosensitizer. 3. A polyimide resin obtained by curing the polyimide precursor according to claim 1. 4. A polyimide resin obtained by curing the polyimide precursor composition according to claim 2. 5. An electronic component comprising a polyimide resin obtained by curing the polyimide precursor according to claim 1 as an insulating member. 6. An electronic component comprising a polyimide resin obtained by curing the polyimide precursor composition according to claim 2 as an insulating member. 7. The maleic anhydride and maleic acid derivative.
At least one selected from conductor anhydrides has the following general formula
(MA1) (R ²¹ may be the same or different,
Group, unsubstituted or substituted with fluorine atom
Shows a hydride group or a hydrogen atom. )
The polyimide precursor according to claim 1, characterized in that: 8. The method according to claim 7, wherein the polyimide precursor is cured.
Contain polyimide resin as insulating material
Electronic components characterized by the following.