JP3950104B2 - Polyimide precursor, polyimide precursor composition, polyimide resin and electronic component - Google Patents

Description

  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 a bismaleimide-based cured resin produced from these precursors as an insulating film or an insulating substrate. It is related with the electronic component comprised as.

  In recent years, a polyimide resin excellent in heat resistance that can withstand high-temperature heat treatment at 400 ° C. or higher has been used as a material for an interlayer insulating film of a semiconductor device. As such a polyimide resin, Kapton (registered trademark of DuPont) made of a condensation product of pyromellitic dianhydride and 4,4'-oxydianiline is known. In addition, with the increase in capacity, size, weight, reliability, and density of electronic components, multilayer wiring board materials include high heat resistance, through-hole adhesion reliability, dimensional stability, electrical characteristics, and flexibility. Organic polymer materials having excellent properties are required. Conventionally, a bismaleimide-based cured resin has been used as a material for a multilayer wiring board. As such a bismaleimide-based cured resin, a cured product of a reaction product of bis (4-maleimidophenyl) methane and methylene-4,4′-dianiline (for example, Japanese Examined Patent Publication No. 46-23250) is known. It has been.

By the way, in the semiconductor device, as the integration becomes higher and the line and space width of the wiring pattern approaches the quarter micron level, the increase in the delay time of the semiconductor device and the increase in the power consumption are significant. It has become a problem. That is, the signal transmission speed V _s is expressed by the following formula: V _s = c × ε _r ^−0.5 (c: speed of light, ε _r : dielectric constant of dielectric). As is clear from this equation, it is important to reduce the dielectric constant of the interlayer insulating film in order to increase the signal transmission speed. Conventionally, the dielectric constant of SiO ₂ generally used as an interlayer insulating film of a semiconductor device is as high as about 3.5, and the dielectric constant of a material used instead is desirably sufficiently lower than this value. Similarly, in a multilayer wiring board, it is an indispensable problem to reduce the dielectric constant of the board.

  From such a background, an organic polymer film capable of realizing a low dielectric constant of 3.0 or less is desired as an insulating member for electronic components. However, both the conventional polyimide resin and bismaleimide-based cured resin have a dielectric constant of about 3.4 and are not so low. In this respect, fluororesins are attracting attention because of their low dielectric constant of about 2.5. However, fluororesins have poor workability and are extremely dimensionally stable under high temperature conditions, especially in the multi-layer process during multi-layer substrate fabrication. There is a disadvantage that it is inferior.

  In addition to the low dielectric constant, insulating members used in semiconductor devices have various characteristics such as improved flatness of the surface of the semiconductor device, low hygroscopicity, and poor chemical decomposition. 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 was obtained when an insulating film was formed on an uneven surface using this polyimide precursor varnish. Flatness is impaired on the surface of the film. In particular, it is difficult to completely fill the inside of a trench having a width of about 0.1 to 0.5 μm formed on the surface of the semiconductor substrate with polyimide resin. Therefore, a polyimide film having a film thickness of 3 to 4 μm is formed with respect to a step of about 1 μm of the underlying wiring 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 apparatus is contaminated by etching products. For this reason, it is desirable that the amount of etchback be as small as possible. From this point, the flatness of the insulating film is required to be good. Moreover, if it is going to fill the inside of a trench with a polyimide resin, a low concentration varnish must be used. When a low concentration varnish is used, the amount of solvent to be volatilized increases. As described above, since the conventional polyimide precursor has a high molecular weight before curing, the fluidity is lost at the stage where the remaining solvent is large. As a result, volatilization of the solvent is suppressed and local shrinkage of the polyimide resin is caused, and voids are easily generated.

  In addition, 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 decomposes by humidification and decomposes, releasing the toluene component. There's a problem.

  Furthermore, in addition to the characteristics described above, the insulating member used for a specific electronic component may be required to have characteristics specific to the electronic component. For example, a polyimide resin used as a liquid crystal alignment film of a liquid crystal display element will be described. In the liquid crystal display element, an STN (super twisted nematic) system is frequently used in order to increase the viewing angle. In the STN type liquid crystal display element, the major axis direction of the liquid crystal molecules is twisted 270 ° in the cell. Therefore, in order to achieve this purpose, a liquid crystal alignment film capable of giving a high pretilt angle to the liquid crystal is required. Further, in a high-definition color liquid crystal display element, a TFT (thin film transistor) is provided in 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 lower is required.

  As a liquid crystal alignment film giving a high pretilt angle, Japanese Patent Application Laid-Open No. 62-174725 discloses a polyimide resin in which a fluoroalkyl group is bonded to chain carbon. However, this polyimide resin has the disadvantages that a stable pretilt angle cannot be obtained and the voltage holding ratio is small. Further, as an alignment film having a low curing temperature, soluble polyimide is known as disclosed in the 9th Polymer Electronics Research Group, Abstract of Lecture, page 32. However, this soluble polyimide has a problem that a high pretilt angle cannot be obtained. Thus, a polyimide liquid crystal alignment film that can give a high pretilt angle and has a large voltage holding ratio has not been realized.

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

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

(X ¹ may be the same or different and each is a divalent oxy group, a thio group, a sulfonyl group, a carbonyl group, a peralkylpolysiloxanylene group, an aliphatic group that is unsubstituted or substituted with a fluoro group. R ¹ represents a hydrocarbon group or a single bond, each R ¹ may be the same or different, and represents a fluoro group, an unsubstituted hydrocarbon group substituted with a fluoro group, a, b and c are An integer of 0 to 4, i is an integer of 1 to 6, j is an integer of 0 to 6, and k is 0 or 1.)
A diamine component containing 0.97 to 1.03 molar equivalents containing at least 0.40 molar equivalents of the aromatic diamine compound represented by the following general formula (DAH1)

(Y represents a tetravalent organic group.)
In the tetracarboxylic dianhydride represented by (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 0.02 It is characterized by having a structure obtained by polymerizing an acid anhydride component containing ˜0.40).

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

(X ² represents a perfluoroalkylene group, a perfluoroalkylidene group, a sulfonyl group, or a single bond, and R ^{0 s} may be the same or different and are each substituted with a fluoro group, unsubstituted or substituted with a fluoro group. Each of R ² may be the same or different, and represents a fluoro group, an unsubstituted hydrocarbon group substituted with a fluoro group or a hydrogen atom, or at least one Is a fluoro group or an aliphatic hydrocarbon group substituted with a fluoro group, and a and b are integers of 0 to 3.)
An amine component containing at least 0.10 molar equivalents of the fluorine-containing aromatic diamine compound represented by formula (DAH1):

(Y represents a tetravalent organic group.)
It has the structure which polymerized the acid anhydride component containing 0.80-0.99 molar equivalent of tetracarboxylic dianhydride represented by these.

More specifically, the second polyimide precursor of the present invention is a diamine compound 0.97 to 1.7 containing at least 0.10 molar equivalent of the fluorine-containing aromatic diamine compound represented by the general formula (DA2). 03 molar equivalents and, the general formula tetracarboxylic dianhydride represented by _{(DAH1) (1-n 2} /2) molar equivalents and dicarboxylic anhydrides n ₂ molar equivalents (n ₂ is 0 to 0.4) preparative polymerization was structure or the general formula fluorinated aromatic diamine compound 0.10 molar equivalents containing more diamine compounds represented by (DA2), (1-n 3/2) molar equivalents and monoamine compound n ₃ It has a structure in which a molar equivalent (n ₃ is 0 to 0.4) and a tetracarboxylic dianhydride 0.97 to 1.03 molar equivalent represented by the general formula (DAH1) are polymerized.

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

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

(Y is a tetravalent organic group, L is a divalent organic group consisting of the residue of the diamine compound represented by the general formula (DA1), and D ¹ may be the same or different, and is photosensitive. And at least one is a photosensitive organic group.)
It contains a polyamic acid derivative having a repeating unit represented by formula (II) and a photopolymerization initiator.

The bismaleimide-based cured resin precursor of the present invention has the following general formula (DM1)

(X ³¹ is a divalent oxy group, thio group, sulfonyl group, carbonyl group, peralkylpolysiloxanylene group, 1,3-phenylenedioxy group, 1,4-phenylenedioxy group, unsubstituted or fluoro group. R ³¹ represents an aliphatic hydrocarbon group substituted with or a single bond, and each R ³¹ may be the same or different and represents a fluoro group or an aliphatic hydrocarbon group which is unsubstituted or substituted with a fluoro group, and at least 1 Is an aliphatic hydrocarbon group substituted with a fluoro group or a fluoro group, and each R ³² may be the same or different, and is an aliphatic hydrocarbon group substituted with a halogen group, an unsubstituted or fluoro group, or Represents a hydrogen atom, and a and b are integers of 1 to 4.)
1 molar equivalent of a bismaleimide compound represented by the formula: a diamine compound represented by the following general formula (DA11) and a divalent phenol compound represented by the following general formula (DP1)

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

  The polyimide resin of the present invention is characterized by curing each of the polyimide precursors described above.

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

  The electronic component of the present invention includes a polyimide resin obtained by curing each of the above polyimide precursors as an insulating member.

  Another electronic component of the present invention is characterized by containing a bismaleimide-based cured resin obtained by curing the above-described bismaleimide-based cured resin precursor as an insulating member.

  According to the present invention, a polyimide resin or bismaleimide-based cured resin that can form a film having excellent flatness on a substrate having fine irregularities, and that has low dielectric constant, low moisture absorption, and excellent environmental stability. Can be provided. Furthermore, the resin as described above is provided as an insulating member, and high-speed operation and power saving can be realized, and a highly reliable electronic component can be provided.

  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 anhydrides n ₂ molar equivalents (n ₂ is 0 to 0.4) formulating and or diamine component (1-n _3/2) molar equivalents and monoamine compound n ₃ molar equivalents (n ₃ is 0 to 0.4), It has a structure in which 0.97 to 1.03 molar equivalent of tetracarboxylic dianhydride is blended and polymerized.

First, the first polyimide precursor (polyamic acid) according to the present invention will be described. The polyimide precursor is (a) 0.97 to 10.3 molar equivalent of a diamine component containing 0.40 molar equivalent or more of an aromatic diamine compound having a specific molecular structure represented by the general formula (DA1); (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 has a structure obtained by polymerizing an acid anhydride component containing 0.02 to 0.40).

  The aromatic diamine compound represented by the general formula (DA1) is (a1) an aromatic diamine compound having one benzene ring and a structure in which two amino groups are bonded to the benzene ring at the meta position, And (a2) a structure having two or more benzene rings, each having two amino groups bonded to the terminal benzene ring at the meta position as viewed from the bonding site of the terminal benzene ring to the other benzene ring. The aromatic diamine compound which has.

  Examples of the aromatic diamine compound represented by the general formula (DA1) include the following. 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- [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-amino Phenoxy) -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-trifluoro Methylbenzene, 1,3-bis (3-amino-5-trifluoromethylphenoxy) benzene, 1,3-bis (3-amino-5-trifluoromethylphenoxy) -5-trifluoromethylbenzene, 3,3 '-Bis (trifluoromethyl) -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] -1,1,1,3,3,3-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 in combination of two or more.

  The polyimide precursor containing an aromatic diamine compound having an amino group at the meta position of the benzene ring represented by the general formula (DA1) includes, for example, an aromatic diamine having an amino group at the para position of the benzene ring. Compared to the above, it has excellent heat resistance, and even when left in the atmosphere, the generation of gas (toluene, xylene, etc.), which is a humidified decomposition product, is extremely small, and a polyimide resin with excellent environmental stability can be obtained. Is preferable. In particular, a polyimide precursor containing an aromatic diamine compound having a plurality of benzene rings as in (a2) is difficult to hydrolyze and has excellent environmental stability.

  In the present invention, the aromatic diamine compound represented by the general formula (DA1) is blended in an amount of 0.40 mole equivalent or more, more preferably 0.70 mole equivalent or more of all diamine components. This is because when the amount of the aromatic diamine compound represented by the general formula (DA1) is too small, it is difficult to obtain a polyimide resin that is difficult to hydrolyze and excellent in environmental stability.

  Among the aromatic diamines represented by the general formula (DA1), the following are particularly preferable aromatic diamine compounds from the viewpoint of heat resistance, environmental stability and low dielectric constant characteristics of the polyimide resin. 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′- Diful Robiphenyl, 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′- Aminobiphenyl, 2,2-bis [3-amino-5- (trifluoromethyl) phenyl) -1,1,1,3,3,3-hexafluoropropane and the like.

In the first polyimide precursor of the present invention, as a diamine component, an aromatic diamine compound represented by the following general formula (DA6), that is, a bis (aminoalkyl) together with an aromatic diamine compound represented by the general formula (DA1). ) A peralkyl polysiloxane compound may be used in combination.

(R ³ may be the same or different, and 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.)
Examples of the bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) include the following. For example, 1,3-bis (aminomethyl) -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-tetramethyldisiloxane, 1,5-bis (3-aminopropyl) -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) -1,1,3,3,5,5,7,7,9,9,11,11,13,13 , 15,15-hexadecamethyloctasiloxane, 1,19-bis (3-aminopropyl) -1,1,3,3,5,5,7,7,9,9,11,11,13,13 , 15, 15, 17, 17, 19, 19-eicosamethyldecasiloxane.

  The bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) has an effect of improving the adhesion and adhesiveness 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 among all diamine components. This is because, although the adhesion and adhesion of a polyimide resin obtained by blending such a compound to, for example, a semiconductor substrate is improved, excessive blending may cause a decrease in the heat resistance of the polyimide resin. is there.

In the present invention, in addition to the aromatic diamine compound represented by the general formula (DA1), other diamine compounds can be used in combination as long as the physical properties of the finally obtained polyimide resin are not impaired. Examples of such other diamine compounds include an aromatic diamine compound in which an amino group is bonded to the para position instead of the meta position of the benzene ring, an aliphatic diamine compound, and the like. Examples of such diamine compounds include the following. 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-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, , 4-Bis (4-aminophen Sulfonylsulfonyl) 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, 2,5-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-fluoro Nilin), 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, Tandiamine, 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-aminocyclohexyl) 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, 1,3-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 and the like.

  Among the other diamine compounds that can be used in combination with the aromatic diamine compound represented by the above general formula (DA1) from the aspects of heat resistance, environmental stability and low dielectric constant characteristics of the polyimide resin, the following diamines are particularly preferable. It is preferable to use a compound. 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, 1,4-bis (4-amino) Phenoxy) benzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2- Bi [4- (4-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2-fluoro-1,4-phenylenediamine, 2,5-difluoro-1,4-phenylene Diamine, 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- Fe Range amine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoro Methyl) -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, etc. It is.

In the 1st polyimide precursor of this invention, as tetracarboxylic dianhydride represented by general formula (DAH1), Y in general formula (DAH1) is a C1-C30 aliphatic hydrocarbon group, An alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group are connected to each other directly or by a bridging group A compound which is a tetravalent organic group selected from the group consisting of polycyclic compound groups can be used. Examples of these tetracarboxylic dianhydrides include the following. For example, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3,6-bis (trifluoro Methyl) 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 dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 3 , 3 ′ ″, 4,4 ′ ″-p-quaterphenyltetracarboxylic dianhydride, 3,3 ″ ″, 4,4 ″ ″-p-kinkphenyltetracarboxylic 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 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-dicarboxyl Nylsulfonyl) benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) 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-dicarboxy) Phenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4 Dicarbo Xylphenoxy) -1,1,3,3-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-phenanthrenetetracarboxylic 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, cyclobuta Tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 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′-biphenyltetra Carboxylic 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′-biphenyltetraca Rubonic dianhydride, 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 acid Dianhydride, 6,6′-difluorooxy-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexafluorooxy-4,4′-diphthalic acid Anhydride,
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'- Phthalic dianhydride, 6,6′-difluorosulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexafluorosulfonyl-4,4′-diphthal Acid dianhydride, 3,3′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic acid Anhydride, 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 acid 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-perfluoro Propylidene-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 dianhydride, 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, 9 Phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic acid Anhydrides, and bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more. Tetracarboxylic dianhydride is used in a total acid anhydride component of 0.80 to 0.99 molar equivalent, preferably 0.90 to 0.98 molar equivalent. The reason for this is that if the amount of tetracarboxylic dianhydride is too small, the heat resistance of the resulting polyimide resin will decrease, and conversely if the amount of tetracarboxylic dianhydride is too large, As the amount of maleic anhydride or maleic acid derivative anhydride is reduced, the intrinsic viscosity of the polyimide precursor solution in the solution increases, and for example, it becomes difficult to fill fine irregularities on the substrate surface without gaps. It is.

From the viewpoint of obtaining a high heat-resistant polyimide resin having a high glass transition point and decomposition temperature, among the tetracarboxylic dianhydrides represented by the general formula (DAH1), the following general formulas (DAH2) to (DAH4) It is preferable to use an aromatic tetracarboxylic dianhydride.

(R ^{11 s} may be the same or different and each represents a fluoro group or an aliphatic hydrocarbon group which is unsubstituted or substituted with a fluorine atom, φ represents an aromatic hydrocarbon group, and a represents 0-10. (It is an integer.)

(X ¹¹ is a divalent oxy group, thio group, sulfonyl group, carbonyl group, peralkylpolysiloxanylene group, an aliphatic hydrocarbon group which is unsubstituted or substituted with a fluorine atom, 1,4-phenylene group, biphenyl. -4,4'-diyl group or a single bond, each R ¹² may be the same or different and represents a fluoro group or an aliphatic hydrocarbon group which is unsubstituted or substituted with a fluorine atom, and b and c is an integer of 0-4.)

(R ¹³ may be different from each other in the same, shows a fluoro group or an unsubstituted or fluorine-substituted aliphatic hydrocarbon group,, d and e is an integer of 0-4.)
Examples of the aromatic tetracarboxylic dianhydride represented by the general formula (DAH2) include the following. For example, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3,6-bis (trifluoro Methyl) pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetra Carboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid Dianhydrides, 2,3,6,7-phenanthrenetetracarboxylic dianhydride, 2,3,8,9-naphthacenetetracarboxylic dianhydride, and the like.

Examples of the aromatic tetracarboxylic dianhydride represented by the general formula (DAH3) include the following. For example, 3,3 ′, 4,4′-benzophenone tetracarboxylic 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 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′-diphthalate Acid 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 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 Anhydride, 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 (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic Acid 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′-difluoro Sulfonyl-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 acid 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-perfluoro Propylidene-4,4′-diphthalic dianhydride, 5,5′-bis (trifluoro (Romethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 6,6′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthal Acid 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 dianhydride, 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- Such as tetracarboxylic dianhydride.

  Among the aromatic tetracarboxylic dianhydrides represented by the general formulas (DAH2) to (DAH4), the following are particularly used in terms of heat resistance, environmental stability and low dielectric constant characteristics of the polyimide resin. It is preferable. For example, pyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Biphenyltetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-diphthalic dianhydride, oxy-4,4'-diphthal Acid 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 acid Such as dianhydride.

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).

(R ²¹ may be the same or different and each represents a halogen group, an unsubstituted or substituted aliphatic hydrocarbon group substituted with a fluorine atom, or a hydrogen atom.)
Examples of these maleic acid anhydrides or maleic acid derivative anhydrides include the following. For example, maleic anhydride, citraconic anhydride, dimethylmaleic anhydride, ethylmaleic anhydride, diethylmaleic anhydride, propylmaleic anhydride, butylmaleic anhydride, chloromaleic anhydride, dichloromalein Examples of the acid anhydride include bromomaleic anhydride, dibromomaleic anhydride, fluoromaleic anhydride, difluoromaleic anhydride, trifluoromethylmaleic anhydride, and bis (trifluoromethyl) maleic anhydride. These maleic anhydrides or maleic acid derivative anhydrides may be used alone or in combination of two or more.

  These maleic acid anhydrides or maleic acid derivative anhydrides have the effect of lowering the viscosity of the solution by lowering the molecular weight of the polyamic acid which is a polyimide precursor. Further, the maleimide skeleton introduced at the terminal of the polyamic acid is crosslinked at the time of curing directly or via an excess diamine component. Maleic anhydride or maleic acid derivative anhydride is used in an amount of 0.02 to 0.40 mole equivalent, preferably 0.05 to 0.20 mole equivalent, of all acid anhydride components. This is because 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, particularly width 0.1 This is because it becomes difficult to fill a trench of about 0.5 μm with a polyimide resin without a gap, and conversely, if the amount is too large, the heat resistance of the polyimide resin is lowered.

  Although the method of synthesizing the polyamic acid which is the first polyimide precursor of the present invention is not particularly limited, the diamine component containing the aromatic diamine compound represented by the general formula (DA1) in the organic solvent and the general formula (DAH1) A method in which a tetracarboxylic dianhydride represented by the formula (1) and an acid anhydride component containing a maleic acid anhydride or a maleic acid derivative anhydride are reacted 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-imidazolidine, 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 or in combination of two or more. The reaction temperature is usually 250 ° C. or lower, preferably 200 ° C. or lower. The reaction pressure is not particularly limited, and can be sufficiently 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 intrinsic viscosity at 30 ° C. of an N-methyl-2-pyrrolidone solution having a concentration of 0.5 wt% of 0.2 to 0.7 dL / g, more preferably 0.3 to 0.6 dL / g. It is preferable that the degree of polymerization be in the range. The reason for this is that if the intrinsic viscosity of the polyamic acid is too low, that is, if the degree of polymerization is too low, there is a possibility that a polyimide resin having sufficient heat resistance cannot be obtained thereafter, and conversely, the intrinsic viscosity is too high, that is, polymerization. When the degree is too high, it becomes difficult to fill the fine irregularities on the substrate surface with the polyimide resin without gaps.

  In order to produce a polyimide resin from the polyamic acid which is the first polyimide precursor of the present invention, the polyamic acid is heated to 100 to 450 ° C. to imidize, and the polyamic acid is irradiated with light to imidize. Or a chemical treatment method in which the polyamic acid is chemically imidized using an imidizing agent such as acetic anhydride. The polyimide resin obtained by these methods can be formed as a film having excellent flatness even on a substrate having fine irregularities because the viscosity of the solution containing the polyamic acid which is the precursor is low, and also has a dielectric constant and a hygroscopic property. Is low and excellent in thermal stability and environmental stability. In addition, even a relatively low molecular weight polyimide precursor having a low viscosity of the solution has a maleimide skeleton at the terminal, so that the maleimide skeleton is crosslinked directly or through an excess diamine component when cured 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 is composed of an amine component containing at least 0.10 molar equivalent of the fluorine-containing aromatic diamine compound represented by the general formula (DA2), and a tetracarboxylic dianhydride represented by the general formula (DAH1). It has the structure which polymerized the acid anhydride component containing 0.80-0.99 molar equivalent of the thing. 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 equivalent of tetracarboxylic dianhydride represented by the general formula (DAH1). It has a polymerized structure. Unlike the first polyimide precursor according to the present invention, this polyimide precursor does not need to contain 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 formulas (DA3) to (DA5).

(X ³ in the general formula (DA3) is a perfluoroalkylene group or a perfluoroalkylidene group, and R ⁰ , R ² , a, and b are as defined in the general formula (DA2).)
Examples of the aromatic diamine compound represented by the general formula (DA3) include the following. 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- (to Fluoromethyl) phenyl] -1,1,2,2-tetrafluoroethane, 1,3-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,2,2,3,3- 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.

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

  Examples of the aromatic diamine compound represented by the general formula (DA5) include the following. For example, 3,3′-diamino-5,5′-difluorodiphenyl sulfone, 3,3′-diamino-5,5′-bis (trifluoromethyl) diphenyl sulfone, 3,3′-diamino-5-fluorodiphenyl Sulfone, 3,3′-diamino-5- (trifluoromethyl) diphenylsulfone, and the like.

  These aromatic diamine compounds can be used alone or in admixture of two or more.

The aromatic diamine compound represented by the general formula (DA3) can be synthesized by the following method. (1) First, by heating the compound represented by the general formula (DZ1) and the compound represented by R ² —X in an autoclave without 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 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, dimethyl sulfoxide, sulfolane, nitrobenzene, benzene, and naphthalene. . Examples of the reducing agent used when 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.

(Z represents an iodo group, a bromo group or a chloro group, and X ³ and R ² have the same definitions as 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 an organic solvent in the presence of a copper powder catalyst to cause a coupling reaction, and the fluorine-containing 3, represented by the general formula (DN2) A 3′-dinitrobiphenyl compound is synthesized. Next, the fluorine-containing 3,3′-diaminobiphenyl represented by the general formula (DA4) is reduced by reducing the nitro group of the fluorine-containing 3,3′-dinitrobiphenyl compound represented by the general formula (DN2). Compounds can be synthesized.

Examples of the nitrobenzene compound represented by the general formula (NZ1) include 3-chloro-5-fluoronitrobenzene, 3-bromo-5-fluoronitrobenzene, 3-iodo-5-fluoronitrobenzene, and 3-chloro-5-nitrobenzofluoride. And 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 when reducing the nitro group to an amino group include the same as those listed in the description of the synthesis method of the general formula (DA3).

(Z represents an iodo group, a bromo group or a chloro group, and R ² has the same definition as in the formula (DA3).)
In the 2nd polyimide precursor (polyamic acid) of this invention, the fluorine-containing aromatic diamine compound represented by general formula (DA2) has the effect | action which improves the thermal stability of a polyimide resin. From the viewpoint of sufficiently improving the thermal stability of the polyimide resin, the fluorine-containing aromatic diamine compound represented by the general formula (DA2) is used in an amount of 0.10 molar equivalents or more of all amine components, and 0.20 It is preferable to use a molar equivalent or more.

  Also in the 2nd polyimide precursor of this invention, similarly to the 1st polyimide precursor of this invention, the diamine represented by general formula (DA6) in the range which does not impair the physical property of the polyimide resin finally obtained. A compound and other diamine compounds can be used in combination.

  In the 2nd polyimide precursor of this invention, as the tetracarboxylic dianhydride represented by general formula (DAH1), the thing similar to what is used in the 1st polyimide precursor of this invention is used. The tetracarboxylic dianhydride represented by the general formula (DAH1) is used in an amount of 0.80 molar equivalents or more, preferably 0.90 molar equivalents or more of the total acid anhydride components. 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 decomposition temperature, among the tetracarboxylic dianhydrides represented by the general formula (DAH1), the general formulas (DAH2) to (DAH4) described above are particularly preferable. It is preferable to use an aromatic tetracarboxylic dianhydride represented by

  In the 2nd polyimide precursor of this invention, a dicarboxylic anhydride or a monoamine compound is used as needed.

  Examples of the dicarboxylic acid anhydride include the following. For example, maleic anhydride, citraconic anhydride, dimethylmaleic anhydride, ethylmaleic anhydride, diethylmaleic anhydride, propylmaleic anhydride, butylmaleic anhydride, chloromaleic anhydride, dichloromalein Acid anhydride, bromomaleic anhydride, dibromomaleic anhydride, fluoromaleic anhydride, difluoromaleic anhydride, trifluoromethylmaleic anhydride, bis (trifluoromethyl) maleic anhydride, cyclobutanedicarboxylic acid Anhydride, cyclopentanedicarboxylic acid anhydride, cyclohexanedicarboxylic acid anhydride, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, phthalic anhydride, methylphthalic acid , Ethylphthalic anhydride, dimethylphthalic anhydride, fluorophthalic anhydride, difluorophthalic anhydride, chlorophthalic anhydride, dichlorophthalic anhydride, bromophthalic anhydride, dibromophthalic anhydride, nitrophthalic anhydride 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxydiphenyl ether anhydride, 3,4-dicarboxydiphenyl ether anhydride, 2,3-dicarboxydiphenyl sulfone Anhydride, 3,4-dicarboxydiphenylsulfone anhydride, 2,3-dicarboxybiphenyl anhydride, 3,4-dicarboxybiphenyl anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic Acid anhydride, 1,8-naphthalenedicarboxylic acid Water, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid anhydride, 2,3-pyridine dicarboxylic acid anhydride, 3,4-pyridine dicarboxylic acid Such as anhydrides.

  Examples of monoamine compounds include the following. 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 , Cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, aminoadamantane, aminobenzocyclobutane, aminocaprolactam, 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, aminophenylphthalimide, aminobiphenyl, aminoterphenyl, amino Naphthalene, aminoacridine, aminoanthraquinone, aminofluor , Aminofluorenone, aminopyrrolidine, aminopiperazine, aminopiperidine, aminohomopiperidine, aminomorpholine, aminobenzoxol, aminobenzodioxane, aminopyridine, aminopyridazine, aminopyrimidine, aminopyrazine, aminoquinoline, aminocinnoline, amino Phthalazine, aminoquinazoline, aminoquinoxaline, aminopyrrole, aminoimidazole, aminopyrazole, aminotriazole, aminooxazole, aminoisoxazole, aminothiazole, aminoisothiazole, aminoindole, aminobenzimidazole, aminoindazole, aminobenzoxazole, amino Benzothiazole, benzylamine, phenethylamine, phenylpropylamine, phenylbuty And ruamine, benzhydrylamine, aminoethyl-1,3-dioxolane, aminoethylpyrrolidine, aminoethylpiperazine, aminoethylpiperidine, aminoethylmorpholine, aminopropylimidazole, aminopropylcyclohexane and the like.

  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 tetra represented by the general formula (DAH1). A method of reacting with an acid anhydride component containing a carboxylic dianhydride is preferred. The organic solvent used in this reaction and the reaction conditions such as temperature, pressure, and time are the same as in the case of the first polyimide precursor of the present invention. In addition, it is preferable that the polyamic acid obtained has a polymerization degree such that the intrinsic viscosity at 30 ° C. of a 0.5 wt% N-methyl-2-pyrrolidone solution is in the range of 0.5 dL / g or more. If the degree of polymerization of the polyamic acid is too low, it may be impossible to obtain a polyimide resin having sufficient heat resistance 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 substrate with fine irregularities without gaps on the substrate surface. When forming a film having excellent properties, 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 also the same as in the case 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 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. Moreover, the polyimide precursor using the aromatic diamine compound represented by general formula (DA4) or (DA5) is preferable at the point from which the glass transition point and decomposition temperature are low and the polyimide resin excellent in heat resistance is obtained.

  Next, the polyimide precursor which has photosensitivity based on this invention is demonstrated.

  The first photosensitive polyimide precursor of the present invention contains (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, the photosensitive agent is an amine compound having a double bond as shown below, preferably a tertiary amine compound having a double bond, or a compound having an azide group. Can be mentioned. 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, 4-N , N-dimethylaminobutyl acrylate, cinnamic acid-2-N, N-dimethylaminoethyl, and the like. Moreover, the compound shown by following chemical formula as a photosensitizer is also mentioned.

  As the photosensitizer, at least one selected from the group consisting of the above compounds is used. The addition amount of the photosensitizer is preferably 0.1 to 120 parts by weight, and more preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the polyimide precursor. The reason is as follows. That is, when the addition amount of the photosensitive agent is less than 0.1 parts by weight, the sensitivity of the photosensitive polyimide precursor to exposure is not sufficient, and there is no difference in the dissolution rate in the developer between the exposed part and the unexposed part. . On the contrary, if the addition amount of the photosensitive agent exceeds 120 parts by weight, the residue of the photosensitive agent component becomes a problem after development.

  In the 1st photosensitive polyimide precursor of this invention, you may mix | blend a sensitizer as needed. Examples of the sensitizer include the following. For example, benzophenone, anthraquinone, benzoquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 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-benzimidazolyl) -7-diethylaminocoumarin, N-phenylglycine, 2- (dimethylamino) ethylbenzoate, ethyl (4-dimethylamino) benzoate, diethylthioxanthene, i Propylthioxanthene, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethyl ketal, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 1-hydroxycyclohexyl phenyl 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 compounding amount of the sensitizer is 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the photosensitive agent. When a sensitizer is added, the photosensitive characteristics of the first photosensitive polyimide precursor of the present invention can be further improved.

  The first photosensitive polyimide precursor of the present invention is obtained by dissolving a photosensitive agent and a sensitizer used as necessary in a solution of a predetermined polyimide precursor synthesized in an organic solvent as described above. 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, other solvents may be used in addition to the organic solvent for the purpose of adjusting the viscosity and improving the coating property to the substrate. Examples of such a solvent include isopropanol, methanol, ethylene glycol, butyl acetate, cellosolve, butyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and xylene. Moreover, in the 1st photosensitive polyimide precursor of this invention, you may mix | blend surfactant, a silane coupling agent, etc. according to the intended purpose.

A method for forming an insulating film pattern of a semiconductor device, for example, using the first photosensitive polyimide precursor of the present invention will be described. First, the photosensitive polyimide precursor varnish is filtered to remove fine insolubles, and then applied onto a semiconductor substrate by a method such as spin coating or dipping. By drying this at 60-100 degreeC, the layer of the photosensitive polyimide precursor is formed. A mask having a predetermined pattern is placed on the photosensitive polyimide precursor layer, and exposure is performed through irradiation with energy rays such as X-rays, visible light, infrared rays, ultraviolet rays, and electron beams. The photosensitive agent reacts during the exposure, and the polymer chain of the resin component is crosslinked in the exposed portion. The reaction at this time differs depending on whether the photosensitive agent 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 produced 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, or the like is caused to cross-link a polymer chain in an exposed portion. (2) When amine compounds having double bonds such as acrylate are used as photosensitizers, biradicals are generated by irradiation of energy rays at the double bond sites of these compounds, and recombination between radicals proceeds in a chain. To 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. In addition, you may heat-process at 80-200 degreeC with respect to the layer of the photosensitive polyimide precursor after exposure for 5 second-60 minutes as needed. When the heat treatment is performed in this manner, the cross-linked state of the polymer chain of the resin component becomes even stronger.

  Next, the photosensitive polyimide precursor layer is developed using a developer by a method such as an immersion method, a spray method, or a paddle method. At this time, since the polymer chain is not crosslinked in the unexposed area, it is dissolved in the developer. On the other hand, since the polymer chain is crosslinked in the exposed area, it becomes insoluble in the developer. As a developing solution, the organic solvent used for manufacture of a polyimide precursor can be used, for example. Also, for the purpose of smooth development processing, together with such organic solvents, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, acetone, cellosolve, methyl cellosolve, butyl cellosolve, ethylene glycol monoethyl ether acetate, toluene, xylene Water or the like may be used in combination. Further, for the purpose of removing the developer residue and the like after the development treatment, a rinse treatment may be performed using water, alcohol, acetone, or the like, followed by a treatment such as baking.

  Finally, the developed photosensitive polyimide precursor having a predetermined relief pattern is heated under predetermined conditions. By this heat treatment, the photosensitizing agent that crosslinks the polymer chain of the polyimide precursor is removed, the solvent remaining in the pattern is volatilized, and a ring closure of amic acid occurs to form a polyimide film pattern. In this step, it is desirable to gradually raise the temperature from room temperature to 150 to 450 ° C. which is the final heating temperature. When the final heating temperature is less than 150 ° C., some polyimide precursors remain without being imidized, which may impair thermal stability. On the other hand, if the final heating temperature exceeds 450 ° C., the imidized polymer may be decomposed to impair the thermal stability.

  Next, the 2nd photosensitive polyimide precursor of this invention is demonstrated. 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 photosensitivity, it is preferable that 25% or more of the repeating unit represented by the general formula (PA11) is contained in all repeating units.

In General Formula (PA11), Y is a tetravalent organic group derived from tetracarboxylic dianhydride, and L is a residue of a diamine compound represented by 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.

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

  In the second photosensitive polyimide precursor of the present invention, the photopolymerization initiator is an azide compound among the photosensitive agents described in relation to the first photosensitive polyimide precursor of the present invention, and sensitization used as necessary. At least one agent can be used. The compounding quantity of a photoinitiator is 0.05-30 weight part with respect to 100 weight part of polyamic acid derivatives represented with general formula (PA11), Preferably it is the range of 0.1-20 weight part.

  The method for forming the pattern of the insulating film 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. The bismaleimide-based cured resin precursor is represented by (a) a bismaleimide compound represented by the general formula (DM1), and (b) a diamine compound represented by the general formula (DA11) and the general formula (DP1). And a molecular structure in which at least one compound selected from the group consisting of dihydric phenol compounds is blended and reacted to some extent. In the general formula (DM1), the fluoro group or the aliphatic hydrocarbon group (R ³¹ ) substituted with the fluoro group is in the meta position as seen from the bonding site of the benzene ring to the maleimide ring and other benzene rings. It is preferably introduced.

  Examples of 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, include the following. For example, 3,3′-dimaleimido-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′-dimaleimido-5,5′-bis (trifluoromethyl) benzophenone, 1,3-bis [3 -Maleimido-5- (trifluoromethyl) phenyl] -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, , 4-bis [3-maleimido-5- (trifluoromethyl) phenoxy] benzene, 3,5-bis [3-maleimidophenoxy] benzotrifluoride, 3,5-bis [3-maleimido-5- (trifluoro) Methyl) phenoxy] benzotrifluoride, 3,3′-difluoro-5,5′-dimaleimidobiphenyl, bis (3-fluoro-5-maleimidophenyl) ether, bis (3-fluoro-5-maleimidophenyl) sulfide, Bis (3-fluoro-5-maleimidophenyl) sulfone, 3,3′-difluoro-5,5′-dimaleimidobenzophenone, 1,3-bis (3-fluoro-5-maleimidophenyl) -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, in an organic solvent, 1 molar equivalent of an aromatic diamine compound represented by the general formula (DA31) and 2 molar equivalents of maleic anhydride or maleic acid derivative anhydride represented by the general formula (MA1) By reacting, a bismaleamic acid compound represented by the following general formula (DMA1) is synthesized. (2) Next, 2 to 4 molar equivalents of acetic anhydride as a dehydrating agent are added to 1 molar equivalent of the bismaleamic acid compound represented by the general formula (DMA1) in an organic solvent, and 0.05 to 2 molar equivalents of a base and In the presence of 0.0005 to 0.2 molar equivalent of catalyst, dehydration cyclization is performed to synthesize a bismaleimide compound represented by the general formula (DM1).

(X ³¹ , R ³¹ , R ³² , a and b are as defined in the general formula (DM1).)
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- (trifluoro) Methyl) 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- (trifluoro) Fluoromethyl) 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-fluorophene) Noxy) 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 acid anhydride or maleic acid derivative anhydride represented by the general formula (MA1) are as described above.

  The following are mentioned as an organic solvent used at the time of reaction of (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-dimethoxy Acetamide, 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, dimethylsulfoxy , Sulfolane, and the like. These organic solvents may be used alone or in combination 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 can be sufficiently 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.

  Examples of the base used in the reaction (2) include alkali metal acetates and tertiary amines. For example, sodium acetate, potassium acetate, trimethylamine, triethylamine, tributylamine and the like.

  As a catalyst used in the reaction of (2), an alkaline earth metal oxide, or iron (II), iron (III), nickel (II), magnesium (II), manganese (III), copper (I) , Copper (II), cobalt (II) or cobalt (III) carbonate, sulfate, phosphate or acetate. 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 solvent as that used in the reaction (1) can be used. Therefore, it is not necessary to isolate the bismaleamic acid compound which is the reaction product of (1) during this reaction. The reaction temperature is 200 ° C. or lower, preferably 20 to 120 ° C. The reaction pressure is not particularly limited, and can be sufficiently carried out at normal pressure. The reaction time varies depending on the type of the bismaleamic acid compound and solvent, but 0.5 to 24 hours is sufficient. After the completion of the reaction, the precipitated bismaleimide compound can be obtained by filtering the precipitated crystals or placing them in water or methanol.

Among the components (b) of the bismaleimide-based cured resin precursor of the present invention, the diamine compounds represented by the general formula (DA11) include the following. 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′-diamino Benzophenone, 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] -1,1,1,3,3,3-hexa Fluoropropane,
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-di Aminonaphthalene, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,6-diamino-4- (trifluoromethyl) pyridine, 2,5-diaminopyrazine, 2,4-diamino-s-triazine, methane Diamine, 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-aminocyclohexyl) 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, 1,3-xylylenediamine, 1,4-xylylenediamine and the like. These diamine compounds may be used alone or in combination of two or more.

  From the viewpoint 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'-dia Nodiphenylmethane, 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, -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-biphenyl [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, etc. is there.

  Moreover, you may use together the bis (aminoalkyl) peralkyl polysiloxane compound represented by the general formula (DA6) mentioned above with these diamine compounds. The bis (aminoalkyl) peralkylpolysiloxane compound has the effect of improving the adhesion and adhesion of a 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 among all diamine components. Although this improves the adhesion and adhesiveness of the bismaleimide-based cured resin obtained by blending such a compound 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, examples of the divalent phenol compound represented by the general formula (DP1) include the following. 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-hydroxy Phenoxy) 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] -1,1,1,3,3,3-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-hexamethyltrisiloxane, 1,7-bis [3- (4-hydride) Xylphenyl) 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. 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 that are the component (b) (curing agent component) is the component (a). 0.01 to 2 molar equivalents are used per 1 molar equivalent of the bismaleimide compound. Furthermore, it is preferable to add 0.2 to 0.8 molar equivalent in the case of a diamine compound and 0.7 to 1.3 molar equivalent in the case of a dihydric phenol compound with respect to 1 molar equivalent of the bismaleimide compound. . 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 lowered. . In this case, since an excessive amount of the bismaleimide compound (a) is blended, maleimide molecules react with each other during the curing reaction, and the flexibility of the resulting cured resin is impaired. Conversely, if the amount of the curing agent component (b) is too large, an excessive curing agent component remains 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 added as a curing agent component to 1 molar equivalent of a bismaleimide compound, the curing reaction of the composition proceeds most efficiently. .

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

  The bismaleimide-based cured resin precursor of the present invention is prepared in the form of a varnish by dissolving the above-described components in an organic solvent. Examples of the organic solvent used here include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, and 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, dimethyl sulfoxide, sulfolane and the like. These organic solvents may be used alone or in combination of two or more.

  Further, the obtained varnish is usually A-staged before being used as an interlayer insulating film of an electronic component. That is, heating at 50-150 ° C. for 5 minutes to 5 hours to allow some progress of the addition reaction of the diamine compound or dihydric phenol compound to the bismaleimide compound, so that it is convenient to apply the varnish, Viscosity is increased.

  A method for forming an insulating film of an electronic component, for example, 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. This film is heated at 50 to 150 ° C. for 5 to 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. Although this heating temperature changes with structures, such as a bismaleimide compound used, it is normally set to the range of 100-450 degreeC. In this way, an insulating film made of a bismaleimide-based cured resin is formed.

  As a result, the resulting bismaleimide-based cured resin is not only excellent in heat resistance, but compared to conventional bismaleimide-based cured resins, it can be used for toluene, xylene, etc. The amount of gas generated is very small, the environmental stability is excellent, and the dielectric constant and moisture absorption are low.

  Next, the electronic component of the present invention will be described. The electronic component of the present invention comprises a polyimide resin obtained by curing the polyimide precursor described above or a bismaleimide-based cured resin obtained by curing a bismaleimide-based cured resin precursor as an insulating member such as an insulating film or an insulating substrate. It is. Such an electronic component can realize high-speed operation and power saving because of the low relative dielectric constant of the polyimide resin or bismaleimide-based cured resin constituting the insulating member, and the insulating member has low hygroscopicity and thermal stability. In addition, it is highly reliable because of its excellent environmental stability.

  More specifically, the polyimide resin or bismaleimide-based cured resin according to the present invention is an insulating film such as an interlayer insulating film, a moisture-resistant protective film, an α-ray blocking film of a semiconductor device, a carrier film, a flat cable, a flexible printed board, It is useful as an insulating member for electronic parts such as 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. Furthermore, the polyimide resin according to the present invention is very suitable for a liquid crystal alignment film of a liquid crystal display element. 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. However, in most cases, a bismaleimide-based cured resin may be used instead of the polyimide resin.

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

  FIG. 2 is a cross-sectional view of a package in which a semiconductor chip having a passivation film made of polyimide resin formed on the surface thereof as shown in FIG. 1 is resin-molded. In FIG. 2, a semiconductor chip 20 having a passivation film 19 made of polyimide resin formed on its surface 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 manufactured from a precursor according to the present invention is applied to an interlayer insulating film of a thin film magnetic head. In FIG. 3, a lower alumina 32, a lower magnetic body 33, and a gap alumina 34 are sequentially formed on the surface of the 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 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 are opposed to each other with the gap alumina 34 interposed therebetween at the tip of the magnetic head.

  FIG. 4 is a cross-sectional view showing an example in which a polyimide resin produced from a precursor according to the present invention is applied to an interlayer insulating film of a high-density wiring board. In FIG. 4, a thermal oxide film 42 and a first layer copper wiring 43 are sequentially formed on a silicon substrate 41. An interlayer insulating film 44 made of polyimide resin is formed on the entire surface. A contact hole is formed in the interlayer insulating film 44, and a second layer copper electrode 45 connected to the first layer copper electrode 43 is formed. Further, a passivation film 46 made of polyimide resin is formed on the entire surface. A contact hole is formed in the passivation film 46, and a barrier metal 47 and a Pb / Sm bump 48 are formed so as to be connected to the second-layer copper wiring 45.

  FIG. 5 is a cross-sectional view showing an example in which a polyimide resin produced from a 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 polyimide resin is formed on the entire surface thereof. Further, a permalloy 54 is formed on the interlayer insulating film 53.

  FIG. 6 is a cross-sectional view showing an example in which a polyimide resin produced from a precursor according to the present invention is applied to a heat-resistant transparent resin layer of a solar cell. In FIG. 6, a heat resistant transparent resin layer 62 made of polyimide resin is formed on the entire surface of a glass substrate 61. 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 step of the wiring can be greatly relaxed and a flat wiring structure can be obtained. The reliability of electronic parts can be improved. In addition, as described above, the insulating member obtained by curing the polyimide precursor of the present invention has a low relative dielectric constant, so that high speed operation and power saving can be realized, and it has low moisture absorption and is excellent in thermal stability and environmental stability. ing.

  FIG. 7 is a cross-sectional view of a liquid crystal display element having a liquid crystal alignment film made of a polyimide resin produced from a 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, a common electrode 75 is formed on the glass substrate 74, and a liquid crystal alignment film 76 made of polyimide resin is further coated on the entire surface thereof. These glass substrates 71 and 74 are placed parallel to each other with a predetermined gap with the liquid crystal alignment films 73 and 76 inside, and a liquid crystal 77 is sealed between them. Note that a substrate provided with a color filter may be used for colorization of the liquid crystal display element.

  As the substrate, in addition to glass, a transparent film such as polycarbonate, polyetheretherketone, polyethersulfone, or polyethylene terephthalate may be used. As the electrodes, transparent oxides such as ITO (Indium Tin Oxide) and indium oxide are used. The film thickness of the liquid crystal alignment film is set in the range of 5 to 1000 nm, preferably 20 to 200 nm. The polyimide resin constituting the liquid crystal alignment film is obtained by applying a polyamic acid varnish, which is a precursor thereof, to a substrate on which electrodes are formed, preliminarily drying at 90 to 120 ° C., and then heat-treating at 200 to 350 ° C. It is formed. 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 when the cells are assembled, the rubbing directions are the same, 90 ° twisted, or 200-290 ° twisted. The In order to stabilize the orientation of the liquid crystal, the liquid crystal display element may be annealed after the liquid crystal is sealed.

  In addition to the effects described above, 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 and also has an effect of high voltage holding ratio.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

Examples 1-1 to 1-45 and Comparative Examples 1 to 5
(1) Synthesis of Polyimide Precursor (Polyamide Acid) Polyamide acid was synthesized as follows using the raw materials shown in Tables 1 to 7 at a predetermined blending ratio (expressed in molar equivalents). First, 50 mL of N-methyl-2-pyrrolidone is put in a separable flask cooled to −5 to 0 ° C. with a refrigerant in a nitrogen gas atmosphere, and tetracarboxylic acid dicarboxylic acid represented by the general formula (DAH1) is used as an acid anhydride component. A predetermined amount of anhydride was added and dissolved with stirring. 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) as a diamine component is added to this solution as N-methyl-2. -A solution dissolved in 50 mL of pyrrolidone was slowly added dropwise from a dropping funnel equipped with a pressure equilibrium tube. After stirring for 2 hours, a solution prepared by dissolving a predetermined amount of maleic anhydride in 50 mL of N-methyl-2-pyrrolidone was slowly added dropwise from a dropping funnel equipped with a pressure equilibrium tube. The mixture was further stirred for 4 hours to obtain a varnish containing the target polyamic acid.

  The 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- (trifluoro Methyl) 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) benzotrifluoride 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-4,4′-dianiline PDA: 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) -1,1,3,3-tetramethyldisiloxane Comparative Example 1 is commercially available. Polyamic acid (manufactured by Sumitomo Bakelite Co., Ltd., CRC-6061), PMA (pyromellitic dianhydride), CBDPA (3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride) and pODA (oxy-4) , 4′-dianiline). In Comparative Examples 2 to 5, an aromatic diamine compound not included in the general formula (DA1) is used.

  The intrinsic viscosity of a 0.5 wt% N-methyl-2-pyrrolidone solution of each synthesized polyamic acid was measured at 30 ° C. These results are shown in Tables 1-7. From Tables 1 to 7, it was confirmed that a polyamic acid having a low 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 measurement results of the following physical properties of the polyimide film.

(A) Decomposition start temperature A polyamic acid varnish was applied on a glass plate having a size of 1 mm × 130 mm × 150 mm to a thickness of 75 μm by a bar coater, and then 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. In a dryer introduced with nitrogen gas, this was heated from room temperature, heated at 150 ° C., 250 ° C., and 350 ° C. for 1 hour, and finally heated at 400 ° C. for 30 minutes. A polyimide film was formed. The temperature rising time between each temperature was 1 hour. The obtained polyimide film was subjected to thermogravimetric analysis / differential thermal analysis (TG / DTA) in a nitrogen stream, and the temperature at which 0.5 wt% weight loss occurred was measured to determine the decomposition start temperature of the polyimide film. As a result, it was confirmed that the polyimide films of Examples 1-1 to 45 have heat resistance equivalent to that of the comparative example.

(B) Adhesion to Silicon Substrate A polyamic acid varnish was spin-coated on a 4-inch diameter silicon substrate so that the film thickness after curing was 5 to 10 μm. In a dryer introduced with nitrogen gas, this was heated from room temperature, heated at 150 ° C., 250 ° C., and 350 ° C. for 1 hour, and finally heated at 400 ° C. for 30 minutes. A polyimide film was formed. The temperature rising time between each temperature was 30 minutes. The silicon substrate on which the polyimide film was formed was left in a pressure cooker in an atmosphere of water vapor at 2 atm and 120 ° C. for 24 hours. Thereafter, a cellophane tape was applied to the surface of the polyimide film, and when it was peeled off under certain conditions, the ratio of the film peeled off from the substrate was examined to obtain a value indicating adhesion. As a result, it was confirmed that the polyimide films of Examples 1-1 to 45 were superior in adhesion to the silicon substrate as compared with those of Comparative Examples 1 to 5.

(C) Fillability in trench A varnish of polyamic acid is formed on a 4 inch diameter silicon substrate having a trench having a width of 0.3 μm and a depth of 1.0 μm on the surface, and the film thickness after curing is 5 to 10 μm. It spin-coated so that it might become, It was made to harden | cure on the conditions similar to (b), and the polyimide film was formed. Then, the cross section of the trench was observed with a scanning electron microscope (SEM), and the filling property to the trench was examined. As a result, in Examples 1-1 to 45, the trench was completely filled with polyimide without any gap. 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 A varnish of polyamic acid was spin-coated on an aluminum plate having a size of 1 mm × 100 mm × 100 mm 2 to 4 times so that the film thickness after curing was 40 to 60 μm. In a dryer introduced with nitrogen gas, this was heated from room temperature, heated at 150 ° C., 250 ° C., and 350 ° C. for 1 hour, and finally heated at 400 ° C. for 30 minutes. A polyimide film was formed. The temperature rising time between each temperature was 30 minutes. About the obtained polyimide film, the dielectric constant in 10 kHz was measured. As a result, it was confirmed that the polyimide films of Examples 1-1 to 45 have a dielectric constant of 3.0 or less, which is extremely lower than that of Comparative Example 1, and excellent dielectric properties.

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

Examples 2-1 to 2-11
(1) Synthesis of fluorinated aromatic diamine compound [Synthesis Example 2A] 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoro Synthesis of propane (6Fm6FDA) (a) Synthesis of 2,2-bis [3- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane (compound 2Aa) In a 500 mL autoclave 2,2-bis (3-iodophenyl) -1,1,1,3,3,3-hexafluoropropane 44.5 g (80.0 mmol), trifluoromethyl iodide 40.0 g (204 mmol), dried N, N-dimethylformamide (150 mL) and copper powder as a catalyst were added, and the mixture was heated and stirred at 150 ° C. for 24 hours. After allowing to cool, copper powder was filtered off from the reaction solution, and the filtrate was subjected to fractional distillation 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%
Elemental analysis:
Carbon Hydrogen Fluorine Calculated 46.4% 1.8% 51.8%
Analytical value 46.6% 1.8% 51.6%
(B) Synthesis of 2,2-bis [3-nitro-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane (compound 2Ab) obtained by (a) 26.5 g (60.2 mmol) of Compound 2Aa was dissolved in 60 mL of 95% concentrated sulfuric acid, 20 mL of 90% fuming nitric acid was slowly added with a dropping funnel, and the mixture was heated and stirred at 50 ° C. 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 collected with a separatory funnel and washed twice with 300 mL of 5% aqueous sodium hydroxide 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 value 38.5% 1.1% 43.0% 5.3%
Analytical value 38.8% 1.2% 42.8% 5.3%
(C) Synthesis of 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane (6Fm6FDA) obtained in (b) 26.5 g (50.0 mmol) of Compound 2Ab, 50 mL of isopropyl alcohol, and 1.5 g of 5% -Pd / C reducing agent (50% water-containing product) were placed in a reducing device and reacted at 80 ° C. for 4 hours in a hydrogen atmosphere. . After completion of the reaction, insoluble matters 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 target 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 value 43.4% 2.1% 48.5% 6.0%
Analytical value 43.6% 2.2% 48.3% 5.9%
Infrared absorption spectrum (KBr method):
3480cm ^-1 N-H reverse symmetrical stretching vibration (primary amine)
3390cm ^-1 NH symmetrical stretching vibration (primary amine)
1600cm ^-1 N-H in-plane bending angle (scissors) vibration (aromatic primary amine)
1320, 1250, 1220, 1190, 1140 cm ⁻¹ C—F stretching vibration and bending vibration (CF ₃ group).

Synthesis Example 2B Synthesis of 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl (6FmBPDA) 3-iodo-5-nitrobenzotrifluoride 15.9 g (50.2 mmol) , N′-dimethylformamide was dissolved in 50 mL, and 20 g of copper powder was added thereto, followed by heating under reflux for 72 hours. After allowing to cool, insoluble matters were removed by suction filtration, and the filtrate was concentrated under reduced pressure and dried in vacuo. The obtained residue was dissolved in 50 mL of isopropyl alcohol, and 1.5 g of 5% -Pd / C reducing agent (50% water-containing product) was added thereto, followed by reaction at 80 ° C. for 4 hours in a hydrogen atmosphere. After completion of the reaction, insoluble matters were removed by suction filtration, and the reaction solution was concentrated under reduced pressure to precipitate crude crystals. Recrystallization from a 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:
Carbon Hydrogen Fluorine Nitrogen Calculated 52.5% 3.1% 35.6% 8.7%
Analytical value 52.6% 3.0% 35.6% 8.8%
Infrared absorption spectrum (KBr method):
3500cm ^-1 N-H reverse symmetrical stretching vibration (primary amine)
3400cm ^-1 NH symmetrical stretching vibration (primary amine)
1600cm ^-1 N-H in-plane bending angle (scissors) vibration (aromatic primary amine)
1320 cm ^-1 CF ₃ symmetric deformation vibration 1200 cm ^-1 C-N stretching vibration (primary amine)
1140 cm ⁻¹ CF ₃ inverse symmetric deformation vibration.

[Synthesis Example 2C] Synthesis of 3,3′-diamino-5,5′-bisfluorobiphenyl (2FmBPDA) Using 13.4 g (50.2 mmol) of 3-fluoro-5-iodonitrobenzene, the same as Synthesis Example 2B The target compound (2FmBPDA) was obtained by the method.

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 value 65.4% 4.6% 17.3% 12.7%
Analytical value 65.7% 4.6% 17.1% 12.6%
Infrared absorption spectrum (KBr method)
3520cm ^-1 N-H reverse symmetrical stretching vibration (primary amine)
3420cm ^-1 NH symmetrical stretching vibration (primary amine)
1605cm ^-1 N-H in-plane deflection (scissors) vibration (aromatic primary amine)
1240cm ^-1 C-F stretching vibration (fluorobenzene)
1205cm ^-1 CN stretching vibration (primary amine)
(2) Synthesis of Polyimide Precursor (Polyamide Acid) Polyamide acid was synthesized as follows using the raw materials shown in Tables 8 and 9 at a predetermined blending ratio (expressed in molar equivalents). First, 50 mL of N-methyl-2-pyrrolidone is placed in a separable flask cooled to −5 to 0 ° C. with a refrigerant in a nitrogen gas atmosphere, and tetracarboxylic acid dicarboxylic acid represented by the general formula (DAH2) is used as an acid anhydride component. A predetermined amount of anhydride was added and dissolved with stirring. Fluorine-containing aromatic diamine compound represented by general formula (DA2) and bis (aminoalkyl) peralkylpolysiloxane compound represented by general formula (DA6) synthesized as described above as a diamine component in this solution A solution prepared by dissolving a predetermined amount in N-methyl-2-pyrrolidone was slowly dropped from a dropping funnel equipped with a pressure equilibrium tube. The mixture was stirred for 6 hours to obtain a varnish containing the target polyamic acid.

  Abbreviations used in Table 8 and Table 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 Product 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 Table 8 and Table 9 show the results of measuring the intrinsic viscosity of the polyamic acid solution and the decomposition start temperature, dielectric constant and moisture absorption rate of the polyimide film in the same manner as in Example 1. As a result, it was confirmed that the polyimide films of Examples 2-1 to 2-11 had heat resistance equivalent to that of Comparative Example 1 and had a very low dielectric constant.

Examples 3-1 to 3-8
(1) Synthesis of Polyimide Precursor (Polyamide Acid) Polyamide acid was synthesized as follows using the raw materials shown in Table 10 at a predetermined blending ratio (expressed in molar equivalents). First, 50 mL of N-methyl-2-pyrrolidone is put in a separable flask cooled to −5 to 0 ° C. with a refrigerant in a nitrogen gas atmosphere, and tetracarboxylic acid dicarboxylic acid represented by the general formula (DAH1) is used as an acid anhydride component. A predetermined amount of anhydride was added and dissolved with stirring. A predetermined amount of the fluorinated aromatic diamine compound represented by the general formula (DA5) and the bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA6) is added to this solution as a diamine component. A solution dissolved in 2-pyrrolidone was slowly dropped from a dropping funnel equipped with a pressure equilibrium tube. The mixture was stirred for 6 hours to obtain a varnish containing the target polyamic acid.

  The 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′-diphthal Acid dianhydride CBDPA: carbonyl-4,4′-diphthalic dianhydride 6FDPA: 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride Product SDPDA: 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 and the decomposition of the polyimide film Table 10 shows the results of measuring the starting temperature, dielectric constant and moisture absorption. 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.

Examples 4-1 to 4-15
(1) Synthesis of Polyimide Precursor (Polyamide Acid) Polyamide acid was synthesized as follows using the raw materials shown in Tables 11 and 12 at a predetermined blending ratio (expressed in molar equivalents). First, 50 mL of N-methyl-2-pyrrolidone is put in a separable flask cooled to −5 to 0 ° C. with a refrigerant in a nitrogen gas atmosphere, and tetracarboxylic acid dicarboxylic acid represented by the general formula (DAH1) is used as an acid anhydride component. A predetermined amount of anhydride was added and dissolved with stirring. 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) as a diamine component is added to this solution as N-methyl-2. -A solution dissolved in 50 mL of pyrrolidone was slowly added dropwise from a dropping funnel equipped with a pressure equilibrium tube. The mixture was stirred for 6 hours to obtain a varnish containing the target polyamic acid.

  Abbreviations used in Table 11 and Table 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′-diphthal Acid 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- (trifluoro Methyl) 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) 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'-di Nilin TSL 9306: 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane Intrinsic viscosity of each synthesized polyamic acid in 0.5 wt% N-methyl-2-pyrrolidone solution Was measured at 30 ° C. These results are shown in Table 4. From Table 4, it was confirmed that when maleic anhydride was used, a low-viscosity polyamic acid having an intrinsic viscosity of 0.5 or less could be synthesized.

(2) Preparation of photosensitive polyimide precursor Example 4-1
To 20 g of a 16 wt% N-methyl-2-pyrrolidone solution of polyamic acid (4-1), 1.57 g (0.01 mol) of 2-N, N-dimethylaminoethyl methacrylate as a photosensitizer and 2,6-di- After dissolving 0.37 g (0.001 mol) of (4-azidobenzal) -4-hydroxycyclohexanone to obtain a uniform solution, the solution 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, a 16% by weight N-methyl-2-pyrrolidone solution of polyamic acid and a photosensitizer, and if necessary, a sensitizer at a predetermined blending ratio (expressed by weight), were carried out. A photosensitive polyimide precursor was prepared in the same manner as in Example 4-1.

  The abbreviations used in Table 13 and Table 14 will be described.

(Photosensitive agent)
DMAEA: 2-N, N-dimethylaminoethyl acrylate DMAEM: 2-N, N-dimethylaminoethyl methacrylate DMABM: 4-N, N-dimethylaminobutyl methacrylate DABMCH: 2,6-di (4-azidobenzal) -4 -Methylcyclohexanone DABHCH: 2,6-di (4-azidobenzal) -4-hydroxycyclohexanone (sensitizer)
BDMK: benzyl dimethyl ketal

(3) Evaluation of photosensitive characteristics About each obtained photosensitive polyimide precursor, the photosensitive characteristics were evaluated in accordance with the method shown below. First, the photosensitive polyimide precursor was spin-coated on a silicon substrate and heat-dried at 90 ° C. for 6 minutes to form a coating film having a thickness of 4 to 6 μm. Next, ultraviolet rays were irradiated through a mask provided on the coating film using an exposure apparatus (PLA-500F manufactured by Canon Inc.). Next, development was performed with a developer composed 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 relief pattern thus formed was observed with a scanning electron microscope. Table 15 shows the initial film thickness, light irradiation amount, development time, remaining film ratio, and resolution.

As shown in Table 15, a relief pattern having a minimum line width of 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.

(4) Fillability in trench Aluminum was deposited on the surface of a 6-inch diameter silicon substrate and patterned to form a trench with a line and space of 0.3 μm and a depth of 1.2 μm. Each photosensitive polyimide precursor was spin-coated and heat-treated at 90 ° C. for 1 hour, 150 ° C. for 30 minutes, 250 ° C. for 30 minutes, and 400 ° C. for 1 hour to form a polyimide film. Then, the cross section of the trench was observed with a scanning electron microscope, and the filling property to the trench was examined. As a result, in Examples 4-1 to 15, the trench was completely filled with polyimide without a gap. In contrast, in Comparative Examples 6 and 7, it was confirmed that the trench was not completely filled with polyimide, and a large gap remained. Thus, it turned out that there is a big difference in the fluidity | liquidity and castability of a photosensitive polyimide precursor solution by the molecular structure of a polyimide.

Example 5
To a 100 mL four-necked flask having a nitrogen inlet tube, 8.88 g of 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride (6FDPA) ( 0.02 mol) and 5.2 g (0.04 mol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 6 days to obtain 6FDPA diester. The solution was kept at -15 ° C and thionyl chloride was added slowly. Then, while continuing stirring, the temperature of the reaction solution was gradually raised and maintained at 5 ° C. and reacted for 4 hours. To this solution, 7.04 g (0.02 mol) of 1,3-bis (3-amino-5-trifluoromethylphenoxy) benzene and 4.4 g (0.044 mol) of trimethylamine were added to N-methyl-2-pyrrolidone. A solution dissolved in 25 g was gradually added. This solution was kept at 5 ° C. under a nitrogen atmosphere and stirred for 8 hours, and then the resulting precipitate was removed by filtration under reduced pressure. 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, 0.05 g of 4,4′-bis (diethylamino) benzophenone and 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropanone-1 (0.01 g) was added, and the mixture was filtered through a 0.5 μm filter to obtain a photosensitive polyimide precursor.

  This photosensitive polyimide precursor was spin-coated on a silicon substrate and dried by heating at 90 ° C. for 5 minutes. Next, using an exposure apparatus (PLA-500F, manufactured by Canon Inc.), exposure was performed by irradiating with ultraviolet rays for 60 seconds through a mask provided on the coating film. Subsequently, it developed with the developing solution which consists of 7 volume parts of N-methyl-2-pyrrolidone and 3 volume parts of methanol, and rinsed with water. Furthermore, heat treatment was performed at 150 ° C. for 30 minutes, 250 ° C. for 30 minutes, and 350 ° C. for 60 minutes to obtain a relief pattern having a film thickness of 5 μm and a line and space of 6 μm.

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

  Moreover, the filling property to the trench of the photosensitive polyimide precursor was investigated similarly to Example 4 (4) using the silicon substrate which provided the aluminum pattern of line and space 0.3 micrometer and depth 12 micrometer. 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 element)
(1) Production of liquid crystal cell Example 6-1
An N-methyl-2-pyrrolidone solution of polyamic acid synthesized in Example 1-3 was diluted with butyl cellosolve acetate to prepare a solution having a concentration of 8% by weight. This solution was filtered with a filter having a pore size of 0.2 μm to remove insoluble matters such as dust, and then applied to a glass substrate on which an ITO electrode was formed by screen printing. This glass substrate was dried at 100 ° C. for 5 minutes, and subjected to heat treatment at 150 ° C. for 30 minutes and 250 ° C. for 30 minutes to form a 60 nm polyimide film. Next, using a rubbing machine having a roll wound with a nylon cloth, the polyimide film was rubbed at a roll rotation speed of 450 RPM and a stage moving speed of 1 cm / sec to obtain a liquid crystal alignment film. A pair of glass substrates having a liquid crystal alignment film that was rubbed in this manner was produced. The peripheral portions of these glass substrates were bonded to each other by heating and curing an epoxy-based adhesive containing beads as spacers at 180 ° C. to produce a cell with a cell gap of 10 μm. Finally, nematic liquid crystal (ZLI-1565, manufactured by Merck & Co., Inc.) was injected from the liquid crystal injection port, and the injection port was sealed with a photocurable epoxy resin to prepare a test liquid crystal cell.

Examples 6-2 and 6-3
A test liquid crystal cell was produced in the same manner as in Example 6-1, except that the polyamic acid synthesized in Example 1-39 or Example 3-9 was used instead of the polyamic acid in Example 1-3. did.

Comparative Example 6
Pyromellitic dianhydride 10.921 g (0.05 mol) and 60 g of N-methyl-2-pyrrolidone are placed in a four-necked flask equipped with a stir bar, thermometer, and nitrogen introduction tube, and dehydrated nitrogen is allowed to flow. Stir to a suspension. This suspension was maintained at 5 ° C., and 24.892 g (0.048) of 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane. Mol)) and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 0.495 g (0.002 mol) dissolved in N-methyl-2-pyrrolidone 120 g. Slowly added. Thereafter, stirring was continued at 5 ° C. to room temperature for 6 hours to synthesize polyamic acid. To 50 g of this solution, 35 g of N-methyl-2-pyrrolidone and 25 g of butyl cellosolve acetate were added to prepare an 8% by weight polyamic acid solution. Using this solution, a test liquid crystal cell was produced in the same manner as in Example 6-1.

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

  Here, the pretilt angle is calculated according to Journal of Applied Physics, Vol. 10, pp. 2013-3 (1980).

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

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

Examples 7-1 to 7-16 and comparative examples 7-1 to 7-4
(1) Synthesis of Bismaleimide Compound [Synthesis Example 7A] Synthesis of 3,3′-dimaleimide-5,5′-bis (trifluoromethyl) biphenyl (6FmBPDM) 50 mL of dimethylformamide was placed in a flask and stirred with stirring 10.8 g (110 mmol) of acid was dissolved. To this solution at room temperature, a solution of 16.0 g (50.0 mmol) of 3,3′-diamino-5,5′-bis (trifluoromethyl) biphenyl (6FmBPDA) in 50 mL of dimethylformamide was slowly added from the dropping funnel. It was dripped. After stirring for 3 hours, 2.4 g of triethylamine, 100 mg of magnesium (II) oxide and 10 mg of cobalt (II) acetate tetrahydrate were added, and 13 g of acetic anhydride was added dropwise from the dropping funnel over 30 minutes at room temperature. 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 this solution was decanted into 1 L of water to precipitate crystals. This operation was repeated once more, and purified crystals were collected by filtration. The crystals were vacuum dried 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% 2.1% 23.8% 5.8%
Infrared absorption spectrum:
1780, 1720 cm ⁻¹ C═O stretching vibration (cyclic imide)
1320, 1140 cm ⁻¹ C—F symmetrical bending vibration (CF ₃ group).

Synthesis Example 7B Synthesis of bis [3-maleimido-5- (trifluoromethyl) phenyl] ether (6FmODM) Oxy-5,5′-bis (3-trifluoromethylaniline) (6FmODA) instead of 6FmBPDA Using 16.8 g (50.0 mmol), the 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 value 53.2% 2.0% 23.0% 5.6%
Analytical value 53.3% 2.0% 22.9% 5.7%
Infrared absorption spectrum:
1780, 1720 cm ⁻¹ C═O stretching vibration (cyclic imide)
1320cm ^-1 C-F symmetrical bending vibration (CF ₃ group)
1245cm ^-1 C-O-C reverse symmetric stretching vibration (aromatic ether)
1140 cm ⁻¹ C—F symmetrical bending vibration (CF ₃ group).

Synthesis Example 7C Synthesis of bis [3-maleimido-5- (trifluoromethyl) phenyl] sulfone (6FmSNDM) 1,1′-bis [3- (trifluoromethyl) phenyl] sulfone (6FmSNDA) instead of 6FmBPDA ) Using 19.2 g (50.0 mmol), the target compound (6FmSNDM) was obtained by the same method as in Synthesis Example 7A.

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 value 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)
1320cm ^-1 C-F symmetrical bending vibration (CF ₃ group)
1310cm ^-1 S = O reverse symmetrical stretching vibration (sulfone)
1160cm ^-1 S = O symmetrical bending vibration (sulfone)
1140 cm ⁻¹ C—F symmetrical bending vibration (CF ₃ group).

Synthesis Example 7D Synthesis of 2,2-bis [3-maleimido-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane (6Fm6FDM) Instead of 6FmBPDA, Synthesis using 23.5 g (50.0 mmol) of 2,2-bis [3-amino-5- (trifluoromethyl) phenyl] -1,1,1,3,3,3-hexafluoropropane (6Fm6FDA) The target compound (6Fm6FDM) was obtained in the same manner as in Example 7A.

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% 1.6% 36.1% 4.5%
Infrared absorption spectrum:
1780, 1720 cm ⁻¹ C═O stretching vibration (cyclic imide)
1320, 1250, 1220, 1190, 1140cm ^-1 C-F stretching vibration and bending vibration (CF ₃ group)
(2) Preparation of bismaleimide-based resin varnish As shown in Table 17 to Table 19, a bismaleimide compound and an aromatic diamine compound or a dihydric phenol compound are used at a predetermined blending ratio (expressed in molar equivalents), and N, N -Dissolved in dimethylacetamide to prepare a 50 wt% solution of the resin composition. The solution was heated at 80 ° C. for about 1 hour to allow some reaction between the bismaleimide compound and the diamine compound or dihydric phenol compound (A-stage conversion), and then N, until the viscosity of the solution reached about 1 poise. N-dimethylacetamide was added to prepare a bismaleimide resin varnish.

  Abbreviations used in Table 17 to Table 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-maleimide-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-propylidene-3,3′-dianiline 6FpBPDA: 4,4′-diamino-2, 2′-bis (trifluoromethyl) biphenyl pMDA: methylene-4,4′-dianiline p6FDA: 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 are included in the general formula (DM1) The bismaleimide compound is not used.

(3) Measurement of physical properties of bismaleimide-based cured resin film (a) Decomposition start temperature Bismaleimide-based varnish is applied to a glass plate having a size of 1 mm × 130 mm × 150 mm to a thickness of 75 μm by a bar coater. And then prebaked at 110 ° C. for 1 hour. In a dryer introduced with nitrogen gas, this was heated from room temperature, heated at 150 ° C., 250 ° C., and 350 ° C. for 1 hour and finally heated at 400 ° C. for 30 minutes. A bismaleimide-based cured resin film was formed. The temperature rising time between each temperature was 1 hour. The obtained bismaleimide-based cured resin film is subjected to thermogravimetric analysis / differential thermal analysis (TG / DTA) in a nitrogen stream, and the temperature at which a weight loss of 0.5 wt% is measured is measured. The decomposition start temperature of was determined. 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) Dielectric constant A bismaleimide-based varnish was spin-coated 2 to 4 times on an aluminum plate having a size of 1 mm × 100 mm × 100 mm so that the film thickness after curing was 40 to 60 μm. In a dryer introduced with nitrogen gas, this was heated from room temperature, heated at 150 ° C., 250 ° C., and 350 ° C. for 1 hour and finally heated at 400 ° C. for 30 minutes. A bismaleimide-based cured resin film was formed. The temperature rising time between each temperature was 30 minutes. About the obtained bismaleimide type cured resin film, the dielectric constant at 100 kHz was measured. As a result, the bismaleimide-based cured resin films of Examples 8-1 to 16 have a dielectric constant as low as 3.0 or less, and have superior dielectric characteristics as compared with those of Comparative Example 1 that is generally used. Was confirmed.

(C) Generation amount of humidified decomposition gas Bismaleimide resin varnish was spin-coated on a 4-inch diameter silicon substrate so that the film thickness after curing was 5 to 10 μm. In a dryer introduced with nitrogen gas, this was heated from room temperature, heated at 150 ° C., 250 ° C., and 350 ° C. for 1 hour and finally heated at 400 ° C. for 30 minutes. A bismaleimide-based cured resin film was formed. The temperature rising time between each temperature was 30 minutes. The silicon substrate on which the bismaleimide-based cured resin film was formed was left for 1 week at 20 ° C. under saturated steam. Thereafter, the bismaleimide-based cured resin film was introduced into pyrofoil, heated with a Curie pyrolyzer at 358 ° C. for 3 seconds, and the generated gas component was analyzed by GC-MASS. The amount of toluene generated as a humidified decomposition gas was evaluated based on the value obtained by converting the integral value of the toluene signal in the ion chromatograph per 1 mg of the sample. As a result, it was confirmed that the bismaleimide-based cured resin films of Examples 8-1 to 16 had much less generation amount of toluene gas and excellent environmental stability than the comparative examples.

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 package in which a semiconductor chip having a passivation film made of a polyimide resin manufactured from a precursor according to the present invention is resin-molded, FIG. 3 is a 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 a precursor according to the present invention, FIG. 5 is a cross-sectional view of a magnetic bubble memory element 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 produced from a precursor according to the present invention, FIG. 7 is a cross-sectional view of a liquid crystal display element having a liquid crystal alignment film made of a polyimide resin produced from a precursor according to the present invention, FIG. 8 is a circuit diagram of a circuit used for measuring the pretilt angle and voltage holding ratio of the liquid crystal display element, and waveform diagrams of VS and VD.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 11 ... Silicon substrate, 12 ... Field oxide film, 13 ... Diffusion layer, 14 ... Thermal oxide film, 15 ... CVD oxide film, 16 ... First layer Al electrode, 17 ... Interlayer insulating film, 18 ... Second layer Al Electrode, 19 ... Passivation film, 20 ... Semiconductor chip, 21 ... Bed, 22 ... Lead, 23 ... Wire, 24 ... Sealing resin, 31 ... Substrate, 32 ... Lower alumina, 33 ... Lower magnetic body, 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 insulation Membrane, 45 ... second layer copper electrode, 46 ... passivation film, 47 ... barrier metal, 48 ... Pb / Sm bump, 51 ... garnet substrate, 52 ... conductor, 53 ... interlayer insulation 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.

Claims (6)

The following general formula (DA2)

(X ² represents a perfluoroalkylene group, a perfluoroalkylidene group, a sulfonyl group, or a single bond, and each R ² may be the same or different and is substituted with a fluoro group, an unsubstituted group, or 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, R ⁰ is hydrogen, and a and b are 3.
An amine component containing 0.10 mole equivalent or more of a fluorine-containing aromatic diamine compound represented by:
The following general formula (DAH1)

(Y represents a tetravalent organic group.)
A polyimide precursor characterized by having a structure obtained by polymerizing an acid anhydride component containing 0.80 to 0.99 molar equivalent of tetracarboxylic dianhydride represented by the formula: 0.97 to 1.03 molar equivalent of a diamine compound containing at least 0.10 molar equivalent of the fluorine-containing aromatic diamine compound represented by the general formula (DA2), and a tetracarboxylic acid represented by the general formula (DAH1). represented by dianhydride (1-n _2/2) molar equivalents and dicarboxylic anhydrides n ₂ molar equivalents (n ₂ is 0 to 0.4) and the polymerization was structure or the general formula, (DA2) that fluorine-containing aromatic diamine compound diamine compound containing 0.10 molar equivalent or more and (1-n _3/2) molar equivalents and monoamine compound n ₃ molar equivalents (n ₃ is 0 to 0.4), the general formula The polyimide precursor according to claim 1, which has a structure obtained by polymerizing 0.97 to 1.03 molar equivalent of tetracarboxylic dianhydride represented by (DAH1). The fluorine-containing aromatic diamine compound represented by the general formula (DA2) is represented by the following general formulas (DA3) and (DA4).

(Wherein X ³ is a perfluoroalkylene group or a perfluoroalkylidene group, R ^{2 s} may be the same or different and are each a fluoro group, an unsubstituted or substituted aliphatic hydrocarbon group substituted with a fluoro group, or A hydrogen atom, at least one is a fluoro group or an aliphatic hydrocarbon group substituted with a fluoro group, R ⁰ is each hydrogen, and a and b are 3.
The polyimide precursor according to claim 1, wherein the polyimide precursor is represented by any one of the following. A polyimide precursor composition comprising the polyimide precursor according to any one of claims 1 to 3 and a photosensitizer. A polyimide resin obtained by curing the polyimide precursor according to any one of claims 1 to 3. An electronic component comprising a polyimide resin obtained by curing the polyimide precursor according to any one of claims 1 to 3 as an insulating member.

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