JPS6151033A - Production of organic solvent-soluble polyimide compound - Google Patents

Abstract

PURPOSE:To produce the titled compound of excellent heat resistance in a one- step reaction, by heating at least two aromatic tetracarboxylic acids and a specified aromatic diamine in a phenolic solvent. CONSTITUTION:A mixture of at least two aromatic tetracarboxylic acids (a group consisting of a particular aromatic tetracarboxylic acid and its derivative) is reacted by heating with an aromatic diamine of formula I [wherein X is O, S, CO, SO2, CONH, a group of formula II, wherein n is 1-4, or a group of formula III, wherein R and R' are each a (fluorine-substituted) lower alkyl or a halogen] in a molar ratio of about 0.7-1.3 at about 100 deg.C or higher for about 10min-50hr in a phenolic solvent (e.g., m-cresol) to produce an organic solvent- soluble polyimide compound of excellent heat resistance.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an organic solvent-soluble polyimide compound, and more specifically, an organic solvent-soluble polyimide compound having a high glass transition temperature and a high thermal decomposition temperature and particularly excellent heat resistance. This invention relates to a method for producing polyimide compounds.

[Prior Art] Polyimide compounds generally have excellent heat resistance, so they are very useful as raw materials for films used at high temperatures, wire coating materials, TAM agents, paints, etc., and are used in the electronics and aerospace industries. There are great expectations in the field of cutting-edge technology such as

Conventional polyimide compounds include polymerizing an aromatic tetracarboxylic dianhydride such as anhydrous pyromellit M with an aromatic amine in a polar solvent to obtain an aromatic polyamic melt, and then using this solution as a base material. There is known a film-like aromatic polyimide compound which is insoluble in a solvent and is obtained by applying the compound to a film, forming it into a film, and then dehydrating and ring-closing it by a method such as heating.

However, in the case of conventional aromatic polyimide compounds, the stability of the aromatic polyamic acid, which is the precursor thereof, is poor, and when left at room temperature, the viscosity of the polyamic butylene solution decreases, and when left for a long time, some has disadvantages such as dehydration and ring closure to form polyimide, which becomes insolubilized and becomes cloudy. For this reason, conventional solutions of aromatic polyamic dairy products have to be stored at low temperatures and have the drawback of requiring care when handling them.

In addition, in the above method for producing polyimide compounds, the temperature is usually 400°C when imidizing the polyamic acid applied to the base material.
It is disadvantageous from the point of view of energy saving because it requires heating at higher temperatures than above for a long time, and since imidization involves a dehydration reaction, defects such as voids and pinholes occur in the resulting film, making it smooth and homogeneous. It is difficult to obtain a film of a polyimide compound.

Therefore, if the polyimide compound itself is soluble in a certain organic solvent, a polyimide compound film can be obtained by simply casting the solution onto a smooth surface and removing the solvent. Development has been desired and attempts have been made.

Many of the soluble polyimide compounds that have been proposed so far are
For example, stereoregularity can be achieved by introducing asymmetric monomer units, structural units with flexible skeletons and high mobility, or monomer units with bulky substituents into polymer chains through homopolymerization or copolymerization. The aim was to lower the solubility of the resulting polyimide compound.

For example, when introducing an asymmetric monomer unit,
A soluble polyimide compound that uses phenylindane diamine, which is an asymmetric diamine, as a diamine component is known (Japanese Patent Application Laid-open No. 82300/1983). Although it is soluble, it has the disadvantage of a lower thermal decomposition temperature than conventional aromatic polyimide compounds obtained from pyromellitic acids and aromatic diamines.

In addition, as a polyimide compound that is soluble due to the high flexibility and mobility of the polymer chain, a polyimide compound having the following structure is known (Japanese Patent Publication No. 47-3043
7), this polyimide compound is soluble in organic solvents due to the high mobility of its structural units, especially around ether bonds, but its glass transition temperature is 217°C, which is higher than that of conventional pyromellitic dianhydride and aromatic compounds. It has a disadvantage of poor heat resistance in that the mechanical strength at high temperatures is reduced because it is considerably lower than that of aromatic polyimide compounds obtained from diamines (250 to 400''O).

Based on the same idea as above, polyimide compounds made soluble in organic solvents by increasing the mobility of polymer chains include 1, 2, 3 aliphatic tetracarboxylic acids as the tetracarboxylic acid component. .A polyimide compound obtained by reacting 4-butanetetracarboxylic acid with an aromatic diamine (Japanese Patent Publication No. 4G-2238, No. 47-14503); Hexamethylene diamine, an aliphatic diamine, is used as the diamine component. Use, 3.3
Polyimide compounds obtained in combination with 4.4'-benzenenetetracarboxylic acid are known (Japanese Patent Publication No. 47-23191), but these polyimide compounds have Since it contains aliphatic units, its thermal decomposition temperature is higher than that of conventional aromatic polyimide compounds, and in this respect it has the disadvantage of inferior heat resistance.

In addition, as an example of increasing solubility by introducing a bulky substituent into the structure of a polyimide compound, there is a case in which caldopoly-y-(
V, V. Korshak et al., Macromol.

Cheap, CI 1, 45 (1974)
), but since the monomers that are the raw materials for producing these polyimide compounds require a complicated synthesis process that spans several steps, it is difficult to manufacture them on an industrial scale from economical and other points of view. It is not suitable.

Furthermore, at least 60 mol% of 3.3', 4,
4°-hensiphenotetracarboxylic acids and at least 60 mol % of the following general formula [wherein X is -〇H2-1-o-].

R is a lower alkyl group, a lower alkoxyl group, a halogen,
An aromatic polyimide compound obtained by reacting a diamine containing one or more aromatic diamines represented by -Cool (, -0H; l is -5O3HT) in a phenolic solvent is known. There is (Special Public Service 1977-1)
7145), this polyimide compound has a lower symmetry than the p,p'-diaminodiphenylene compound in order to make it soluble in phenolic solvents.

A p, p'-diamino m, m'-substituted diphenylene compound further having a substituent R at the mo-position (the above general formula (1)
) and m, m'-diaminodiphenyl compounds (general formula (II) above), etc., must be used in an amount of 60 mol% or more, but as a result, this polyimide compound becomes soluble in phenolic solvents. On the other hand, it has the disadvantage that both the thermal decomposition temperature and the glass transition temperature are lower than the conventional polyimide compounds using p, p'-diaminodiphenylene compounds, and the heat resistance is inferior.

Further, as another soluble aromatic polyimide compound, a tetracarvone brewing component consisting of at least 50 mol% of 3.3', 4,4'-benzophenone tetracarpones and 50 mol% or less of pyromellitic butyric compounds; at least 7
5 mol% of 4.4°-diaminodiphenyl ether and 2
A method for producing an aromatic polyimide compound is known in which an aromatic diamine component consisting of 5 mol% or less of P-phenylenediamine is heated in a halogenated phenol at 100 to 200°C (Japanese Patent Laid-Open No. 187430/1983). This aromatic polyimide compound has high thermal decomposition temperature and high glass transition temperature, and has excellent heat resistance, but the solvent in which it can be dissolved is limited to halogenated phenols, and it is difficult to dissolve in other general-purpose organic solvents. However, halogenated phenols that can be used for dissolution are more expensive than general-purpose phenolic solvents such as m-cresol, and have drawbacks such as being nonflammable and therefore difficult to dispose of. . Existing equipment that is configured to use general-purpose phenolic solvents such as m-cresol has the disadvantage that polyimide compounds that are soluble only in halogenated phenols as described above cannot be used. Moreover, the obtained temperature was as high as 70''C), which was unsatisfactory in terms of workability.

C Problems to be Solved by the Invention] As mentioned above, conventional organic solvent soluble polyimide compounds are generally less soluble than conventional insoluble aromatic polyimide compounds produced from pyromellit H etc. and aromatic diamines. They had the disadvantage of having a low thermal decomposition temperature and/or a low glass transition temperature, and poor heat resistance, which is an important characteristic of polyimide compounds. Further, in the case of soluble polyimide compounds having excellent heat resistance, there is a problem in that they are soluble only in halogenated phenols, and general-purpose organic solvents such as m-cresol cannot be used.

Therefore, one purpose of the present invention is to solve these problems and provide a method for producing a polyimide compound that has high heat resistance comparable to conventional insoluble aromatic polyimide compounds and is soluble in general-purpose organic polar solvents. It's about doing.

' [Means for solving the problems] The present invention provides aromatic tetracarboxylic compounds of 2!1 or more and general formula (I) [wherein, X is -0-1-S-1-CO-1] -502+
, -CONH-1-(CH2)n- (n is 1-y4, preferably an integer of 1 to 2), and lower alkyl groups such as -CH3, -c2H5, -CF3, - and at least one type of aromatic diamine represented by a divalent group selected from fluorine-substituted lower alkyl groups such as C2F5 or halogen atoms such as F, CI, and Br in a phenolic solvent. The present invention provides a method for producing an organic solvent-soluble polyimide compound by a one-step reaction characterized by the following.

In the present specification ID, aromatic tetracarboxylic acid refers to 4
Aromatic tetracarboxylic acids refer to tetravalent carboxylic acids in which four carboxyl groups are directly bonded to an aromatic ring. esters and tetraalkyl esters (where the alkyl group is, for example, methyl).

means a lower alkyl group such as ethyl or propyl (hereinafter, these are referred to as "aromatic tetracarboxylic acid MW form"). Therefore, for example, pyromellitic acids mean pyromellitic acid and pyromellitic dianhydride, dialkyl ester, and tetraalkyl ester, which are pyromellitic acid derivatives.

Such aromatic tetrapower is used in the present invention.

Specific examples of luponic acids include pyromellitic acids, 3,
3°, 4,4°-benzophenonetetracarboxylic acids,
3.3', 4.4'-biphenylsulfonetetracarboxylic mW, 1,2,5.6-naphthalenetetracarboxylic acids, 1,4,5.8-naphthalenetetracarboxylic acids, 2,3,6°7- Naphthalenetetracarboxylic acids, furantetracarboxylic acids, 3.3', 4.4'-biphenyl ethertetracarboxylic acids, 3.3°, 4°4"
-dimethyldiphenylsilanetetracarboxylic acids, 3.
Examples include 3', 4,4'-tetraphenylsilane tetracarboxylic acids, 3,3°, 4,4°-perfluoroisopropylidene biphenyl tetracarboxylic acids, and the like.

In the production method of the present invention, it is essential to use a combination of 12 or more types of aromatic tetracarboxylic assembling-resistant beads in order to obtain an organic solvent-soluble polyimide compound. That is, when using two compounds that are, for example, aromatic tetracarboxylic acids or aromatic tetracarboxylic derivatives, the two compounds must be compatible with different aromatic tetracarboxylic acids; Two types of compounds belonging to aromatic tetracarboxylic acids, such as pyromelli
Even if i and a pyromellitic derivative are combined, the requirements of the present invention cannot be met, and the resulting polyimide compound becomes insoluble in organic solvents. Furthermore, when combining two or more aromatic tetracarboxylic acids, it is necessary that the amount of aromatic tetracarboxylic acids not exceed 97 mol%, preferably not exceed 95 mol%, based on the weight of any aromatic tetracarboxylic acid used. .

Aromatic tetracarboxylic acids in an amount exceeding 97 mol%
,! ! However, if it exists, it is difficult to obtain the effect of combining other types of aromatic tetracarboxylic acids, and the resulting aromatic polyimide compound often has insufficient solubility in organic solvents. ,
When a plurality of compounds present therein are used in combination, their total amount must of course not exceed 97 mol%.

There are no particular restrictions on the combination of two or more aromatic tetracarboxylic skeletons, for example, 2! ! Examples of combinations of aromatic tetracarboxylate include S pyromellitic vinegars and 3.3', 4.4°-henzophenone tetracarboxylic acids; modified pyromellitic acids and 3.3', 4.4°- Biphenylsulfonetetracarboxylic acids; 3.3', 4.4°-benzophenonetetracarboxylic acids and 3,3°, 4,4°-biphenylsulfonetetracarboxylic acids; 3.3°, 4,4°-biphenyltetra Carboxylic acids and 3.3',4.4'-benzophenonetetracarboxylic acids; 3.3',4,4°-biphenyltetracarboxylic acids and 3,3°,4.4°-biphenylsulfonetetracarboxylic acids; Pyromellitic acids and 3.3',4.4'-biphenyl ethertetracarboxylic acids; 1.2,5.6-naphthalenetetracarboxylic acids and 3.
3°, 4.4'-Biphenyl ether tetracarboxylic acids; 3.3', 4.4'-dimethyldiphenylsilane tetracarboxylic acids and pyromellitic acids; 3.3°, 4.4'
-dimethyldiphenylsilanetetracarboxylic acids and 3.
3',4,4°-benzophenonetetracarboxylic acids; 3.3'',4.4°-dimethyldiphenylsilanetetracarboxylic acids and 3,3°,4,4°-biphenylsulfonetetracarboxylic acids;3. 3°, 4'-dimethyldiphenylsilane tetracarboxylic acids and 3.3', 4
．． 4"-isopropylidene diphenyltetracarboxylic acids: 3.3', 4.4'-tetraphenylsilane tetracarboxylic acids and pyromellitic acids; 3.3°, 4,4°-tetraphenylsilane tetracarboxylic acids and 3,3°,4,4°-benzophenonetetracarboxylic acids: 3.3°,4.4'-tetraphenylsilanetetracarboxylic acids and 3,3°,4,4'-biphenylsulfonetetracarboxylic acids: 3 .3', 4.4'-Perfluoroisopropylidene diphenyltetracarboxylic acids and pyromellitic acids; 3.3°, 4,4°-perfluoroisopropylidene diphenyltetracarpone 6P=M and 3,3°.

4.4°-benzophenonetetracarboxylic acids 3.3°
, 4.4″-perfluoroisopropylidene diphenyltetracarboxylic acids and 3.3′.

4.4°-biphenylsulfonetetracarboxylic acids; 3.3°, 4.4'-isopropylidene diphenyltetracarboxylic acids and pyromellitic acids: 3.3°, 4.4
'-isopropylidene diphenyltetracarboxylic acids and 3.3',4.4'-benzophenonetetracarboxylic acids; 3.3',4.4°-isopropylidene diphenyltetracarboxylic acids and 3,3°,4 , 4°-biphenylsulfone tetracarboxylic acids; perylene-3,4,9,10
-tetracarboxylic acids and 3.3',4.4°-benzophenonetetracarboxylic acids; perylene-3,4,9,to-tetracarboxylic acids and 3
．． 3',4,4'-perfluoroisopropylidene diphenyltetracarboxylic acids; perylene-3,4,9,t
o-Tetracarboxylic acids and 3.3',4,4°-biphenyl ether tetracarboxylic acids; 3.3',4,4°-biphenyl sulfide tetracarboxylic acids and 3.3',4.4°-benzophenone Tetracarboxylic acids; 3.3°, 4.4'-biphenylsulfide tetracarboxylic acids; 3°, 4.4°-biphenylsulfone tetracarboxylic acids; 3.3°, 4.4'-biphenylsulfide tetracarboxylic acids; Examples of combinations of carboxylic acids and 3.3', 4.4'-biphenyl ether tetracarboxylic acids include pyromellitic acids and 3.3', 4.4'-biphenyl ether tetracarboxylic acids. , 4°+ hair sophenonetetracarboxylic acids and 3.3', 4°4'-
Biphenylsulfonetetracarboxylic acids Pyromellitic acids and 3.3',4.4'-Henzophenonetetracarboxylic acids and 3,3°,4°4'-biphenyltetracarboxylic acids; 3.3',4 .4'-benzophenonetetracarboxylic acids and 3.3',4,4°-biphenylsulfonetetracarboxylic acids and 3.3',4,4°-biphenyltetracarboxylic acids;1.2,5.6-naphthalene Tetracarboxylic acids and 3.
3', 4.4°-benzophenonetetracarpone M
and 3.3°,4.4'-biphenylsulfonetetracarboxylic acids: 1.2,5.6-naphthalenetetracarboxylic compounds and 3.
3',4,4°-benzophenonetetracarboxylic acids and 3.3',4.4°-biphenyl ethertetracarboxylic acids; pyromellitic butyric acids and 3,3°,4,4'-benzophenonetetracarpones Acids and 3.3', 4°4°-Biphenyl ether tetracarboxylic acids and pyromellitic acids and 3
．． 3', 4.4''-henzophenonetetracarboxylic acids and 3.3', 4゜4'-impropylidene diphenyltetracarboxylic acids; Pyromellitic acids and 3,3°, 4,4°- Henzophenonetetracarboxylic acids and 3.3',4゜4'-perfluoroisopropylidene diphenyltetracarboxylic acids; Pyromellitic acids and 3.3',4.4'-benzophenonetetracarboxylic acids and 3 .3',4゜4゛-dimethyldiphenylsilanetetracarboxylic acids; pyromellitic acids and 3,3°,4.4'-henzophenonetetracarpon 6'AM and 3,3°,4゜4゛-Tetraphenylsilane tetracarboxylic acids, pyromellitic acids, 3.3', 4.4'-isopropylidenediphenyltetracarboxylic acids, and 3゜3', 4,4°-henzophenone tetracarpon butyric compounds ; Perylene-3,4,9,10-tetracarvone is class and 3
, 3°, 4.4'-henzophenone tetracarboxylic acids and 3.3', 4.4"-biphenylsulfone tetracarboxylic acids; pyromellitic acids and 3.3', 4,4"-henzophenone tetracarboxylic acids Zophenonetetracarponaceous acids and 3,3°, 4°4°-biphenyl sulfide tetracarboxylic acids can be used in a variety of ways, but the polyimide compound obtained has particularly excellent IIV18 property and solubility in Yutsuki melt, and is further used. Particularly preferred combinations include the following, since aromatic tetracarboxylic acids are easy to obtain or synthesize.

Pyromellitic acids and 3,3',4,4'-benzophenonetetracarboxylic acids; 3.3',4,4'-benzophenonetetracarboxylic acids and 3.3',4,4'-biphenylsulfonetetracarboxylic acids Acids; 1° pano-acids and 3.3° 4.4'-<yso: phenonetetracarboxylic acids and 3.3', 4. .

4'-biphenylsulfonetetracarboxylic acids, pyromellitic acids and 3.3', 4.4'-biphenyltetracarboxylic acids; 3.3', 4.4'-benzophenonetetracarboxylic acids and 3.3', 4, 4°-biphenyltetracarboxylic acids; 3.3', 4.4'-biphenyltetracarboxylic acids and 3.3', 4,4''-biphenylsulfone tetracarboxylic acids; Pyromelligua and 3.3', 4 .4'-benzophenonte I lacarboxylic acids and 3,3°, 4°4°-biphenyltetracarboxylic acids; 3,3', 4,4°-perfluoroisopropylidene diphenyltetracarboxylic acids and pyromellitic acids; 3.3', 4.4'-perfluoroisopropylidene diphenyltetracarboxylic acids and 3,3°.

4.4'-benzophenonetetracarboxylic acids, pyromellitic acids, 3.3',4.4'-benguaenonetetracarcipones, and 3.3',4'4'-perfluoroisopropylidene diphenyltetracal Ponic acids.

> Specific examples of the aromatic diamine of general formula (I) used in the production method of the present invention include 4,41-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide,
, 4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminophthalamide, 4,4°-diaminodiphenylmethane, 4,4°-diaminodiphenylethane, 2,2-bis(4- aminophenyl)propane, 2,2-bis(4-7minophenyl)hexafluoropropane, 3,3-bis(4-aminophenyl)pentane, 2,2-bis(4-aminophenyl)butane, bis(4 -7minophenyl)dichloromethane, bis(4-aminophenyl)dibromomethane, bis(4-7minophenyl)octafluorobutane, 2,2
-bis(4-7minophenyl)tecafluoropentane,
Mention may be made of 2.2-bis(4-7minophenyl)octafluorobutane.

In the production method of the present invention, the above-mentioned aromatic diamines can be used alone or in combination of two or more.
When combining two or more types of aromatic diamines, there are no particular restrictions on the combination. For example, a combination of two types of aromatic diamines is 4.4°-diaminodiphenyl ether and 4°4°-diaminodiphenylmethane; 4.4°-diaminodiphenyl ether and 4°4°-diaminodiphenylsulfone; 4.4°-diaminodiphenylmethane and 4.4”-diaminodiphenylsulfone; 4.4°-diaminobenzophenone and 4.4”-diaminodiphenyl ether: 4.4'-Diaminobenzophenone and 4.4'-diami/diphenylmethane; 4.4°-Diaminobenzolieone and 4,4°-diaminodiphenylsulfone; 2.2-bis(4-7minophenyl)hexafluoro Propane and 4.4′-diaminodiphenyl ether; 2,
2-bis(4-7minophenyl)hexafluoropropane and 4,4''-diaminodiphenylmethane; 2,2-bis(4-7minophenyl)hexafluoropropane and 4
．． 4°-diaminodiphenylsulfone; 2,2-bis(
4-7minophenyl)hexafluoropropane and 4゜4
'-Diaminobenzophenone: 2.2-bis(4-7minophenyl)propane and 4.4
°-Diaminodiphenyl ether; 2,2-bis(4-
2.2-Bis(4-aminophenyl)furopane and 4.4°-diaminodiphenylsulfone; 2.2
-bis(4-7minophenyl)propane and 4.4°-diaminobenzophenone; 2.2-bis(4-7minophenyl)furopane and 2.2
-bis(4-aminophenyl)hexafluoropropane, and a combination of three aromatic diamines.

4.4'-diaminodiphenyl ether, 4°4'-diaminodiphenylmethane and 4,4'-diaminodiphenylsulfone;4.4'-diaminodiphenyl ether, 4'4'-diaminodiphenylmethane and 4.4'-diaminobenzophenone: 4 .4'-diaminodiphenyl ether and 4'4'-diaminodiphenylmethane and 2,2-bis(4-7minophenyl)hexafluoropropane; 4.4'-diaminodiphenyl ether and 4'4'-diaminodiphenylmethane and 2.2 -bis(4-7minophenyl)propane; 4.4°-diaminodiphenyl ether and 4°41-diaminobenzophenone and 4.4'-diaminodiphenylsulfone; 4.4°-diaminodiphenylmethane and 4,4''-diaminobenzophenone 4.4°-diaminodiphenylsulfone; 4.4°-diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone and 4.4′-diaminobenzophenone: 4.4°-diaminodiphenylmethane and 2,2-bis(
4-7minophenyl)propane and 2,2-bis(4-7
4,4'-diaminodiphenyl ether and 2,2-bis(4-7minophenyl)propane and 2,2-bis(4-aminophenyl)hexafluoropropane; 4,4'-diaminodiphenyl ether and 4,4′-diaminodiphenylsulfone and 4,4°-diaminobenzophenone; 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone and 4,4”-diaminobenzophenone; 4,4′-diaminodiphenylmethane and 4,4'-diaminodiphenylsulfone, 2,2-bis(4-7minophenyl)hexafluoropropane, 4,4'-diaminodiphenylmethane, 4,4°-diaminodiphenylsulfone, and 2,2-bis(a- aminophenyl)propane; 4,4'-diaminodiphenylsulfone and 2,2-bis(4-7minophenyl)propane and 2,2-dos(4-
Aminophenyl) hexafluoropropane: 4 + 4'-diaminobenzophenone and 2,2-bis(4-7minophenyl)propane and 2,2-bis(4
-7minophenyl)hexafluoropropane and the like.

Among these combinations, particularly preferred combinations include: 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether; 4,4'-diaminodiphenylmethane and 4,4°-diaminodiphenylsulfone 4,4°-diaminodiphenyl ether; 4.

4”-diaminodiphenylsulfone; 4,4′-diaminodiphenylmethane and 4,4.

-diaminobenzophenone; 4,4'-diaminodiphenyl ether and 4.

4'-Diami/benzo7ene;4,4'-diaminodiphenylmethane and 4,49-diaminodiphenyl ether and 4.4°-diaminodiphenylsulfone; 4,4'-diaminodiphenylmethane and 4.41-diaminodiphenyl ether Examples include 4,4'-diaminobenzophenone.

The method for producing the polyimide compound of the present invention is carried out by heating the above-described two or more aromatic tetracarboxylic acids and the aromatic diamine of the general formula CI) in a phenolic solvent, and the reaction of these monomers. The process proceeds in one step to obtain the desired polyimide compound as a solution in a phenolic solvent.

Specific examples of phenolic solvents used as reaction solvents include phenol, 0-cresol, m-cresol,
p-cresol, 2,3-dimethylphenol, 2.4
-dimethylphenol, 2,5-dimethylphenol,
2.6-dimethylphenol, 3.4-dimethylphenol, 3.

Examples include 5-dimethylphenol. These phenolic solutions. Among the media, m-cresol is particularly suitable because it is liquid at room temperature and is easy to handle. Also,
Other 7-enol solvents can also be used by lowering the melting point by using them as a mixed solvent with m-cresol. In addition, other solvents other than the phenolic solvent may be added to this reaction solvent in an amount of about 30% by weight or less, if necessary. For example, depending on the purpose, O-chlorophenol, m-chlorophenol, p- Chlorphenol,
o-fromphenol, m-bromophenol, P
- In cases where halogenated phenols such as 7'-romophenol are added to enhance the solvent's solubility, or when water is produced as a by-product in one reaction.

Solvents that are azeotropic with water, such as methylcyclopentane, cyclohexane, hexane, inhexane, methylcyclohexane, heptane, ethylcyclohexane, octane, 2,2,4-trimethylpentane, nonane, decane,
benzene, toluene.

Add xylene, ethylbenzene, cumene, etc., and remove by-product water from the system by azeotropy.
It is also possible to allow the reaction to proceed smoothly. In addition, an organic solvent that does not impair the reaction can be added as a diluent or the like within a range that does not precipitate the polyimide compound.

Aromatic tetracarboxylic acids to be subjected to reaction and general formula (I)
The molar ratio of the aromatic diamine is preferably 0.7 to 1.3 in order to obtain a high molecular weight polyimide compound, and especially approximately 1.
is preferred.

In addition, the molecular weight of the resulting polyimide compound can be adjusted by changing the molar ratio of aromatic tetracarboxylic acids and aromatic diamines, or by adding aromatic monoamines such as aniline or aromatic dicarboxylic anhydrides such as phthalic anhydride. This can be done by adding.

The concentration of these monomers in the reaction solution is 3-501! amount%
, and more preferably 5 to 30 mm%.

The reaction temperature when carrying out the present invention is usually above 100°C, preferably above 100°C and below 200°C, particularly preferably between 120°C and 200°C. In the production method of the present invention, polyimidation is carried out in one step. However, in order to promote polyimidation, a temperature exceeding 100°C is desirable;
Polyimidization does not proceed smoothly at temperatures below 100° C. Under such reaction conditions, the reaction is usually completed in 10 minutes to 50 hours.

The intrinsic viscosity η1nh (Ci degree 0.5 g/room 1, solvent m-cresol, 30°C) of the polyimide compound obtained in this way is 0.05 dl/g or more, especially 0.
．． 05 to 20 dl/g is preferred.

If the intrinsic viscosity is less than 0.05 dl/g, the moldability as a polyimide compound will be insufficient, which is undesirable.The intrinsic viscosity ηinh is as follows: (t is the flow rate of the polymer solution, to is the flow rate of m-cresol) It is the viscosity expressed by

[Effect of the invention] The aromatic polyimide compound obtained by the production method of the present invention is soluble in general-purpose phenolic solvents, and especially when m-cresol is used as a solvent, it has a relatively low viscosity and is fluid at room temperature. It is easy to handle because it is obtained as a solution. Therefore, in addition to extremely high workability when producing a film, it is possible to produce a homogeneous film without defects such as pinholes by simply drying it after forming it by a conventional method such as casting or spin coating.

Further, this aromatic polyimide compound has high stability in a solution state of a phenolic solvent.

It can be stored for a long period of time without any deterioration such as a decrease in viscosity or insoluble analysis.

Furthermore, this polyimide compound has a high thermal decomposition temperature and a high glass transition temperature, and has excellent heat resistance comparable to conventional solvent-insoluble aromatic polyimide compounds.

The polyimide compound of the present invention is also excellent in terms of mechanical properties, electrical properties, chemical resistance, etc., and is useful for, for example, high-temperature films, adhesives, paints, etc., and specifically for printed wiring boards. , flexible wiring boards, surface protection films or living room insulation films for semiconductor integrated circuit elements, liquid crystal alignment films,
For enameled wires: Useful for $ covering materials, various VI layer plates, gaskets, etc.

[Examples] The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples.

Example 1 4.4″-diaminodiphenylmethane (hereinafter referred to as DDM) was placed in a single capacity flask equipped with a thermometer, stirrer, and cooling tube.
) 24.90 g (0,125 mol, 100 mol % as aromatic siamite component) and m-cresol 488
g, and heated this mixture with a spatula until it reached 120 g.
The temperature was raised to 0.degree. C. to dissolve DDM. After dissolving pyromellitic dianhydride (hereinafter referred to as PMDA) 6, 70
g (0,031 mol, 25 mol% as an aromatic tetragluponic acid component) and 3.3,4.4''-benzophenonetetracarpon are dithermal hydrates (hereinafter referred to as BTDA).
) A mixture of 30.29 g (0,094 mol, 75 mol % as aromatic tetracarboxylic acid component) was quickly added as a powder to the above m-cresol solution. Thereafter, the temperature of the reaction mixture was increased to 160 °C, and at that temperature
The reaction was carried out for 51 hours to obtain a transparent and viscous solution of the polyimide compound.

When the infrared absorption spectrum of the obtained polyimide compound was measured, absorption of carbonyl stretching vibration of imide carbonyl based on imide ring formation was observed at 1780 cm'' and 1720 cm~1, and in this polyimide compound, absorption of carbonyl stretching vibration of imide carbonyl based on imide ring formation was observed at 1780 cm'' and 1720 cm~1. It was found that the above imidization was progressing.The m-cresol solution (concentration: 10.4% by weight) of the polyimide compound obtained had sufficient fluidity at room temperature.

Table 1 shows the viscosity, intrinsic viscosity, 10% thermal decomposition temperature and glass transition temperature of the obtained polyimide compound.

Furthermore, the obtained solution of the polyimide compound was directly cast onto the smooth surface of a glass plate in the form of a film, and then heated in an oven to completely remove the m-cresol solvent, which revealed defects such as pinholes. A homogeneous and smooth polyimide film was obtained. The tensile strength and dielectric constant of this polyimide film are also shown in Table 1.

Examples 2 to 14 Polyimide compounds were produced in the same manner as in Example 1, except that the types and amounts of aromatic tetracarboxylic acids and aromatic diamines used were changed as shown in Table 1.

(1) From the results of infrared absorption spectra of the obtained polyimide compounds, it was found that imidization of 95% or more had progressed in all Examples. - (2) The viscosity of the polyimide compound solution obtained by the above production was measured. The results are shown in Table 1 along with the polyimide compound concentration in the solution.

The intrinsic viscosity, 10% thermal decomposition temperature, glass transition temperature, tensile strength and dielectric constant of the obtained polyimide compound formed into a film in the same manner as in Example 1 are shown in Table 1.
The meanings of the compound abbreviations in are as follows.

BSTA: 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride DDE: 4,4'-diaminodiphenyl ether DDS: 4,4''-diaminodiphenylsulfone Solution of polyimide compound obtained in this example Even when stored at room temperature for one month, no turbidity or precipitates were generated, and the solution viscosity did not change, indicating extremely excellent storage stability.

Example 15 0.125 mol of ¥ DD', 0.094 mol of 3.3', 4.4''-benzophenone tetracarboxylic acid, and 488.73 g of Niecresol were charged all at once into a flask.
This mixture was gradually heated from room temperature to 160"C.
The 0 reaction, which was carried out at 0° C. for 5 hours, proceeded homogeneously, and a uniform reddish-brown polyimide compound solution was obtained after the reaction. It was found from the infrared absorption spectrum that at least 95% of the resulting polyimide compound had been imidized. Further, the obtained polyimide has a ηinh of 0.
It was 54 dl/g.

Example 16 3,3',4.4''-benzophenone tetracarpone modified used in Example 15 was replaced with 3.3'.

4. The reaction was carried out in the same manner as in Example 15, except that 0.094 mol of 4'-benzophenone tetracarpon dimethyl ester was used. The reaction proceeded homogeneously, and after the reaction, a uniform red polyimide was formed. A compound solution was obtained. It was found from the infrared absorption spectrum that at least 95% of the resulting polyimide compound had been imidized.

In addition, the r) inh of the obtained polyimide is 0.55d
It was l/g.

Example 17 In Example 6, m-cresol 488g was replaced with m-cresol.
- The reaction was carried out in the same manner as in Example 6, except that 488 g of a solvent consisting of cresol/phenol = 70/30 (volume ratio) was used. The reaction proceeded homogeneously, and a uniform reddish-brown polyimide compound was formed after the reaction. A solution was obtained. The obtained polyimide compound has an infrared absorption spectrum of at least 9
It was found that 5% imidization had progressed. The obtained polyimide (7)'7inh was 0.83 d
It was l/g.

Comparative Examples 1 to 9 As shown in Table 2, one aromatic tetracarboxylic compound and one aromatic diamine were used, and the reaction was carried out in the same manner as in Example 1. The reaction proceeded in a heterogeneous system, resulting in a uniform No polyimide compound solution was obtained.

Comparative Example 10 PMD A9.0 as aromatic tetracarboxylic acid component
20 mol and BTDAo, 080 mol were reacted in the same manner as in Example 1 using DDEo, 090 mol as aromatic diamine and 0.010 mol of p-7 enylenediamine, but the polymerization reaction proceeded in a heterogeneous system. and uniform poly,
No imide compound solution was obtained.

Comparative Example 11 0.100 of BTDA as aromatic tetracarboxylic compound
Mol as aromatic diamine 3゜3'-dichloro-4
, 4'-diami/diphenylmethane (0.100 mol), 413 g of m-cresol was added, the temperature was raised from the point of overflowing, and the reaction was carried out at 160°C for 5 hours. The obtained polyimide compound is.

It was confirmed from the infrared absorption spectrum that at least 95% of imidization had progressed. Moreover, ηinh of the obtained polyimide compound was 0.76 dl/g.

However, the 1O% thermal decomposition temperature was 515°C, and the glass transition temperature was 266°C, which were lower than the polyimide compound obtained by the present invention.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Representative Patent Attorney Shuji Iwamiya Procedural amendment stamp September 21, 1982

Claims (1)

[Scope of Claims] Two or more aromatic tetracarboxylic acids, general formula ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ [In the formula, X is -O-, -S-, -CO-, -SO_2
-, -CONH-, -(CH_2)_n- (n is 1 to 4
) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R
and R' are the same or different divalent groups selected from a lower alkyl group, fluorine (substituted lower alkyl group or halogen atom)] and at least one aromatic diamine represented by the following in a phenolic solvent. A method for producing an organic solvent-soluble polyimide compound by a one-step reaction characterized by heating.