JPS58180530A - Novel fluorine-containing polyamide and polyimide - Google Patents

Abstract

NEW MATERIAL:Polyamides having a repeating unit of formula I (wherein -NH- is situated in position ortho or meta with respect to the arom. ether linkage -O-; R<1> is a tetravalent org. group; R<2> is H, a monovalent org. group) and polyimides having a repeating unit of formula II (wherein -N< is situated at position ortho or meta with respect to the arom. ether linkage; R<1> is as defined above). USE:Moisture-resistant, heat-resistant materials such as protective film for semiconductor device, interlayer material (e.g. LSI) or alpha ray-shielding film. Surface stabilizing film on the exposed end part of PN junction. Interlayer insulating film for multi-layer wiring. PREPARATION:A diamine contg. at least one member selected from fluorine- contg. diamines of formulas III, IV, V is reacted with a tetracarboxylic acid derivative. The reaction mixture is treated, e.g., heated to obtain the polyimide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an imide yarn polymer having both heat resistance and moisture resistance, and a precursor thereof. In addition, semiconductor device protection d1
The present invention relates to moisture-resistant and heat-resistant materials useful for 1-related materials such as m, LsI, and α-ray shielding films.

Polyimide-based polymer is used for exposed 14i8 (S
It is well known that it is useful as a surface stabilizing film on top, an insulating film between layers of multilayer wiring, and a shielding film for preventing soft errors in memory devices caused by natural radiation (particularly alpha rays). However, for these uses, ordinary polyimides have drawbacks such as high moisture absorption and moisture permeability, and large deterioration of adhesive properties due to moisture absorption. That is, when such a film absorbs moisture, there is a problem that leakage current at the PN junction increases, and in the case of multilayer wiring or an α-ray shielding film, the wiring and electrode material (for example, An) corrode. Friend, if the moisture absorption rate is high, there may be a problem in the manufacturing process that the polyimide film will swell due to rapid heating.

The present inventors synthesized polyimides with various chemical structures,
Characteristic evaluation results 1 For example, polyimide-siloxane copolymer (W)CH having the following chemical structure.

・・・・・・・・・(■) Due to the siloxane skeleton, it has good heat resistance and is easy to be mixed with cedar agent. The purpose of the present invention is to melt the present invention using a removal method, etc.
Eliminates the drawbacks of the above conventional technology.

It is an object of the present invention to provide a polyimide material useful as a material for a semiconductor coating film, which has both low hygroscopicity and thermal stability.

The feature of the present invention is the following repeating unit (1)
A fluorine-containing polyimide having the following repeating units is obtained by reacting % of a fluorine-containing polyamide having a fluorine-containing polyamide.

CF, ・・・・・・・・・(1)
C.F.

・・・・・・・・・ml The position of σ- or m- relative to the chill bond -〇-.

R1 is a tetravalent organic group Th R' is hydrogen or a monovalent organic group) The present inventors synthesized polyamides or polyimides with various chemical structures and evaluated their characteristics. It has been found that when the above repeating unit (conversion) is introduced into , the @tii ratio is greatly reduced and the thermal stability is also very good.

The polyamide of the present invention usually has the following chemical structure fil~(
It is obtained by the reaction of diamine (II) containing at least one type of fluorine diamine having the formula 3) with a tetracarboxylic conductor. Next, a polyimide is obtained by treatment such as heating. In general, polyimide is rolled into a ball that is difficult to dissolve in solvents, and its precursor, polyamide, is rolled in the form of a face.

Polyimide is usually obtained by coating a polyamic acid face, drying, and curing to obtain a polyimide film. The polyamide, which is the precursor of the polyimide in the above chapter, has excellent solubility in solvents and is commonly used in N-methyl-2.
-Pyrrolidone (NMP).

Dimethylacetamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide (DMSO)
In addition to polar solvents such as, it can also be used in combination with general-purpose organic solvents such as cresol, phenol, acetone, and diacetone alcohol.

If solvent resistance is a problem, the solvent resistance can be further improved by the following modification method.

(1) By modifying with a compound represented by the general formula (■) or ω, a pyrrolone structure or isoindoroquinazolinedione Jj1ft is introduced to carve a rigid ladder structure.

A bornene group is introduced and three-dimensional hardening occurs when heated.

GID Aromatic amine with ethynyl group or cyano group (expletive) or heptalic acid derivative (Xlli) t-
and three-dimensional crosslinking by heating.

Z R' NH* ・” ”・・・・
(XI) 4ψ phenolic hydroxyl group or carbo/
The following tetracarboxylic acids can be used to synthesize a polyamic acid into which an acid-containing aromatic diamine is introduced, and then add a crosslinking agent to three-dimensionally crosslink it.

Further, in the present invention, the following commonly used aromatic diamines may be used in combination. Examples include the following: m-phenylenediamine, p-phenylenediamine, pendidi/.

4.4"-diaminoterphenyl, 4,4///-diaminoquaterphenyl, 4.4'-diaminodiphenyl ether%414'-diaminodiphenylmethane,
Diaminodiphenylsulfone, 2゜2-bis(p-aminophenyl)propane, 2゜2-bis(p-aminophenyl)hexafluoropropane, 1.5-diaminonaphthalene, 2.6-diaminonaphthalene, 3.3 '-dimethylbenzidine, 3.3'-dimethoxybenzidine, 3.
3'-dumenal-4,4'-diaminodiphenyl ether, 3.3'-dumenal-4,4'-diaminodiphenylmethane% 1.4-bis(p-aminophenoxy)benzene, 4.4'- Bis(p-7minophenoxy)biphenyl, 2,2-bis(4-(p-aminophenoxy)
phenyl) propane.

general formula %formula% Examples include phenylenediamine.

9.For the purpose of improving adhesion with glass, ceramics, metals, etc., the general formula (R10 is a divalent organic group, R'' is a -valent organic group, p.

A silicone-containing diamine represented by (q is a princess number greater than 1) may be used in combination.

Tetracarboxylic acid derivatives that can be used in the present invention include:
Pyromellitic acid, 3.3', 4.4' -tetracarboxybiphenyl, 2,3.3', 4' di-tetracarboxylic acid, phenyl, 3.3', 4.4'
-Tetracarboxydiphenyl ether, 2.3゜3
/, 4/-tetracarboxydiphenyl ether, 3.
3', 4,4'-tetracarboxybenzophenone,
2,3.3', 4'-tetracarboxybenzophenone, 2.3,6.7-titracarpoxynaphthalene, 1
, 4,5.7-tetracarboxynaphthalene, 1,2.
5.6-Citracarpo-sinaphthalene, 3.3', 4
．． 4'-tetracarboxydiphenylmethane, 2.2-
Bis(3゜4-dicarboxyphenyl)propane, 2゜2-bis(3,4-dicarboxy7enyl)hexafluoropropane, 3.3',4.4'-tetracarboxydiphenylsulfone, 1 , 2,7.8-tetracarboxyperylene, 2.2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propa/-11↓, 2.2
-bis(4-(a.

Aromatic tetracarboxylic acids such as 4-dicarboxyphenoxy(phenyl)hexafluoropropane, their acid dianhydrides, and partially esterified products with lower alcohols can be used.

However, if high heat resistance is not available, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid may be used.

When (1) is used as a method for improving bath agent resistance, compounds with the general formula that give a ladder structure include 1,2,3-)riaminobenzene,
1,2.4-triaminobenzene, 1,2゜4.5-tetraaminobenzene, 3-aminobenzidine, 3.3'
-diaminobenzidine, 3,4°4'-) IJ aminodiphenyl ether Th313'14.4'-tetraaminodiphenyl ether, 3°4.4'-triaminobenzophenone, a*a's4.4'-tetraaminobenzophenone, 3,4°4'-triaminodiphenylmethane % a, 3/14.4'-tetraaminodiphenylmethane, 3°4.4'-1 riaminodiphenyl sulfide.

3.3',4.4'-Tetraaminodiphenyl sulfide, 3,4.4'-)riaminodiphenylsulfone, 3.3',4.4'-tetraaminodiphenylsulfone, 2.2-bis(3 ,4-diaminophenyl)furopane% 4s 4/-bis(3゜4-diaminophenoxy)biphenyl, 2.2-bis(4-(3,4-diaminophenoxy)phenyl)propane, 2.2-bis(4
-(3,4-diaminophenoxy)phenyl)hexafluoropropane and other triamines are tetraamines, 1.3
-cyamine-2-carbamoylbenzene, 1゜3-diamino-4-carbamoylbenzene, 1,4-diamino-
2-carbamoylbenzene, 1,4-diamino-2,5
-Dicarbamoylbenzene, 3-carbamoylbenzidine, 3.3'-dicarbamoylbenzicine, 3-carbamoyl-4,4'-diaminodiphenyl ether, 3
．． 3'-Dicarbamoyl-4,4'-diaminodiphenyl ether, 3-carbamoyl-4,4'-/aminobenzophenone, 3,3'-dicarbamoyl-4゜4
-diaminobenzophenone, 3-carbamoyl-4,4
'-Diaminodiphenylmethane, 3゜3'-dicarbamoyl-4,4'-diaminodiphenylmethane, 3-carbamoyl-4,4'-)aminodiphenyl sulfide, 3,3'-dicarhamoyl-4,4' ,) amino-diphenyl sulfide, 3-carbamoyl-4,4
'-Diaminodiphenylsulfone, 3,3'-dicarbamoyl-4,4'-diaminodiphenylsulfone, 2゜2-bis(3-carbamoyl-4-aminophenyl)propane, 2,2-bis(s-carbamoyl-4) -7 minophenyl) hexafluoropropa.

4,4'-bis(3-carbamoyl-4-aminophenoxy)biphenyl, 2,2-bis(4-(3-carbamoyl-4-7minophenoxy)phenyl)propane, 2,2-bis(4- Aromatic diamines having one or two carbamoyl units such as (3-carbamoyl-4-7enoxy)phenyl)hexafluoropropane,
1,3-diamino-2-sulfamoylbenzene, 1.
3-diamino-4-sul7amoylbenzene, 1.4-
Diamino-2-sulfamoylbenzene ThL4-diami/-2,5-disulfamoylbenzene, 3-sulfamoylbenzidine%3.3'-disulfamoylpenzidine, 3-sulfamoyl-4,4'-diamino Diphenyl ether, 3゜3'-disulfamoyl 4.4
'-Diamino diphenyl ether, 3-sulfamoyl-4,4'-diaminobenzophenone% as 3/-
Disulfamoyl-4*4'-)aminobenzophenone, 3-sulfamoyl-4,4'-diaminodiphenylmethane, 3.3'-disulfamoyl-4゜4'-diaminodiphenylmethane, 3-sulfamoyl-4,4'
-diaminodiphenyl sulfide, 3,3'-disulfamoyl 4,4'-diaminodiphenyl sulfide), 3-sulf7 amoy, 4,4'-diaminodiphenylsulfone, 3#3'-disulfamoyl 4 .4'
-diaminodiphenylsulfone, 2,2-bis(3-sulfamoyl-4-aminophenyl)propane, 2゜2
-bis(3-sulfamoyl-4-7minophenyl)hexafylpropane, 4.4'-bis(3-sulfamoyl-4-aminophenoxy)biphenyl, 2.2-bis(4-(3-sulfamoyl-4-amino) There are aromatic diamines having one or two sulfamoyl groups, such as phenoxy)phenyl)propane and 2,2-bis(4-(3-sulfamoyl-4-aminophenoxy)phenyl)hexafluoropropane.

When using the GiD method as a method for improving solvent resistance, the following compounds are available as compounds having an ethynyl group or a cyan group. For example, m-edenylaniline,
p-ethynylaniline, 4-ethynyl-4'-fumi/ni'phenyl, 4-ethynyl-4'-7mi/diphenyl ether, 3-ethynyl-3'-aminodiphenyl ether, 4-ethynyl-4'-amino Benzophenone, 4-
Compounds having an ethynyl group and an amino group, such as ethynyl-4'-aminodiphenylsulfone, (p-ethynylphenyl)p-aminobenzony), (p-aminophenyl)p-ethenylpenzoate, m-cyano Aniline, p-cyanoaniline, 4-cyano-4'-aminobiphenyl, 4-Schiff/-4'-aminodiphenyl ether, 4-cyano-4'-aminodiphenyl ether, 4-
cy1/-4'-aminobenzophenone, 4-cyano-4
'-Aminodiphenylsulfone, (p-cyanophenyl)p-aminobenzoate, (p-aminophenyl)p
- Compounds having a cyano group and an amino group such as cyanobenzoate, 3-ethynyl phthalic anhydride, (p-ethynylphenyl) trimellitate anhydride.

3-(4-enanylphenoxy)phthalic anhydride.

Alternatively, compounds having an ethynyl group and a dicarboxylic acid derivative such as these free dicarboxylic acids or esterified products with lower alcohols, 3-cyanophthalic anhydride, (p
Examples include compounds having a cyano group and a dicarboxylic acid derivative, such as 3-(4-cyanophenoxy)phthalic anhydride*, or esterified products of these with free dicarboxylic acids or lower alcohols.

When using method 4v) as a method for improving solvent resistance,
Examples of diamines having a carboxylic acid in the phenolic hydroxyl group include the following. For example, diaminophenol, bis(p-7minophenoxy)phenol, I) (diaminophenyl)phenol, 3.
5-bis(p-aminophenoxy)phenol, 2.4
-bis-(p-aminophenylmethyl)phenol, 2
．． 6-bis(p-aminophenylmethyl)phenol,
There are diaminophenols such as 3°3'-dihydroxybenzidine.

In the present invention, the following organic diamines containing carboxylic acids can be used in combination. For example 2.14-
Diaminobenzi, tI, folic acid, 3.5-diaminobenzoic acid, @, folic acid, 2.5-diaminobenzoic acid, 3-carboxybenzidine, 3.3'-dicarboxybenzidine, 4.4'-
Diamino-3-carboxydiphenyl ether, 3.3
'-dicarboxy-4,4'-diaminodiphenyl ether, 3,3'-dicarboxy-4,47-diamitudiphenylmethane, 2,2'-dicarboxy-4,4'
-diaminodiphenyl ether, 1,5-diamino-4
-Carboxynaphthalene, 4,4'-diamino-3-carboxydiphenylsulfone, 4,4'-diamino-3
, 3'-dicarboxydiphenyl sulfone, 2-(4-
7minophenyl)-2-(3-carboxy-4-aminophenyl)propane, 2,2-bis(3-carboxy-
4-aminophenyl)furopane, 2,2-bis(3-carboxy-4-aminophenyl)hexafluoropropane, 2,4-bis(p-aminophenoxy)an-11 acid,
3.5-bis(p-aminophenoxy)amt', aromatic acid,
p-bis(3-carboxy-4-aminophenoxy)benzene, 4.4'-bis(3-carboxy-4-aminophenoxy)biphenyl, p-bis(3-carboxy-
4-aminophenoxy)tetrafluorobenzene, 4.
4'-bis(3-carboxy-4-aminophenoxy)
Octafluorobiphenyl, 2,2-bis(4-(a-
Carboxy-4-aminophenoxy)phenyl)propane, 2.2-bis(4-(3-carboxy-4-aminophenoxy)phenyl)hexafluoropropane, 4.
4'-bis(3-carboxy-4-aminophenoxy)
Diphenylsulfone, 1,2-bis(3-carboxy-
4-aminophenyl)ethane, 1,2-bis(3-carboxy-4-aminophenyl)tetrafluoroethane,
1゜3-bis(3-carboxy-4-aminophenyl)
Propane, 1.3-bis(3-carboxy-4-aminophenyl)hexafluoropropane, 1゜5-bis(3
-carboxy-4-aminophenyl)pentane, 1.5
-bis(3-carboxy-4-aminophenyl)decafluoropentane and the like.

Further, in place of the above-mentioned carboxylic acid-containing modest diamine, lower alkyl esters such as methyl ester, edel ester, furoyl ester, butyl ester, or phenyl ester nato esters may be used.

When a diamine having a phenolic hydroxyl group is used, the curing agent for three-dimensional crosslinking after polyamic acid (or polyimide) synthesis may include epoxy groups, carboxyl groups and their derivatives, or incyanate groups, which react directly with the phenol hydroxyl group. A compound having at least two functional groups and a compound of the general formula (S) when the active water X1 has it at the ortho or para position with respect to the phenolic OH group;
For FE/-/'41, a fat hardening agent or a phenol resol resin can be used.

R” +CH!
XIV) Dichloride 1m-xylylene dichloride.

halomethyl group compounds of dichloromethyl diphenyl ether, dichloromethyl diphenylmethane, dichloromethyl bi7enyl, dichloromethyl naphthalene, bis(chloromenalphenoxy) diphenylsulfonate, hydroxyl compounds obtained by hydrolyzing these halomethyl groups,
Alkoxylated products obtained in the presence of a basic compound in alcohol, or acetylated products obtained by acenalization, etc. are effective. Although halomethylated compounds are basic, they are not preferred because they involve a dehydrohalogenation reaction in the curing reaction.

In the case of hydroxylated or alkoxylated products, the condensate is preferably water or alcohol.

In addition, when the functional group for three-dimensional crosslinking is a carboxylic acid or its ester, the crosslinking agent may be an epoxy group,
There are compounds having at least two or more isocyanate groups, masked isocyanate groups, amino groups, and hydroxyl groups.

In the present invention, in the reaction of the fluorine-containing diamine and the tetracarboxylic acid derivative, the blending ratio C, cyamine 1
When using a diamine having a tetracarboxylic acid I ruboxyl group relative to 4-l, it may be counted as a diamine. When using other amino groups, or phthalic acid or nazic plate compounds, 1.8 to 2 carboxyl groups (or derivatives thereof) per equivalent of amino group.
A ratio of 2 equivalents is preferable.

Regarding the reaction conditions, each raw material may be reacted in a molten state, but
Usually, the above-mentioned reaction is carried out in an organic solvent at a relatively low temperature,
A polyamic acid (precursor) varnish is first obtained, processed by coating, and dried by heating under pressure waves.

The ring is closed to obtain a 1jlk final polyimide (or modified polyimide). When using crab anhydride as the tetracarboxylic acid derivative, the temperature is preferably about -20 to 50C, and in the case of free carboxylic acid or ester compound, the temperature is about 40 to 50C.
200C @ degree range is good.

After that, in order to make a polymer with electric current, such as imide ring closure,
200-500 (:') high temperature heating is required.

Next, the present invention will be explained in more detail by showing examples.

However, the present invention is not limited to the following examples.

Example 1 Reflux condenser with stirring bar and water metering receiver.

33.6 g of hexafluorobisphenol A (0,
1 mol), 150 g of dimenal sulfoxide, and 60 gt of toluene were added, stirred and mixed to dissolve the solution. To this, add hydroxide) IJum8. Og (0.2 mol) was dissolved in 8.0 g of water, a pressurized aqueous solution was added, and the mixture was refluxed with stirring to dehydrate. When water stopped coming out, the capacitor was placed in a Liebig condenser and heated to around 150C to distill off the remaining water and toluene. Next, L fCm VC was cooled to about 100 C, and 31.5 g (0.2 mol) of m-chloronitropenzene was added thereto, and the mixture was reacted for about 5 hours with stirring. The reaction mass is then poured into 1000 m6 of water and a yellow precipitate forms. This was taken from door to door and thoroughly washed with water. After washing and drying at 60C under reduced pressure, 2#2-
515 gm of bis-14-(m-nitrophenoxy)phenyl)hexafluoropropane were obtained. It was confirmed from the infrared m-absorption spectrum that the -OH group had disappeared and it had become an aromatic ether.

Then, 2,2-bis(4-(m-nido aphenoquine)
phenyl) hexafluoropropane 28.9 g (0.05
Dissolve 200 g of Henzea (mol) and add activated iron consisting of 93 g of iron powder and 23 g of #hydrochloric acid.

The mixture was heated and stirred at 70C for 2 hours. 20 g of water was added and reflux was continued for another 2 hours, and after cooling, the benzene layer was separated. Evaporation of the benzene solution gave a yellow powder. Infrared absorption spectroscopy confirmed that the nitro group was reduced to an amino group. This is called 6FDMAPP.

Example 2 CF-containing diamine 6FDMAPP synthesized in Example 1
36.95gt-N-methyl-2-pyrrolidone (NM
After dissolving 297.5g of P) and cooling it in an ice water bath for about 5CK, dissolve pyromellitic dianhydride (with stirring).
Add 15.55 g of PMDA little by little. After the pyromellitic dianhydride is almost dissolved.

Remove the water bath and let the reaction take place at room temperature for about 2 hours.

It becomes entangled with the stirring rod. This was heated to 80 to 85C and reacted until the viscosity at 20C became 100P to obtain a polyamic acid varnish.

This varnish was applied on a glass plate for 150 tons. /lh
A strong polyimide film was obtained by heating at +300c/2h. The saturated moisture absorption of this film under the condition of 75% 25G was 0.58%, which was found to be extremely small for a polyimide. Next, in the air on a thermobalance,
When heated at a temperature increase rate of 5C/death, the temperature at which weight loss starts (
The temperature at which the weight loss reaches 0.5% excluding water is 470t.
:'I found it to be very good.

Example 3 Instead of pyromellitic dianhydride in Example 2.

Benzophenone tetracarboxylic dianhydride (BTDA)
A polyamic acid varnish was obtained under similar conditions using the following ratios.

Next, a polyimide film was produced in the same manner as in Example 2, and the moisture absorption rate and weight loss starting temperature were measured.

The moisture absorption rate of this film was 0.63% at the saturation value of 25C7S%RH. , and the weight loss starting temperature is 4
It was 65C.

Comparative Example 1 Polyamic acid was synthesized using p-phenylenediamine (p-PDA) instead of 6FDNAAPP in Example 2. The reaction rate is as follows.

Next, a polyimide film was produced, and its absorption rate and weight loss onset temperature were measured. However, the imidization conditions are 15 QC
/1 h+300C/1 h+40 QC/lh Toshitomo. @Humidity was 4.8%, and weight loss starting temperature was 500C. However, this polyimide film has the drawback of being very brittle and having poor mechanical properties.

Comparative Example 2 4,4'-diaminodiphenyl ether (DDE) was used for the 6FDMAPP in Example 3. The reaction rate is the following notice.

Next, a polyimide film was produced, and its moisture absorption rate and weight loss onset temperature were all measured. However, the imidization conditions are 150C/
1 h + 30 (1/1 h + 40 (1/15 min). The buoyancy rate was 27%, and the weight loss starting temperature was 460C.

Example 4 Instead of PNDA in Example 2, 2.2-bis(4(3
,4-dicarboxyphenoxy)phenyl)hexafluoropropane dimhydrate (6FT('PPA)) was used.The reaction ratio is as follows.

Next, a polyimide film was prepared in the same manner as in Example 2, and the moisture absorption rate and weight loss starting temperature t were measured. The resulting film was extremely strong, had a moisture absorption rate of 0.39%, and a weight loss initiation temperature of 455C.

Next, it was applied onto a silicon wafer with a diameter of 3 inches using a spinner coater and cured so as to have a film thickness of 20 μm after being heated and cured. This was immersed in trichlorobenzene at 120C for 20 minutes, and the amount of decrease in coating film thickness was measured. As a result, the film thickness decreased by about 12 μm and the solvent resistance was poor.

Comparative Example 3 Instead of 6FDMAPP in Example 2, 2,2-bis(4-(4-aminophenoxy)phenyl)propane (
A polyamic acid varnish was synthesized using DAPP. The blending ratio is as follows.

Next, a polyimide film was produced from this polyamide acid, and its moisture absorption rate and weight loss initiation temperature were measured.

As a result, the polyimide film is stiff and strong.
The moisture absorption rate is excellent at 0.8%, but the start of weight loss is
It's inferior to something like 410C.

Example 5 Rounding to improve the solvent resistance of Example 4 and modification with tetraaminobiphenyl (TABP) were carried out.

The reaction ratio is as follows, and the synthesis conditions are the same as in Example 4.

The modified polyimide film was exploded in the same manner as in Example 4, and its moisture absorption, weight loss initiation temperature, and solvent resistance were measured. However, the imidization conditions are 150C/1h+300C/1h+40
It was set to 0c/15 minutes. As a result, the moisture absorption rate was 0.43%.
When the weight loss initiation temperature was 460C, trichlorobenzene was used, there was almost no change in film thickness (0.2 μm or less).

Example 6 fflJ,! :L,te,3-carbamoyl-4,4'-
In addition to using diaminophenolethek (DDEC),
A polyamic acid varnish was synthesized in the same manner as in Example 5.

The blending ratio is a first order υ.

Next, a modified polyimide film was prepared in the same manner as in Example 5, and the moisture absorption rate, weight loss starting temperature, and solvent resistance were determined to 5r#1. As a result, the moisture absorption rate was 0.44%, and the weight loss starting temperature was Fi4.
60c,) The decrease in film thickness during heating in dichlorobenzene was almost 7't (0.2^m or less), which was good.

Example 7 Polyamic acid was synthesized in the same manner as in Example 4 except for using diaminophenol (DAPH) as a modifier and using compressed air.The reaction ratio is as follows.

Claims (1)

[Claims] 1. A polyamide CF resin characterized by containing the following repeating unit (1):
1) (However, -NH- is at the 0- or m-position with respect to the aromatic ether bond -〇-, R1 is a tetravalent organic group,
R2 is hydrogen or a monovalent organic group) 2 Polyamide containing the following repeating unit (1) and (ID) (However, the -NH- bond is an aromatic ether bond -O- On the other hand, at the 0- or m-position, R1 is tetravalent (however,
R1 is a 3iIII+ organic group, -Y is -NH, -(9 groups selected from "0-NH,, -80, -NH,")
λ A polyamide characterized by having the following repeating units (1) and is tetravalent (however, S
R' is a tetravalent organic group, -Y is -NH,. CONHm, Son NHt)
4. Polyamide containing the following repeating units (1), (II) and , R″ is a tetravalent organic group &
R” is hydrogen or a monovalent organic group)
■) (However, R1 is a trivalent organic group, -Y is -NH, (However, Ft'ti is a tetravalent organic group, -Y is -NH, and a group selected from CONHt -Sow NHt)
A polyimide characterized by having the following repeating unit axis...Chapter 7 (0- or m-position k R1' is a tetravalent organic group)) The following repeating unit axis and (to) in the polyimide position or m- position, R1 is a tetravalent organic group) (However, Rs is a trivalent organic group, -Y= is -N=. -(bond left over from '0-N=, -sow -N=) 7. A polyimide CF characterized by having the following repeating unit ωd■, ... group... and 0 - or m- position Th R' is a tetravalent organic group) (However, Th R' is a tetravalent organic group, -Y= is a bond selected from -N=.CON", 80*N=)8 ,
A polyimide CF characterized by having the following repeating units (lVl, (V) and (to)), ++ +++- (IV)
σ- or m- position 11, R1 is a tetravalent organic group) (However, &R” is a trivalent organic group, -Y= is % N =
*-Co-N=, -801-N= group) (
However, R4 is a tetravalent organic group, -Y= is k N '' +
-CO-N=, -80. -N= group)