JPH03221524A - Fluorine-containing polyamic acid-based resin and fluorine-containing polyimide - Google Patents

Abstract

PURPOSE:To obtain a fluorine-containing polyamic acid-based resin, having specific recurring units, capable of providing fluorine-containing polyimide-based resins with specified recurring units by curing, having low hygroscopicity and dielectric constant, excellent in heat resistance and suitable as insulating films. CONSTITUTION:A fluorine-containing polyamic acid-based resin, obtained by dissolving a fluorine-containing bifunctional diamine, e.g. 2,2-bis[4-(4- aminophenoxy)phenyl]hexafluoropropane and a tetracarboxylic acid (derivative) such as a fluorine-containing pyromellitic acid (derivative) in a solvent such as N-methylpyrrolidone and carrying out reaction at ambient temperature overnight, having recurring units expressed by formula I (R1 and R2 are H or alkyl; R3 is bifunctional group having fluorine atom and 1-4 benzene rings; n is 2-10), capable of providing fluorine-containing polyimide resins expressed by formula II by curing and having preferably 0.3-2.0dl/g intrinsic viscosity.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a specific fluorine-containing polyamic acid resin and a fluorine-containing polyimide obtained by curing the resin.

(b) Conventional technology Polyimide resins having an imide structure have been widely used in the electronics and electronics industries due to their excellent properties such as insulation properties, heat resistance, and dimensional stability of molded products. ing.

However, while ordinary polyimide is superior to this, it has the disadvantage of low temperature resistance.

That is, the well-known pyromellitic dianhydride and 4,
Polyimide obtained from 4'-diaminodi7enyl ether has a saturated moisture absorption rate of about 2.0 to 2.5% (25°C, relative humidity 80%), and a polyester has a saturated moisture absorption rate of 0.4 to 0 under the same conditions. .6%, and this causes dimensional changes in polyimide molded products due to changes in temperature and humidity.As a result, the insulation of various electronics such as multilayer wiring of semiconductors and circuit boards The miss characteristics as a film deteriorate.

In addition, when the saturated moisture absorption rate is as high as this, it is difficult for LSI
This appears as problems such as corrosion of the wiring materials such as aluminum and copper, disconnection, swelling of the insulating film during rapid heating during soldering and bonding processes, and an increase in leakage current at the PN4'1 joint.

Furthermore, when using 7lexiple printed circuit boards, voids are likely to occur due to moisture evaporation during lamination and soldering, and to prevent this, it is necessary to pre-dry the polyimide molded product before laminating or soldering. There are problems such as complicating the manufacturing process.

By the way, printed wiring boards and prepreg sheets used in electronic devices, especially computers, etc.
Due to the demand for faster signal propagation, a substrate with a low dielectric constant is required. Therefore, these resin materials, polyamic acid P, and polyimide obtained by curing the resin must also have low dielectric properties.

Therefore, recently, fluorine-containing polyamic acid, fluorine-containing polyamic acid, Studies have been made to synthesize 1% resin and fluorine-containing polyimide resin.

That is, *KOKAI Publication No. 60-104129 N+: As disclosed above, the following - formula % formula % ((wherein, Y1 and vY2 are the same or different, a kylene group, each X is the same or different, an alkyl group, a 7-substituted alkyl group or a halogen, R' is hydrogen or an alkyl group, and R is a residue obtained by removing the two amino groups from a diamine,
Polyamic acid derivatives and polyimides obtained by curing the same have been proposed, which are characterized by containing a repeating unit represented by the formula (2) is 0 to 3, and n is a number of θ to 4.

In addition, in the proceedings of the 38th (198941-) Annual Conference of the Society of Polymer Science and Technology, page 38, a polymer chain is characterized by containing a repeating unit structure that is attenuated by the following formula (■). We have proposed polyamic acid derivatives and polyimides obtained by curing them.

(c) Problems to be Solved by the Invention The polyamic acid derivative disclosed in JP-A-60-104129 and the polyimide obtained by curing the same have a C-0-1 group in the main chain of the molecule. This ester group is susceptible to hydrolysis during heating and curing, is unstable, and cannot be said to have sufficient heat resistance.

Also, the fluorine-containing polyamide! ! Fluorine-containing polyimide obtained by heating and curing a dielectric has a high dielectric constant of about 2.7, and cannot meet the demand for faster signal propagation.

On the other hand, the fluorine-containing polyimide disclosed in the above-mentioned Proceedings of the Society of Polymer Science and Technology, No. 38, has a dielectric constant of 2.6.
However, as printed circuit boards become more flexible, there is a demand for the development of resins with lower dielectric constants.

The present invention has been completed in view of the above-mentioned technical problems, and has an extremely low saturation moisture absorption rate, that is, low moisture absorption, excellent heat resistance, and has a low dielectric constant, making it suitable for various insulating films used in electronics. An object of the present invention is to provide a novel fluorine-containing polyamic acid resin and a fluorine-containing polyimide that are useful for the following applications.

(d) Means for Solving Problem 11 In order to achieve the above object, the fluorine-containing polyamic acid resin and the fluorine-containing polyimide of the present invention have the following general formulas (1) to (1'V), respectively. 6, that is, the fluorine-containing polyamic acid resin of claim 1 of the present application, which has a structure mainly composed of repeating units represented by the following formula (I), which may be the same or different from each other, Furthermore, R1 has a fluorine atom and 2 having 1 to 4 benzene rings in a circular manner.
It is a valent organic group. Further, n represents a number from 2 to 10. ) is characterized by including repeated weighting expressed as .

All books! The fluorine-containing polyide of claim 2 has the following general formula (TI) (wherein R1 has a fluorine atom and one benzene ring
It is a divalent organic group having ~4 pieces. Further, it is characterized in that it contains a repeating unit represented by the following (n represents a number from 2 to 10).

The heptad-containing polyamic acid P and resin of claim 3 are as follows-
Formula (III) may be the same or different, and R3 is a divalent valent group having a fluorine atom and 1 to 4 benzene rings. p and q represent numbers from 2 to 10, and may be the same or different from each other. ) is characterized by containing a repeating unit represented by

The fluorine-containing polyimide of claim 4 of the present application is prepared by the following formula (■
) is a divalent organic group having 1 to 4 . Furthermore, p and q represent numbers from 2 to 10, and may be the same or different. ) is characterized by containing a repeating unit represented by

In other words, the fluorine-containing polyimide of the present invention and its precursor, the fluorine-containing polyamic acid group resin, have 77 atoms in noamine, which is its raw material, and in the aromatic ring of tetracarboxylic acid, which is another raw material, and its derivatives. It can be obtained by introducing a barfluoroalkyl group in which n is 2 to 10 and reacting them.

The present invention will be explained in detail below.

In the fluorine-containing polyamic acid group resin of this ms requirement 1,
Specific examples of the diamine containing 77 elementary atoms and an aromatic ring, which is one of the It-forming raw materials, include the following.

That is, 2.2-bis(4-(4-7mino7e/xy)phenyl 1hexafluoropropane, 2.2-bis[3-
(3-7minor-4-hydroxy)phenyl-1hexafluoropropane, 2,2-bis[4-7minophenyl]hexafluoropropane, 2,2-bis[3-amino-4
-methylphenyl]hexafluoropropane, 2,2-
Bis(4-(3-7mi/phenoxy)phenyl)hexafluoropropane, 1,3-bis(2-(4-aminobenzyloxy)hexafluoroisopropyl 1benzene, 1,4-bis[2-( 4-7minobennoroxy)hexafluoroisopropyl 1benzene, 2,2-bisF
4-(4-ami/-3-triple-omethylphenoxy)phenylj hexafluorobutapan, 1f3-no7mi/-2,4,5,6-thiolatrourobenzene, perfluorobenzudine, 1, 3-diami/-4゜6-bis(1,1,11-trihydroxy-perfluoroundecyloxy)benzene, 1,3-diami/-4,6-bis(2,2,2-)lifluoro ethoxy)benzene, etc.

Among these, a particularly desirable example is 2,2-bis[4
Examples include -(4-7minophenoxy)phenyl]hexafluoropropane C1/ and V2.2-1:'s(4-7min/phenyl)hexafluoropropane.

The acid component, which is one of the other raw materials of the present invention, is a fluorine-containing pyromellitic acid derivative characterized by having a structure as shown in formula (V).

(In the formula, n represents a number from 2 to 10.) Note that the fluorine-containing pyromellitic acid derivative herein refers to acid anhydrides, acid halides, esters, 11 free acids, and the like.

In this way, -CnF 2n*+ (n=
2-10) The introduction of groups significantly lowers the dielectric constant and the saturated moisture absorption rate, and provides an excellent electrical insulating film with chemical stability. This will greatly improve your sexuality.

The solvents used in the production of the fluorine-containing polyamic acid resin of the present invention include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), dimethylacetamide (DM
Ac), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), sulfolane, and other polar solvents, as well as general-purpose solvents such as tetrahydro-7-lane, butyrolactone, cyclohexanone, acetone, methyl ethyl ketone, and diacetone alcohol.
These may be used alone or in a mixture of two or more.

I-Liichi Now 1. J Tatami Ze II 7 Selehaura V Tsuji is prepared by mixing the above-mentioned fluorine-containing bifunctional diamine and the above-mentioned tetracarboxylic acid or its derivative in equimolar amounts, and adding N-methylpyrrolidone (hereinafter abbreviated as NMP) to these. )
, dimethylacetamide (DMAe), dimethylformamide (DM F ), or the like is added and dissolved, and the mixture is subjected to a multiple reaction at room temperature.

The solution of the fluorine-containing polyamic acid resin thus obtained has an intrinsic viscosity (NMP solution, measured under constant conditions at a temperature of 30°C) of 0.3 to 2. O,/d1 is preferable; if the intrinsic viscosity is less than 0.3 g/d1, the resulting film will have poor flexibility, which is undesirable;
If it exceeds d1, it is difficult to cast into a film, which is not desirable. Therefore, from these points of view, it is particularly desirable to have an intrinsic viscosity in the range of 0.5 to 1.5 g/di.

Here, the intrinsic viscosity is calculated by the following formula, and the viscosity in the formula is measured by a capillary viscometer.

The fluorine-containing polyamic acid resin thus obtained is extremely useful as an intermediate for the fluorine-containing polyimide described below.

Next, book 1IilI! The fluorine-containing polyimide of claim 2 will be explained.

This fluorine-containing polyimide is obtained by heating or chemically imidizing the fluorine-containing polyamic acid resin of claim 1, and contains a repeating unit represented by the following formula (TI) in the molecule. It is something that

That is, this fluorine-containing polyimide has the following formula (1) It is a divalent organic group having 1 to 4 rings.

Further, it is characterized in that it includes a repeating simplex represented by n is a number from 2 to 10.

By the way, the conditions for heating or chemically imidizing the fluorine-containing polyamic acid resin according to claim 1 include heating the fluorine-containing polyamic acid resin at a temperature of 50 to 400°C for 1 to 40 hours. In particular, it is sufficient to promote desolvation and dehydration and ring closure.

Furthermore, if the fluorine-containing polyimide to be produced is soluble in a solvent, it can be produced as follows.

That is, xylene or toluene is added to a fluorine-containing polyamic acid resin solution, and the solution is heated at 110 to 200°C for 1 to 4
Obtained by heating for 0 hours. At this time, water obtained by condensation is distilled out of the system together with xylene or toluene.

In this case, the heating step for removing the organic solvent and imidization when forming the fluorine-containing polyimide from the fluorine-containing polyamide Wl-based resin solution is performed under vacuum (under reduced pressure) or under an inert gas atmosphere. You can. Furthermore, if it is dark for a short period of time, it will eventually heat up to around 400 degrees Celsius,
The properties of the resulting fluorine-containing polyimide can be improved.

Alternatively, it can also be obtained by adding acetic anhydride and birinone to a fluorine-containing polyamic acid group resin solution and stirring the solution at room temperature.

In this case, the fluorine-containing polyimide can be obtained by adding the solution after the reaction to water, filtering the resulting solid matter, and drying it.

In this way, an insulating film with a particularly low dielectric constant and low saturated water content can be obtained, and the insulating film is not only chemically stable but also excellent in both error characteristics and dimensional stability.

The fluorine-containing polyamic acid M resin of Item 3 will be explained in detail.

That is, this fluorine-containing polyamic acid group resin has the following formula (
Tel) In the formula, R1 and R7 are hydrogen or an alkyl group, which may be the same or different from each other, and R1 is a divalent organic compound having a fluorine atom and 1 to 4 benzene rings. It is the basis. p and q represent numbers from 2 to 10, and may be the same or different. ) is characterized by containing a repeating unit represented by

The present invention will be explained in detail below.

In the 771 polyamide acid group resin of claim 3 of the present application,
Specific examples of the diamine containing 77 elementary atoms and an aromatic ring, which is one of the raw materials for its production, include the following.

That is, for example, 2.2-bis[4-(4-7mino-7e/xy)phenyl-1hexafluoropropane, 2°2-bis(3-(3-7mino-4-hydroxy)7enyl-1hexafluoropropane, Fluoropropane, 2.2-bis[4-7mi/phenyl]hexafluoropropane, 2゜2-bis[3-ami7-4-methylphenyl 1hexafluoropropane, 2
．． 2-bis[4-(3-7mino7ethoxy)phenyl 1
Hexafluoropropane, 1,3-bis(2-(4-7
minobenzyloxy)hexafluoroisopropyl 1benzene, 1゜4-bis[2-(4-amino/benzyloxy)hexafluoroisopropyl 1benzene, 2.2-
Bis[4-(4-ami/-3-)lifluoromethylphenoxy>phenyl 1 hexafluoropropane, 1゜3-
Noami/-2,4,5,6-titrafluorobenzene, perfluorobenzucine, 1,3-diamino-4,6
-bis(1,1,11-trihydroxy-perfluoroundecyloxy)benzene, 1°3-diamino-4,
6-bis(2,2,2-)lifluoroethoxy)benzene and the like.

Among these, 2.2-bis[4-(
Examples include 4-aminophenoxy)phenyl-1hexafluoropropane and 2,2-bis(4-7minophenyl)hexafluoropropane.

The acid component, which is one of the other raw materials of the present invention, is a fluorine-containing pyromellitic acid derivative characterized by having a structure as shown in formula (Vr).

(In the formula, p and q represent numbers from 2 to 10.) Note that the fluorine-containing pyromellitic acid derivative herein refers to acid anhydrides, acid halides, esters, and 11 free acids.

When a perfluoroalkyl group is directly introduced into an aromatic ring in this way, the dielectric constant and moisture absorption rate are drastically reduced, and an excellent electrical insulating film can be obtained, which is also chemically stable. It will greatly improve your sexuality.

The fluorine-containing polyamic acid resin thus obtained is useful as an intermediate for the fluorine-containing polyimide represented by the general formula (■) in Book *1*Claim 4, which will be described later. , the fluorine-containing polyimide of the present m-network requirement 4 will be explained in detail.

This fluorine-containing polyimide is used in the present application 1Ill! 5FC Section 3
It is obtained by heating and imidizing a fluorine-containing polyamic acid resin, and has a repeating unit represented by the following formula (W) in the molecule.

That is, this fluorine-containing polyimide is a divalent organic group having the following formula () from 1 to 4@. Further, p and q represent numbers from 2 to 10, and may be the same or different from each other.

By the way, the conditions for this imidization are the same as in the case of claim 2 of the present application III.

In this way, an insulating film with a particularly low dielectric constant and low saturated moisture absorption rate can be obtained, and the insulating film is chemically stable and has excellent electrical properties and dimensional stability.

(e) Effect In claims 1 and 2 of the present invention, it is not clear why the dielectric constant is markedly lowered, the saturated water absorption rate is also extremely lowered, and an excellent electrical insulating film is obtained. In the invention, as shown in the general formula (1) and -numerical formula (ff), a repeating unit shown in the general formula (V) is introduced into the backbone of the molecular main chain.

(n indicates a number from 2 to 10.) In this way, -Cn F tn or (n=
By introducing groups 2 to 10), the 77 element content rate increases and the water repellency due to fluorine atoms increases, and therefore the saturated moisture absorption rate decreases, and the ratio of 77 element atoms in the molecule increases. The ratio of fluorine atoms in the molecule increases because the perfluoroalkyl group is directly bonded to the aromatic ring instead of the trifluoromethyl group in the molecule, which is understood to decrease the dielectric constant. It is understood that this increases the dielectric constant and significantly lowers the dielectric constant.

Furthermore, although it is not clear why claims 3 and 4 of the present invention have excellent hour-opening properties, especially in the present invention -
As shown in the formula (m) and -formula (W,), the repeating unit represented by the general formula (Vl) is directly introduced into the aromatic ring in the backbone of the main chain of the molecule.

In this way, by directly introducing a perfluoroalkyl group into the aromatic ring in the molecule at a site that is in the rose position with respect to 2@, the content of 77 atoms increases significantly, and the water repellency due to the 77 atoms further increases. For this reason, it is understood that the saturation@humidity rate decreases significantly.

Compared to fluorine-containing polyimides containing trifluoromethyl groups, by bonding a perfluoroalkyl group to an aromatic ring, the fluorine content per molecule is significantly increased. It is considered to be a material that achieves low dielectric properties.

In addition, as the ratio of 77 elementary atoms in the molecule steadily increases, the permanent twin moment in the partial structure represented by the general formula (Vr) decreases due to the symmetry of the molecule.
It is understood that the dielectric constant of the polymer as a whole is further reduced.

(f) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

In addition, the abbreviations of names of compounds in Examples are collectively shown below.

BAPF: 2.2-bis(4-(4-7 mino7
e/xy)phenyl-1 hexafluoropropane BAAF: 2,2-bis(4-7mino-7enyl)hexafluoropropane PDA: p-phenylenenoamine DDE Nidiamitunophenylmethane DCBFP
: 6F-DA : 2.2-bis[4-(3,4-dicarboxybenzoyloxy)phenyl 1 hexafluoropropane dianhydride 2.2-bis[3,4-dicarboxyphenyl]hexafluoropropane dianhydride Product NMP: Synthesis example of N-methylpyrrolidone mo7perfluorohexylpyromellitic anhydride A) Synthesis of monoperfluoroalkyl compound (2) 2.3.
5.6-hexamethyliodobenzene (1) (8,70
g, 33, 4-ooo and copper powder (2,56 g, 40
, 3 mmol) into a three-necked 7-rasp fitted with a rubber septum, and the system was purged with nitrogen. To this, 7 methyl sulfoxide (60I10, perfluorohexyl yogate (
18.0 g, 4 Q, 3 w-of) was slowly added via the septum using a syringe. This solution was stirred at 110° C. overnight, and then added to a saturated aqueous ammonium chloride solution (300 mj') to stop the reaction.

The target product was extracted with ether, and the ether layer was washed with water and dried over magnesium sulfate. After removing the desiccant, the solvent was distilled off, and the resulting residue was purified by silica sol chromatography (silica gel 4
Purified with 0 g 1 hexane).

Yield 8.47. (56%) IR1 confirmed (295
0cm-', CH3, 1200-1250CF2)
B) Synthesis of monoperfluorohexypyromellitic acid (3) 1) Alkyl compound (2) obtained in A) (100 mg,
0,22 mmoZ) of nitric acid water (commercially available nitric acid:water=
1:1) (10-0 is sealed in a glass sealed tube, 1
Heated at 60°C overnight. After cooling the reaction solution, insoluble matter was collected by filtration and thoroughly washed with cold water. The obtained crystals were dried in a desiccator.

Yield Quantitative IR, confirmed (1720c++-' C00H, 1200-125
0CF2) C) Monoperfluorohexylpyromeryt
Synthesis of toric acid s hydrate (4) Pyromellitic acid (3) obtained in Section B) (600 mg
, l, 05 ■of) was suspended in anhydrous Wl (3 ml) and heated to reflux at 160°C. After reacting overnight, acetic anhydride was distilled off under reduced pressure to obtain a yellowish white solid. Toluene (10 ml×3 times) was added to this, and the remaining acetic anhydride was completely distilled off to obtain the desired acid anhydride.

Yield Quantitative 560mg This reaction process is briefly summarized below.

(1) (2) (3) (4) C, F131...perfluorohexylyogate^
Ca0...Synthesis example of acetic anhydride-fluorohexylpyromellitic anhydride A) Synthesis of 1,6-noiodo2.3.5.6-titramethylbenzene (6) Glacial acetic acid (15+f), water (3mi'), concentrated sulfuric acid (0,4
2.3.5.6-titramethylbenzene (2.68 g, 20 mmoo (5
), metafilofolic acid and iodine were added and stirred, and the reaction solution was heated at 70° C. for 3 hours, then added to a saturated aqueous solution of Hypo, and the target product was extracted using hexane.

After thoroughly washing the hexane layer with water, it was dried over magnesium sulfate. After the desiccant was filtered off, the hexane was distilled off under reduced pressure to obtain the desired product in the form of white crystals with 100% purity.

Yield 110.8g (56%) IR confirmed (C)l,
2950cm-', 580cm-'-1
) B) 1,6-no(perfluorohexyl-2,3,4
Synthesis of (6-titramethylbenzene) (7) Rubber the substance (6) (1.4 g, 3.63-100 obtained in A) above and copper powder (0.70 g, 10.88 m-ol). Place in a three-bottle flask with a septum, and replace the system with 1 nitrogen.Add dimethyl sulfoxide (14 w/L par 77
Rheolohexyl Yoke ()' (4.9g, 10.88m
mof) was gradually added through the septum using a syringe. After stirring this solution at 110°C overnight, the reaction was stopped by adding saturated ammonium chloride aqueous solution (100-0). The target product was extracted with ether, and the ether layer was washed with water.
Dry with magnesium sulfate. After removing the desiccant, the solvent was distilled off, and the resulting residue was purified by silica sol chromatography (20 g of silica gel, hexane).

Yield 11 8.47g (56%) IR1 confirmed H
=, 2950es+ -', 1200-1250cm
-' CF2) C) Synthesis of Tuba-fluorofurokylpyromellitic acid (8) Substance (7) obtained in B) (100 mg, 0.13
So-〇〇 and nitric acid water (commercially available nitric acid:water = 1:1) (1,0
111) was sealed in a glass sealed tube and heated at 160°C overnight. After cooling the reaction solution, insoluble matter was collected by filtration and thoroughly washed with cold water. The obtained crystals were dried in a desiccator.

Yield Quantitative IR confirmed D) Tuba-fluoroalkylpyromellitic anhydride (9
), the substance obtained in C) (80300 leaves, 0.336
mmof) was suspended in acetic anhydride (2 ml) and heated to reflux at 160°C. After reacting overnight, acetic anhydride was distilled off under reduced pressure to obtain a yellowish white solid. To this, toluene (10mNX
a) was added, and residual acetic anhydride was completely distilled off to obtain the desired acid anhydride.

Yield Quantitative 288+1g This reaction process is briefly summarized below.

Monoperfluorohexylpyromellitic anhydride (600%
+ur, 1,05 button-01) and 2,2-bis(4-noamituphenyl)hexafluoropropane (350 mg,
1,05-mof) to N-7 tilvirolidone (
4mf) and stirred at room temperature overnight.

In this way, a solution of the fluorine-containing polyamic acid resin of the present invention was obtained. This fluorine-containing polyamic acid resin was pale yellow in color and had an intrinsic viscosity of 0.89 g/dl.

Example 2 This fluorine-containing polyamic acid resin was spread thinly on a glass plate, heated at 100°C for 1 hour, then heated at 200°C for 1 hour, and further heated at 300°C for 1 hour to form a fluorine-containing polyimide film ( 50 μ-) was obtained.

Table 3 shows the moisture absorption rate (saturated moisture absorption rate) and dielectric constant of the fluorine-containing polyimide film thus obtained.

Examples 3 to 19 Using the method shown in Example 1, fluorine-containing noamines and fluorine-containing tetracarboxylic dianhydrides as shown in Tables 1 and 2 were reacted, and the corresponding 7-containing dianhydrides were reacted. A base polyamic acid P and FA fat was formed.

The intrinsic viscosity of each of the obtained fluorine-containing polyamic acid resins was measured.

The results are shown in Tables 1 and 2.

Examples 20 to 36 The obtained fluorine-containing polyamic acid group resins were imidized in the same manner as in Example 2.

The moisture absorption rate (saturated moisture absorption rate) and dielectric constant of each of the obtained fluorine-containing polyimide films were measured.

The results are shown in Tables 3 and 4.

Comparative Example 1 B A P F (0, 161 mob) and 6F-
Insert DA (0,161mof) and add this DMAc (
800a1) was added, dissolved and stirred. After 5 hours of reaction, a pale yellow polyamic acid solution containing Plan 77 was obtained.

This 7-containing polyamic acid solution was spread thinly on a glass plate and heated at 100°C for 1 hour, then at 200°C for 1 hour, and then at 300°C for 1 hour to form a 77-containing polyimide film (approx. 50 μm) was obtained.

Also, when measuring the intrinsic viscosity of these, y=o, 91g/d
Table 4 shows the @humidity (saturated @humidity) and dielectric constant of the fluorine-containing polyimide film thus obtained.

Comparative Example 2 PDA 2°OS was placed in a 4-necked 7-glass tube equipped with a stirring 4IP device, a reflux condenser, a thermometer, and a nitrogen gas inlet, and NMP 85. DCBFP was dissolved in 3 then immersed in the flask in a 20 °C water bath while suppressing heat generation
2.95 g of I was added in portions. After DCBFP was dissolved, the water bath was removed and the reaction was continued for 5 hours at around room temperature.6 Also, when measuring the intrinsic viscosity of this, y = 0.7 g/dir.
there were.

This varnish was applied on a glass plate and heated for 15 minutes in a nitrogen stream.
1 hour at 0℃, 0.5Mff1 at 250℃, then 400℃
C. for 1 hour to obtain a polyimide film.

Table 4 shows the moisture absorption rate (saturated moisture absorption rate) and dielectric constant of the fluorine-containing polyimide film thus obtained.

Comparative Example 3 In the same manner as in Example 1, a polyamic acid varnish was synthesized with the following formulation.

C nF E-40aD
CBFP 1 1. 60gNMP
85. When the intrinsic viscosity of this was measured, it was found to be y=0.8 g/di.

Next. A polyimide film was produced under conditions of 1 hour at 150°C and 0.5 hour at 350°C in nitrogen.

The moisture content (saturated moisture absorption rate) and dielectric constant of the fluorine-containing polyimide film thus obtained are shown in Table wS4.

Comparative Example 4 Monotriple olomethylbiromellitic anhydride (10 mmol) represented by the following structural formula and 2,2-bis(trifluoromethyl)-4 were placed in a two-port 7 rack having a stirring bar and a nitrogen gas inlet. ,4'-noaminobiphenyl (10IIw00
was dissolved in N-methylpyrrolidone (30 mN) and heated to room temperature P.
The fluorine-containing polyamic acid group resin thus obtained had an intrinsic viscosity of 0.30 g/d1.

This 7-glue-containing polyamic acid group resin was spread thinly on a glass plate, heated at 100°C for 1 hour, then heated at 200°C for 1 hour, and further heated at 300°C for 1 hour to obtain a T-fluoropolyimide film (50 μII). Ta.

Table 5 shows the moisture absorption rate (saturated moisture absorption rate) and dielectric constant of the fluorine-containing polyimide film thus obtained.

Comparative Example 5 Comparative Example 4 was carried out in the same manner as in Comparative Example 4, except that fluorofluoromethylpyromellitic anhydride represented by the following structural formula was used instead of mono/trifluoromethylpyromellitic anhydride. Fluorine-containing polyimide film (50μ
m) was obtained.

The @humidity rate (saturated @humidity rate) and dielectric constant of the fluorine-containing polyimide film thus obtained are shown in the fifth decay.

In Table 3, Table 4, and Table 5, the dielectric constant is 30°
In Tables 3 and 4S and Table 5, measurements were taken on a film with a C1 film ff 50 μm and an area of 5c112.
Dry for 24 hours in a hot air dryer at 10e
After cutting and weighing the size of 10cm x 25°
C1 A method was adopted in which the sample was left in a desiccator whose humidity was adjusted to 80% relative humidity and weighed for 24 hours, and the weight was calculated from the change in weight.

For reference, a polyester film with a thickness of 50 μm (
The saturated moisture absorption rate of the polyethylene terephthalate film (polyethylene terephthalate film) was investigated in the same way as in Section L, and the result was 0.5%. From the results shown in Tables 3 and 4, as well as Table 15, the Example's saturated moisture absorption rate was 0.5%. It is recognized that both have a lower humidity rate and a significantly higher dielectric constant than those of the above.

In this way, the moisture absorption rate (saturated moisture absorption rate) of each example is extremely low, and not only does the size not change much due to changes in temperature and humidity, but it also does not deteriorate the electrical characteristics of electric/electronic circuits. It is extremely reliable.

In addition, each of the embodiments has an extremely low dielectric constant and can realize high-speed signal propagation.

On the other hand, the comparative examples have extremely high moisture absorption rates (saturated moisture absorption rates), and their dimensions change significantly due to changes in temperature and humidity, deteriorating the electrical and electrical characteristics of electrical and electronic circuits.

Further, each of the embodiments has a high dielectric constant and cannot achieve high speed signal propagation.

(g) Effect of the invention The fluorine-containing polyamic acid resin of the present invention contains a structural weight represented by the general formula (V) in the backbone of the main chain, and the fluorine-containing polyimide obtained by curing it has one molecule. It has a high 771L content, and therefore has an extremely low dielectric constant and can achieve high-speed signal propagation.Moreover, its moisture absorption rate (saturated moisture absorption rate) is extremely low, and its dimensions do not change much due to changes in temperature and humidity. As a result, the electrical characteristics of the electric/electronic circuit are not degraded, resulting in extremely high reliability.

Furthermore, the fluorine-containing polyamic acid P and resin of the present invention contain a structural unit represented by the general formula (Vl) in the backbone of the main chain, and the base-containing polyimide obtained by curing this unit contains 77 elements per molecule. As a result, the dielectric constant is much lower and signal propagation speeds up even more. As a result, there is no significant dimensional change, so the electrical characteristics of electrical and electronic circuits do not deteriorate! −? This produces effects such as an even higher tD*.

Claims (4)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (In the formula, R_1 and R_2 are hydrogen or alkyl groups, and even if they are the same, they are different. You can also use R_
3 is a divalent organic group having a fluorine atom and 1 to 4 benzene rings, and n represents a number of 2 to 10. ) A fluorine-containing polyamic acid resin characterized by containing a repeating unit represented by: (2) General formula (II) below ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R_3 is a divalent compound having a fluorine atom and 1 to 4 benzene rings. is an organic group, and n is 2 to 10
Indicates the number of ) A fluorine-containing polyimide resin characterized by containing a repeating unit represented by: (3) General formula (III) below ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III) (In the formula, R_1 and R_2 are hydrogen or alkyl groups, and they may be the same or different. Furthermore, R has a fluorine atom and 2 having 1 to 4 benzene rings.
It is a valent organic group. p and q represent numbers from 2 to 10, and may be the same or different. ) A fluorine-containing polyamic acid resin characterized by containing a repeating unit represented by: (4) General formula (IV) below ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼・・・・・・(IV) (In the formula, R_3 is a divalent compound having a fluorine atom and 1 to 4 benzene rings. is an organic group, and p and q are 2
-10, and may be the same or different from each other. ) A fluorine-containing polyimide resin characterized by containing a repeating unit represented by: