JPH036227A - Fluorinated polyamic acid resin and fluorinated polyimide - Google Patents

Abstract

PURPOSE:To prepare a fluorinated polyimide (acid) with a low moisture absorption, high heat resistance and low dielectric constant and useful as insulation films in electronics by preparing a polymer having a structure mainly comprising specific repeating units. CONSTITUTION:A fluorinated polyamic acid resin comprising a polymer contg. repeating units of formula I (wherein R1, R2, R3, R4, and R5 are each H, lower alkyl, CF3, lower alkoxy, Cl, Br, or F; R6 and R8 are each H or alkyl; and R7 is a tetravalent org. group contg. 1-4 benzene rings), and a fluorinated polyimide comprising a polymer contg. repeating units of formula II (wherein R1, R2, R3, R4, and R5 are each H, lower alkyl, CF3, lower alkoxy, Cl, Br, or F; and R7 is a tetravalent org. group contg. 1-4 benzene rings).

Description

DETAILED DESCRIPTION OF THE INVENTION (&) Industrial Application Field The present invention subjects a specific fluorine-containing polyamide R-based resin and a fluorine-containing polyimide obtained by curing the same to rR.

(b) Conventional technology Polyimide resins with an imide structure have been widely used in the electronic and electrical industries due to their properties such as electrical insulation, heat resistance, and dimensional stability of molded products. There is.

However, while ordinary polyimide has these advantages, it has the disadvantage of low moisture resistance.

That is, the well-known pyromellitic dianhydride and 4.
The polyimide film obtained from 4'-noami7nophenyl ether has a saturated moisture absorption rate of 2 to 2.5% (at 25°C,
The relative humidity is about 80%), which is considerably higher than the saturated moisture absorption rate of polyester, which is about 0.4 to 0.6% under the same conditions. As a result, the electrical properties of insulating films for various electronics such as semiconductor multilayer wiring and circuit boards deteriorate.

If the saturated moisture absorption rate is high in this way, practical problems such as corrosion and disconnection of aluminum and copper, which are the wiring materials for LSIs, swelling of insulating films during rapid heating during soldering and bonding processes, and problems at PM joints. This appears as a problem such as an increase in leakage current.

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

Also, electronic 8! Printed wiring boards and prepreg sheets used in devices such as combinators and combinators are required to have low dielectric constant substrates due to the demand for faster signal propagation. Therefore, the polyimide obtained by curing the polyamic acid resin, which is one of these resin materials, also needs to have low dielectric properties.

Therefore, recently, fluorine-containing polyamic acid group resins and fluorine-containing polyamide acid-based resins have been developed using fluorine-based compounds in which 77 atoms have been introduced into either or both of tetracarboxylic acid or its anhydride and diamine, which are synthetic materials for polyimide. Studies have been made to synthesize 7-/element polyimide resins.

That is, as disclosed in Japanese Patent Application Laid-Open No. 6O-i04129, SoshideR
indicates a residue obtained by removing two amino groups from a diamine, 马 indicates the number of O to 3, and n indicates the number of θ to 4) A polyamic acid derivative characterized by containing a repeating unit represented by And polyimides obtained by curing this have been proposed.

(c) Problems to be Solved by the Invention However, although this product has a C-0-1 group in its molecular main chain, this ester group is easily hydrolyzed and unstable during heating and curing. Moreover, it cannot be said that the heat resistance is sufficient.

Moreover, the 7 element-containing polyamide ai* shown by the above-mentioned formula
Fluorine-containing polyimide, which is obtained by heating and curing a conductor, has a dielectric constant of about 2.7, but with the increasing density of printed circuit boards, there are expectations for the development of resins with lower dielectric constants. Ta.

The present invention has been completed in view of the above technical problems, and has an extremely low saturation moisture absorption rate, that is, low humidity, excellent heat resistance, and has a low dielectric constant, making it useful for various insulating film applications in electronics. Another object of the present invention is to provide a novel fluorine-containing polyamide acid group resin and a heptadium-containing polyimide.

(d)! Means for Solving the Problems In order to achieve the above object, the fluorine-containing polyamide acid group resin and the fluorine-containing polyimide of the present invention each contain repeating units represented by the following general formulas [I] to [VI]. It has a structure mainly composed of.

That is, the polyamic acid-based resin of Claim 1 of the present application has the following formula (I): a fulkyl group, a 17-fluoromethyl group, a lower flukoxy group, chlorine, bromine, or 72 atoms, which may be the same or different from each other. Also, R and R6 are hydrogen or an alkyl group, and may be the same or different from each other, and furthermore, I R? is a tetravalent organic group having 1 to 4 benzene rings. ) Repetition represented by! , the unit is included.

The heptadron-containing polyimide of this win requirement 2 is expressed by the following formula (
II) (In the formula, R, %R2, R3, R1 and Rg represent hydrogen, lower fulkyl group, 17 fluoromethyl group, lower alkoxy group, chlorine, bromine or fluorine, and may be the same or different from each other. , and R2 is a tetravalent organic group having 1 to 4 benzene rings.

Book 11 [The fluorine-containing polyamic acid group resin of claim 3 may have or differ from the following formula (III), and R1 is a fluoroalkylene group, C(CFz)z-, an alkylene group, or a sulfonyl group. It is characterized by containing a repeating unit represented by (which is a group).

The fluorine-containing polyimide of Claim 4 of Book 811 is expressed by the following formula (
f'/) represents an alkyl group, a trifluoromethyl group, a lower alkoxy group, chlorine, bromine, or 77 atoms, and may be the same or different from each other (also, R@ and R8 are hydrogen or an alkyl group) They are the same as each other and represent an alkyl group, trifluoromethyl group, lower alkoxy group, chlorine, bromine or fluorine, and may be the same or different from each other, and
R1 is a fluoroalkylene group, "'-C(CF3)t
-, an alkylene group or a sulfonyl group. ) is characterized by containing a repeating unit represented by

Book IIaII! The fluorine-containing polyamide Al-based resin of claim 5 has the following formula (V), the following formula (Vl), an alkyl group, )+7 fluoromethyl group, lower alkoxy group, chlorine, bromine, or fluorine, and are the same as each other. may also be different, and Ro and R- are hydrogen or an alkyl group, and may be the same or different from each other, and R is a fluoroalkylene group, -C(CF,
l), -fulkylene group or sulfonyl group. ) is characterized by containing a repeating unit represented by

The fluorine-containing polyimide of claim 6 of the present application exhibits an alkyl group, a trifluoromethyl group, a lower alkoxy group, chlorine, bromine, or 77 atoms, which may be the same or different from each other, and R2 is a fluoroalkylene group. group, -c (c
F3) 2-Fulkylene group, sulfonyl group or ether group. ) is characterized by containing a repeating unit represented by:

In other words, the fluorine-containing polyimide of the present invention and the fluorine-containing polyamide a-based resin which is its precursor are obtained by introducing a fluorinated alkyl group into the aromatic ring or main chain of the raw material noamine and/or tetracarboxylic acid and its derivatives. , obtained by reacting them.

The present invention will be explained in detail below.

In the hepta-fluorine-containing polyamide a-thread resin of this M specification item 1,
Examples of tetracarboxylic acids containing aromatic rings, which are one of the raw materials for their production, include the following.

However, although 11 carboxylic acid groups are exemplified below, functional derivatives thereof such as acid dianhydrides, acid halides, and esters are also extremely useful, and therefore, these are also included in the present invention.

These are (trifluoromethyl)pyromellitic acid, bis(trifluoromethyl)pyromellitic acid, 5゜5゛-bis(trifluoromethyl)-3,3°, 4.4'-tetracarboxybiphenyl, 2.2 ', 5.5'-
Tetrakis(trifluoromethyl)-3-3't4t4
'-Tetracarboxybiphenyl, 5.5'-bis(trifluoromethyl)-3,3',4.4'-tetracarboxydiphenyl ether, s,s'-bis(17fluoromethyl)-3,3',4 .4'-Tetracarboxybenzo7enone, bis[(lJfluoromethyl)dicarboxyphenoxyJbenzene, bis[(trifluoromethyl)dicarboxy7e/xy](trifluoromethyl)benzene, bis[()lifluoro methyl)dicarboxy7eth/xy]bis(trifluoromethyl)biphenyl, bis[()lifluoromethyl)dicarboxyphenoxy1nophenyl ether, bis(dicarboxyphenoxy)(trifluoromethyl)benzene, bis(dicarboxy phenoxy)bis(trifluoromethyl)benzene, bis(dicarboxy7e/xy)tetrakis(trifluoromethyl)benzene, bis(dicarboxyphenoxy)bis()lifluoromethyl)biphenyl, bis(
dicarboxyphenoxy)tetrakis(trifluoromethyl)biphenyl, 2,2-bis(4-(3,4-dicarboxy7e/xy)phenyl 1 hexafluoropropane, 2,2- and s[4-(3, 4-dicarboxyphenoxy)-3-bromophenyl 1-hexafluoropropane, 2,2-bis[4-(3,4-dicarboxyphenoxy)-3,5-dichromo7-enyl 1-hexafluoropropane, 2. 2-bis[4-(3,4-dicarboxyphenoquine)-3,5-trifluoropropane, 2,2-bis(4-(3,4-dicarboxyphenoquine)-3,5-trifluoromethyl phenoxy) 7enyl 1 hexafluoropropane, 2,2-bis(3t4-dicarboxyphenylonhexafluoro apropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, pyromellitic acid, 3 .3', 4.4'-tetracarboxybienyl, 2.3.3', 4-tetracarboxybiphenyl, 3.3', 4.4'-tetracarboxydiphenyl ether, 2,3.3', 4- Tetracarboxydiphenyl ether, 3.3'4.4'-
Tetracarboxybenzophenone, 2°3.3°, 4-
Tetracarboxybenzophenone 2t3.6.7-tetracarboxynaphthalene, 1,4°5.8-tetracarboxynaphthalene, 1,2,5°6-tetracarboxynaphthalene, 3,3°,4,4-tetracarboxydiphenylmethane, 2.2-bis(3,4-dicarboxyphenyl)propane, 3.3ゝ,4.4′-tetracarboxy972yl, 2.2-bis[4-(3,4-dicarboxyoxy)phenyl 1 Propane, bis(4-(3
,4-]carboxyphenoxy)phenyl]sulfone,
Bis[4-(2,3-7carboxy7e/xy)phenyl 1 sulfone, bis[4-(2,3-]carboxy7e/xy)-2,5-trimethylphenyl]sulfone, bis[4 -(2,3-dicarboxy7eth/xy) -2-/
tylphenyl] sulfone, bis(4-(2-]carboxy)-2-)lifluoromethylphenyl 1-sulfone, bis(4-(2,3-7carboxy)-2,5-nodorifluoromethylphenyl)sulfone, etc. Among these, particularly desirable ones include pyromellitic acid, 2,2-bis[4-(3,4-dicarboxyphenoxy)7enyl]hexafluoropropane,
Examples include 2,2-bis[3,4-dicarboxyphenyl-1hexafluoropropane.

The noamine component, which is one of the other raw materials of the present invention, has a structure as shown in the general formula (■) in the main chain skeleton, as shown in the above-mentioned formulas (1) to (Vl), respectively. It is a fluorine-containing cyamine.

It represents a fulkyl group, )+7 fluoromethyl group, a lower alkoxy group, chlorine, bromine, or 7 fluorine groups, and may be the same or different from each other. ) When 10 (CFz)z- groups are introduced into the main chain in this way, the dielectric constant decreases significantly, the saturated moisture absorption rate also decreases extremely, and an excellent electrical insulating film can be obtained. Moreover, chemical stability is greatly improved.

As described above, examples of the cyamine having the structure represented by the above-mentioned formula (■) in the main chain skeleton include the following, but are not limited to these in any way.

For example, 1,3-bis(2-(4-7 minopencyloxy)hexafluoroisopropyl Jbenzene, 1,4-
Bis[2-(4-aminobencloxy)hexafluoroisopropyl 1benzene, 1,3-bis[2-(4-
aminobenzyloxy)hexafluoroisopropyl 1
-5-fluorobenzene, 1゜3-bis[2-(4-7
/benzyloxy)hexafluoroisopropyl]-
5-)+J fluoromethylbenzene, 1,3-bis[2
1,3
-bis(2-(4-7minobenbulcarponyloxy)
Hexafluoroisopropyl 1benzene, 1,4-bis(2-(4-7minobennorcarbonyloxy)hexafluoroisopropyl Jbenzene, 1,3-bis[2-
(4-7 minobennorcarponyloxy) hexafluoroisopropyl 1-5 − ) +7 fluorobenzene, 1,3-bis[2-(4-7 minobenzoyloxy) hexafluoroisopropyl 1 benzene, 1,4-bis [2-(4-7minobenzoyloxy)hexafluoroisopropyl 1benzene, 1,3-bis(2-(4-
7mi/benzoyloxy)hexafluoroisopropyl]-5-trifluorobenzene, 1,3-bis(2-(
4-7minophenyl ethoxy)hexafluoroisopropyl1benzene, 1,3-bisE2-<4-7minophenylptoxy)hexafluoroisopropyl]benzene, 1,3-bis[2-(4-(4 -7mi/phenyl)-
Examples include 2,2,3,3-tetrafluorobutoxy-hexafluoroisopropyl)]benzene, and the like.

The solvents used in the production of the fluorine-containing polyamide a-based resin of the present invention include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), trimethylacetamide (D
MAe), dimethylformamide (DMF),
Examples include polar solvents such as dimethyl sulfoxide (DMSO) and sulfolane, and general-purpose solvents such as tetrahydro-7-lane, butyrolactone, cyclohexanone, acetone, methyl ethyl ketone, and diacetone alcohol, which may be used alone or in a mixture of two or more. is used.

By the way, as a method for producing a fluorine-containing polyamic acid resin, equimolar amounts of 7-containing bifunctional cyamine and a tetracarboxylic acid or a derivative thereof are mixed, and N-methylpyrrolidone (hereinafter abbreviated as NMP) is added to the mixture. , dimethylacetamide (DM Ac), dimethylformamide (D
It can be obtained by adding a solvent such as M F ) to dissolve it and reacting it overnight at room temperature.

t! of the fluorine-containing polyamic acid resin thus obtained. I
The I liquid has an intrinsic viscosity of 0.3 to 3.0. /dl is preferable, and the intrinsic viscosity is 0.3 g/. If it is less than d1, the visibility of the produced film is poor, so it is undesirable (
On the other hand, if it exceeds 3.0g/de, it is difficult to cast into a film, which is not desirable. Therefore, from these points of view, those having an intrinsic viscosity of 0.5 to 2.0 g/dZ are particularly desirable.

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

(Viscosity of solution) Natural logarithm (Viscosity of solvent) wI-3 meeting! *1 = The fluorine-containing polyimide acid group resin thus obtained is extremely useful as an intermediate for the fluorine-containing polyimide described below.

Next, the fluorine-containing polyimide of Requirement 2 of the present advisor will be explained.

This fluorine-containing polyimide is the fluorine-containing polyamide 11! of claim 1! It is obtained by heating and imidizing a system resin, and is represented by the following formula (II).

That is, this fluorine-containing polyimide has the following formula (ff): an alkyl group, a fluoromethyl group, a lower alkoxy group, chlorine, bromine, or fluorine, which may be the same or different from each other; represents the benzene ring from 1 to 41
It is a tetravalent organic group having 1. ) is characterized by containing a repeating unit represented by:

By the way, the conditions for imidization are as follows:
What is necessary is to promote desolvation and dehydration and ring closure by heating for a period of time.

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 group 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 7-/element polyimide I! When forming a fluorine-containing polyimide from an Il-based resin solution, the heating process for removing the organic solvent and imidization is performed under vacuum (under reduced pressure).
Alternatively, it may be struck under an inert gas atmosphere.Furthermore, the properties of the resulting fluorine-containing polyimide can be improved by finally heating it to a temperature of around 400°C for a short time.

The thus obtained fluorine-containing polyamic acid j1% fat has a characteristic of α to intrinsic viscosity (NMP solution, temperature 30°C).
(measured under certain conditions) is preferably set within the range of 0.3 to 3.0, particularly preferably within the range of 0.5 to 2.0.

In this way, an insulating film having a particularly low dielectric constant and low saturated water content can be obtained, and the insulating film has excellent both electrical properties and dimensional stability.

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

That is, this fluorine-containing polyamic acid j1% resin has the following -
Formula (DI) represents a furkyl group, a trifluoromethyl group, a lower alkoxy group, chlorine, bromine, or 77 atoms, and may be the same or different from each other, and %RI and R8 are hydrogen or a furkyl group, and each They may be the same or different, and R2 is a fluoroalkylene group, -CCCF3)
2-Alkylene group or sulfonyl group).

Examples of the aromatic ring-containing tetracarboxylic acids that are one of the raw materials of the present invention include the following.

However, below i! Illustrated with L-free carboxylic acid group,
Functional derivatives of these acid dianhydrides, acid halides, and esters are also extremely useful.

These are 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane, 2.2
-bis[4-(3,4-dicarboxyphenoxy)-3
-Fromophenyl] hexafluoropropane, 2,2-
bis[4-(3,4-dicarboxyphenoxy)-3,
5-dichromophenyl 1 hexafluoropropane, 2,
2-bis[4-(3,4-dical.

Hoxif/xy)-3,5-dimethylphenyl]hexa7fluoropropane, 2,2-bis[4-(3゜4-dicarboxy-2-trifluoromethyl7eth/xy)phenyl]hexafluoropropane, etc. Among these, particularly desirable ones are 2,
Examples include 2-bis[(3,4-nocarboxyphenoxy)phenyl]hexafluoropropane.

The diamine component, which is one of the other raw materials of the present invention, is the diamine used in claim 1, that is, the above formula (
Items similar to those shown in (2) can be mentioned.

By using these raw materials and reacting in the same manner as in claim 1, a fluorine-containing polyamide R-based resin represented by formula (III) in which a -C' (CFaL- group is introduced into the main chain) is obtained. is obtained.

Introducing 10 (CF3)2- groups into the main chain in this way not only significantly lowers the dielectric constant but also extremely lowers the saturated moisture absorption rate, and moreover, an excellent electrical insulating film can be obtained. Moreover, chemical stability is also greatly improved.

The fluorine-containing polyamic acid group resin thus obtained is extremely useful as an intermediate for the fluorine-containing polyimide represented by the general formula (II/) of the present M claim described below.

Next, the fluorine-containing polyimide of claim 4 of the present application will be explained in detail.

This fluorine-containing polyimide is
It is obtained by heating and imidizing a polyamic acid resin, and is represented by the following formula (■).

That is, this fluorine-containing polyimide has the following formula (1'/) (wherein R,, R,, R3, R2 and R1 are hydrogen, a lower alkyl group, a trifluoromethyl group, a lower fluorine group,
Represents chlorine, bromine or fluorine, which may be the same or different, and R is a fluoroalkylene group,
-C(CF,)2- is a fullkylene group or a sulfonyl group. ) is characterized by containing a repeating unit represented by

By the way, the conditions for this imidization are as set forth in claim 2 of the present application.
The same is true for .

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

The fluorine-containing polyamide fit-based resin of claim 5 will be explained in detail.

That is, 1 ml of this fluorine-containing polyamide is as follows:
The following formula (V) represents an alkyl group, a trifluoromethyl group, a lower alkoxy group, chlorine, bromine or fluorine, and may be the same or different from each other, and R6 and R are hydrogen or an alkyl group; , may be the same or different from each other, and Rt is a fluoroalkylene group, -C(CF, )
, -fulkylene group or sulfonyl group).

Examples of tetracarboxylic compounds containing an aromatic ring, which are one of the raw materials of the present invention, include the following.

However, below i! Illustrated with L-free carboxylic acid group,
Functional derivatives of these acid dianhydrides, acid halides, and esters are also extremely useful.

These are 2,2-bis(3,4-dicarboxy7enyl)hexafluoropropane, 2,2-bis(2°3-dicarboxyphenyl)hexafluoropropane, 2,2
-Bis(3,4-dicarboxy7enyl)propane, bis(4-(2,3-dicarboxyphenoxy)phenyl-1-sulfone, bis(3-(2,3-dicarboxyphenoxy)phenyl)sulfone, etc. Among these, particularly desirable ones are 2,2-
Examples include bis(3,4-dicarboxyphenyl)hexafluoropropane and 2°2-bis(2,3-dicarboxyphenyl)hexafluoropropane.

Examples of the fluorine-containing diamine component, which is one of the other raw materials of the present invention, include the fluorine-containing cyamine used in claim 1, that is, the same as that represented by the above-mentioned formula (■).

Then, by using these raw materials and reacting in the same manner as in claim 1, a fluorine-containing compound represented by formula (V) is obtained, in which 10(CF,)2- groups are introduced into the main chain. A polyamic acid resin is obtained.

Introducing the -C(CF3L-) group into the main chain in this way not only significantly lowers the dielectric constant but also extremely lowers the saturated moisture absorption rate, and provides an excellent electrical insulating film. Chemical stability is also greatly improved.

Claim 6 of the present application, wherein the fluorine-containing polyamic acid P and resin thus obtained are represented by the general formula ('/I) described below.
It is extremely useful as an intermediate for fluorine-containing polyimide.

Next, the fluorine-containing polyimide of claim 6 of the present application will be explained in detail.

This fluorine-containing polyimide is obtained by heating and imidizing the heptad-containing polyamic acid P of claim 5 of the present application and a resin, and has the following formula (Vll).

That is, this fluorine-containing zariimide has the following formula (Vl) and represents an alkyl group, a trifluoromethyl group, a lower alkoxy group, chlorine, bromine, or fluorine, which may be the same or different from each other, and R1 is characterized by containing a repeating unit represented by a fluoroalkylene group, -C(CF3)2-fulkylene group, sulfonyl group or ether group).

The method of heating and imidizing the fluorine-containing polyamic acid M resin of Claim 5 of the present application may be carried out in the same manner as in Claim 2 of the present invention.

In this way, an insulating film with a low dielectric constant and low saturated water content can be obtained, and the insulating film has excellent electrical properties and dimensional stability.

(e) Effect In the present invention, the reason why the dielectric constant decreases drastically and the saturated water absorption rate also decreases extremely, and an excellent electrical insulating film is obtained is not clear, but in the present invention, - formula ( 1
) to (■), the general formula (■) is attached to the main chain skeleton.
It is manufactured using a fluorine-containing diamine component having the structure shown in the following as a raw material.

It represents an alcohol group, )+7 fluoromethyl group, a lower alkoxy group, chlorine, bromine, or fluorine, and may be the same or different from each other. ) In this way, by introducing 10 (CF*)z- groups into the main chain skeleton, the fluorine content increases and the water repellency due to the fluorine atoms increases, which reduces the saturated moisture absorption rate. It is also understood that the dielectric constant decreases as the ratio of 7 silicon atoms in the molecule increases.

Examples The present invention will be explained in detail based on Examples below, but the present invention is not limited thereto.

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

6F-DA: 2t 2-bis[3,4-dicarboxy7enyl 1 hexafluoropropane anhydride 6FB-DA; 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl 1 hexafluoropropane anhydride PM-DA; pyromellit a anhydride 1.3-HFAB-BN; 1.3-bis(2-(4-aminobenoloxy)hexafluoroisopropyl 1 benzene 1.4-HFAB -BN: 1.4-bis[2-(4-7
minobenzoloxy)hexafluoroinpropyl 1benzene P D A : P -phenylenenoamine N M P
; N-methyl-2-pyrrolidone DCBFP: 2,2-bis[4-(3,4-dicarboxybenzoyloxy)phenyl 1xafluoropropane anhydride J DDE: 4,4'-di7minonophenyl ether BAP
F; 2,2-bis[4-(4-7mi/phenoxy)phenyl]hexafluoropropane 7? 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene 50% in a 3-necked 7 flask equipped with a diamine stirring rod, a thermometer, and a calcium chloride tube. Of! (0122 moles)
and dimethyl sulfoxide (SOOml), stir and mix to dissolve, and add 27 mL of potassium-poxide to this.
．． 4 g (0,244 mol) was gradually added and stirred at room temperature. After 1 hour, this was treated with p-nitrobenclupromide 52.
8 g (0,244 mol) was gradually added and stirred at room temperature.

After 2 hours, the reaction solution was added to water in Step 51, and the precipitated solids were collected by filtration, washed with water, and then dried. By recrystallizing and purifying this solid from ethanol, 74.0 g of yellow powder of the intermediate dinitro compound was obtained.

Furthermore, this noni) mouth body 74.01+ and ethyl acetate (70
0w1) was placed in a two-bottom flask equipped with a hydrogen gas introduction device, stirred and mixed to dissolve, and a catalytic amount of palladium on carbon was added thereto. Hydrogen gas was introduced into this solution for several hours at room temperature, the catalyst was filtered off, and then the solvent was removed. The obtained residue was subjected to silica sol chromatography (silica sol 10
00g, I opening solvent (roloform/acetone = 4/1), and the purified product was crystallized with toluene to obtain 36g of a diamine compound with a purity of 100%.

Hereinafter, this will be abbreviated as 1.3-HFAB-BN.

Example 1 1.3-HFAB-BNloo was placed in a three-loaf flask equipped with a stir bar, a thermometer, and a nitrogen gas inlet.

Add Og (0,161 mol) and 71.6 g (0°161 mol) of 6F-DA, and add 83 g of dimethylacetamide.
0 ml was added and stirred to dissolve.

Next, by reacting at a temperature of 30°C for about 5 hours,
A solution of the fluorine-containing FF lyamic acid-based fat of the present invention was obtained.

This fluorine-containing polyamide lIl-based resin has a light color,
Intrinsic viscosity is 1.2g/dj! Met.

Example 2 A solution of this fluorine-containing polyamic acid PS resin was spread thinly on a plastic plate, heated at 100°C for 1 hour, and then heated at 200°C.
The mixture was heated at 300°C for 1 hour and then at 300°C for 1 hour to obtain a fluorine-containing polyimide film (thickness: 50μ).

Table 2 shows the moisture absorption rate (saturated moisture absorption rate) and dielectric constant of the fluorine-containing polyimide film thus obtained.

Example 3 The solution of heptadium-containing polyamic acid fruit resin obtained in Example 1 was
The mixture was placed in a four-bottle flask equipped with a stirring rod, a thermometer, and a reflux condenser and equipped with a nitrogen gas inlet, and 100 m&' of toluene was added thereto for mixing. The temperature of this solution was raised to 160'C over 60 minutes while stirring. A dehydration reaction occurred at 140 to 145° C. in this external temperature, and a mixture of water and toluene was distilled out of the system.

Next, a uniform black-brown high viscosity solution of polyimide was obtained by reacting at 160° C. for about 5 hours.

The intrinsic viscosity of the polyimide thus obtained is y=1.
It was 2.

This polyimide solution was poured onto a glass plate to form a film, and after drying in a hot air dryer at 120°C for 30 minutes,
It was dried at 200°C for 60 minutes to obtain a polyimide film with a thickness of 50±5μ.

Table 2 shows the moisture absorption rate (saturated moisture absorption rate) and dielectric constant of the fluorine-containing polyimide film thus obtained.

Examples 4 to 8 Using the method shown in Example 1, a fluorine-containing diamine and a fluorine-containing tetracarboxylic dianhydride as shown in Table 1 were reacted to form the corresponding 7-containing boron 177. A mic acid-based resin was formed.

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

The results are shown in Table 1.

(The following is a blank space) Table 1 In Table 1, the intrinsic viscosity was measured by dissolving a dry solid in NMP in a constant temperature bath at 30°C.

Examples 9 to 13 The obtained fluorine-containing poly-7-V acid resin was 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 Table 2.

(Left below) 2nd! ! Measurement conditions: 100 KHz; (Ando Electric) Dielectric loss automatic measurement i'! In the second fi of TR-1100, the dielectric constant is 30
The measurement was carried out using a film having an area of approximately 5 cm 2 at a temperature of 50 μm and a film thickness of 50 μm.

In Table #12, the method for measuring the moisture absorption rate (saturated moisture absorption rate) is as follows:
Dry the fluorine-containing polyimide film with hot air at 50℃fffi
Let it dry for 24 hours in a 10 cm x 10 cm
After weighing the size, store at 25℃ and relative humidity 80%.
The sample was left in a humidity-controlled desiccator for 24 hours, weighed, and determined 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 manner as above, and the result was 0.5%.

Comparative Example 1 A three-necked 7-laser glass with a stir bar, a thermometer, and a nitrogen gas inlet, BAPF (0,161 mol), and 6F-〇A (0,1
61 mol) was added thereto, and DMAc (800 ml) was added thereto and dissolved and stirred. After reacting for about 5 hours, a pale yellow fluorine-containing polyamic acid solution was obtained.

Spread this polyamic acid solution thinly on a glass plate and
A film was prepared by heating at ℃ for 1 hour.

The mixture was further heated at 200°C for 1 hour and at 300°C for 1 hour to obtain a fluorine-containing polyimide film (about 50μ brass).

Moreover, when the intrinsic viscosity of this was measured, it was found that y=1.3.

Including 7 thus obtained? Table 2 shows the moisture absorption rate (saturated moisture absorption rate) and V dielectric constant of the basic polyimide film.

Comparative Example 2 2.05 g of PDA was placed in a 4-necked 7-flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet.
Then, the flask was immersed in a water bath at 20°C, and DCBFP12.
95g was added in portions. After DCBFP is dissolved,
The water bath was removed, and the reaction was continued for about 5 hours at around room temperature.

Moreover, when the intrinsic viscosity of this was measured, it was found that y=0.8.

This varnish was applied on a glass plate and heated for 15 minutes in a nitrogen stream.
A polyimide film was obtained by curing at 0°C for 1 hour, at 250°C for 0.5 hours, and further at 400°C for 1 hour.

Table 2 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.

DDE 3.40g DCBFP 11.60g NMP 85. og Moreover, when the intrinsic viscosity of this was measured, it was found that y=0.9.

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

Table 2 shows the moisture absorption rate (saturated moisture absorption rate) and dielectric constant of the fluorine-containing polyimide film thus obtained.

From the results shown in Table 1, it can be seen that the samples of the Examples are extremely superior in both moisture absorption and dielectric constant compared to those of the Comparative Examples.

Also, from the results shown in Table 2, the moisture absorption rate (
Not only does it have an extremely low saturated moisture absorption rate (saturated moisture absorption rate), its dimensions do not change much due to changes in temperature or humidity, but it also has extremely high reliability because it does not deteriorate the electrical characteristics of electrical and electronic circuits.

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 an extremely high moisture absorption rate (saturated moisture absorption rate), and change in size due to changes in temperature and humidity causes a deterioration in the electrical characteristics of electric/electronic circuits.

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

(g) Effects of the invention The fluorine-containing polyamic acid-based resin of the present invention is extremely useful as a derivative of fluorine-containing polyimide having a structure as shown in the general formula (■) in the main chain skeleton. be.

(In the formula, R, R2, R3, R1 and R1 are hydrogen, lower alkyl group, 17 fluoromethyl group, lower alkoxy group,
They represent chlorine, bromine, or fluorine, and may be the same or different. ) Moreover, the fluorine-containing polyimide of the present invention has an extremely low moisture absorption rate (saturated moisture absorption rate) due to the introduction of 10(CF3)2- groups into the main chain skeleton, and is resistant to changes in temperature and humidity. Not only does it not undergo much dimensional change, it also does not degrade the electrical characteristics of electrical and electronic circuits, making it extremely reliable.It also has an extremely low dielectric constant (which can speed up signal propagation). It has the following effects.

Claims (6)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1, R_2, R_3, R_4 and R_5 are hydrogen, lower alkyl group, trifluoromethyl group, lower alkoxy group , represents chlorine, bromine or fluorine, and may be the same or different from each other, and R_6 and R_8
They are hydrogen or an alkyl group, and may be the same or different from each other, and R_7 is a tetravalent organic group having 1 to 4 benzene rings. ) 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_1, R_2, R_3, R_4 and R_5 are hydrogen, lower alkyl group, trifluoromethyl group, lower alkoxy group , represents chlorine, bromine or fluorine, and may be the same or different from each other, and R_7 is a tetravalent organic group having 1 to 4 benzene rings. A fluorine-containing polyimide characterized by: (3) General formula (III) below ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_1, R_2, R_3, R_4 and R_5 are hydrogen, lower alkyl group, trifluoromethyl group, lower alkoxy group , represents chlorine, bromine or fluorine, and may be the same or different from each other, and R_6 and R_8
are hydrogen or an alkyl group, which may be the same or different, and R_7 is a fluoroalkylene group, -C(CF_3)_2-, an alkylene group or a sulfonyl group). A fluorine-containing polyamic acid resin comprising: (4) General formula (IV) below ▲Mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R_1, R_2, R_3, R_4 and R_5 are hydrogen, lower alkyl group, trifluoromethyl group, lower alkoxy group , represents chlorine, bromine or fluorine, and may be the same or different from each other, and R_7 is a fluoroalkylene group, -C(CF_3)_2-, an alkylene group or a sulfonyl group. A fluorine-containing polyimide characterized by containing a repeating unit. (5) General formula (V) below ▲Mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R_1, R_2, R_3, R_4 and R_5 are hydrogen, lower alkyl group, trifluoromethyl group, lower alkoxy group , represents chlorine, bromine or fluorine, and may be the same or different from each other, and R_6 and R_8
are hydrogen or an alkyl group, which may be the same or different, and R_7 is a fluoroalkylene group, -C(CF_3)_2-, an alkylene group or a sulfonyl group. ) A fluorine-containing polyimide acid resin characterized by containing a repeating unit represented by: (6) General formula (VI) below ▲Mathematical formulas, chemical formulas, tables, etc.▼(VI) (In the formula, R_1, R_2, R_3, R_4 and R_5 are hydrogen, lower alkyl group, trifluoromethyl group, lower alkoxy group , represents chlorine, bromine or fluorine, and may be the same or different from each other, and R_7 is a fluoroalkylene group, -C(CF_3)_2-, an alkylene group, a sulfonyl group or an ether group). A fluorine-containing polyimide characterized by containing the following repeating unit.