JPH0420527A - Modified polyimide resin and its production - Google Patents

Abstract

PURPOSE:To obtain a modified polyimide resin lowered in moisture absorption, permittivity and a coefficient of thermal expansion by introducing specified fluoroalkyl groups into at least part of the aromatic rings of an aromatic hydrocarbon polyimide resin. CONSTITUTION:An aromatic hydrocarbon polyimide resin (A) is reacted with 0.1-50mol, per unit (mol) of the monomer of component A, of a di(haloacyl) peroxide (B) of formula I or II (wherein X is F, Cl or H; n is 1-10; and m is 0-8) at 0-100 deg.C for 30min to 20hr to obtain a modified polyimide resin wherein fluoroalkyl groups of formula III or IV are introduced into at least part of the aromatic rings of component A.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a modified polyimide resin useful for electronic materials, etc., and a method for producing the same.

<Conventional technology> Conventionally, SiO,
, Si, N4, and other silicon-based materials are used.
Recently, polyimide resins have attracted attention because of their ease of manufacturing process, as well as their ability to be flattened. However, conventional polyimide resins have the drawbacks of high hygroscopicity and high electrical properties, that is, high dielectric constants, and also have a high coefficient of thermal expansion compared to substrates such as silicon.
There is a problem that distortion and cracks are likely to occur. In order to solve the above problems, attempts have been made to introduce fluorine into polyimide resins. For example Poly
er Preprints, Japan, vo13
8, No. 3.

434 (1989), a polyimide resin produced by introducing a trifluoromethyl group into pyromellitic anhydride was also produced by Polymer Preprints
.

Japan, vol138. No.3.433 (1989
), a fluoroalkoxy group (CF, (CF2)n CH2O-1n"316
Polyimide resins produced by introducing 97.10) have been proposed.

However, with the above-mentioned fluorine-containing polyimide resin,
It is strongly desired to develop a polyimide resin that does not satisfy the above-mentioned problems and has lower hygroscopicity, lower dielectric constant, and lower coefficient of thermal expansion.

<Problems to be Solved by the Invention> Therefore, an object of the present invention is to provide a polyimide resin having low hygroscopicity and low dielectric constant, and low coefficient of thermal expansion, and a method for producing the same.

<Means for Solving the Problems> According to the present invention, at least a portion of the aromatic ring in the aromatic hydrocarbon group-containing polyimide resin is represented by the following general formula (1) (I) (wherein, X is fluorine). a chlorine atom or a hydrogen atom, and n represents an integer of 1 to 10) or a fluoroalkyl group represented by the following general formula (ff) (wherein m represents an integer of 0 to 8) A modified polyimide resin is provided.

Further, according to the present invention, the following general formula (III) (wherein,
represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n is 1 to
(represents an integer of 10) or a di(haloacyl) peroxide represented by the following general formula (mV) (mV) (in the formula, 1m represents an integer of 0 to 8) and an aromatic hydrocarbon group-containing polyimide At least a portion of the aromatic rings in the polyimide resin are reacted with the polyimide resin to form the following general formula (1) (I) (wherein, X represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n represents 1 to A method for producing a modified polyimide resin, characterized by introducing a fluoroalkyl group represented by the following general formula (II) (in which m represents an integer of O to 8): is provided.

The present invention will be explained in more detail below.

The modified polyimide resin of the present invention is a resin in which a fluoroalkyl group is introduced into at least a portion of the aromatic rings in an aromatic hydrocarbon group-containing polyimide resin.

The aromatic hydrocarbon group-containing polyimide resin used in the present invention may be any polyimide resin containing an aromatic hydrocarbon group, and preferably a resin having a structural unit represented by the following formula (I). can be mentioned.

[In the formula, R□ and R2 are the same or different groups and represent an aromatic hydrocarbon group, and R3 represents an aromatic hydrocarbon group or a fluoro-substituted aromatic hydrocarbon group. Y is an oxygen atom, methylene group, ethylene group, dimethylmethine group, sulfone group, bis(trifluoromethyl)methine group, or (A is an oxygen atom, methylene group, ethylene group, dimethylmethine group, bis(trifluoromethyl) methyl) methine group,
It represents a sulfone group, and j represents an integer of 0 to 3. ), and further, Q each represents 0 or 1] R1 and R2
Preferred examples of the aromatic hydrocarbon group include the following, and preferred examples of the aromatic hydrocarbon group of R1 include the following.

The polyimide resin can be prepared by reacting an aromatic tetracarboxylic dianhydride and its derivative with an aromatic diamine in an organic polar solvent. Examples of the aromatic tetracarboxylic dianhydride and its derivatives include 1. pyromellitic dianhydride; 3.
3',4,4'-benzophenonetetracarboxylic dianhydride, 3゜3'4,4'-biphenyltetracarboxylic dianhydride, 2,3.3',4'-biphenyltetracarboxylic dianhydride Anhydride, 4,4'-oxysiphthalic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide anhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 3.3'4゜4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,6.7-naphthalenetetracarboxylic dianhydride, 1,2,5.6-naphthalene Examples include tetracarboxylic dianhydride and 1,4,5.8-naphthalenetetracarboxylic dianhydride, which can be used alone or as a mixture.

Further, examples of the aromatic diamine include m-phenylenediamine and p-phenylenediamine.

2.4-tolylenediamine, 2.6-tolylenediamine, 4,6-dimethyl-m-phenylenediamine, 4-chloro-m-phenylenediamine, 3゜5-diaminobenzoic acid, 5-nitro-m- phenylene diamine, 3,3'
-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3.3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3.3'-
Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone,
4,4'-diaminobenzophenone, 2゜2-bis(3
-aminophenyl)propane, 2゜2-bis(4-aminophenyl)propane, benzidine, 3,3'-dimethylbenzidine, 3゜3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-dimethyl -4,4'
-diaminodiphenylmethane, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, -aminophenyl)
Benzene, bis(4-(3-aminophenoxy)phenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis (4-aminophenoxy)biphenyl, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(4- (4-aminophenoxy)phenyl]propane,
2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-(4-
Examples include aminophenoxy)phenyl]hexafluoropropane, which can be used alone or as a mixture. Further, the number average molecular weight of the polyimide resin is preferably in the range of 500 to 1.000,000.

If the number average molecular weight is less than 500, the properties of polyimide will not be exhibited, and if it exceeds 1,000,000, it will be difficult to manufacture.

The fluoroalkyl group introduced into at least a portion of the aromatic ring in the polyimide resin has the following general formula (I) -(CF2)nX (1)
or represented by the following general formula (II), where X represents a fluorine atom, a chlorine atom or a hydrogen atom,
n represents an integer of 1 to 10, and 1m represents an integer of 0 to 8.

The fluoroalkyl group represented by the general formula (1) is -CF3°F (CF 2 + 2- F (CF z + 3
, F(CF2+-.

F(CF,+,,F(CF,+,,F(CF,-)ff
tF(CF2-)-,,F(CF,-)-9,F(CF
2+,. .

ClCF2-, C1(CF2-)-2, C1(CF2-
),.

Cl (CF, +,, Cl (CF, -),, CI
(CF, +6°Cl (CF2-)-,, Cl (C
F,+,,Cl (CF2+,.

CI (CF,+,.,HCF-2,H(CF2+2゜H(CF,-)-,,H(CF2-)-,,H(CF,
+5゜H(CF2-)-,,H(CF2-)-,,H(
CF,±,.

Specific examples include H(CF2-)-, 'H(CF2+).

Further, as the fluoroalkyl group represented by the general formula (II), -CF(CF,)QC3F7°-CF(C
F, ) (OCF, CF (CF, )) □○C,F,.

-CF (CF3) [OCF, CF (CF, )) 20C
3F.

-CF(CF,)(OCF,CF(CF,)),○C,
F.

-CF(CF,)(OCF2CF(CF,)),OC,
F.

-CF(CF,)(OCF,CF(CF,)],OC
,F.

-CF(CF,)(OCF,CF(CF,)),OC,
F7゜-CF(CF,)(OCF, CF(CF,)),
OC,F.

-CF(CF3)(OCF2CF(CF, )), OC,
F.

can be specifically mentioned.

Introducing the fluoroalkyl group represented by the general formula (I) or (II) into at least a portion of the aromatic rings in the aromatic hydrocarbon group-containing polyimide resin may mean that the fluoroalkyl group is introduced. , the fluoroalkylation rate to the aromatic ring (100% is when one fluoroalkyl group is introduced per aromatic ring) is 1.
The range is preferably 100%.

The modified polyimide resin of the present invention can be obtained by directly reacting a specific di(haloacyl)peroxide with an aromatic hydrocarbon group-containing polyimide resin.

In the production method of the present invention, the specific di(haloacyl)peroxide is represented by the following general formula ([1) or the following general formula (IV), ... (IV) where X is a fluorine atom, chlorine Indicates an atom or a hydrogen atom,
n represents an integer of 1 to 10, and 1m represents an integer of 0 to 8.

As the di(haloacyl)peroxide represented by the general formula (m), the fluoroalkyl group in the formula, that is, X
(CF2) Compounds in which n- is a fluoroalkyl group specifically listed as the fluoroalkyl group represented by the above general formula (I) can be preferably mentioned. Further, as the di(haloacyl)peroxide represented by the general formula (IV), the fluoroalkyl group in the formula, (I
As the fluoroalkyl group represented by I), the compounds specifically listed as fluoroalkyl groups can be preferably mentioned.

The di(haloacyl)peroxide can be produced, for example, by reacting the corresponding acyl chloride or acyl chloride with hydrogen peroxide in the presence of an alkali catalyst.

In the production method of the present invention, the reaction temperature at which the di(haloacyl) peroxide and the polyimide resin are reacted is preferably in the range of 0 to 100°C. If the reaction temperature is less than 0°C, the reaction time becomes long and
If the temperature exceeds 00°C, the pressure during the reaction will become high and the reaction operation will become difficult, which is not preferable. In addition, the reaction time at this time is preferably about 30 minutes to 20 hours, and industrially it is about 30 minutes to 20 hours.
It is particularly preferable to carry out the treatment for a period of 10 hours. When the reaction time is less than 30 minutes, one reaction does not proceed sufficiently,
Further, even if the reaction is allowed to proceed for more than 20 hours, no progress of the reaction is observed, which is not preferable.

The molar ratio of the polyimide resin to the di(haloacyl) peroxide to be charged is preferably 0.1 to 50 moles of the di(haloacyl) peroxide per unit (1 mole) of the polyimide resin monomer.

Furthermore, when carrying out the above reaction, a solvent can be used for the purpose of handling the di(haloacyl)peroxide and carrying out the reaction more quickly. As the solvent, halogenated aliphatic solvents can be preferably mentioned, and specifically, for example, 2-chloro-1,2-dibromo-1,1,2-
)-lifluoroethane, 1,2-dibromohexafluoropropane, 1,1-difluorotetrachloroethane,
1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, l,1,1,3-tetrachlorotetrafluoropropane, 1,1,1'-trichloropentafluoropropane, Examples include 1,1,2-trichlorotrifluoroethane, methylene chloride, chloroform, and carbon tetrachloride, which can be used alone or as a mixture. In addition, when using the solvent, it is desirable to adjust the concentration of the di(haloacyl)peroxide in the solvent to 1 to 30% by weight before carrying out the reaction.

In the production method of the present invention, fluoroalkane carboxylic acid is also produced as a by-product, but after the reaction is completed,
The obtained resin can be sufficiently purified by fractionating and washing with an aqueous alkaline solution or the like.

<Effects of the Invention> Since the modified polyimide resin of the present invention has a fluoroalkyl group directly covalently bonded to the aromatic ring in the aromatic hydrocarbon group-containing polyimide resin, it has useful properties due to the fluoroalkyl group, In other words, water and oil repellency, chemical resistance,
Heat resistance and low dielectric properties can be maintained extremely permanently, and therefore low moisture absorption and low dielectric properties are strongly required.
It is useful as a material for insulating films such as SI. Furthermore, by the method for producing a modified polyimide resin of the present invention, an aromatic hydrocarbon group-containing polyimide resin can be easily produced in a short time.

Furthermore, a fluoroalkyl group can be directly introduced without using a reaction catalyst or special equipment.

<Examples> The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited thereto.

2. By polycondensation reaction of 2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 2,2-bis(4-aminophenoxyphenyl)hexafluoropropane, the following Polyimide resin shown by the structural formula (
(hereinafter referred to as resin A) was obtained.

(Mn=159000.Mw/Mn=2.0 (Molecular weight measured by GPC, measurement solvent: DMF)] Also, a 1,1.2-trifluorotrichloroethane solution containing 24 mmon of perfluoroheptanoyl peroxide 219
．． Then, 3.7 g of the polyimide resin prepared as a reaction solution was added to the solution, and the reaction temperature was 4.
The reaction was carried out at 0°C for 5 hours under stirring and nitrogen flow. After the reaction is complete, add chloroform to the reaction solution.

After making a homogeneous solution, impurities were removed by washing with water and washing with a 1% aqueous sodium hydroxide solution. Next, drying was performed using a molecular sieve to remove the solvent, and drying was performed under vacuum.

As a result, a modified polyimide resin in which a perfluorohexyl group was introduced into the aromatic ring in the polyimide resin was obtained with a yield of 6.8
Obtained in g. The molecular weight, 13F-NMR data and "F" of the obtained perfluorohexylated polyimide resin
-The results of the perfluorohexylation rate determined by NMR are shown below.

Molecular weight: Mn=175000 (Mw/Mn=1.6) "F-NMR (CDCQ3.ext, CF3CO2
H) δ=12.1 (CF,), 11.0 (CF,)
.

-5,3 (CF, ), -32,7 (,CF2).

−46,0 (CF, ), −47,1 (CF, ).

-50,0 (CF,) Perfluorohexylation rate: 18% The perfluoroalkylation rate was calculated assuming that 100% is the case where one fluoroalkyl group is introduced per one aromatic ring in the polyimide resin. .

In addition, the obtained modified polyimide resin was dissolved in an organic solvent to create a film, and 4274A Multi-Fre
The dielectric constant was measured using a quench LCR meter (YF(P). Furthermore, the temperature of the obtained film was 23.
The water absorption rate after 24 hours at ℃ was also measured. The results are shown in Table 1.

Amount of perfluoroheptanoyl peroxide: 219.5
The reaction and purification were carried out in the same manner as in Example 1 except that g was replaced with 329 g (36 mmoQ) to obtain modified polyimide resin 7.
．． 5g was obtained. Further, the obtained resin was tested in the same manner as in Example 1. The molecular weight, 1'F-NMR, and perfluorohexylation rate are shown below, and the dielectric constant and water absorption are shown in Table 1.

Molecular weight: Mn=190000 (Mw/Mn=1.5) 19F-NMR (CDCA, ext, CF, C
o, H) δ=12.1 (CF, ), 11.0 (CF
,).

−5,3 (CF, ), −32,7 (CF, ).

-46,0 (CF2), -47,1 (CF2).

-50,4 (CF2) Perfluorohexylation rate: 32% 1
The reaction and purification were carried out in the same manner as in Example 1 except that 6.2 g of modified polyimide resin was obtained.

Further, the obtained resin was tested in the same manner as in Example 1. The molecular weight, F-NMR, and perfluoropropylation rate are shown below, and the film properties are shown in Table 1.

Molecular weight: Mn=155000 (Mw/Mn=1.6) 1″F-NMR (CDCQ, ext, CF, Co2H
) δ=12.5 (CF, ), 11.7 (CF, ).

−4,5 (CF, ), −49,7 (CF, ).

-50,2 (CF,) Perfluoropropylation rate = 25% Lost seed ± Instead of perfluoroheptanoyl peroxide.

Perfluorobutyryl peroxide 204.6g (24mv
Reaction and purification was carried out in the same manner as in Example 1, except that SOQ) was used to obtain 5.9 g of a modified polyimide resin. Further, the obtained resin was tested in the same manner as in Example 1. The molecular weight, F-NMR, and perfluoropropylation rate are shown below, and the dielectric constant and water absorption are shown in Table 1.

Molecular weight: Mn = 142000 (Mw/Mn =
1.8) 1″F-NMR (CDCQ, ext, CF, Co2H
) δ=12.5 (CF, ), 11.8 (CF, ).

−4,5 (CF, ), −49,6 (CF, ).

-50,1 (CF2) Perfluoropropylation rate: 18% When cold, perfluoroheptanoyl peroxide was replaced with peroxide ω-
Hydroperfluorobutyryl 200.8g (24■■o
The reaction and purification were carried out in the same manner as in Example 1 except that Q) was used to obtain 9.9 g of a modified polyimide resin. Further, the obtained resin was tested in the same manner as in Example 1. molecular weight,
The F-NMR1ω-hydroperfluoropropylation rate is shown below, and the dielectric constant and water absorption are shown in Table 1.

Molecular weight: Mn=166000 (Mw/Mn=1.9) 1gF NMR (CDCM3.ext, CF, C02
H) δ=12.3 (CF, ), 11.6 (CF
,).

-45,6 (CF2), -52,2 (CF).

-60,1(CF2) ω-Hydroperfluoropropylation rate: 50% benzophenone-3,3',4,4'-tetracarboxylic dianhydride and 2,2-bis(4-aminophenoxy) Obtained by polycondensation reaction with (phenyl)hexafluoropropane. Polyimide resin shown by the following structural formula (hereinafter referred to as resin B) (Mn=135000.Mw/Mn=2
．． Reaction was carried out in the same manner as in Example 1 except that 3.3 g of 2) was used.
Purification was performed to obtain 5.3 g of modified polyimide resin.

The results of the molecular weight, "F-NMR" and perfluorohexylation rate determined by "F-NMR" of the obtained perfluorohexylated polyimide are shown below, and the dielectric constant and water absorption properties are shown in Table 1.

Molecular weight: Mn=143000 (Mw/Mn=1.8) 19F-NMR (CDCQ, ext, CF, CO
2H) δ=11.3 (CF, ) , -5,4(CF
,).

-32,5 (CF2), -46,8 (CF2).

-47,3(CF2), -50,3(CF2) Perfluorohexylation rate: 26% Kansankane 2.2-bis(3,4-dicarboxyphenyl)hexafluoropropanihydride and 2, A polyimide resin (hereinafter referred to as resin C) obtained by a polycondensation reaction with 2-bis(4-aminophenyl)hexafluoropropane and represented by the following structural formula (Mn=113000.Mw/Mn=
Reaction and purification was carried out in the same manner as in Example 1 except that 2.1) was used to obtain 5.4 g of a modified polyimide resin. The molecular weight of the obtained perfluorohexylated polyimide resin, "F
-NMR and perfluorohexylation rate are shown below, and dielectric constant and water absorption are shown in Table 1.

Molecular weight: M n = 123000 (Mw/M n
= 1.9) "F-NMR (CDCM, ext, CF, Co2H)
δ=12.3 (CF, ), -5,3 (CF, ).

−32,5 (CF, ), −46,9 (CF2).

;, 47.0 (CF2), -50,8 (CF2) Perfluorohexylation rate: 44% Perfluoro-2-methyl-3-oxa-hexanoyl peroxide 20 instead of perfluoroheptanoyl peroxide
Reaction and purification were carried out in the same manner as in Example 1, except that 4.6 g (24 mmoR) was used, and 7.9 g of modified polyimide resin was obtained.
I got it. Molecular weight, "F-NMR and perfluoro-2-
The (3-oxa)hexylation rate is shown below, and the dielectric constant and water absorption are shown in Table 1.

Molecular weight: Mn=172000 (Mw/Mn=1.7) "F-NMR (CDCQ, ext, CF, Co2H)
δ=12.5 (CF3), 11.8 (CF, ).

-〇, 4 to -5.24 (8F), -53,1 (2F)
, -47,3(21F) Perfluoro-2-(3-oxa)hexylation rate: 34
% Comparative Examples 1 to 3 Films were prepared using each of Resin A (Comparative Example 1), Resin B (Comparative Example 2), and Resin C (Comparative Example 3).
The dielectric constant and water absorption were measured in the same manner as above. The results are shown in Table 1.

As is clear from Table 1, it was found that the modified polyimide resin of the present invention had significantly lower water absorption and lower dielectric constant than unmodified polyimide resin.

Claims (1)

[Claims] 1) At least a part of the aromatic ring in the aromatic hydrocarbon group-containing polyimide resin has the following general formula (I) -(CF_2)nX...(I) (wherein, X is represents a fluorine atom, chlorine atom, or hydrogen atom, and n represents an integer from 1 to 10) or the following general formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, m is A modified polyimide resin into which a fluoroalkyl group represented by (representing an integer from 0 to 8) is introduced. 2) The following general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, X represents a fluorine atom, chlorine atom, or hydrogen atom, and n represents an integer from 1 to 10. ) or the following general formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... (IV) (In the formula, m represents an integer from 0 to 8) di(haloacyl) peroxide and aromatic A hydrocarbon group-containing polyimide resin is reacted with the polyimide resin to form at least a portion of the aromatic ring in the polyimide resin with the following general formula (I) -(CF_2)nX...(I) (wherein, X is a fluorine atom) , represents a chlorine atom or a hydrogen atom, and n represents an integer from 1 to 10) or the following general formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, m is 0 to 10) 1. A method for producing a modified polyimide resin, which comprises introducing a fluoroalkyl group represented by (representing an integer of 8).