JPH0243230A - Composite sheets and laminates - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Application) The present invention relates to a composite sheet and laminate using a fluorine O (fatty base material), and the composite sheet and laminate can be used for, for example, a space satellite broadcasting antenna circuit board. It is useful for high-frequency laminated boards used as space satellite broadcast receiving converter circuit boards, wireless communication FF1FI circuit boards, electrical measurement equipment circuit boards, high-speed computer circuit boards, and other high-frequency application equipment circuit boards.

(Prior Art) Conventional printed wiring boards used in electronic devices include, for example, glue knot boards made of plus epoxy, paper 7-el, plus polyimide, plus-bonded tetrafluoroethylene, and flexible boards made of polyimide, polyester, etc. The board is known.

Among these, plus epoxy and paper phenol are conventionally
-It is used in the shell, but the dielectric constant and dielectric loss tangent are large.
Therefore, signal propagation delay or high frequency transmission loss is large,
It is difficult to apply it to computers that require high speed and circuits that use high frequencies.

Plus polyimide has high heat resistance and good dimensional stability and is used for multilayer laminates, etc., but its dielectric constant and dielectric loss tangent are large and it is not satisfactory for high frequency applications. Plus polytetrafluoroethylene has a low dielectric constant and low yJ electric loss tangent, but #! There are other problems, such as poor adhesion to foils, unstable coefficient of thermal expansion in the thickness direction, and difficulty in processability. Furthermore, flexible boards have features such as easy wiring between parts and easy three-dimensional wiring, but the dielectric constant,
The dielectric loss tangent is large (difficult to use for high frequency circuits).

(Problems to be Solved by the Invention) An object of the present invention is to provide a composite sheet and laminate for high frequencies that have a small dielectric constant and dielectric loss tangent, are immersed in high frequency characteristics, and have excellent heat resistance and dimensional stability.

(Means for Solving the Problems) The present invention relates to a composite sheet in which a fluororesin base material is impregnated with fluorine-containing polyimide, and a laminate characterized in that a metal layer is formed on the composite sheet.

In the present invention, various materials can be used as the fluorocarbon resin base material, such as polytetrafluoroethylene, polychlorotrialoethylene, tetrafluoroethylene hexafluoro-a-pyrene copolymer, and f) lafluoroethylene. Examples include porous bodies of fluororesins such as ethylene perfluorovinyl ether copolymers, fiber cloths, and nonwoven fabrics. The fluororesin used here itself has a small dielectric constant and dielectric loss tangent. For example, polytetrafluoroethylene has a dielectric constant of 2.05 and a dielectric loss tangent of 0.00002 (I M
Hz). Further, since this porous body has pores, the I electric constant is further small, and the porosity is 30 to 90%, and the dielectric constant is 1.8 to 1.1.

The fluorine-containing polyimide of the present invention has the general formula [wherein R' is a residue obtained by removing two acid anhydride groups from an aromatic tetracarboxylic dianhydride, and R2 is a residue obtained by removing two acid anhydride groups from an aromatic noamine. At least one of R1 and R2 has a perfluoroalkyl group Rr' of C-Rr: Cl-1* in the main chain.
: C1-2+1/)z<-7% D 7 Alkyl group 1) 20 or an integer from 1 to 3 q: 0 or an integer from 1 to 3 ": 0 or 1 ・] 20 or an integer from 1 to 5 1 : 0 or an integer of 1 to 5 Y : Same definition as X, or hydrogen atom, 7-enyl group, substituted phenyl group (example of substituent: C7-5 alkyl group)
, 01~. Alkyl i, C, ~, haloalkyl group (
Halogen includes a group represented by a fluorine atom, a chlorine atom, or a bromine atom. n represents an integer of 1 to 2.000.

] is included.

In the above, preferable examples of X are CF, CH2Cl+2
[' Group, preferred examples of Y are CF, group, hydrogen atom, C-6 alkyl group, 2. Specific examples of the haloalkyl group and other R are as follows.

Specific examples of the above R include, for example, CI□) n-S- N- C1-10 furkyl group, aryl group (e.g. phenyl group, naphthyl group), substituted 7-aryl group (substituent example: C1-,
(alkyl group) 1 (Examples of 1) -C-1, ) 11]1 (R3 has the same meaning as above, Z is the same or different hydrogen atom T
-, CI'SRr again 1! NO=, w is the 9th number of -4)
Further, as other specific examples of R2 [wherein, R1 has the same meaning as above]. ] Aromatic tetracarboxylic dianhydride represented by the general formula % formula % (3) [wherein 1 and 2 have the same meanings as in Section 111j. ] can be reacted with the aromatic noamine represented by -maximum % formula % (Z and l are the same as above), etc.

The polyimide of the present invention has the general formula [wherein F and 1 (2 has the same meaning as in 111j,
It represents an integer of ~2.0+10, preferably 1~I,000. It can be obtained by producing a polyamic acid represented by the following formula and then converting this polyamic acid into polyimide.

Compounds containing the above-mentioned maximum (2) aromatic tetracarboxylic dianhydride (X+C (Yl- group are, for example, XC0
It can be easily obtained by a Grignard reaction as shown in the formula obtained by reacting the compound represented by Y' (5) (X and Y are the same as above a) with 0-xylene in the presence of a Lewis acid.

(2) CF, C00CH.

It can be synthesized by oxidizing and dehydrating the compound shown in

Examples of the compound represented by general formula (5) include Cm
F l 7 CH□CH2COCF.

C, F 70 C (CF 3 ) F CH2CH2C
OCF-C,F,C) (2CH,C0CF.

c,F,,Cl12CI(zC)011C,F,□C1
12C112COC11, C112CF2CF2 (OC
FICF2CF2)1F (n=1-5) H(CF2CF2)3CH2CHICOCF.

+1(CF2CF2 LCII□Cl12COC1I□
CIl. Examples include C11F, , and the like.

The compound represented by maximum (5) above is, for example, the following [wherein Rr, RrZ III Ql rH'; and [ have the same meaning as above. ] 0- per equivalent of the compound represented by maximum (5) above.
React two or more equivalents of xylene. As a Lewis acid,
Hydrogen fluoride, aluminum chloride, iron chloride (I[l), zinc chloride, boron trifluoride, H8bPIIA5F6, H
PF6. Examples include HBF, etc., and hydrogen fluoride is preferable for 1 and Y. The amount of Lewis acid used is 15 to 100 times, preferably 20 to 50 times, the amount of the compound represented by the general formula (5).

In carrying out the reaction, it is preferable to use a 78 medium, such as trimethylformamide sphoramide (HMPA), trimethylacetamide (D
MAe), N-methylpyrrolidone, 1.1.2.2,-
Te) Fuchloro1.2-fluoroethane, trimethyl sulfoxide (r) MSO), tetrahydro-7rane (TH
F) etc. can be used. Note that the hydrogen fluoride used as the Lewis acid can also be used as a solvent for Ie.

The reaction temperature is usually 50-200'C, preferably 70-200'C.
The temperature is 150°C. The pressure is usually 5 to 20 kg/c2,
Preferably it is 7-15 to 6/cI112. The reaction time may vary depending on the reaction temperature, etc., but is usually in the range of 1 to 24 hours.

The reaction product can be recovered by the usual H method, for example, by extracting the reaction product with trichlorotrioleoethane, chloroform, etc., and removing the solvent from the extract.

Oxidation of the compound of general formula (6) obtained in Section-42 is usually carried out by using an oxidizing agent, and preferred oxidizing agents include FI4 acid, nitrous acid, chromic acid, permantic acid, chlorine N
l? ? An example of the oxidation reaction is 140
It is carried out at ~200°C, preferably 170-190°C, with stirring. The reaction time is usually 0.5 to 10 hours, preferably 2 to 4 hours.

Dehydration of the compound represented by the formula obtained by the oxidation is carried out at 100 to 2) 0°C, preferably 140 to 0°C, under reduced pressure or under a nitrogen gas flow.
This is done by heating to 180°C. The pressure during depressurization is 10 to 200 + 6 + * I (g, preferably 20 to 100 + am II g. Also, dehydration can also be carried out using a solvent), the above compound (7)
It is carried out by dissolving in a solvent and heating it to the boiling point of the solvent used. Examples of solvents include xylene,
Chlorobenzene, toluene, 11-octane, 1,1.
Examples include 1,2-tetrachloroethane and 1,1,2,2-tetrachloroethane.

A representative example of the aromatic tetracarboxylic dianhydride containing the -(X)C(Y)- group is, for example, 1,1-bis(3,4
-nocarboxyphenyl)-1-phenyl-2,2,2
-F-lifluoroethane, 2,2-bis(3,4-nocarboxyphenyl)-hexafluoropropane dianhydride,
2.2-bis(3,4-nocarpoxyphenyl)-1,
3-fuchloro-1.1,3.3-tetrafluoropropane dianhydride, 2,2-bis(3,4-)carboxyphenyl)-1-chloro-1,1,3,3,3-bentafluoropropane Examples include dianhydrides and compounds represented by the formula.

-Among the maximum (3) aromatic noamines-(X)C(Y
) - Group-containing compound is, for example, a compound represented by the formula obtained by reacting the above-mentioned compound (5) with toluene, and then a nocarboxylic acid represented by the formula and a heptanohydrohydric acid in the presence of a strong acid. It can be synthesized by the following reaction. Here, compound (8) and compound (9) can be synthesized in the same manner as in the case using 0-xylene.

Here, the amount of heptanohydric acid used is preferably 1 to 2 mol per 1 mol of the compound represented by maximum (9) above. As the strong acid, sulfuric acid, hydrochloric acid, nitric acid, etc. can be used. The amount used is 20 to 50 equivalents relative to the compound represented by general formula (9). Reaction is 40-60°
C1 Preferably carried out at 50-60°C'' while stirring.

The reaction time is usually 1 to 10 hours, preferably 2 to 4 hours. The reaction is preferably carried out in the presence of a solvent, and chloroform or the like can be used as the solvent.

Representative examples of aromatic noamines containing a -(X)C(Y)- group include 1,1-bis(4-7mi/phenyl)
-1-phenyl-2,2,2-)lifluoroethane, 2
．． 2-bis(4-7minophenyl)-hexafluoropropane, 2.2-bis(4-7minophenyl)-I,:
l-fucrolol 1.1,1. :t, -tetrafluorophane 0pan, 2,2-bis(4-7minophenyl)-1=chloro-1,1,3,3,3-pentafluoro 70pan,
Alternatively, compounds represented by the formula % can be mentioned.

In the present invention, η containing a group represented by the above formula (G,)
In addition to the ``J′f amine containing h-tetracarboxylic dianhydride and the group represented by formula (G2), aromatic tetracarboxylic dianhydrides and aromatic diamines can be used, Of course, a combination is selected in which at least one of the aromatic tetracarboxylic dianhydride and the aromatic diamine contains fluorine.

Specific examples of other aromatic tetracarboxylic dianhydrides that can be used include pyromellitic dianhydride,
2,3,6.7-su7talentetracarboxylic dianhydride, 3.4. :1',4'-diphenyltetracarboxylic dianhydride, 1,2,5.8-7talentetracarboxylic dianhydride, 2. :1.2',3'-diphenyltetracarboxylic dianhydride, 2.3.3',4'-7 phenyltetracarboxylic dianhydride, 2.2-bis(3t4-dicarboxyphenyl)propani Anhydride, bis(3,4
-dicarboxyphenyl)sulfone dianhydride, 3,4.
9.10-Perylenetetracarboxylic dianhydride, bis(
3,4-dicarboxyphenyl)ether dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propanihydride, 1. 1-Bis(2,3-dicarboxyphenyl)ethane dianhydride, 1.1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1.1-bis(:
1.4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)7tanni anhydride,
Bis(3,4-dicarboxyphenyl)thioether dianhydride, 3,4.3'4',-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethylsilanhydride, Bis(3,4-)carboxyphenyl)noethylsilanihydride, bis(3,4-)
-dicarboxyphenyl)nophenylsilane dianhydride, and the like.

Specific examples of aromatic diamines that can be used include 4,4°-noami/nophenyl ether,
3.3'-7minonophenyl ether, :l, 4
'-Noami/nophenyl ether, 414'-noami/nophenyl thioether, 3,3'-noaminophenyl thioether, 3,4°-noaminophenylthioether, 4,4'-noaminobenzophenone, 3 .3
°-Noaminobenzophenone, 3,4′-noaminobenzophenone, 4,4′-noaminophenylsulfone,
3,3°-Noami/Schiffenylsulfone, 3.41Noami7nophenylsulfone, 4.4-Noaminonophenylmethane, 3. :('-Noami/diphenylmethane, 3
, 4°-noaminophenylmethane, 2.2-bis(4
-aminophenyl)propane, 2,2-bis(3ami/
phenyl)propane, benzunone, 3.3゜noamitubiphenyl, 3.4'-noamitubiphenyl, p-phenylenediamine, m-phenylenediamine, bis(4-7mi/phenyl) dinotylsilane, bis(4-7mi/ Examples include phenyl)noethylsilane, bis(4-7mi/phenyl)nophenylsilane, and the like.

In the present invention, the fluorine-containing polyimide is usually obtained by dehydrating a polyamic acid obtained by stirring and mixing equimolar amounts of -J dianhydride and diamine in the presence of a solvent. The reaction temperature between the acid anhydride and the diamine is 0 to 60°C2, preferably 20 to 40°C, and the reaction time is 1
~24 hours, preferably 3 to 12 hours. The solvent used is N-methyl-2-pyrrolidone (NM
P), dimethylacetamide (DMAc), trimethylformamide (DMF), sulfolane, tetrahydro7
Ran (THF) and the like can be exemplified. In addition, an acid anhydride containing a group represented by the above formula (G1) and the above formula (G2)
When reacting an aromatic diamine containing a group represented by C, a mixture of the above-mentioned solvent and a halogenated solvent such as tetrachlorohexafluorobutane, trichlorotrifluoroethane, tetrachloronofluoroethane, perchlorethylene, etc. Preferably, a solvent is used. The polyamic acid produced by the above reaction can be converted into polyimide by a conventional method. For example, polyamic acid can be conveniently converted into polyimide by heating and dehydrating it at 200° C. or higher, for example 2°C to 400°C.

In the present invention, a method for impregnating a fluororesin base material with fluorine-containing polyimide is a method of immersing the fluororesin base material in a solution of the fluororesin polyimide and drying it, or a method of impregnating a fluororesin base material in a solution of polyamic acid as a precursor. Soak the material,
Examples include a method of heating and dehydrating a dried material to imidize it.

Examples of solvents include N-methyl-2-pyrrolidone (NM
P), trimethylacetamide (DMAc), dimethylformamide (DMF), sulfolane, tetrahydrofane (THF), etc., and to these, tetrachlorohexafluorobutane, trichlorotrifluoroethane, tetrachlorodifluoroethane, perchlorethylene, etc. Examples include mixed solvents containing halogenated solvents.

According to the present invention, it is also possible to obtain a laminate in which a metal layer is formed on a substrate in which a fluororesin base material is impregnated with a fluorinated polyimide. Imidization of the polyamic acid-impregnated base material is performed at 200°C or higher.
For example, it is carried out by heating at 230 to 400°C. Examples of the metal constituting the metal layer include copper, aluminum, nickel, iron, and alloys thereof, and the metal layer can be formed by adhesion by adhesion of foils of these metals, electroless plating, sputtering, vacuum evaporation, It can be formed by ion blating or the like. The thickness of the metal layer is preferably in the range of about 5 to 100 microns. In the present invention, the metal layer can be formed on one or both sides of the composite sheet, or a plurality of fluorine-containing m-based substrates impregnated with the fluorine-containing polyimide having a metal circuit layer can be laminated. In that case, the metal layers are laminated so that they do not come into contact with each other. Alternatively, a plurality of fluorine-containing polyimide-impregnated substrates forming metal scraps may be laminated, and then a metal layer may be provided.

The laminate of the present invention can be used as a high-frequency printed circuit board by forming an electric circuit by conventional methods such as etching. When a porous body is impregnated with fluorine-containing polyimide, pores remain inside, but the surface of the base material is also coated during impregnation, and etching agents etc. do not penetrate inside.

(Effects of the Invention) The present invention uses a fluorine-containing polyimide with a low dielectric constant and a low dielectric loss tangent, which is obtained by introducing fluorine into a polyimide with good heat resistance and dimensional stability, and a fluorine-containing polyimide with a low dielectric constant and a low dielectric loss tangent. By using this, it is possible to obtain a high-frequency laminate with excellent heat resistance, dimensional stability, and high-frequency characteristics, and it can be used in high-frequency circuits such as high-frequency arithmetic circuits and communication device circuits.

(Example) The following is an explanation using reference examples and practical examples.

Reference example 1 5 equipped with cooling pipe, thermometer, nitrogen introduction pipe and stirrer
4-) Magnesium 24.31g (1
mol), 150 ml of dry noethyl ether and a small amount of iodine crystals were added, and the mixture was stirred while introducing nitrogen. C, F, dissolved in Noethyl Ether 6001.

CI-12CH,I (5748, 1 mol) was gradually added dropwise, and after the addition was completed, the mixture was heated under reflux for 2 hours. Next, the reaction solution was returned to room temperature, CF, CO2Ct (, (128 g,
] mol) was added dropwise, and the mixture was stirred for 2 hours after the dropwise addition.

After the reaction was completed, a sulfuric acid solution was added to the reaction solution to make it acidic, and the noethyl ether layer was washed three times with water, dried over sodium sulfate, and further dried over phosphorus pentoxide. This noethyl ether layer was distilled under reduced pressure to obtain CsF, 7CHZCH2
COCF) is a ketone compound (boiling point 96-98℃/1
7+*sHg) were obtained (17411 (yield 32%)).

T R (NaCl)'(c++-' ): 17so,
tzso, 1210°1150, 1010'F-NMR (CC1,) δ (pp y) ;-12,
7(s, 3F), 2,30. 3 F >, 3
5.9 (broad, 2 F), 43.2 (bro
ad, 6F), 44.0(broad, 2F
), 44.3 (broad, 2 F >, 47.5
(broad, 2F) Reference Example 2 Toluene 15.2. (
0,165 mol), C, F,, CH obtained in Reference Example 1
2CH.

COCF, (40.9 g, 0.075 mol) and hydrogen fluoride 401 were added to the first reactor at a temperature of 9 with stirring.
The reaction was carried out for 18 hours at a temperature of 0 to 100° C. and a pressure of 9 kg/cm.

After the reaction was completed, hydrogen fluoride was removed and the reaction product was extracted with trichlorotrioleoethane.

Trichlorotrifluoroethane was distilled off from this extract under reduced pressure to obtain 38.9 g (yield: 73%) of the compound represented by the formula.

IR(NaC1)l'(cm-'); 2900.
1520. 14851330, 1240. 12
10. 115G, 1010. 815°730,
710 H-NMR (CCL/TMS) δ (pp brass); 1.
5-3.3 (m, 4 H), 2.30 (s, 6 H
), 7.05 (s, 8 H) 9F-NMR (CC1,/TFA) δ (pl) import]
;-12,1(s, 3F), 2.8(t, 3F
), 36.3 (broad, 2 F ), 43.5 (
broadI6F), 44.4(broad, 2
F), 44.7 (broad, 2 F), 47
．． 9 (broad, 2F) Reference Example 3 20.0 g (0,028 mol) of the compound represented by formula (1) obtained in Reference Example 2 and 7 mol of acetic acid were placed in a 1001 autoclave.
3-1 was prepared, and chromium oxide (Vl) 18.38 was added while stirring at a temperature of 80°C.
The mixture was stirred for 12 hours while maintaining the temperature at 90°C.

After the reaction was completed, acetic acid was distilled off from the reaction product under reduced pressure. Add 400 ia of 5% sodium hydroxide solution to the remaining solids.
chromium oxide (II+ >
We parted ways. When a sulfuric acid aqueous solution was added to the first solution to make it acidic, a white solid was precipitated, and when this white solid was separated and dried, 18.5 g (yield: 86%) of the compound represented by the formula was obtained.

rR(KRr)ν(cm-'); 3000. 1700
．． 16+5°1425, +330. 1285.
1240. 1200. 1150°1+20. 1
010. 855. 810. 780. 725°)
1-NMR (DMSo-d!/TMS) δ[ll+tm
l; 1.6-3.1 (m, 4 fl), 7.57
(dd, J = 81-1 z.

57Hz, 8H), 9.5-10.5 (broad,
2 H)'F N M R (D M S Oas/
T F A ) J fppml knee 1:1.0 (s,
3F), 2.1(t, 3F), 35.9(bro
ad, 2 F), 43.0 (broad, 6
F ), 44.0 (broad, 2 F ), 4
4.3 (broad, 2 F) 47.3 (bro
ad, 2F) Reference Example 4 The formula (■
) +5. Og (0,0195 mol),
63 g of concentrated sulfuric acid and 200 ml of chloroform were added.

While heating to 40-50℃, add hydrazoic acid (1,OO
58.5 ml of N ) was added dropwise and refluxed for 2 hours.

After the reaction is completed, the reaction solution is returned to room temperature and water 4001
When poured into #I, a precipitate formed. This precipitate was filtered and fractionated, made alkaline by adding sodium hydroxide solution, and extracted with chloroform. When chloroform was distilled off from this extract, a compound represented by the formula 8. : 14 g (yield 60%) was obtained.

IR(KBr) ν(eta-'): 345
0- 3370+ 1630w1520, 1370
．． 1335. 1280. 1250. 1230°1200, 1150. 1110. 1005.
960. 825°820, 705'H-NMR (CDCI, /TFA) & [ppm]
:1.5-2.9(m, 4H), 3.62
(s+4H), 6.72(dcl, J=
8 Hz, 37 Hz, 8 H)'F-NMR (
CDCI3/TEA) δFppsl ;-12,2(
s, 3F), 2.1(t, 3F), 35.
7 (broad, 2 F), 43.0 (broad)
d, 6F), 44.0(broad, 2
F), 44.3 (broad, 2 F), 47
．． 2 (broad, 2 F) Reference Example 5 〇-xylene lf, 17 in a 100 mm autoclave
g (0,1617 mol), C, F,, CH2CH, C0
C.F.

(40.0g, 0.0735l) and 37 servings of hydrogen fluoride were added.While stirring, the temperature was 90~1.
The reaction was carried out at 00'C1 pressure and 9 kg/am2 for 18 hours.

After the reaction was completed, the reaction product was extracted with trichlorotrifluoroethane. Trichlorotrioleoethane was distilled off under reduced pressure from this extract, which was then extracted with ether. When the ether was distilled off from this extract, a compound represented by the formula 38.3. (yield 70%) was obtained.

IR (KBr) ν[cm-'): 2950.
+510. 1470°1450, 1375. 13
30. +200. 1145. 1110°+02
0. 990. 965. 880. 820. 73
5゜1-1-101-1-N, /TMS) δ[111)
III; 1.6-3.3 (ring, 4H), 2.22 (
s, 12H), 6.94 (s, 61-1) Reference Example 6 The formula obtained in Reference Example 5 (
Compound 38.IV) Of+ (0.05 mol), 58 ml of 60% nitric acid and 57+ nl of water were charged, and 1
The reaction was carried out at 70-180°C for 2 hours.

After the reaction was completed, the reaction product was filtered, and the remaining solid was dissolved in 5% sodium hydroxide solution to remove '4P. An aqueous sulfuric acid solution was added to the first solution to obtain 39.7 g (yield: 90%) of an acidic compound.

IR(KBr)ν(Cm-'); 3400.
3000. 1710°1615, 1580. 15
+0. 1425. +210. 1160°111
0, 1070. +020. 980. 820.
800°725, 705 H-NMR (acetone u6/TMS) δ[p1+1*
]: 1.7-3.3 (Yuzu, 41-1), 6.6
~7.6(broad, 4H), 7.6 =
8. O (within +, 61-61-1)9F-N acetone-
a6. 'T E A ) δ[ppm1 :11.5<s
, 3 F ), 3.6(t, 3 F ), :1
6.9 (broaJ, 2F), 44.3 (br
oad, 6F), 45.2(broad, 2
F), 45.5 (broad, 2 F), 48.
6 (l+road, 2 F > Reference Example 7 39.7 g of the compound represented by formula (V) obtained in Reference Example 6 (
0,046 mol) into 2001 eggplant-shaped 7 Rasf,
Heated at reduced pressure r temperature 150-+60'C for 6 hours.

After the heating was completed, the reaction product was taken out from the eggplant-shaped flask and recrystallized from ether to obtain compound 22.78 (yield: 60%) represented by the formula of white crystals.

IR(KBr)ν [cw+-':l; 1860.
1780. 1620°+490. 1470.
+4:15. 1400. I:'175. 1
335°+205. 1180. 1155. 112
0. 1015. 900°740, 725. 70
0 +I −N M R (thermal CDCl, /TMS) δ[11
1111] ;1.6~:1.2 (+self, 4H), 7
．． 5-8.1 (ring, 6 days),'F-NMR
(heat CDCl, /TFA) δ[+'1llll knee l
:1.2 (s13F), 2. t(t, 3F),
35.8 (broad, 2 F), 43.0 (b
road, 6F), 44.0(l+road,
4F), 47.2(l+road, 2F
) Example 1 14.25 g of an aromatic compound represented by the formula ([1) C (
0.02 mol) to N-methyl-2-pyrrolidone (NM
P) 35g and 65g of tetrachlorohexafluorobutane
After dissolving in a mixed solvent with g, 16.458 (0.02 mol) of the acid anhydride represented by formula (■) was gradually added and reacted with stirring at a temperature of 25°C for 8 hours. After the reaction is complete,
Viscosity 14000cps (23℃), concentration 23.5% by weight
of polyamic acid was obtained. This polyamic acid was adjusted to an appropriate viscosity with NMP, and the thickness was 0. ]+n-1 porosity 5
It was impregnated with 5% polytetrafluoroethylene porous material (Xytex (+104) manufactured by Two-Tone Co., Ltd.), dried at 150°C, and heated at 300°C for 20 minutes to obtain an imide-1 atomized composite sheet.

Eight of these composite sheets were placed through a 12.5 μ(1) PFA (tetrafluoroethylene-perfluorovinyl ether copolymer) film, and then PFA was applied to the top and bottom surfaces of the film.
A 35 μm thick copper foil was placed through the F A film, placed in the opening of a hot plate, and heated and pressed for 10 minutes at a temperature of 330° C. and a pressure of 40 kg/c to form a laminate. The dielectric constant of this material is 2.18, and the dielectric loss tangent (JISC648LI
M summer (z) was 0.0009.

Example 2 p-7 22-diamine as aromatic amine 2.16
g (0.02 mol) and the solvent was N M P (55
g), tetrachlorohexafluorobutane 11. A mixed solvent of Daikin, Polyflon Paper P A-S L,
A composite sheet was obtained in the same manner as in Example 1 except that the thickness was 0.55 mm and the porosity was 75%. A laminate was formed in the same manner as in Example 1 using two of these composite sheets. The dielectric constant of this material was measured in the same manner as in Example 1 and was 2131.
The % dielectric constant was 0.0017.

Example 3 Using 4.36 g (0.02 mol) of pyromellitic dianhydride as the aromatic tetracarboxylic acid, the solvent was NMP (6
0 g), and the base material is a nonwoven fabric mixed with 70,000 short polytetrafluoroethylene fibers with a thickness of 0.5 mm and a porosity of 60% (
A composite sheet was obtained in the same manner as in Example 1 except that the ratio was 80:2 (1-heavy ratio). A 35 μm thick PFA film is interposed on the upper and lower surfaces of this composite sheet through a 12.5 μm thick PFA film.
A layer of M was formed and heated and pressed at 330° C. and 40 kg/c#a2 for 10 minutes to form H171 body. Example 1
The dielectric constant measured in the same manner as 2.52 and the dielectric loss tangent are o
, oots.

Example 4 Same as Example 1 except that the base material was a polytetrafluoroethylene short fiber/aromatic polyamide short fiber iR paper nonwoven fabric (90:10 weight ratio) with a thickness of 0.5su* and a porosity of 60%. A composite sheet was obtained in the same manner. Using this composite sheet, a laminate was formed in the same manner as in Example 3.

The dielectric constant of this material was measured in the same manner as in Example 1: 2.
35, and the dielectric loss tangent was 0.0028.

Example 5 11-phenylenediamine 2.1 as aromatic noamine
6 g (0.02 mol) and the solvent was N M P (55
8), a mixed solvent of tetrachlorohexafluorobutane Img, and a polytetrafluoroethylene iwAm cloth (
Example except that plain weave, fabric weight 188FI/a+2)
A composite sheet was obtained in the same manner as above. A laminate was formed using this composite sheet in the same manner as in Example 3. This material was measured in the same manner as in Example 1, and the dielectric constant was 2.60, and the dielectric loss tangent was 0.0022.

Example 6 4.36 g (0.02 mol) of pyromellitic dianhydride was used as the aromatic tetracarboxylic acid, and NMP (6 mol) was used as the solvent.
0g), the base material is PFA fiber/aromatic polyamide fiber mixed fabric (90:10 weight ratio, plain weave, basis weight 163g/m')
) A composite sheet was obtained in the same manner as in Example 1 except that. A laminate was formed using this composite sheet in the same manner as in Example 3. The dielectric constant of this material was measured in the same manner as in Example 1 and was 2.61. The dielectric loss tangent was 0.0033.

Example 7 Fluorine-containing polyimide having the following repeating unit was NMP
The solution was dissolved in water, adjusted to an appropriate viscosity, and impregnated into the same porous polytetrafluoroethylene sheet as in Example 1 at 200°C.
A composite sheet was obtained.

A laminate was formed using this composite sheet in the same manner as in Example 1. This material was measured in the same manner as in Example 1, and the dielectric constant was 2.20, and the dielectric loss tangent was o.ooto.

Example 8 2,2-bis[4-(4-7minophenoxy)phenyl 1-hexafluoropropane 10 as aromatic noamine
．． 05g (0.02 mol) was used, and the solvent was NMP (60
g) A composite sheet was obtained in the same manner as in Example 1, except that the base material was the same polytetrafluoroethylene nonwoven fabric as in Example 2. A laminate was formed using this composite sheet in the same manner as in Example 3. This material was measured in the same manner as in Example 1, and the dielectric constant was 2.21, and the dielectric loss tangent was 0.0013.

Example 9 A fluorine-containing polyimide having the following structure was dissolved in NMP and heated to an excessive viscosity. L. The same polytetrafluoroethylene 'JrL fiber/quartz short fiber mixed nonwoven fabric as in Example 3 was impregnated and dried at 200°C to obtain a composite sheet.

A laminate was formed using this composite sheet in the same manner as in Example 3. This material was measured in the same manner as in Example 1, and the dielectric constant was 2.40.16, and the electric loss tangent was 0.0012.

A composite sheet was prepared in the same manner as in Example 1, except that NMP (60 g) was used as the solvent and the same polytetrafluoroethylene short fiber/aromatic polyamide short fiber mixed nonwoven fabric as in Example 4 was used as the base material. A laminate was produced in the same manner as in Example 3 using this composite sheet. This product was measured in the same manner as in Example 1, and the value of 3 electric currents was 2.28, and the dielectric loss tangent was 0.0020.

(The above) Applicant Daikin Industries, Ltd. Agent Patent attorney 1) Iwao Mura Example 10

Claims (4)

[Claims] (1) A composite sheet characterized by impregnating a fluororesin base material with fluorine-containing polyimide. (2) A laminate characterized in that a metal layer is formed on a composite sheet in which a fluororesin base material is impregnated with fluorine-containing polyimide. (3) The composite sheet or laminate according to claim 1 or 2, wherein the fluororesin base material is a porous fluororesin material, a fiber cloth, or a nonwoven fabric. (4) Fluorine-containing polyimide has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 is the residue obtained by removing two acid anhydride groups from aromatic tetracarboxylic dianhydride, R^2 is a residue obtained by removing two amino groups from an aromatic diamine, and at least one of R^1 and R^2 has a ▲ mathematical formula, chemical formula,
There are tables, etc. ▼
f': Perhaloalkyl group of C_1_-_2_0 p: 0
or an integer of 1 to 3 q: 0 or an integer of 1 to 3 r: 0 or 1 s: an integer of 0 or 1 to 5 t: an integer of 0 or 1 to 5 Y: the same definition as X or a hydrogen atom , phenyl group, substituted phenyl group (examples of substituents: C_1_ to_5 alkyl group), C_1_ to_8 alkyl group, and C_1_ to_8 haloalkyl group. n represents an integer from 1 to 2,000. ] Claims 1 to 3 are fluorine-containing polyimides represented by
The composite sheet or laminate according to any one of the above.