JPS6076558A - Metal-filled polyimide/polyepoxide blend with improved electroconductivity - 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 The present invention relates to improved conductive resins based on noble metal filled formulations of carbinol-containing polyimides and conventional liquid polyepoxides and their use as self-crosslinking adhesives.

It is known in the art to combine polyepoxides with polyimides or polyamide-polyimide resins or precursors or qualities thereof. For example, JP-A-51
-904004 Publication (0, A, Jl) 193528q
) describes that a polyimide resin with improved heat resistance is produced by reacting maleic anhydride with a diamine and an epoxy resin;
-596S5 (0, A, 87169355b) discloses that a polyimide solution is stirred with an epoxy resin,
and used as a coating for electrical insulation >1+-JI
+tb:+*wshi41. arrogant side' (A 4 a J O
e j! , in the report (C, A, 85194591a),
The use of polyamide-polyimide resins in combination with epoxy resins as adhesives is described and in U.S. Pat. It's been done-
By blending diamines, and organic peroxides with epoxy resins, curable formulations useful for producing composite materials and excellent resistance to mechanical deformation at high temperatures and inorganic materials such as metals and ceramics are obtained. It is stated that molded articles are provided that have excellent adhesion to materials.

It is also known to obtain crosslinked polyimide epoxy polymers by adding to epoxy formulations amide-imide powder, polyamic acid with anhydride end groups or polyimide with amine end groups. For example, the epoxy resin is cured by mixing it with a solution of a finely divided solid of amide-imide in an organic anhydride, and crosslinking is caused by the anhydride in the powder to form an epoxidized resin. Electrostatic coating powder was manufactured (July 29, 1969)
(See U.S. Pat. No. 145a595, published in Japan); crosslinking the reaction product of a polyamic acid with anhydride end groups with an epoxy compound provides outstanding thermal stability and electrical properties, especially dielectric properties. A resin having a value of
(Refer to column 1, lines 42-50 of the issue published on May 16, 1972)
It has been described that easy-to-handle, heat- and solvent-resistant polymers are produced by using polyimides with amine-terminated groups copolymerized with I and polyepoxides (U.S. Pat. .277.585 specification (
(Reference: Published July 7, 1981).

It is also known to crosslink carbinol-containing polyimides with other compounds having reactive groups, such as isocyanates, epoxides (e.g. diglycidyl ether of bis-phenol A), alkyl titanates, carboxylic acid anhydrides, carboxylic acid halides and siloxanes. (See European Patent Application No. 8240184S6.7 (published as No. 0077718 on April 27, 1983), page 15, lines 12-16).

There are pigment dyes, organic, inorganic or metallic fillers,
It is also stated that inert ingredients such as adhesive powders, heat- and oxidative stability additives, blowing agents, etc. can be added.

Furthermore, electrically conductive adhesives, coatings, It is also known that moldings and the like can be obtained. However, the excellent conductivity
Even high proportions of metals are not always achieved. For example, U.S. Patent No. 4,210.704
No. C (issued July 1, 1980) discloses the use of conductivity enhancers in the formulation of silver-filled epoxy resin adhesives to increase conductivity and reduce resistance. has been done.

Mitsuru Kanaoka' 1 polyimide is used in most applications. Therefore, there is a need for metal-filled polyimides with improved electrical conductivity.

The present invention provides metal-filled polyimide/polyepoxide blends having the following structure: identical or different aromatic groups having an attached carbonyl group, and R is a divalent aliphatic, cycloaliphatic, aromatic or heterocyclic group) Carbinol-containing polyamic acids 25-50%; C1 about 1-35% liquid, substituted or unsubstituted aliphatic, cycloaliphatic, aromatic and/or heterocyclic polyepoxides having at least two epoxy groups ; and (phrase 15-74% organic solvent for the above polyimide)
; where (a), the percentages of (bl and (C1) are by weight and add up to 100%; and tell about 45-90 wt rr% conductive noble metal powder; where (al
The percentages are weight % based on the total weight of polyimide and polyepoxide; characterized by an improved electrical conductivity over that of a weak formulation containing polyepoxide after curing; The fully filled polyimide/polyepoxide blend is provided.

The above formulation shows an unexpected improvement in electrical conductivity after curing. These cured products exhibit good thermal stability and satisfactory to good tensile shear strength. Inclusion of polyepoxide also increases wetting time (i.e., handling time) and also increases the Bolier d! in the uncured state. The oxide acts as an excellent second solvent for the polyimide, thus reducing the viscosity of metal-filled resin formulations. If desired, typical catalytic amine curing agents may be added to the adhesive.

Preferably, the formulation contains 25-40% polyimide, 6-32% polyepoxide, and 25-70% solvent, and most preferably 30-40%, 1%, respectively.
5-25%, and 30-55%. The preferred amount of metal powder in the formulation is 50-85%, most preferably 55-80%. If used, the catalytic curing agent is present in an amount of 1 to 8% by weight, based on the weight of the polyepoxide in the formulation.

The polyimide used here is a polyimide with anhydride, acid, ester and/or amine end groups containing self-crosslinking carbinol moieties and preferably flexibilizing moieties.

They contain suitable carbinol-containing tetracarboxylic acid compounds, such as bis(methyl half esters) of S, 5', 4.4-benzhydro-rutetracarboxylic acids, to polyfunctional aliphatic, cycloaliphatic, aromatic compounds. or by reacting with a primary heterocyclic polyamine, preferably a diamine having a flexibilizing moiety. This reaction is carried out in an inert organic solvent that is a solvent for the polyimide. The temperature used should be sufficient to cause polymerization and imidization (ie, ring closure (to imide)).

Suitable diarylcarbinol-containing tetracarboxylic acid compounds include: a) dianhydrides of the formula %; b) dianhydrides of the formula %, where X is 10H; ); and C) diester-diacids of the formula where X is -OH and Y is -OR', or isomers thereof . Ar has the same meaning as above. R' is the same or different lower alkyl group, typically aI-a, . . . , preferably 0K-0, and most preferably 01-c
, is. Dino-roformyl diesters are also known to be useful in making polyimides and would be suitable for use in the present invention. It is also possible to use mixtures of carbinol-containing and non-carbinol-containing tetracarboxylic acid compounds.

Representative are 3.5', 4,4'-benzhydroltetracarboxylic acid, its dianhydride or its diester-like bis(methyl half ester), the preparation of which is described in Example 1. It is a diacid.

Such polyimides are described in European patent application Aa 2401
g 66, 7 (supra).

The polyimides described therein contain an aromatic diamine with tetranisder of benzhydrol-3,3',4,4'-tetracarboxylic acid, or its diester-diacid, in excess of either monomer. or preferably approximately equimolar amounts of each monomer dissolved in a suitable solvent.

In this case, it is preferred to use an excess of the tetracarboxylic acid compound or to use stoichiometric amounts of the tetracarboxylic acid compound and the polyamine. Although polyimides made with excess polyamine are preferred, the presence of residual unreacted polyamine is undesirable. This is because amines are toxic and easily oxidized.

Suitable polyfunctional amines include those well known in the art and described in US Pat. No. 7, issued September 15, 1970! , 52a950, are included. Aromatic diamines with flexibilizing moieties, such as 4,4'-methylene dianiline, 4,4'-oxydianiline, 4,4'-sulfonyldianiline, 4.
4'-bis(3-aminobenzoyl)diphenyl ether and 1,3-bis(3-aminophenoxy)benzene are preferred. However, in the present invention,
Also useful are m-phenylene diamines, which are aromatic diamines without flexibilizing moieties. Aliphatic diamines suitable for use herein include bis(3-aminopropyl)tetramethyldisiloxane and 1,6-hexanediamine.

When one or more of the polyamines or diamines mentioned above are reacted with a carboxylic acid compound, suitably in an inert organic solvent, the reaction conditions used for the preparation of the polyimide are , depends not only on the diamine used, but also, in particular, on the tetracarboxylic acid compound used. Reaction conditions will also depend on the chosen solvent and the desired concentration and molecular weight in the final solution to be imidized. Fully imidized polymers are preferred which have maximum heat and oxidation resistance and do not release volatile by-products during use. The reaction is carried out under anhydrous conditions using pure monomer and dry solvent. Molecular weight is controlled by stoichiometry and reaction time and temperature. Preferred.Although the polyimide resin can be recovered in a dry state (by precipitation with a non-solvent such as water), it must then be dissolved in a suitable solvent before being mixed with the epoxy resin. Will.

The reaction mixture formed by the solvent and reactants is heated at a temperature of 80° C. or higher, preferably 100° C., until the composition reaches the desired intrinsic viscosity (approximately 1 tl//f).
Heated to ~150°C.

The solvent used should dissolve at least one, preferably both, of the reactants and should be an excellent solvent for fully imidized resins. Carbinol-containing polyimides are more soluble than conventional polyimides (as described in European Patent Application No. 82401866.7, supra). In a suitable solvent, e.g. dimethylformamide, dimethylacetamide, N-methyl-2-
Pyrrolidinone (hereinafter referred to as N-methylpyrrolidinone). N-cocoa sialkyl-2-pyrrolidone, N-(2
-hydroxyethyl)2-pyrrolidone, y -(N,N
-dimethylamino)-propyl-2-pyrrolidone, triethylene glycol dimethyl ether (triglyme),
diethylene glycol dimethyl ether (Sifrim),
Diethylene glycol ethyl ether, -butyrolactone, 2-(2-ethoxy)ethyl acetate (calbito) acetate (2-butoxyethyl acetate (butylcellulose acetate), which contains 41 ha of food.

These solvents may be used alone or in combination with other solvents such as benzene, benzonitrile, dioxane, xylene, toluene and cyclohexane. A preferred solvent is N-methylpyrrolidinone.

It is desirable to store the polyimide formulation under dry conditions prior to use. It is also possible to use blends of carbinol-containing and non-carbinol-containing polyimides, provided that the carbinol groups are present in a sufficient amount to provide improved electrical conductivity.

Liquid polyepoxides suitable for use herein are conventional and have at least two epoxide groups [7 and aliphatic, optionally substituted with non-interfering substituents;
Includes cycloaliphatic, aromatic and/or heterocyclic polyepoxides such as glycidyl esters, glycidyl ethers, or epoxidized olefins. They typically have an epoxy equivalent weight of about 130-190. As discussed below, solid polyepoxides and liquid monopolyepoxides are not suitable for use in the present invention. U.S. Pat. No. 10547.885 (issued December 15, 1970), U.S. Pat.
No. 066.624 r published January 3, 1978) describes some suitable polyepoxides. 1.4-
Preferred polyepoxides, such as butanediol diglycidyl ether and aliphatic dievoxycarboxylate, have low molecular weight and low viscosity. Medium viscosity polyepoxides such as glycidyl polyethers made from epichlorohydrin and bisphenol h (4,4'-isopropyritine diphenol made from phenol and acetone) are also useful. .

High viscosity polyepoxides such as novolak (phenol-formaldehyde soluble resin) are also suitable.

Suitable metal powders (flake) include conductive noble metal powders. The term noble metal, as used herein, shall mean metals that do not easily oxidize, such as gold, silver, platinum, palladium, iridium, rhodium, mercury, ruthenium and osmium. Mixtures of metals may also be used. My favorite metal is silver.

Metal-filled polyimide/polyepoxide blends are made by mixing the components until the mixture is smooth and homogeneous. Preferably the liquid components are mixed and the metal is added thereto. The above formulation is an adhesive,
Polyimides are typically used as coatings, moldings, or in other applications where electrical conductivity is required. They are usually prepared on a suitably prepared substrate surface (
They may be formulated with other fillers (i.e. non-metals), thickeners, pigments, etc., if desired. Alternatively, they can be poured from solution into a film and then applied. If not necessary, the substrates are allowed to stand before assembly to allow some or all of the solvent to evaporate. The treated surfaces to be joined are assembled by means of a press, clamp or press, and the assembled substrates are cured.

The resins in the formulation are co-cured by heating to provide a crosslinked product.

Heat curing is done at a low temperature to remove the solvent.
That is, about 0.5 to 2 hours at about 100 to 250 degrees Celsius,
Preferably carried out at about 150°C for about 0.5 to 1 hour.
Then, further curing may be performed at about 200° C. for about 1 hour. These curing temperatures are approximately 7°C lower than those required to cure conventional metal-filled polyimides.
5℃ lower. Longer cure times may be used at lower temperatures and shorter cure times at higher temperatures, and it is within the skill of the art to determine the appropriate cure time and temperature. Depending on the amine used in its preparation, relatively high molecular weight polyimides may require higher curing temperatures to exceed the softening point of the resin.

When adhesives are being manufactured #7i, in some formulations it may be desirable to use catalytic amine curing agents that are known to be useful with polyepoxides. Such catalysts include 1°5-diazobicyclo(s,4.0)undecene-(5), benzyldimethylamine, N,N-dimethylpiperazine, triethylenediamine, 2-ethyl-4-methylimidazole and the like. In some cases, the use of a catalyst can include
Improves the tensile shear strength of adhesive bonds.

In the following examples, all parts and percentages are by weight and all temperatures are in degrees Celsius, unless otherwise noted.
It is shown in The intrinsic viscosity of the polyimide resin is measured for 1 t per 25°C solution in N-methylpyrrolidinone.
Measured using 4-T3 alloy aluminum panels. The panels are etched with chromic acid before gluing with the adhesive to be tested. Adhesive is applied between the panels and partially clamped to create a 0.5 inch overlap, thereby providing a 0.5 square inch area to be tested. After prescribed curing,
Instron (engineering n8trr)n) cooled panel
It is pulled apart using a testing machine at a tensile speed of o, o s in/min. The procedure is generally described in ASTM D1002.

Volume Resistivity Volume resistivity (VR) is measured by applying two pieces of tape (e.g., 1 Scotch to 3M Mirac) 0.100 inches apart along the length of a standard glass slide measuring 1 x 3 inches. (3M Miracle8cotch tape)
It was measured by placing the two in parallel. Place a small amount of the adhesive to be tested between the two tapes. Using one razor blade held at an angle of 4c/), spread an even spacing of 100 mm between the test tapes. Remove the tape and place the coated slide in a preheated open to cure at the specified time and temperature. Measure the resistance of a 1 inch long cured contact strip by placing the inboard contacts exactly 1 inch apart.If a two-pole bridge is used, , the resistance of the leads is subtracted. To convert the reading to Ohm ffi, multiply the resistance value (R1 by 0.0005.

This factor assumes a strip width of 0,001 inches, a cured adhesive thickness of 0,002 inches, and a distance between contacts of 1 inch. The formula is: Alternatively, the width of the strip is 1001 inches;
If the thickness of the cured adhesive is not as wide as listed above, use a conversion factor of 0.254 for any thickness (inches).

The lower the volume resistivity, the better the electrical conductivity.

example! This example describes the preparation of carbinol-containing polyimides by reaction of bis(methyl half ester) of A A'4.4'-benzhydroltetracarboxylic acid with various diamines. It also describes the preparation of the above half-esters.

s i 4. 241.7 f (α75 mol) of a'-benzophenonetetracarboxylic dianhydride was refluxed with 400 d of methanol under stirring for 2 hours. The solution was cooled and charged into a K 1 t autoclave with 100 d of methanol, 10 F of 5-thipalladium on activated carbon and 5 drops of 11-diethylnicotinamide. Hydrogenation of the bis(methyl half ester) of I-benzhydroltetracarboxylic acid to the obtained 4ft',a I-benzhydroltetracarboxylic acid was carried out at 100~'l 50 pgL at 25-30 °C until the hydrogen uptake rate decreased sharply. It was carried out in

This solution was filtered by gravity for 1 hour, and the mixture was washed with methanol. Yield ij 58 t 6
y, which corresponded to 779.5 f of solution per mole. (The 11m IJMR spectrum showed that the hydrogenation of the ketone to carbinol was completed by 90 cycles, and there was no hydrolysis of the alcohol (i.e., OR,
No production of ft was shown.

Preparation of polyimide In a round-bottomed, four-necked flask with a capacity of 500 liters, a solution containing the above half-ester was added, 112 mol (95 sr), 4.4
2-methylene dianiline (109 mol (17,8 t)
and N-methylpyrrolidinone (IMF) 85- were charged. Pot temperature of 110°C and 20 w+Hg
Methanol was removed by vacuum distillation to a vacuum of . A total of 65 mm of toluene was added and the flask was fitted with a 30 mm Dean-Stark receiver. Until the generation of water-methanol mixture stops (approximately 3 to 4 hours)
time), the solution was refluxed. The toluene was then removed by vacuum distillation. Obtained polyimide (mu-1) tj, α
It had an intrinsic viscosity of 10.

Other polyimides were prepared using the same general procedure except that the above half ester was used and equimolar amounts of starting material or excess diamine and excess half ester were used! Manufactured by I14. The diamines used, their molar ratios and intrinsic viscosities are shown below.

A-14,4'-methylene dianiline 4/3 α10
A-24,4'-methylene dianiline 2/1 α17
A-34,4'-, methylene dianiline 5/4 [1
18A-44,4'-methylene dianiline 615 α
29A-54,4'-methylene dianiline 9/8 0
．． 09mu-64,4'-methylene dianiline 12/1
1 0.19B 4.4'-oxydianiline 4/3
α220 4,4'-sulfonyl dianilly 4/3
α17 ethyl Fm-phenylenediamine 4/3 α21G 1,6
-Hexanediamine 47S [119I-1” 4.
4-oxydianiline 1/1 α18N-2” 4.
4'-oxydianiline 1/1 α12-14,4
'-Oxydianiline 3/4 αo8-24,4'
-oxydianili7 5/6 [110' to -54,4
'-Oxydianiline 7/8 α12 脣 Said European patent application? ! 1824018647 manufactured according to the procedure of Example 3.

Inverted This example describes the preparation of a silver-filled polyimide/polyepoxide blend and illustrates the improved conductivity afforded by the addition of polyepoxide +λ-Senda 4 Jt Anzu 1
It was a polyimide prepared from dianiline using a molar ratio of 4/3 and designated as 9B (see Example!). Polyepoxide, 1,4-butanediol diglycidyl ether (ED
DGB”).

It is a liquid aliphatic dieboxide (Olba-Geigy) having the following structure and an epoxy content of about 134
It is commercially available as DY-026 from ).

The powdered silver used has a hole (H
All ) A product called Silver Flake AB with an apparent density and particle size of minus 325 mesh (Kemet Co., Ltd. (! hemet Car
p, commercially available from ). The compound is polyimide (P)
When a solution of N-methylpyrrolidone (IMF) is mixed with polyepoxide (PIc), silver (Ag) is added, and the mixture is manually mixed until smooth and homogeneous, the r? They were evaluated for electrical conductivity by measuring the volume resistivity, and after curing for 1 hour at 15011 and 1 hour at 200°C, they were evaluated for electrical conductivity by measuring the volume resistivity. and evaluated as an adhesive by measuring tensile lap shear strength. In formulations designated as D-1 and D=2, 1,5-diazobicyclo(5,4,O)undecene-(5) (DBU) was used as the catalytic curing agent. PI, NMP and PR1 in the indicated amounts
A control adhesive containing Ag but without Ag was also prepared and evaluated.

The formulation and conductivity test results are shown in Table 1.

The effect of silver addition on tensile D# breaking strength is shown in Table 8.

Table 1 Comparison 40 - 60 80 - - [10038A
-1406548078-0,00026B-1401
8428073-l10000450-1 37 31
．． 5 31.5 80 68 - 1000035D-
1401842807520,000039D-240
1842807380,000037 control 40 -
60 60 - - 'Extremely large E-14012486
053-0,006a, PI b, PI, PR, and DBtl Chi Off scale (hill is > I M ohm) Table contrast 1520 (1[L48) 2990 (2[1
62) Mu-1910 (428) 1420 (9,79)
B-1490 (53B) 1710 (11,79)0
-1 620 (4,28) 2000 (1579)
D-1870 (6) 1710 (11,79) D-2
720 (4,97) 1710 (11,79) The resulting formulation containing polyepoxide exhibits an unexpectedly large increase in conductivity, as shown by a 10Q-fold decrease in resistivity. It is shown that. Formulations containing as little as 6% polyepoxide showed this increase. Increasing the amount of polyepoxide in the formulation above 18% did not significantly change the resistivity, but did adversely affect the tensile shear strength. The decrease in shear strength is
By adding a catalyst, the shear strength was reduced from as low as 490 (B-1) to 870 and 720.
(D-1 and D-2). The filled polyimide controls and the filled polyimide/polyepoxide blends were compared to the unfilled polyimide (152
0 to 299 Q psi 1 and unfilled polyimide/polyepoxide blends (490 to 910 p
si vs. 1420-2000).

The results also show that there was a significant improvement in conductivity when only 60 qb of silver was used in the formulation.

Example ■ This example shows the results obtained when polyimide 03) above was used in conjunction with other polyepoxides. The polyepoxide used had the following structure (epoxy equivalent weight of about 131-143, average molecular weight of about 252, and viscosity of about 350-450 ape at 25°C) f! :liquid alicyclic dievoxycarboxylate) (AI)EC
) (commercially available as jj) OY-179 by Tever Geigy) and the following formula (epoxy equivalent weight of about 172-176, average molecular weight of about 350, and about 4.000-6.000 at 25°C)
liquid bisphenol panosyglycidyl ether (DGICBPA) (commercially available as DER3!S2 by Dow Chemical Co.) having a viscosity of 100% and 100% ape, respectively.

The formulation and test results are shown in Table m.

DBU'i gold-containing silver-filled polyepoxide was also evaluated as a catalyst for comparison.

The result is a very large drop in resistivity, i.e. pm
This shows a decrease of more than 400 times that of the P control sample that does not contain l. The shear strength is better than that of the control sample;
It was also superior to that of the catalyst cured formulation of Example M (870 and 720 for D-1 and D-2 vs. 1250 and 1280 for A and B).

Metal-filled polyepoxides varied in resistivity and had very low shear strength.

Example ■ This example shows the results obtained using other polyimides. Polyimides (see Example 1) include Mu-1, Mu-2 and Mu-6 [4,4'-methylene dianiline to 4/3.
prepared using molar ratios of 2/1 and 12/11]:O[4/3 from 4,4'-sulfonyldianiline
]: D C4,4'-bis(
4/3 from 3-aminobenzoyl) diphenyl ether
Produced using a molar ratio of 4/3 from E[bis(3-aminopropyl)tetramethylsifu0xane]: p[m-:y from enylenediamine 4/ I-1 and K-2 [produced from 4,4'-oxydianiline using a 1:1 molar ratio]; x-1, K-2 and K-3 [ 4,
4'-oxydianiline to 3/4, 5/6 and 7/
manufactured using a molar ratio of 8]. The epoxide used is indicated.

The formulation and test results are shown in Part ①. Curing is 150
℃ for 30 minutes and then at 200℃ for 1 hour.

The results show comparable and also greater reductions in resistivity obtained by adding various polyepoxides. The results also indicate that polyimides made with equimolar amounts of the tetracarboxylic acid compound and diamine or an excess ft- of the tetracarboxylic acid compound or diamine may be used. Polyimides without flexibilizing moieties (made from m-phenylenediamine) can also be used in formulations according to the invention. The effect of the addition of polyepoxide on shear strength varies depending not only on the type of polyepoxide used, but also on the polyimide used. For example, formulations B-1 and B- where the same polyimide is used
In formulations 0-1 and 0-2, shear strength decreased or increased depending on the polyepoxide used; in formulations 0-1 and O-2, both polyepoxides had improved shear strength; It can be seen that blends M-1 and M-2 do not improve shear strength.

This example thus illustrates the use of other solvents. The formulation was prepared as a liMP solution (Example 1 (D B
) 4.35% polyimide made from 4'-oxydianiline, polyepoxide BDDGFi 19.5
%, the indicated amount of solvent and silver 80% (based on In)-72% (based on B and BDDGEt). Curing was carried out at 150°C for 30 minutes and at 200°C for 1 hour. The results are shown in Table v.

Table V NMP 45.5 α000059 1JMP 31.0 α000069 Dimethylacetamide 145 11MP 31.0 α000061 Butyl cellosolve acetate 145 NMP 31.0 0.000065 Carpitol acetate 145 The above results indicate that the decrease in volume resistivity is related to mixed solvents. were comparable and slightly less when using NMP1. The NMP control sample was B! 15e4. NMP
It contained 65% Ag, 80 ft (based on B), and the epoxy had a volume resistivity of 11029 ft.

Example ■ This example examines the effect of adding polyepoxide on thermal stability. The formulations evaluated were polyimides made from 464'-oxydianiline (B' in Example I) 3
51%, 195% epoxy labeled ADEO, 11
MP 45.5 units, silver powder 80 units (based on B) -
Section 72 (based on B and ADBOt standards), and D
It contained 5% (based on ADICO) ft of BU catalyst. It was heated at 150°C for 30 minutes and 2
Cured for 1 hour at 00°C. The scanning rate was 1/min over a temperature range of 30 to 630°C in a nitrogen atmosphere.
It was 0°C. Qb weight loss up to 250°C was minimal. At 350°C it was 48 parts; at 400°C it was 3%; and at 630°C it was only about 13 parts.

Similar formulations containing epoxide BDDGIC (instead of 8DEC) 195T and the same amounts of other ingredients were cured and evaluated. The % weight loss up to 250°C is
It was minimal. It 1-t2.2 at 350°C: ij4.3 at 400°C: and 630
At ℃, it was only 9%. Thermal stability is MuDF
It was better than when used in iO1.

Control samples containing no polyepoxide or catalyst also showed minimal weight loss up to 250°C and 35°C.
t8% and 2 at 0.400 and 630°C, respectively
．． It showed a loss of weight 1 of 4% and about 6%. These results indicate that at temperatures above 250° C., the thermal stability was reduced by some more than that of the control sample, but was still acceptable.

Example ■ This example shows that the use of a polyimide that does not contain carbinol groups did not result in improved conductivity? This is an example.

A polyimide resin was produced in the same manner as in Example 1, but
l 5. '4.4'-benzophenonetetracarboxylic dianhydride was only converted to bis(methyl half ester), and the carbonyl group was converted to carbide. The diamine used was 45'-bis(3-minophenoxy)-benzene. The molar ratio of tetracarboxylic acid compound to diamine was 4/3. The obtained polyimide is NM
It had an intrinsic viscosity of 114 in P.

Epoxy 20%, NMP designated as BDDGIC
47%, and A[g80% (based on PI)
-71 ft (based on PI and BDDGE ft) ft: Silver-filled formulations of the above polyimide (33 qb) containing no decrease in volume resistivity - formulations and control samples (D] containing IC The reading for (no) was too large to measure (outside the scale - ie R was >1 M ohm). Hardening is 15011
: for 30 minutes and at 200° C. for 1 hour. Polyimide 3 containing 13% epoxide, 52% NMP, and 80% silver (based on p-type)
A 5% silver-filled formulation similarly showed no reduction in volume resistivity (as shown in the R-base formulation and the Comparative Example IK-B section, prepared from the same amine and containing carbinol). Polyimides made with tetracarboxylic acid compounds have shown improved conductivity.

Example ■ (Comparative Example) This example illustrates that no improvement in conductivity is observed when metals other than noble metals are used. The polyimide used was prepared from 4,4'-oxydianiline (see Example I, B); the polyepoxides used were designated BDDGE and ADFfO. The metal powder was 7 lakes of nickel with an apparent density of 1.309/CC (Nopamet Co., Ltd.
commercially available from ovamet). The formulation and test results are shown in Table ■. Curing was carried out at 150°C for 30 minutes and at 200°C for 1 hour.

■Table ) Standard a, b.

35 - 65 80 - - 1101 (control) 35 19.5 45.5 80 72 - α31D
DGFi a, P engineering 11. The results obtained for P, BE, and DEU showed no decrease in resistance (in fact, there was an increase). NMP4
5.596, D and gold a8o% (based on P work) to 72q6 (based on P work, Plii and DEU)], the volume resistivity is 200ohh.
It was larger than m-cm.

Example ■ This example demonstrates the use of other epoxides, including aliphatic monoepoxides, solid polyepoxides, and other liquid polyepoxides.

Part A (comparative example) The polyimide used was prepared from 1,3-bis(3-aminophenoxy)benzene (see Example H).

The monoepoxide designated AMle (commercially available from Chipper Geigy under the name DY-27) is a mixed glycidyl ether of octatool and decanol represented by the formula there were. Its epoxy equivalent weight is about 215-235, average molecular weight is about 228, and viscosity at 25°C is 5-15.
It was cps. The polyepoxide designated as solid DGkBPA (commercially available from The Dow Chemical Company under the name DHR661) is a diglycidyl ether of the bis-phenolic form. It had an epoxy equivalent weight of about 475-575 and an average min+f of 1050 (formula shown in Example 2).

l! The liquid polyepoxide (
BDDGF! , Mu DRC and DGlnBPA) and other liquid polyepoxides (mpnpx
and DGIBPF) were evaluated along with the above polyimides. The epoxide (commercially available from The Dow Chemical Company under the designation DBR431), expressed as xpbpm, had an epoxy weight of about 172-179 and an average molecular weight of about 350. It had the following formula: DGBBPF Epoxide (marketed by Dainippon Ink Chemicals (Tama) under the name 830-8) diglycidyl ether of bisphenol F. Met. It had an epoxy equivalent weight of about 170-190 and an average molecular weight of about 360. It was expressed by the following formula: Prescriptions and test results for parts M and B.
Shown in the table. Curing was at 150°C for 30 minutes and 2
The test was carried out for 1 hour at 00°C.

■Table a, b.

40 12AIJE48 80 75 tjiL, thick d.

(Comparative example) (Comparative example) 40 12 BDDGI 48 80 75 [100
00554012ADF! 0 48 80 75 [1
0000534012DGFiBP? 48, 80 7
5 0.00007840 12 ][1PNP]e
48, 80 75 α 00084c, Rij)
It was I M ohm. d, Rke: >20Kohm
Met.

The results obtained show that no improvement in conductivity is observed when liquid monoepoxides or solid polyepoxides are used.

The same polyepoxide in liquid form (ie, DGBP) showed an increase in electrical conductivity (see Table m). These tests also show that other liquid polyepoxides provide a 4-voltage improvement.

In summary, the present invention provides noble metal-filled formulations of carbinol-containing polyimides and liquid polyepoxides characterized by improved electrical conductivity.

Agent Hikaru Esaki Agent: Hikaru Esaki

Claims (1)

Claims: 1. In a metal-filled polyimide/polyepoxide blend, (a) having the structure essentially: 0 0 0 0 (wherein Ar is located on an adjacent carbon atom in the Ar group) identical or different aromatic groups with two pairs of bonded carbonyl groups, and R is a divalent aliphatic, cycloaliphatic, aromatic or heterocyclic group. Shocking → -7, J, Il, 1/
l,, lI6-t ☆ 4211 no StΦ应 et al. 50% 1 (bl) Liquid, substituted or unsubstituted aliphatic, cycloaliphatic, aromatic and/or
or heterocyclic polyepoxide about 1-35% i and +01 organic solvent solution for the above polyimide 15-74
%; where the percentages of (al, lbl and (C1) are by weight, totaling 100%, t and (middle conductive noble metal powder approximately 45-90% by weight; here the percentage of 1 dl is the percentage of polyimide and polyepoxide % by weight, based on the total weight of the metal-filled polyimide/polyepoxide blend, characterized in that it has an improved electrical conductivity after curing over that of a blend without polyepoxide. OH, OH. -OH, -OH, -01% -OH, -OH, -OH, -
X S or the polyepoxide is a low molecular weight, low viscosity polyepoxide; the solvent is selected from the group consisting of N-methylpyrrolidinone, dimethylacetamide, butylceronlebua heptatate and carpitol acetate, or a mixture thereof; and the metal powder is selected from the group consisting of gold, silver, platinum, palladium and iridium or a mixture thereof. E. Polyimide is present in an amount of about 25-40% -OH!
-OH, -OH, -OH, -C! 2. A formulation according to claim 1, which is H, -0 horse-Xl or. 4. Polyepoxides are present in an amount of about 6-32%, and aliphatic dieboxides, cycloaliphatic jepoxycarboxylates, diglycidyl ether of bisphenol A, bisphenol? The formulation of claim 1 which is a low molecular weight, low viscosity polyepoxide selected from the group consisting of diglycidyl ethers and epoxyphenol novolacs. 5. Claims in which the solvent is present in an amount of about 25-70% and is selected from the group consisting of monomethylpyrrolidinone, dimethylacetamide, butylseron rub acetate, and carpitol acetate, or mixtures thereof. A formulation according to paragraph 1. modified metal powder is present in an amount of about 50-85% and gold,
A formulation according to claim 1 which is selected from the group consisting of silver, platinum, palladium and iridium or a mixture thereof. l An aliphatic geboxide has the following structure: I or a cycloaliphatic gepoxycarboxylate has the following structure: I4 The diglycidyl ether of bisphenol A has the following structure: (where m is O or 5. A formulation according to claim 4, wherein the epoxyphenol novolac has the following structure: a polyimide is present in an amount of about 50-40%; repolyebogicide is present in an amount of about 15-25%; i a solvent is present in an amount of about 30-40%;
8. A formulation according to claim 7, wherein the metal is present in an amount of about 55% and is N-methylpyrrolidinone; and the metal is present in an amount of about 55% to 80% and is silver. -0H1-C%-CH2-0H (01%-0H2-1 spanning 10, carbinol-containing polyimide is s, 31
, 4. Polymerization of bis(methyl half ester) of 1-benzhydroltetracarboxylic acid (7 parts, 4°4
'-Methy1/dianiline, 4,4'-oxydianiline, 4;4'-sulfonyldianilino, 4,4'-bis(3-aminobenzoyl)diphenyl ether, bis-
(5-aminopropyl)tetramethyldisiloxane, m
- 12 to 11 to 7 diamines selected from the group consisting of -phenylenediamine, 1,6-he-V-sandithamine, and 1,3-bis(3-aminophenox7)benzene in a solvent for polyimide. Using a molar ratio of the above tetracarboxylic acid compound to the above diamine of 8:1. 2. A composition according to claim 1, which is produced by imidization.