JPH03250082A - Conductive adhesive - Google Patents

Abstract

PURPOSE:To improve the heat resistance, airtightness, and handleability by dispersing a mixture of a polymeric precursor of a silazane ceramic with a conductive inorg. powder in an org. solvent. CONSTITUTION:A mixture of 100 pts.wt. polymeric precursor of a silazane ceramic (e.g. perhydropolysilazane) with 10-10000 pts.wt. conductive inorg. powder having a particle diameter of 0.1-20 mum and comprising a metal or a (non) oxide ceramic (e.g. silver powder with a particle diameter of 0.2mum) is dispersed in a solvent (e.g. xylene) in an amt. of 90 wt.% or lower, pref. 10-50 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a conductive adhesive having excellent heat resistance, which is made by incorporating a conductive inorganic powder into a silazane ceramic precursor polymer.

[Conventional technology]

Conventionally, IC chips are bonded to insulating substrates and electrodes.

Alternatively, conductive adhesives are known that are used for adhering and electrically connecting a semiconductor heating element to a metal plate. This type of conductive adhesive includes (1) a mixture of organic polymers such as epoxy resin, phenol resin, and polyimide with conductive metal powder added to it; (2) a mixture of silicone and modified silicone with conductive metal powder added; Mixtures (3) Mixtures in which alkali metal silicate, phosphate, silica sol, etc. are added as a binder to a conductive metal bundle are known. Furthermore, bonding using low melting point metals such as solder has been practiced for a long time.

However, the conductive adhesive (1) has poor heat resistance and its adhesive strength decreases significantly when the temperature rises.
There is a drawback that it cannot be used in environments above 0℃, (2)
The conductive adhesive has poor adhesive strength.

Due to evaporation and scattering of silicone as the temperature rises.

There was a problem that it could not be used in a temperature range of 350°C or higher. On the other hand, inorganic adhesives (3) can be used at temperatures above 1000°C and have excellent heat resistance, but they are inferior in airtightness and have poor adhesive strength with some metals or ceramics. It has the disadvantage of being extremely low. Note that low melting point metals such as solder cannot be used above the melting point of the metal, and pretreatment is often required to improve wettability with metals and ceramics.

[Problem to be solved by the invention]

The present invention has been made in view of the above-mentioned state of the prior art, and it is an object of the present invention to provide a conductive adhesive that has excellent heat resistance and airtightness as well as excellent handling properties.

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventors discovered that a conductive adhesive containing a conductive inorganic powder in a silazane-based ceramic precursor polymer is effective, thereby completing the present invention. reached.

That is, according to one aspect of the present invention, there is provided a conductive adhesive characterized by containing a silazane-based ceramic precursor polymer and a conductive inorganic powder.

Since the conductive adhesive of the present invention has the above-mentioned structure, it has conductivity and exhibits strong adhesive strength even at high temperatures of 500° C. or higher, so it has il! Parts exposed to high temperatures in child parts 1 For example, temperature sensing elements, combustion sensors 5 Ignition elements, electrodes for electrical discharge machining, etc. Parts where Joule heat is generated For example, highly integrated ICs, electrodes of piezoelectric vibrators, heating elements It is effectively used as an adhesive for electrodes, infrared generating elements, etc.

Furthermore, since this adhesive has excellent airtightness, it can also be used as a sealant.

The present invention will be explained in more detail below.

As the silazane-based ceramic precursor polymer used in the present invention, any of those that are converted into ceramics after firing, such as organopolysilazane, perhydropolysilazane, polysiloxazane, and polymetallosilazane, can be used, but preferably has a number average molecular weight 500-1500 silazane-based ceramic precursor polymers are used.

If the number average molecular weight of the silazane precursor polymer is less than 500, the adhesive curing time will be long and the loss of evaporation will be large, resulting in weak adhesive strength at high temperatures. This is not preferable because the curing time becomes too fast, which impairs its handling and also reduces adhesive strength and airtightness.

The silazane-based ceramic precursor polymer preferably used in the present invention has, for example, a skeleton composed of repeating units represented by the following general formula.

Examples include polysilazane having a number average molecular weight in the range of 500 to 1,500. In the above general formula, R1, R2 and R3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalxy group, an aryl group, or a group other than these groups in which the group directly bonded to silicon is carbon is an alkylsilyl group, an alkylamino group. group, alkoxy group, etc. Examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group,
Examples include nonyl group, decyl group, etc., and alkenyl groups include vinyl group, allyl group, butenyl group, pentenyl group,
Examples include hexenyl group, heptenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, and the like. or,
Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Cycloheptyl group etc., phenyl group as allyl group,
l~lyl group, xylyl group, naphthyl group, etc. are used.

Specific examples of preferred polysilazane include the general formula (wherein R1 and R2 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a group other than these groups in which the group directly bonded to silicon is carbon , an alkylsilyl group, an alkylamino group, an alkoxy group. Particularly preferred for the production of the matrix of the present invention, R'' and R'' in the above formula are lower alkyl groups.

Such polysilazane can be obtained, for example, by reacting a halosilane, for example dichlorosilane, with a base such as pyridine, and then reacting an adduct of dichlorosilane and a base with ammonia.

In addition, the silazane high polymer proposed by the present inventors, namely,
Polysilazane or A, 5toc as mentioned above as a raw material
k, and K, Somiesk Ber Dtsc
h, Chew, Ges.

54, p740 (1921), W, M, 5cantl
in, Inorganic Chemistry, 11
(1972), D., 5eyferth, U.S. Pat.
, 397.328, etc., is added to a basic solvent or a non-basic solvent containing a basic compound, and a polycondensation reaction is performed at 178°C to 300°C. Average molecular weight 200-500,
000, preferably 500 to 1,500, can be used.

Examples of the basic compound or basic solvent include a compound 1 having a basic element such as nitrogen or phosphorus, such as a tertiary amine, a secondary amine having a sterically hindered group, phosphine, etc., such as trimethylamine, Trialkylamines such as dimethylethylamine, diethylmethylamine and triethylamine, tertiary amines such as pyridine, picoline, dimethylaniline, pyrazine, pyrimidine and pyridazine, as well as pyrrole, 3-pyrroline and pyrazole.

2-pyrazoline, mixtures thereof, etc. can be mentioned. Examples of non-basic solvents include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons; halogenated hydrocarbons such as halogenated alkanes and halogenated benzene; aliphatic ethers; Ethers such as cyclic ethers can be used. Preferred solvents include halogenated hydrocarbons such as methylene chloride and chloroform, ethers such as ethyl ether and isopropyl ether, pentane, hexane, isohexane, methylcyclopentane,
These include hydrocarbons such as cyclohexane, benzene, toluene, and xylene.

The polycondensation reaction is carried out in the solvent as described above, and the concentration of the raw material inorganic silazane in the solvent is 0.1 to 50% by weight, preferably 1 to 12% by weight.

Furthermore, a polymer obtained by the modification reaction of the inorganic polysilazane shown in (1) above according to the proposal of the present inventors has a crosslinking bond -+NH+-n (n = 1 or 2), Atomic ratio of nitrogen and silicon bonded to silicon atoms (N/Si
) is 0.8 or more and the number average molecular weight is 200 to soo, oo
o, preferably 500 to 1,500.

This modified polysilazane can be produced by subjecting a polysilazane having a skeleton represented by general formula (I) and a number average molecular weight of 100-so, ooo to a dehydrogenation polycondensation reaction with ammonia or hydrazine under basic conditions. I can do it. Basic conditions mean that a basic compound such as tertiary amines, secondary amines having a sterically hindered group, phosphine, etc. are present in the reaction system. or by using a basic solvent or a mixture of a basic solvent and a non-basic solvent as the reaction solvent. The amount of the basic compound added is at least 5 parts by weight per 100 parts by weight of the reaction solvent. As the basic solvent.

As mentioned above, for example, trialkylamines such as trimethylamine, dimethylethylamine, diethylmethylamine, and triethylamine, tertiary amines such as pyridine, picoline, dimethylaniline, pyrazine, pyrimidine, and pyridazine, as well as pyrrole-23-pyrroline, etc. In addition, as non-basic solvents, aliphatic hydrocarbons,
Alicyclic hydrocarbons.

Hydrocarbon solvents such as aromatic hydrocarbons, halogenated hydrocarbons, etc. can be used (Patent application No. 62-202767).
issue).

Furthermore, polymetallosilazanes proposed by the present inventors in Japanese Patent Application No. 62-223790 etc. are mainly represented by the general formula (R1 and R2 are each independently a hydrogen atom, an alkyl group,
These include alkenyl groups, cycloalkyl groups, aryl groups, groups other than these groups in which the group directly bonded to silicon is carbon, alkylsilyl groups, alkylamino groups, and alkoxy groups. ) having a number average molecular weight of 100 to 50,000 and having a main skeleton consisting of units represented by M(OR4)n (M is a metal of Group 11a and Groups One or more metals selected from the group are capable of forming an alkoxide, and R4 is a hydrogen atom, an alkyl group or an aryl group having 1 to 20 carbon atoms, which may be the same or different; At least one R4 is the above-mentioned alkyl group or aryl group. ．． Preferably 500-1
500 can also be used.

Particularly preferred polymetallosilazanes have a main skeleton consisting of units represented by (wherein R, , R, are each independently a hydrogen atom or a lower alkyl group) and have a number average molecular weight of 500 to 2,000. It is obtained by reacting polysilazane with the above-mentioned metal alkoxide.

5 to 100 polysiloxazane (JP-A-62-1950
24) can also be used.

In the above formula, R'', R'', and R3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, or a cycloalkyl group.

These include an aryl group or a group other than these groups in which the group directly bonded to silicon is carbon, an alkylsilyl group, an alkylamino group, and an alkoxy group.

Further, one example of the conductive inorganic powder used in the present invention is as follows.

For example, Pt, Au, Pd, Cu, Ni, ^g, Cr,
Metals such as Fe, Ti, C, 5rCoO, LaCr0.
, MgCr0:l, LaMn0. , SrMn
0. , BaTiO3゜In2O,, SnO,, Ti
e,,Bi,O,Jez031M+102. ZnO, (
, ac03, NiO, CoO, MnFezO1, CoF
e2O,, ZnFe20. , CaTi0. Oxide ceramics such as SzCr VCr TxCp TxN +
Examples include non-oxide ceramics such as ZrB, tTIBZIMoSi, etc., and these may be used alone or in a mixture of two or more.

The shape of the conductive inorganic powder is preferably spherical, and the particle size is suitably about 0.1 to 20 pm.

The amount of the conductive inorganic powder to be used varies depending on the type of silazane ceramic precursor polymer to be combined with it, the solvent used, its purpose, etc., but it is usually 10 parts by weight per 100 parts by weight of the silazane ceramic polymer.
The amount is 10,000 parts by weight, preferably 50 to 5,000 parts by weight. If it is less than 10 parts by weight, the contact ratio between conductive particles will be low, and the conductivity of the adhesive will be low.
If the amount exceeds 1 part by weight, the adhesive force will be weakened, which is not preferable.

In order to obtain the conductive adhesive of the present invention, the silazane ceramic precursor polymer and the conductive inorganic powder are preferably dissolved and dispersed in an organic solvent. in this case,
Organic solvents include aliphatic hydrocarbons, alicyclic hydrocarbons,
Hydrocarbon solvents such as aromatic hydrocarbons, halogenated hydrocarbons such as halogenated methane, halogenated ethane, and halogenated benzene, and ethers such as aliphatic ethers and alicyclic ethers can be used. Preferred solvents are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride,
Halogenated hydrocarbons such as ethylidene chloride, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, ethers such as 2-dioxyethanedioxane, dimethyldioxane, tetrahydrofuran, tetrahydropyran, pentanehexane, Isohexane, methylpentane, heptane, isohexane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane.

These include hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

When using these solvents, two or more types of solvents may be mixed in order to adjust the solubility of the silazane ceramic precursor polymer and the evaporation rate of the solvent. The amount (ratio) of the solvent to be used is selected to improve the workability of the adhesive method employed, and it also varies depending on the average molecular weight distribution and structure of the silazane ceramic precursor polymer. It can be mixed up to about 90% by weight, preferably in the range of 10 to 50% by weight.

The conductive adhesive composition of the present invention prepared as described above can be uniformly dissolved or dispersed to form adhesive parts that require conductivity.
For example, it is applied to electrodes, etc. As the coating means, conventional coating methods such as dipping, roll coating, bar coating, brush coating, spray coating, flow coating, etc. are used. Before application, the surface of the object may be treated by sanding, degreasing, various types of blasting, etc. Also, if it is applied in such a manner, thoroughly dried, and then heat treated, the silazane ceramic polymer will not crosslink. , condenses and hardens, exhibiting strong adhesive strength.

The above heat treatment conditions vary depending on the molecular weight and structure of the silazane ceramic precursor polymer, but the treatment is performed at a temperature in the range of 0.5 to b.

〔effect〕

Since the conductive adhesive of the present invention has the above-mentioned structure, it has conductivity and exhibits strong adhesive strength even at high temperatures of 500°C or higher, and has excellent airtightness, so it can be used in electronic components etc. exposed to high temperatures. Adhesion of parts such as temperature sensing elements, combustion sensors, ignition elements, electrodes for electrical discharge machining, parts that generate Joule heat such as electrodes of highly integrated IC piezoelectric vibrators, electrodes of heating elements, infrared ray generating elements, etc. Effectively used as an agent or sealant.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

[Reference example 1] of perhydropolysilazane A gas blowing tube is placed in a four-loaf flask with an internal volume of IQ.

Mechanical star sea, after purging the inside of the 8 reactor equipped with a dewar condenser with deoxygenated dry nitrogen, 490 d of degassed dry pyridine was put into a 5 4-bottle flask.
This was chilled on ice. Next, when 51.6 g of dichlorosilane was added, 7 ducts (Sin, CQ, 2C, H
, N) was generated. The reaction mixture was ice-cooled, and while stirring, 51.0 g of purified ammonia was blown into the reaction mixture through a sodium hydroxide tube and an activated carbon tube.

After the completion of the reaction, the reactor mixture was centrifuged, washed with dry pyridine, and further filtered under nitrogen atmosphere to obtain filtrate 8.
Obtained 50m. When the solvent was distilled off from the filtrate 5- under reduced pressure, 0.102K of resin solid perhydropolysilazane was obtained.

The number average molecular weight of the obtained polymer was 980 as measured by GPC. Also, the IR of this polymer
Examining the (infrared absorption) spectrum (solvent: dry O-xylene; concentration of perhydropolysilazane: fO, 2g/Q), the wave number (cm-1) is 3350 (apparent extinction coefficient t = 0.55712g-1cm- 1) and 1175
Absorption based on NH: S of 2170 (t = 3.14)
Absorption based on i: 1020-820 Si and 5iNS
It was confirmed that it exhibits absorption based on i.

In addition, the IINMR (proton nuclear magnetic resonance) spectrum (60M tlz solvent CDCQ, /
When examining the reference material (TMS), it was confirmed that all of them exhibited a wide range of absorption. i.e. 64.8 and 4.4
(br, 5ill): 1.5(br.

Absorption of NH) was confirmed.

[Reference Example 2] A four-loaf flask made of polyzirconosilazane and having an internal volume of 1001112 was equipped with a condenser sealant cap, a thermometer, and a magnetic star. After purging the inside of the reactor with dry nitrogen, a benzene solution of perhydropolysilazane obtained in Reference Example 1 (concentration of perhydropolysilazane:
4.45% by weight) and zirconium tetraisopropoxide 4,00g (1
A solution of 2.2 mmoU in 6.4 mm of dry benzene was added using a syringe, and one reaction was carried out under reflux.

After the reaction was completed, the reaction solution was fractionated by GPC to obtain polyhydrozirconosilazane as a pale yellow solid.

The number average molecular weight of the produced polymer was 2100 as measured by freezing point depression method (solvent: dry benzene). As a result of elemental analysis, the polymer had an Sj of 34.0.
Zr:18.6. N:13.0,0:13,2. C:1
4.4 and ) l:5.1 (by weight).

3340c for IR spectrum (dry benzene)
Absorption based on N)I of rs-” and 1175: 2160
Absorption based on 5ill of cm-”: 102102O-
Absorption based on 820” SiH and 5iNSi: 13
65 cm-' and 1335 cm-'' (δ(C)I,)
2CH-); 1170cm-1(v(C-0)Zr)
;930cm-” (v 5iOZr, v (C-
0) Zr) absorption was observed.

[Reference example 3] N-methylsilazane The reaction was carried out using the same apparatus as in Reference Example 1.

That is, 450 g of degassed dry tetrahydrofuran was placed in the four-loaf flask shown in Reference Example 1, and 46 g of dichlorosilane cooled in a dry ice-methanol bath was added.
．． Added 2g. The solution was cooled and 44.2 g of anhydrous methylamine was blown in as a mixed gas with nitrogen while stirring.

After the reaction was completed, the reaction mixture was centrifuged, washed with dry tetrahydrofuran, and further filtered under a nitrogen atmosphere to give a filtrate of 820 rni1. I got it. When the solvent was distilled off under reduced pressure, 8.4 g of viscous oily N-methylsilazane was obtained. The number average molecular weight of the obtained polymer was 1100 as measured by GPC.

[Reference Example 4] Polytitanosilazane 5 series Perhydropolysilazane obtained in substantially the same manner as Reference Example 1 (IR spectrum: 3350c+++-" (t =
0.557ng-1cWa-J, 2170cm-' (
t = 3.14) Drying of H number average molecule 11120) 0-
Xylene solution (concentration of perhydropolysilazane 8.30
g/Q) 10.0- to 0.234 g of titanium tetraisopropoxide (0,823n++++o) under nitrogen atmosphere.
When Q) was added and stirred vigorously, the reaction solution 1 changed from colorless to black.

When the IR spectrum (dry 0-xylene) of this reaction solution was measured, it was found to be 3350 cm-' and 2170e++
+-'' apparent extinction coefficient i (Qg-1c+m-')
are 0,356Qg""cwh-" and 2.3, respectively.
It decreased to 4 mg-"cm-". By comparing with the previously prepared calibration curve of perhydropolysilazane, the concentration for NH-based absorption (3350ca+-") was found to be 5.
．． 20g#t, while absorption based on SiH (2170cm
-") corresponded to 5.90 g#l. That is, due to the reaction with titanium tetraisopropoxide, the 5i-II bond in perhydropolysilazane was
9%.

It was also confirmed that about 37% of the N-4 bond had disappeared. In addition to the absorption at 3350 cm-'' and 2170 cm-', the absorption at 1365 cm-'' and 1335 cm'''1 (δ
(CJ)2C)l-);1160cm-", 1125
cwr”” and 100100O” (v (C-0)
Ti); 950 cm-' (v 5iOTi.

ν(C-0)Ti); 615cm-1(vTi-0)
absorption was observed.

[Reference Example 5] Dry 0-xylene solution of perhydropolysilazane used in Reference Example 4 of polyaluminosilazane (concentration of perhydropolysilazane: 8.14 g)
#I) 60.0- was added with 0.4473 g (2.19 mmon) of aluminum triisopropoxide under a nitrogen atmosphere to form a mixed solution consisting of a homogeneous phase. At this time, the ratio of the total number of structural units was approximately 3:2. A reflux reaction was carried out while stirring this mixed solution at 130° C. for 2 hours under a nitrogen atmosphere. The reaction solution changed from colorless to pale yellow.

When the IR spectrum (dry 0-xylene) of this reaction solution was measured, it was found that 3350cn+-' and 2170cm
The apparent extinction coefficient t (Qg-”c+w-1) of −1 is
They decreased to 0.184 and 2°14, respectively. By comparison with the previously prepared calibration curve of perhydropolysilazane, the concentration for absorption based on Ni1 (3350c+m-1) was found to be 2. On the other hand, absorption based on SjH (21
70 cm-”) corresponded to 5.2 g/Q. That is, 5i-H in perhydropolysilazane was
It was confirmed that the bonding was about 36%, and about 69≦NH bonds had disappeared.

[Reference Example 6] Polyborosilazane Pyridine solution of perhydropolysilazane obtained in Reference Example 1 (concentration of perhydropolysilazane: 5.10% by weight)
) was placed in a pressure-resistant reactor with an internal volume of 300 d, 4.0 cc (0,035 moQ) of trimethylborate was added, and the reaction was carried out in a closed system at 120° C. with stirring for 3 hours.

The pressure increased by 0.6 kg/aJ before and after the reaction. The gases generated were hydrogen and methane as determined by gas chromatography (GC). After cooling to room temperature, 100% of dry φ-xylene was added and the solvent was removed at a pressure of 3 to 5 mmHg and a temperature of 50 to 70°C, yielding 5.45 g of a highly viscous liquid. This liquid was soluble in toluene, tetrahydrofuran, chloroform and other organic solvents.

The number average molecular weight of the polymer powder was 1200 as measured by GPC. In addition, as a result of the analysis of its IR spectrum, the wave number (cm-1) was 3350 and 11
absorption based on NU of 75; absorption based on 5i)I of 2170; absorption based on 5ill and 5iNSi of 1020-820; absorption based on CH of 2960.2940.2840; absorption based on SiO of 1090; absorption based on 1550-
It was confirmed that absorption based on BO of 1300 was exhibited.

Furthermore, the “HNMR spectrum (CDC) of the polymer powder
As a result of analyzing Q, , TMS), δ4.8(br,
SiH□), 64.7 (br, 03ill□), δ4
．． 4 (br, SiH,), 63.6 (br.

Absorption of Ctl, O) and δ1,4 (br, NH) was observed. Furthermore, the elemental results of the polymer were as follows: Si: 42.4%, N: 25. ! It%, C: 8.8
%0: 12.7%, R: 7.0%, H: 3.8%.

Example 1 40 ut of perhydropolysilazane obtained in Reference Example 1
%0-xylene solution, Ag powder with a particle size of 0.2 Ωm and Ag powder with a particle size of 10 ps were added to the weight ratio polymer 10.2 μm.
They were mixed at Ag/10 and Ag=1/315 and dispersed using ultrasonic waves to form an adhesive.

Next, AQ20 with dimensions 1csX4cmX0.2c+w
．． After applying the conductive adhesive to the plate and bonding, the temperature was raised from room temperature at 5'C/min in N2, maintained at 600°C for 2 hours, and cooled in a furnace.

Airtightness and adhesion were good. When the specific resistance at room temperature was measured by the DC four-terminal method, it was 0.2 Ω·cm.

Example 2 30 wt% of polyzirconosilazane obtained in Reference Example 2
ZrB2 powder with particle size 0.3 and particle size 1 in toluene solution
0pm ZrB2 powder to weight ratio polymer 10.37aZ
rB2/10psZrB2:1/4/6 was mixed and dispersed using ultrasonic waves to obtain an adhesive.

Next, AQ20. of dimensions 1 cm x 4 cm x 0.2 cm.
After applying the conductive adhesive to the plate and bonding, the temperature was raised from room temperature at 3°C/min in N2, held at 800°C for 1 hour, and cooled in a furnace.

There were no problems with airtightness or adhesion. When the specific resistance at room temperature was measured by the DC four-terminal method, it was 5.8Ω·0.

Example 3 50wt%0 of N-methylsilazane obtained in Reference Example 3
- LaCo0.
Powder and particle size 5pm LaCo0. Powder weight ratio polymer 10.5 μm LaCo0,154LaCoO,=1/
The mixture was mixed in a ratio of 3/3 and dispersed using ultrasonic waves to form an adhesive.

Next, i, 0. of dimensions 1 cm x 4 cm x 0.2 cm. After applying the conductive adhesive to the plate and bonding, the temperature was raised from room temperature to 10°C for 7 minutes in air, maintained at 500°C for 2 hours, and cooled in a furnace. There were no problems with airtightness or adhesion. When the specific resistance at room temperature was measured using the DC four-probe method, it was found to be 100Ω・c.
It was lI.

Example 4 TiN powder with a particle size of 0.1 μm and a particle size of 5
Weight ratio of TiN powder to polymer: 10.1pHITiN
An adhesive was prepared by mixing 1lpHlTiN15IJ/7 and dispersing it using ultrasonic waves.

Next, A1120 with dimensions 1cm x 4cm x 0.2ca
．． After applying the conductive adhesive to the plates and joining them, N11.
In the middle, the temperature was raised from room temperature at a rate of 3°C/min, held at 800°C for 3 hours, and then cooled in a furnace. There were no problems with airtightness or adhesion. When the specific resistance at room temperature was measured using the DC four terminal method, it was found to be 55
It was Ω・C intestine.

Example 5 30 wt% of polyaluminosilazane obtained in Reference Example 5
SiC powder with a particle size of 0.3 Ila and a particle size of 10. The weight ratio of SiC powder to polymer is 10.3.
An adhesive was prepared by mixing n5ic/1OpmSiC=1/3/4 and dispersing it using ultrasonic waves.

Next, AQ20. of dimensions 1 cm x 4 cm x 0.2 cm.
After applying the conductive adhesive to the plate and bonding, the temperature was raised from room temperature at 10 ° C / min in Ar, and held at 1000 ° C for 3 hours,
Furnace cooled. There were no problems with airtightness or adhesion. When the specific resistance at room temperature was measured using the DC four-terminal method, it was 80Ω・
It was C-.

Example 6 A 40 wt % ethylbenzene solution of the polyborosilazane obtained in Reference Example 6 was mixed with MoSi powder with a particle size of 0.5 pm and MoSi powder with a particle size of 107 a, in a weight ratio of polymer 10.
54MoSi2/lO4MoSi, = 1/4/6, was mixed and dispersed using ultrasonic waves to obtain an adhesive.

Next, 1 dimension 1cmX3cmX0,2cs+5uS-
After applying the conductive adhesive to the 304 plate and bonding, the temperature was raised from room temperature at 5° C./min in N2, maintained at 800° C. for 2 hours, and cooled in a furnace. There were no problems with airtightness or adhesion. When the specific resistance at room temperature was measured using the DC four-terminal method, it was 25Ω.
・It was C-Otori.

Claims (1)

[Claims] (1) A conductive adhesive characterized by containing a silazane-based ceramic precursor polymer and a conductive inorganic powder.