JPH02245071A - Conductive paste composition - Google Patents

Abstract

PURPOSE:To prepare a conductive paste compsn. capable of preventing the short circuit caused by migration from occurring even at high temp. and humidity by compounding a heat-resistant thermoplastic resin with a solvent and a specific inorg. filler. CONSTITUTION:100 pts.wt. heat-resistant thermoplastic resin is compounded with 300-5500 pts.wt. solvent capable of dissolving said resin and 350-3500 pts.wt. inorg. filler filler comprising a conductive filler and a metal oxide having an ion-adsorbing power, thus giving a conductive paste compsn. A pref. inorg. filler is a conductive filler comprising silver and 5-50wt.% metal oxide having an ion-adsorbing power. Metal oxides having an ion-adsorbing power included activated alumina, zirconium dioxide, synthetic zeolite, divanadium pentaoxide, cuprous oxide, and cupric oxide. A pref. heat-resistant thermoplastic resin is one with a glass transition temp. of at least 150 deg.C, such as an arom. polyamide, arom. polyamideimide, arom. polyesteramide, polyimide, arom. polyester, or arom. polyether.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a conductive paste composition.

[Conventional technology]

Conductive pastes containing silver as a conductive filler have good conductivity and are therefore frequently used as electrodes and wiring conductors for electronic components such as resistors, capacitors, and wiring boards.

However, when these electronic components are left or used under high humidity, silver ions flow out from the electrodes or wiring conductors, causing a phenomenon called migration, which causes a short circuit between the electrodes. .

In recent years, these electronic components are increasingly required to be smaller and have higher performance, and there is a tendency for defects due to migration to increase.

In order to prevent this silver migration failure, as shown in Japanese Patent Application Laid-Open No. 55-149356, manganese powder is mixed into a silver-based conductive paste, and Japanese Patent Application Laid-Open No. 5.3-35739 As shown in the publication = 7, the product mixed with zinc powder, JP-A-5
As shown in Japanese Patent Application No. 1-146450, there have been proposed methods in which indium powder is mixed in, and in Japanese Patent Application Laid-Open No. 56-62858, in which ion exchanger powder is mixed. There is.

[Problem to be solved by the invention]

JP-A-55-149356, JP-A No. 54-146450, JP-A No. 53-35739, JP-A No. 56-62
The conductive paste composition disclosed in Japanese Patent No. 858 uses conventionally known phenolic, epoxy, cellulose, acrylic, and other binders as organic binders. The cured films of the conductive paste compositions produced by these methods were indeed effective in reducing short-circuit defects caused by silver ion migration at around room temperature. However, these organic binders have low heat resistance and cannot be used under high temperature and high humidity conditions, e.g.
Under conditions such as a pressure comb test at 21° C. and 12 atm, it was observed that a considerable amount of silver ions leaked out of the cured conductive paste film, resulting in a short circuit due to migration.

The present invention provides a conductive paste composition that can prevent short circuit failures due to migration even under high temperature and high humidity conditions.

[Means to solve the problem]

The present invention comprises 100 parts by weight of a heat-resistant thermoplastic resin, 300 to 5,500 parts by weight of a solvent capable of dissolving the resin, and 350 to 3,500 parts by weight of an inorganic filler consisting of a conductive filler and a metal oxide having ion adsorption ability. The present invention relates to a conductive paste composition containing the following.

The heat-resistant thermoplastic resin used in the present invention preferably has a glass transition point of 150''C or higher.

If the glass transition point is too low, the strength of the coating will decrease under pressure tanker conditions (121° C., 12 atm), and silver ions will be observed to flow out of the conductive paste coating. The glass transition point is more preferably 180°C or higher.

The heat-resistant thermoplastic resin used in the present invention is at least one selected from the group consisting of aromatic polyamide, aromatic polyamideimide, aromatic polyesterimide, polyimide, aromatic polyester, and aromatic polyether.
Preferably, seeds are used.

Preferred specific examples of the heat-resistant thermoplastic resins listed above are (
Shown as a) to (h).

(a) - Formula (1) (In the formula, R1, R2, R3 and R4 represent hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom, which may be the same or different, and X is o-- s--c
--so□- R6 and R6 represent hydrogen, a lower alkyl group, a trifluoromethyl group, or a phenyl group, and these may be the same or different, and Ar represents a m-phenylene group, a p-phenylene group, a di- An aromatic polyetheramide resin, which is a type of aromatic polyamide resin and has a repeating unit represented by a phenylene ether group or a diphenylene sulfone group.

Here, when R3, R2, R3 and R4 in the above-mentioned formula (1) are hydrogen, and R5 and R6 in X are hydrogen or a lower alkyl group, 70 mol% or more of Ar is m- A phenylene group is preferred. m
- If the proportion of phenylene groups is less than 70 mol %, it tends to become insoluble in the ether compound. It is preferable that 90 mol% or more of Ar is m-phenylene group, and 10
More preferably, 0 mol % M is m-phenylene group.

The above-mentioned aromatic polyetheramide resin is a known resin, for example, - formula (A) (wherein R,, R,, R
3, R1 and
It can be obtained by reaction according to the method disclosed in the above publication.

As the aromatic diamine mentioned above, for example, 2,2-his(
4-(4-aminophenoxy)phenyl]propane, bis(4-(4-aminophenoxy)phenyl)methane,
2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 22-bis[ 3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 22-bis(1-(
4-aminophenoxy)phenyl]-11,l,3,3
．． 3-hexafluoropropane, etc., and these 1
More than one species can be used.

Examples of aromatic dicarboxylic acids or derivatives thereof include terephthalic acid, isophthalic acid, diphenylene ether dicarboxylic acid, diphenylsulfone dicarboxylic acid, and cybalides thereof.

However, when R3, R2, R3 and R4 in the above formula (1) are hydrogen and R5 and R6 in X are hydrogen or a lower alkyl group, the aromatic dicarboxylic acid or its derivative is isophthalic acid. It is preferable to use cybaride of isophthalic acid in an amount of 70 mol% or more. It is more preferable to use 90 mol% or more. 1
It is particularly preferable to use 00 mol%. As other aromatic dicarboxylic acids or derivatives thereof, terephthalic acid, diphenyl ether dicarboxylic acid, diphenylsulfone dicarboxylic acid, or their civalides are used.

In addition, in the synthesis of the aromatic polyetheramide resin, in addition to the above-mentioned aromatic diamines, other aromatic diamines such as m-phenylene diamine and p-phenylene diamine, and aliphatic diamines such as 2-hexamethylene diamine are used as diamine components. Diamines and silicon diamines may be used to the extent that they do not impede the purpose of the present invention.

As the silicon diamine, for example, - formula (in the formula R
is a divalent hydrocarbon group, R1 and R2 represent a monovalent hydrocarbon group, and may be the same or different,
p is an integer of 1 or more).

R is preferably an alkylene group having 1 to 5 carbon atoms, a phenylene group, or an argyl-substituted phenylene group, and R1 and RZ are preferably an alkyl group having 1 to 5 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group. Specifically, the following compounds may be mentioned: H3 H2N (CH2)3 St 0H3 CH.

CH.

Si (CHz)s Nl2 CH3 CH.

H2N (CH2)-Si OSi (CHz)
4 NHzCH3CH:+ Cb H5 HEN (CH2)3 Si-〇Cb Hs 6H5 Si (CHz:h NH□ bH5 CH, CHz CH3 H2N (CH2)3 Si OSi OSi
(CH□)3-NH2CH, CHs CHl-16= (b)-Formula (n) Aliphatic diamines and silicone diamines similar to those described above may be used to the extent that they do not impede the object of the present invention.

(c) - Formula (III) (wherein, R1, R2, R3, R4 and χ are - Formula (T
) An aromatic polyetheramide-imide resin having a repeating unit represented by ).

This resin is already a known resin, and for example, an aromatic diamine such as the aromatic diamine represented by the above-mentioned formula (A) and a derivative such as trimellitic anhydride or its monochloride are used, for example, in Japanese Patent Publication No. 4215637. , 49-407
It can be synthesized by a solution polycondensation method, an acid chloromethane method, a direct polycondensation method, a melt polycondensation method, etc. shown in No. 7 and No. 408910. As the diamine component, - formula (A
), m-phenylenediamine,
Other aromatic diamines such as p-phenylene diamine, fats such as hexamethylene diamine (wherein R1' and R3
1 is a lower alkyl group, which may be the same or different, R2' represents a lower alkyl group or a halogen atom, and m, m and m'' are RI' and R2, respectively.
' and represents the number of substituents in R%, an integer from 0 to 4,
When rn, m and m'' are each 2 or more, the plurality of R+', R2' and R31 may be the same or different R4', and the two X' may be the same or different, where Ra
' and R and l represent hydrogen, a lower alkyl group, a trifluoromethyl group, or a phenyl group, and these = 17 may be the same or different). Polyamideimide resin.

This resin is a well-known resin, for example, - formula (
B) (However, in the formula, m, m', m, RI', R2'R
, l and X' have the same meanings as in general formula (III)) and a derivative such as trimerino anhydride or its monochloride by the same method as the synthesis method in (b) above. It can be synthesized with

As the aromatic diamine represented by the above formula (B),
For example, 1.3-bis(3-aminophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene,
1.4-bis(4-aminophenoxy)benzene, 4.
．． 1'-(1,3-phenylenebis(1-methylethylidene))]bisaniline, 4.4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 3,
Examples include 3'C1,,3-phenylenebis(1-methylethylidene)]bisaniline. In addition, as in (b) above, other aromatic diamines and/or aliphatic diamines,
Silicon diamine can be used as a diamine component to the extent that the object of the present invention is not impaired.

(d) - Formula (IV) (wherein R1'', R2'', R,'' and R4'' represent a lower alkyl group, a lower alkoxy group, or a halogen atom, which may be the same or different, and X is General formula (1)
An aromatic polyamide-imide resin having a repeating unit represented by (same meaning as in).

This resin is already a known resin, for example, the general formula (
C) aromatic diamine represented by (wherein R1'', R2'', R3'', R4'' and X have the same meanings as in general formula (IV)) and derivatives such as trimellitic anhydride or its monochloride can be synthesized by the same method as the synthesis method (b) above.

As the aromatic diamine represented by the above-mentioned formula (C),
For example, 4,4'-diamino-3,3'5,5'-tetramethyldiphenylmethane, 4°4'-diamino-3,
3'5.5'-tetramethyldiphenylmethane,
4,4′-diamino-3゜3′ 5.5′-tetramethyldiphenyl ether, 4.4′-diamino-3,
3'5,5' -tetraethyl diphenyl ether, 2,2- (4,4 diamino-3,3'5,5'
-tetramethyldiphenyl]propane, etc. Further, as in (b) above, other aromatic diamines, aliphatic diamines, and silicone diamines can be used in combination as diamine components within the range that does not impede the object of the present invention.

(e) - Formula (V) (wherein, R, rrr, R, III, R, rrr, R, J
JT and x have the same meanings as in general formula (]I),
R, "', R, IIIR3' and R, "' are R1,R
2, is a group similar to R3 and R4, and X″ is a group similar to χ, R1, R2, R3, R4, R, “’, R2
An aromatic polyether ester imide resin having a repeating unit represented by #l, R3, #l and R''' may be the same or different, and X and X'' may be the same or different.

This resin is already a well-known resin, for example, a general resin (
Examples include aromatic cyamines such as aromatic diamines represented by A) and sotokydiphenyl)ketone dianhydrides of the general formula (I).

In addition, as the diamine component, other aromatic diamines, aliphatic diamines, and silicone diamines described in the above (a) can be used in combination to the extent that the object of the present invention is not impaired.

(f) - Formula (Vl) o
(D) 0 (in the formula, R, "', R2"', R3"
', Ra' and x'' have the same meanings as in formula (V)) are synthesized by the solution polycondensation method disclosed in JP-A-6049030. - As the aromatic tetracarboxylic dianhydride represented by the formula (T), for example,
2.2-bis(p-trimeritoxyphenyl)propanihydride, 2.2-bis(p-trimerisotoxyphenyl) 3
5-dimethylphenyl)propanihydride, bis(p-
Trimeroxyphenyl) sulponi anhydride, bis(
p-1-rimeri (wherein, A polyimide resin having a repeating unit represented by (representing a residue).

This polyimide resin is already a known resin, and for example, an aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride and an aromatic diamine are used in JP-A-60-4.
It can be synthesized by the solution polycondensation method shown in Japanese Patent No. 9030.

Examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic dianhydride include cyclobutanetetracarboxylic dianhydride, cyclopententetracarboxylic dianhydride, 5.5′-thiobis(norbornane-23-dicarboxylic anhydride), 5.5 ' −
Methylene dithiobis (norbornane-2,3-dicarboxylic anhydride), 5,5'-ethylene dithiobis (norbornane-2,3-dicarboxylic anhydride), 55'-propylene dithiobis (norbornane-23-dicarboxylic acid) Anhydride L5,5'-sulfonyl bis(norbornane-2,3-dicarboxylic anhydride tl), 5,5'-methylenedisulfonyl bis(norbornane-2,3-dicarboxylic anhydride), 5゜5'-ethylene Disulfonylbis(
norbornane 2,3-dicarboxylic anhydride), 5.5'
-Propylene disulfonyl bis(norbornane-23)
-dicarboxylic acid anhydride), 3.5.6-) dicarboxy-2-carboxymethylnorbornane 2:35:6 dianhydride, and 2.3.5-tricarboxycyclopentyl acetic anhydride. Examples of aromatic diamines include:
Diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenylsulfone, 2.2-diaminodiphenylpropane, diaminobenzophenone, 1.3bis(4-aminophenoxy)benzene, 13-bis(3
-aminophenoxy)benzene, 14-bis(4-aminophenoxy)benzene, 4°4'-di(4-aminophenoxy)diphenylsulfone, 22'-bis(4-(
4-aminophenoxy)phenyl]propane, 2.2'
-bis(4-(4-aminophenoxy)phenyl)-1
゜1.1,3,3.3-hexafluoropropane, etc. In addition, as the diamine component, other aliphatic diamines and silicone diamines described in the above (a) can be used in combination to the extent that the object of the present invention is not impaired.

(g) - Formula (■) (In the formula, R1, R2, R8, R4 and X are - Formula (1
), wherein Ar'' represents a p-phenylene group, m-phenylene group, diphenylene ether group or diphenylene sulfone group).

This aromatic polyester resin is already a well-known resin, for example - formula (E) (wherein R,, R,, R3, R4 and X are general formula (■)
For example, aromatic diols and aromatic dicarboxylic acid sybarides represented by
It is synthesized by an interfacial polycondensation method or a method using a phase transfer catalyst as disclosed in JP-A-51094, JP-A-59187022, and the like.

Here, the aromatic diol represented by formula (E) is, for example, 4,4'-dihydroxy-3°3', 5.
5'-tetramethylphenyl-2,2propane, 44'
-dihydroxy-3.3'55'-tetramethyldiphenylmethane, 4°4'-dihydroxy-33', 5.5
'-Tetramethylbenzophenone, etc. Examples of the aromatic dicarboxylic acid civalide include terephthalic acid dichloride, isofucric acid dichloride, diphenyl ether dicarboxylic acid dichloride, and diphenylsulfone dicarboxylic acid dichloride.

(h) - Numerical formula (■) (In the formula, R1, R2, R3, R4, R+ ", R2"
, R3'', Ra'', X and X I+ are general formula (V)
An aromatic polyether resin having a repeating unit represented by (same meaning as in).

This aromatic polyether resin is already a well-known resin, and has the following formula: Aromatic cibaride represented by the general formula (G) (wherein Rl'', RZ'', R'3'', R4'' and χ
″ has the same meaning as in the general formula (■)).
Journal of Polymer Science (J. R.N. Johnson) et al.

Polym, Sci,) Part A-1 (Part A
-1) Obtained by reaction using the solution polycondensation method shown in Vol. 5, p. 2375 (1967). Here, as the aromatic cybaride represented by the above-mentioned formula (F), for example, 4,4'-dichlorodiphenylsulfone, 44'-
Difluorodiphenylsulfone, 4.4'-dichlorodiphenylsulfine, 4°4'-difluorodiphenylsulfine, 4.4'dichlorodiphenylketone, 4.
There are 4'-difluorodiphenyl ketones, and one or more of these are used, and 4,4'-dichlorodiphenyl sulfone is particularly preferably used.

- Examples of aromatic diols represented by formula (G) include 4,4'-dihydroxydiphenyl 2,2-propane, 4,4'-dihydroxydiphenylmethane, 4,4'
-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone, 44'-dihydroxydiphenylethane, 44'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxydiphenyl-2,2'
Butane, 4,4'-dihydroxy-3,3'5,5'-
Tetramethylbiphenyl, 4,4'dihydroxy-3,
3',5,5'-tetramethyldiphenyl-2,2
-propane, 4,4'-dihydroxy-3,3', 5
．． 5'-tetramethyldiphenylmethane, 4.4'-
Examples include dihydroxy-3゜3', 5.5'-tetramethyldiphenylsulfone, and one or more of these are used, particularly 4,4'-dihydroxydiphenyl-2゜2-propane, 4.4'-tetramethyldiphenylsulfone, etc. -dihydroxy-3゜3
',5.5'-tetramethyldiphenyl-2゜2-
Propane is preferably used. As the alkali metal of the alkali metal salt, Li, Na, Ni, etc. are used.

In addition to the resins exemplified above, resins having two or more types of repeating units of formulas (1) to (■) above in the molecule can be used.

The heat-resistant thermoplastic resins (a) to (h) exemplified above have a reduced viscosity (measured as a 0.2 g/d1 dimethylformamide solution at 30°C) of 0.2 to 4. Oa/g is preferable, and 0.2 to 3. Oa/g is more preferable, and 0.2 to 2 dl/g is particularly preferable.

There are no particular restrictions on the solvent used in the present invention, but
Various linear or cyclic ethers are preferred. Examples of linear or cyclic ethers include diethylene glycol dimethyl ether, dioxane, and tetrahydrofuran, which may be used alone or in combination of two or more.

Further, the conductive paste composition of the present invention includes an inorganic filler consisting of a conductive filler and a metal oxide having ion adsorption ability. Silver powder is preferred as this conductive filler. On the other hand, metal oxides having ion adsorption ability are metal oxides that exhibit a silver ion adsorption phenomenon, such as activated alumina, zirconium oxide, synthetic zeolite, vanadium pentoxide, cuprous oxide, cupric oxide, etc. can be used. These metal oxides can be used in the form of powder, and may be used alone or in combination of two or more in any proportion. The inorganic filler used in the present invention preferably contains a metal oxide having an ion adsorption ability in an amount of 5 to 50% by weight.

If the metal oxide content is less than 5% by weight, the effect of inhibiting silver migration by the metal oxide will be insufficient, and if it exceeds 50% by weight, the electrical conductivity will tend to decrease.

Each of the above-mentioned materials contains 300 to 5,500 parts of a solvent capable of dissolving the resin, per 100 parts by weight of the heat-resistant thermoplastic resin.
350 to 3,500 parts by weight of an inorganic filler made of a conductive filler and a metal oxide having ion adsorption ability are used.

If the solvent is less than 300 parts by weight, the solid content will be high, making it difficult to maintain a uniform thickness on the coated surface.
If it exceeds 0 parts by weight, the viscosity will be low, making it difficult to disperse the inorganic filler. If the amount of inorganic filler is less than 350 parts by weight, conductivity will be insufficient, and if it exceeds 3,500 parts by weight, coating will become difficult.

The optimum blending ratio of these can be selected depending on the type of heat-resistant thermoplastic resin used, but it is recommended that 600 to 3,400 parts by weight of the solvent and 500 parts by weight of the inorganic filler to 100 parts by weight of the heat-resistant thermoplastic resin. Preferably, ~3000 parts by weight are used. In addition, silane-based,
Coupling agents such as titanate and aluminum chelate may also be added.

The conductive paste composition of the present invention can be obtained by mixing and kneading the above-mentioned materials by a known method.

The conductive paste composition of the present invention is useful as a conductive adhesive for electronic components, an electrode material, and a wiring conductor for wiring boards.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 (1) Synthesis example of heat-resistant thermoplastic resin having the following repeating unit 2,2-bis(1 -(4-
Aminophenoxy)phenyl]propane 8.2g (0,
02 mol), triethylamine 4.44 g (0.04 mol), triethylamine 4.44 g (0.04
4 mol) and 40 m2 of N-methylpyrrolidone are added and dissolved. The inside of the system was maintained at -10° C., and 10 ml of a cyclohexanone solution in which 4.06 g (0.02 mol) of isophthaloyl chloride was dissolved was added dropwise. At this time, the temperature in the system was controlled to -10 to -5°C. The viscosity of the reaction system increased, so when the desired viscosity was reached, stirring was stopped, the reaction solution was poured into a large amount of methanol, the polymer was isolated, and it was dried under reduced pressure at 180°C to obtain heat-resistant thermoplastic resin A. .

The reduced viscosity of this material (resin 0.2 g/d dimethylformamide solution, 30'C) was measured and found to be 0.82.
It was d1/g. Tg was 203°C.

(2) Preparation of conductive paste composition 100 parts by weight of the heat-resistant thermoplastic resin A obtained in (1) is dissolved in 2,500 parts by weight of diethylene glycol dimethyl ether, and scaly silver powder (hereinafter simply referred to as silver powder) with an average particle size of 2.9μ is dissolved in 2,750 parts by weight of granular aluminum oxide powder (hereinafter simply referred to as aluminum oxide powder) having an average particle size of 0.4 μm were added and kneaded for 2 hours in a milling machine to prepare a silver paste.

Example 2 (1) Heat-resistant thermoplastic resin B having the following repeating unit
Synthesis example of 2,2-bis(4-(4-
Aminophenoxy)phenyl]propane 8.2g (0,
02 mol), triethylamine 2.22 g (0,0
22 mol) and 50 ml of N-methylpyrrolidone,
Dissolved. The inside of the system was maintained at -10°C, and 4.2 g (0.02 mol) of trimellitic anhydride chloride was added. At this time, the temperature in the system was controlled at -10 to -5"C.The viscosity of the reaction system would be high, so when the desired viscosity was reached, 10.0 g of acetic anhydride and 5 g of pyridine were added, and 60.0 g of pyridine was added.
Stirring was continued at ℃ overnight. The reaction solution was poured into a large amount of methanol to isolate the polymer, which was dried under reduced pressure at 180°C to obtain heat-resistant thermoplastic resin B. Reduced viscosity of this material (resin 0
．． 2g/a dimethylformamide solution, 30”C) is 0
．． It was 13 dll/g. Tg was 240°C.

(2) Preparation of conductive paste composition 8100 parts by weight of the heat-resistant thermoplastic resin obtained in (1) is dissolved in 1500 parts by weight of dioxane, and 840 parts by weight of silver powder and 360 parts by weight of aluminum oxide powder are added thereto. A silver paste was prepared by kneading the mixture for 2 hours in a mill.

Example 3 (1) Synthesis example of heat-resistant thermoplastic resin C having the following two types of repeating units In a fourth flask equipped with a stirring device, a nitrogen introduction tube, a thermometer, and a reflux tube, 2.2 g -Heath(1-(4)
-aminophenoxy)phenyl]propane 8.2g (0
, 02 mol), 4.44 g (
0,044 mol) and 50 ml of N-methylpyrrolidone were added and dissolved. At this time, while maintaining the inside of the system at 10°C, 2.03 g of isophthaloyl chloride (0.01
mol) and anhydrous trimellinic acid chloride 2.11
g (0.01 mol) was added.

The temperature in the system was controlled at -10 to -5°C. The viscosity of the reaction system increases, so when the desired viscosity is reached, add 5.0% acetic anhydride.
g and 2.5 g of pyridine were added thereto, and stirring was continued at 60°C all day and night. The reaction solution was poured into a large amount of methanol/l/, the polymer was isolated and dried under reduced pressure at 180°C to obtain a heat-resistant thermoplastic resin C. Reduced viscosity of this material (resin 0.2g/di
, dimethylformamide, 30'C) is 1.2 companies/g
Met. Tg was 220°C.

(2) Preparation of conductive paste composition 0,100 parts by weight of the heat-resistant thermoplastic resin obtained in (1) is dissolved in 1,500 parts by weight of a mixed solvent of tetrahydrofuran/diethylene glycol dimethyl ether-4/6 (weight ratio), and silver powder is dissolved in this. 720 parts by weight and 480 parts by weight of aluminum oxide powder were added, followed by shaking for 10 hours and ultrasonic dispersion for 10 hours to prepare a silver paste.

Example 4 (1) Synthesis example of heat-resistant thermoplastic resin having the following repeating unit Into a three-neck flask equipped with a stirring device, a nitrogen inlet tube, and a fractionating head, 5.044 g (0,022 mol) of bisphenol A and 50 g of bisphenol A were added. % aqueous sodium hydroxide solution and 10 ml of toluene were added, the temperature was raised to 160°C, and the azeotrope of water and toluene was distilled out of the system. After adding 6,318 g (0,022 mol) of dichlorodiphenyl sulfone and 17 g of dimethyl sulfoxide and reacting at 160°C for 1 hour, the reaction solution was poured into a large amount of methanol, the polymer was isolated, and the mixture was vacuumed at 180°C. It was dried to obtain a heat-resistant thermoplastic resin. The reduced viscosity of this product (resin 0.2 g/dg/chillformamide solution, 30'C) was 0.6 Id/g. Tg was] 90'C.

(2) Preparation of conductive paste composition 100 parts by weight of the heat-resistant thermoplastic resin D obtained in (1) was mixed with dioxane/diethylene glycol dimethyl ether-4/
6 (weight ratio) and 1,500 parts by weight of silver powder and 375 parts by weight of aluminum oxide powder.
Parts by weight were added, followed by shaking for 10 hours and ultrasonic dispersion for 10 hours to prepare a silver paste.

Example 5 (1) Heat-resistant thermoplastic resin E having the following repeating unit
500 parts by weight (referred to as Synthesis Example) were added, and shaking was performed for 10 hours and ultrasonic dispersion was performed for 10 hours to prepare a silver paste. Example 6 (1) Heat-resistant thermoplastic resin F having the following repeating unit
Synthesis Example In the synthesis example of heat-resistant thermoplastic resin B of Example 2, 2
．． 2-bis(4-(4-aminophenoxy)phenyl)
1.3- instead of 8.2 g (0.02 mol) of propane
Bis(3-aminophenoxy)henzen 5.84 g
A heat-resistant thermoplastic resin was obtained in the same manner except that (0.02 mol) was used. Reduced viscosity of this material (resin 0.2g
/ag/chillformamide solution, 30'C) is 0.59
df! , 7g, and aTg was 192°C.

(2) Preparation of conductive paste composition 8100 parts by weight of the heat-resistant thermoplastic resin obtained in (1) is dissolved in 1700 parts by weight of dioxane, and 2000 parts by weight of silver powder is dissolved in this.
Particulate zirconium oxide powder (hereinafter simply referred to as zirconium oxide powder in the synthesis example of heat-resistant thermoplastic resin B of Example 2, 2,2-bisC4-C4-aminophenoxy)phenyl]propane having a weight part and an average particle size of 3 μm.8. 2g (0,02
4,4'-diamino-3,3',5
．． 5'tetraethyldiphenylmethane 6.2g (0,0
A heat-resistant thermoplastic resin F was obtained in the same manner except that 2 mol) was used. The reduced viscosity of this material (resin 0.2 g/semi-dimedimethylformamide solution at 0°C) is 0.80 and 7 g.
and Tg was 280°C.

(2) Preparation of conductive paste composition 100 parts by weight of the heat-resistant thermoplastic resin F obtained in (1) is dissolved in 1700 parts by weight of a mixed solvent of tetrahydrofuran/diethylene glycol dimethyl ether-6/4 (weight ratio), and silver powder is dissolved in this. 1,050 parts by weight of zirconium oxide powder and 170 parts by weight of zirconium oxide powder were added and kneaded for 2 hours in a mill to prepare a silver base.

Example 7 (1) Heat-resistant thermoplastic resin G having the following repeating unit
Synthesis example of 2.2-bisC4-C4- in a four-loaf flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux tube under a nitrogen atmosphere.
Aminophenoxy)phenyl]propane 8.2g (0,
02 mol) and 50 mfl of N-methylpyrrolidone were added and dissolved. 11.52 g (0
, 02 mol) was added.

The reaction was allowed to proceed at room temperature for 3 hours, and further at 190° C. for 6 hours. The reaction solution was poured into a large amount of methanol to isolate the polymer, which was dried under reduced pressure at 180°C to obtain heat-resistant thermoplastic resin G. The reduced viscosity of this product [resin 0.2 g/J dimedylformamide solution, 30°C] was measured and found to be 0.69.
It was d1/g. Tg was 214°C.

(2) Preparation of conductive paste composition 6,100 parts by weight of the heat-resistant thermoplastic resin obtained in (1) was dissolved in 1,500 parts by weight of diethylene glycol dimethyl ether, and 2,000 parts by weight of silver powder and 800 parts by weight of granular synthetic zeolite with an average particle size of 5 μm were added to the mixture. Add weight part and shake 1
After 0 hours, ultrasonic dispersion was performed for 10 hours to produce a silver paste.

Example 8 (1) Heat-resistant thermoplastic resin H containing the following repeating unit
Synthesis Example In the synthesis example of heat-resistant thermoplastic resin G of Example 7, 2
,2-bis(4-(4-aminophenoxy)phenyl)
Bis(4
-(4-aminophenoxy)phenyl]sulfone 8.6
A heat-resistant thermoplastic resin H was obtained in the same manner except that 4 g (0.02 mol) was used. Reduced viscosity of this material (resin 0
．． 2g/d dimethylformamide solution, 30°C) is 0
．． 88d1. /g. Tg was 235°C.

(2) Preparation of conductive paste composition 100 parts by weight of the heat-resistant thermoplastic resin H obtained in (1) was dissolved in 1700 parts by weight of a mixed solvent of tetrahydrofuran/diethylene glycol dimethyl ether-6/4 (weight ratio), and silver powder was dissolved in this. 1,800 parts by weight and 200 parts by weight of granular vanadium pentoxide powder (hereinafter simply referred to as vanadium pentoxide powder) having an average particle size of 1 μ were added, and the mixture was shaken for 10 hours.
Ultrasonic dispersion was performed for 10 hours to produce a silver paste.

Example 9 (1) Heat-resistant thermoplastic resin I having the following repeating unit
Synthesis example of 4.4'
-dihydroxyphenyl-2,2-butane 1.2.1
g (0.05 mol), 0.3 g of tetrabutylammonium chloride as a phase transfer catalyst, and 100 g of a 5% aqueous sodium hydroxide solution were added and dissolved. Next, 5.08 g (0,025 mol) of terephthaloyl chloride and 5.08 g (0,02 mol) of isophthaloyl chloride were added.
A solution of 100 mβ of methylene chloride in which 5 mol) was dissolved was added to the vigorously stirred system. React for another 1 hour at room temperature,
The aqueous phase was discarded.

After washing with a large amount of water, the reaction solution was poured into a large amount of methanol to isolate the polymer, which was dried under reduced pressure at 180'C to obtain a heat-resistant thermoplastic resin (2). Reduced viscosity of this material (resin o
, 2g/dll dimethylformamide solution, 30°C) was measured and found to be 0.95 dfl/g. "rg
was 203°C.

(2) Preparation of conductive paste composition 11.00 parts by weight of the heat-resistant thermoplastic resin obtained in (1) is dissolved in 1700 parts by weight of dioxane, and 270 parts by weight of silver powder is dissolved in this.
0 parts by weight and 300 parts by weight of cupric oxide powder (hereinafter simply referred to as cupric oxide) having an average particle size of 1 μm were added, and the mixture was shaken for 1 hour.
After 0 hours, ultrasonic dispersion was performed for 10 hours to produce a silver paste.

Example 10 (1) Heat-resistant thermoplastic resin J having the following repeating unit
Synthesis Example In the synthesis example of heat-resistant thermoplastic resin I of Example 9, 4
,4'-dihydroxydiphenyl-22butane 12, Ig
(0,05 mol) instead of 22-bis(4-hydroxyphenyl)-hexafluorobroban 16°8 g (0
Heat-resistant thermoplastic resin J was obtained in the same manner except that 05 mol) was used.

The reduced viscosity of this product (resin 0.2 g/d dimethylformamide solution, 30''C) was 0.77 surface/g.

Tg was 190°C.

(2) Preparation of conductive paste composition 1,100 parts by weight of the heat-resistant thermoplastic resin obtained in (1) is dissolved in 1,000 parts by weight of diethylene glycol dimethyl ether, and 1,000 parts by weight of silver powder and 2 parts by weight of cupric oxide powder are dissolved therein.
After adding 50 parts by weight, shaking was performed for 10 hours and ultrasonic dispersion was performed for 10 hours to prepare a silver paste.

Example 11 4B= (1) Synthesis example of a heat-resistant thermoplastic resin having the following repeating unit A silver paste was prepared by carrying out the synthesis for 10 hours.

Example 12 (1) Synthesis example of heat-resistant thermoplastic resin having the following repeating units In the synthesis example of heat-resistant thermoplastic resin I of Example 9, 4
．． 4'-dihydroxyphenyl-2,2-butane12.
4゜4'-dihydroxy-3,3'5.5'-tetramethyldiphenyl-2 instead of 1 g (0.05 mol)
A heat-resistant thermoplastic resin K was obtained in the same manner except that 14.2 g (0.05 mol) of 2-propane was used. The reduced viscosity of this product (resin 0.2 g/a dimethylformamide solution, 30'C) is IIdI! ,/g. 'r
g was 230°C.

(2) Preparation of conductive paste composition 100 parts by weight of the heat-resistant thermoplastic resin K obtained in (1) is dissolved in 1000 parts by weight of dioxane, and 2100 parts by weight of silver powder is dissolved in this.
In the synthesis example of heat-resistant thermoplastic resin I of Example 9, 4.4'-dihydroxyphenyl-2, 4゜4'-dihydroxy-3,3',5.5' instead of 2-butane 12, Ig (0.05 mol)
-Tetramethyldiphenyl-2,2-propane 7.1g
(0,025 mol) and 4,4'-dihydroxy-33'
, 5.5'-tetramethyldiphenylsulfone7.
A heat-resistant thermoplastic resin was obtained in the same manner except that 65 g (0,025 mol) was used. Reduced viscosity of this material (resin 0.2 g/d1 dimethylformamide solution, 3
0'C) was 0.59a, 7g. Tg is 259
“It was C.

(2) Preparation of conductive paste composition 5,100 parts by weight of the heat-resistant thermoplastic resin obtained in (1) is dissolved in 1,000 parts by weight of a mixed solvent of tetrahydrofuran/diethylene glycol dimethyl ether-6/4 (weight ratio), and silver powder is dissolved in this. 1000 parts by weight and 100 parts by weight of vanadium pentoxide powder were added, followed by shaking for 10 hours and ultrasonic dispersion for 10 hours to prepare a silver paste.

Example 13 (1) Heat-resistant thermoplastic resin M having the following repeating unit
A heat-resistant thermoplastic resin M was obtained in the same manner except that the synthesis example was used. The reduced viscosity of this product (resin 0.2 g/d dimethylformamide solution, 30''C) was 0.66 di/g. Tg was 217°C.

(2) Preparation of conductive paste composition 100 parts by weight of the heat-resistant thermoplastic resin N obtained in (1) was dissolved in 1,700 parts by weight of diethylene glycol dimethyl ether, and 1,500 parts by weight of silver powder and 500 parts by weight of vanadium pentoxide powder were added thereto. Then, shaking was performed for 10 hours and ultrasonic dispersion was performed for 10 hours to prepare a silver paste.

Example 14 (1) Heat-resistant thermoplastic resin N having the following repeating unit
Synthesis Example In the synthesis example of the heat-resistant thermoplastic resin of Example 4, 44'-dihydroxy-3,3',5,5'-tetramethylphenyl-2,2-propane was used instead of 5.044 g of bisferrule A. 6,248 g In the synthesis example for heat-resistant thermoplastic resin in Example 1, 2.2-bis[4-
(4-aminophenoxy)phenyl]propane 8.2g
(0.02 mol) to 2.2-bis[1-(4-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane 10.36 g (0.02 mol)
4.06 g (0.02 mol) of isophthaloyl chloride was added to 2.03 g (0.01 mol) of isophthaloyl chloride.
mol) and terephthaloyl chloride 2.03g (0,0
A heat-resistant thermoplastic resin N was obtained in the same manner except that a mixture of 1 mol) was used. The reduced viscosity of this material (resin 0.
2g/d1 dimethylformamide solution, 30°C) is 1.
It was 0dIV and 7g. Tg was 240'C.

(2) Preparation of conductive paste composition 100 parts by weight of the heat-resistant thermoplastic resin N obtained in (1) is dissolved in 1,700 parts by weight of diethylene glycol dimethyl ether, and 1,500 parts by weight of silver powder and cuprous oxide with an average particle size of 2 μm are dissolved therein. 500 parts by weight of powder (hereinafter simply referred to as cuprous oxide powder) was added, followed by shaking for 10 hours and ultrasonic dispersion for 10 hours to prepare a silver paste.

Example 15 (1) Heat-resistant thermoplastic resin having the following repeating unit 0
Synthesis Example In the synthesis example of heat-resistant thermoplastic resin G of Example 7, 2
,2-bis(4-(4-aminophenoxy)phenyl)
2.2-bis(4-(4-aminophenoxy)phenyl)-1,1 in place of 8.2 g (0.02 mol) of propane
,1,3,3,3-hexafluoropropane 10.36
g (0.02 mol), 11.52 g of 22-bis(p-trimellitoxyphenyl)propanihydride
(0.02 mol), 5.5'-sulfonylbis(norbornane-2,3-dicarboxylic anhydride) 7.8
Heat-resistant thermoplastic resin 0 was obtained in the same manner except that 8 g (0.02 mol) was used. The reduced viscosity of this substance is 0
．． 6Tg which was 71di/g was 310'C.

(2) Preparation of conductive paste composition 0.100 parts by weight of the heat-resistant thermoplastic resin obtained in (1) is dissolved in 1,500 parts by weight of diethylene glycol dimethyl ether, and 1,200 parts by weight of silver powder and 800 parts by weight of cuprous oxide powder are dissolved therein. A silver paste was prepared by shaking for 10 hours and performing ultrasonic dispersion for 10 hours.

Comparative Example 1 (1) Heat-resistant thermoplastic resin P having the following repeating unit
Synthesis Example A heat-resistant thermoplastic resin P was obtained in the same manner as in Example 1, except that terephthaloyl chloride was used instead of isophthaloyl chloride.

The reduced viscosity of this material is 0.8041/g (0.2g/
dIN-methylpyrrolidone solution, 30°C).

A ζ paste was prepared by kneading the mixture for a while.

Comparative Example 4 As a binder, 100 parts by weight of a mixture of an epoxy resin [Epicoat 825 (oiled shell epoxy ■)] and a curing agent [phenol novolac H-1 (Meisho Kasei ■)] was dissolved in 400 parts by weight of butyl cellosolve. 1 s of silver powder
0 parts by weight and 200 parts by weight of vanadium pentoxide powder were added, and the mixture was kneaded for 2 hours in a grinder to prepare a paste.

The conductive paste compositions obtained in Examples and Comparative Examples,
Apply the cured product to a glass plate so that the film has a thickness of 50 μm,
The volume resistivity of the film when dried at 180°C for one hour is the first
Shown in Table and Table 2.

First, take 2 g of this film, add 10 g of deionized water, and leave it for 24 hours at 12 BiC and 2 atm (pressure tester test conditions), then measure the silver ion concentration in the water. Shown in Table and Table 2.

(Margin below) Tg was 247°C.

(2) Preparation of conductive base l-composition 100 parts by weight of the heat-resistant thermoplastic resin P obtained in (1) was added to N-
The mixture was dissolved in 1,500 parts by weight of methylpyrrolidone, 1,200 parts by weight of silver powder was added thereto, and the mixture was kneaded for 2 hours in a milling machine to prepare a silver paste.

Comparative Example 2 Heat-resistant thermoplastic resin 8100 obtained in Example 2
250 parts by weight of diethylene glycol dimethyl ether
0 parts by weight, 300 parts by weight of silver powder and 700 parts by weight of aluminum oxide powder were added, and the mixture was kneaded for 2 hours in a molding machine to prepare a base.

Comparative Example 3 As a binder, Tg102''C1 reduced viscosity (resin 0.
2g/a, dimethylformamide solution, 30”C) 1
．． 100 parts by weight of polymethyl methacrylate (2 di/g) was dissolved in 2500 parts by weight of n-butyl acetate, 2700 parts by weight of silver powder and 300 parts by weight of aluminum oxide powder were added thereto, and the mixture was heated at 2 o'clock in a sieve machine. Table Volume resistivity and silver ion outflow Table Volume resistivity and silver ion outflow (effects of the invention) The conductive paste composition according to the present invention has excellent heat resistance and mechanical strength, and has excellent heat resistance and mechanical strength. The strength of the conductive paste film is maintained even under high temperature and high humidity conditions, and because there is little silver ion leakage from the conductive paste film, it is possible to prevent short circuit failures due to migration.

The conductive paste composition of the present invention is useful as a conductive adhesive for electronic components, an electrode material, and a wiring conductor for wiring boards.

Claims (1)

[Claims] 1. 100 parts by weight of a heat-resistant thermoplastic resin, 300 to 5,500 parts by weight of a solvent capable of dissolving the resin, and an inorganic filler 350 consisting of a conductive filler and a metal oxide having ion adsorption ability. -3500 parts by weight of a conductive paste composition. 2. The conductive paste according to claim 1, wherein the metal oxide having ion adsorption ability is contained in an amount of 5 to 50% by weight of the inorganic filler consisting of the conductive filler and the metal oxide having ion adsorption ability. Composition. 3. The conductive paste composition according to claim 1 or 2, wherein the heat-resistant thermoplastic resin is a thermoplastic resin having a glass transition point of 150° C. or higher. 4. Claim 1, wherein the heat-resistant thermoplastic resin is at least one resin selected from the group consisting of aromatic polyamide, aromatic polyamideimide, aromatic polyesterimide, polyimide, aromatic polyester, and aromatic polyether.
, 2, 3 or 4. The conductive paste composition according to . 5. Aromatic polyamide has the general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1, R_2, R_3 and R_4 represent hydrogen, lower alkyl group, lower alkoxy group or halogen atom. , these may be the same or different, and X is -O-
, -S-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO
＿２−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, where R_5 and R_6 are hydrogen,
represents a lower alkyl group, trifluoromethyl group or phenyl group, which may be the same or different, Ar represents a m-phenylene group, p-phenylene group, diphenylene ether group or diphenylene sulfone group) 5. The conductive paste composition according to claim 4, which is an aromatic polyetheramide resin having repeating units. 6. Aromatic polyamideimide has the general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1, R_2, R_3, R_4 and X have the same meanings as in the above general formula (I) The conductive paste composition according to claim 4, which is an aromatic polyetheramide-imide resin having a repeating unit represented by the following. 7. Aromatic polyamideimide has the general formula (III)▲mathematical formula,
There are chemical formulas, tables, etc.▼(III) (In the formula, R_1' and R_3' are lower alkyl groups,
These may be the same or different, R_2' represents a lower alkyl group or a halogen atom, m, m' and m''
represents the number of substituents of R_1', R_2' and R_3', respectively, and is an integer from 0 to 4, and when m, m' and m'' are each 2 or more, multiple R_1', R_2' and R_3' may be the same or different, and
' represents -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the two X' may be the same or different, where R_4' and R_5' are hydrogen, lower alkyl group, trifluoro 5. The conductive paste composition according to claim 4, which is an aromatic polyamide-imide resin having a repeating unit represented by a methyl group or a phenyl group, which may be the same or different. 8. Aromatic polyamideimide has the general formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, R_1″, R_2″, R_3″ and R_4″ are lower alkyl groups, lower alkoxy groups, or The aromatic polyamide-imide resin according to claim 4, which has a repeating unit represented by a halogen atom, which may be the same or different, and X has the same meaning as in the general formula (I). Conductive paste composition. 9. Aromatic polyesterimide has general formula (V)▲mathematical formula,
There are chemical formulas, tables, etc.▼(V) (In the formula, R_1, R_2, R_3, R_4 and X have the same meanings as in the above general formula (I),
R_2″′, R_3″′ and R_4″′ are R_1, R_
2, R_3 and R_4 are the same groups, X'' is the same group as X, R_1, R_2, R_3, R_4, R_
1"', R_2"', R_3"' and R_4"' may be the same or different, and X and X" may be the same or different). The conductive paste composition according to claim 4, which is an imide resin. 10. The polyimide has the general formula (VI) ▲ Numerical formula, chemical formula, table, etc. ▼ (VI) (wherein, 2 excluding the group
5. The conductive resin according to claim 4, which is a polyimide resin having a repeating unit represented by (Y represents a tetravalent residue excluding a carboxyl group of an aliphatic or alicyclic tetracarboxylic acid). sex paste composition. 11. Aromatic polyester has the general formula (VII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VII) (In the formula, R_1, R_2, R_3, R_4 and X have the same meanings as in the above general formula (I). , Ar' is m-
The conductive paste composition according to claim 4, which is an aromatic polyester resin having a repeating unit represented by a phenylene group, a p-phenylene group, a diphenylene ether group, or a diphenylene sulfone group. 12. Aromatic polyether has the general formula (VIII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VIII) (In the formula, R_1, R_2, R_3, R_4 and X have the same meanings as in the above general formula (I) Yes, R_1″, R
_2″, R_3″ and R_4″ are R_1, R_2, R_
3 and R_4, X″ is the same group as X, R_1, R_2, R_3, R_4, R_1″, R
_2", R_3" and R_4" may be the same or different, and X and X" may be the same or different. Conductive paste composition. 13. The conductive paste according to claim 1, wherein the conductive filler is silver.