JPH06136300A - Conductive paste composition - Google Patents

Abstract

PURPOSE:To provide a conductive paste composition comprising an epoxy resin, conductive powder, a solvent and a polyamide silicon polymer produced from an aromatic polycarboxylic acid, a diaminosiloxane. etc., excellent in heat resistance and moisture resistance and giving coating films having low elasticity and high strength. CONSTITUTION:The conductive paste composition comprises (A) 100 pts.wt. of a polyamide silicon polymer produced by polycondensing an aromatic dicarboxylic acid (e.g. terephthalic acid) or its reactive derivative with a diamine such as a diaminosiloxane as an essential component or a polyamideimide silicon polymer produced by polycondensing an aromatic tricarboxylic acid or its reactive derivative with a diamine such as diaminosiloxane as an essential component, (B) 1-100 pts.wt. of an epoxy resin, (C) 100-2000 pts.wt. of conductive powder (e.g. active alumina), and (D) 100-3500 pts.wt. of an organic solvent (e.g. diethylene glycol dimethyl ether) are compounded with each other to provide the conductive paste excellent in heat resistance and moisture resistance and giving coating films having low elasticity and high strength.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive paste composition which is excellent in heat resistance and humidity resistance, has low elasticity, and forms a film having excellent coating strength.

[0002]

2. Description of the Related Art In the field of electronic parts, a conductive material such as a metal is kneaded with a resin to form a paste,
It is generally practiced to utilize this for the formation of electric circuits and electrodes. Silver is the most representative conductive material among them, but it is very likely to be ionized under the condition of being applied with a voltage under high humidity conditions, and a migration phenomenon of silver called migration is often observed. When the migration occurs, a short circuit occurs between the electrodes, which causes a decrease in moisture resistance reliability.

In order to solve the above problems, a conductive paste prepared by adding various metal oxides to a silver-based conductive paste has been proposed (for example, Japanese Patent Laid-Open No. 149356/55).
JP-A-53-35739, JP-A-54-
146450). Phenol-based, epoxy-based, and acrylic-based resin binders are used in these conductive paste compositions. All of these resin binders have a drawback that they are insufficient in heat resistance and inferior in reliability under high temperature and high humidity.

Therefore, recently, a conductive paste composition using a high heat resistant thermoplastic resin has been proposed (for example, JP-A-2-245070, JP-A-2-245071, and JP-A-3-35066). reference). However, this has a drawback that the adhesion to the substrate is low, and as a result, the coating film strength is reduced.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and is a highly heat-resistant conductive paste which can obtain a coating film having good adhesion to a substrate and strong film strength. Is provided.

[Means for Solving the Problems]

The conductive paste composition of the present invention is
Polyamide-silicon polymer obtained by polycondensing aromatic dicarboxylic acid or its reactive acid derivative and diaminosiloxane as essential components, or diamine having aromatic tricarboxylic acid or its reactive derivative and diaminosiloxane as essential components 100 parts by weight of a polyamide-imide silicon polymer obtained by polycondensing
Epoxy resin 1 to 100 parts by weight, conductive powder 100 to 2
000 parts by weight and 100 to 3500 parts by weight of an organic solvent.

Next, the conductive paste composition of the present invention will be described in detail. First, the polyamide silicone polymer and the polyamideimide silicone polymer will be described.

These polymers are obtained by polycondensation reaction of aromatic dicarboxylic acids or aromatic tricarboxylic acids or their reactive acid derivatives with diamines containing diaminosiloxane as an essential component.

As the diaminosiloxane (a) which is an essential component of the diamine, the following chemical formula 1 [general formula (I)]

[Chemical 1] (In the formula, Y ₁ represents a divalent hydrocarbon group, Y ₂ represents a monovalent hydrocarbon group, two Y ₁ may be the same or different, and a plurality of Y ₂ are the same as each other. However, they may be different, and m is preferably an integer of 1 or more). In the general formula (I), Y ₁ is preferably an alkylene group having 1 to 5 carbon atoms, a phenylene group or an alkyl-substituted phenylene group, and Y ₂ is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy. A group, a phenyl group or an alkyl-substituted phenyl group. In general formula (I), m is preferably 100 or less. If m is too large, the ratio of the amide bond and the imide bond in the obtained polymer decreases, and the heat resistance tends to decrease.

In the compound represented by the general formula (I),
When m is 6 or more, the resulting polyamide-silicone polymer or polyamide-imide silicon polymer has a low elastic modulus, and when m is 16 or more, the polymer has a low elastic modulus. In addition, the heat resistance is improved.

Examples of the diaminosiloxane represented by the general formula (I) include the following chemical formula 2 [general formula (1)] and chemical formula 3
There are compounds such as [general formula (2)], chemical formula 4 [general formula (3)], chemical formula 5 [general formula (4)], and chemical formula 6 [general formula (5)].

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6] In each of the above formulas, m is a number in the range of 1-100.

Among the diaminosiloxanes, in the above general formula (1), m is 1, those having an average of 10, those having an average of 20, those having an average of 38, and those having an average of 50 are respectively L
P-7100, X-22-161AS, X-22-16
1A, X-22-161B and X-22-161C (all are trade names of Shin-Etsu Chemical Co., Ltd.). These diaminosiloxanes may be used alone or in combination of two or more.

The (a) diaminosiloxane can be synthesized, for example, by the method shown in US Pat. No. 3,185,719.

Diaminosiloxane can effectively prevent a decrease in molecular weight and a decrease in heat resistance, and further, an ether compound such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether, and cyclohexanone, 4 From the viewpoint of good solubility in general-purpose low boiling point organic solvents such as alicyclic ketone compounds such as methylcyclohexanone, it is preferable to use 0.1 to 40 mol% of the total amount of diamine.

From the viewpoint of adhesiveness, heat resistance, transparency, and molecular weight of the produced compound, it is more preferable that the diaminosiloxane (a) is used in an amount of 0.2 to 15 mol% based on the total amount of diamines.

The diamine according to the present invention may be the above-mentioned (a).
The diamine that can be used in combination with the diaminosiloxane is not particularly limited, but the following (b) Chemical formula 7 [general formula (II)] or Chemical formula 9
The aromatic diamine represented by the general formula (III) is preferable.

[Chemical 7] In the general formula (II), R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom, and X is a chemical bond or —O—, —S.
-, - C (= O) -, - SO 2 -, - S (= O) - or in reduction 8 (a) a group of formula, (b) a group of formula represents (c) a group of formula, ( In the formula c), R ₅ and R ₆ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group.

[Chemical 8]

[Chemical 9] However, in the general formula (III), X ′ is —O— or
Wherein R ′ ₄ and R ′ ₅ in Formula 10 are each independently hydrogen, a lower alkyl group, a trifluoromethyl group,
Shows the trichloromethyl group or phenyl group, R _'1,
R is' ₂ and R _'3 are selected from lower alkyl group, a lower alkoxy group or a halogen, x, y and z each represent a number of substituents is an integer of 0 to 4, the two X' is may be the same or different, R when _'1, R' ₂ and R _'3 are a plurality bond respectively, in each, it may be the same or different.

[Chemical 10]

When the diaminosiloxane represented by the general formula (I) having m of 16 or more is used, (b) the aromatic diamine represented by the general formula (II) or the general formula (III) is used in combination. This is advantageous because it facilitates the reaction. A diaminosiloxane represented by the general formula (I), wherein m
When 6 or more are used, (b) the general formula (II)
Alternatively, the combined use of the aromatic diamine represented by the general formula (III) is advantageous because it is possible to simultaneously improve the properties of low elasticity and high heat resistance, which are generally contradictory properties.

Examples of the aromatic diamine having an ether bond represented by the general formula (II) include 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4
-Aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4-]
(4-Aminophenoxy) phenyl] butane, 2,2-
Bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4- (4- Aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- (4 -Aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-carbonylbis (p-phenyleneoxy) dianiline , 4,
4'-bis (4-aminophenoxy) biphenyl and the like. Of these, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferable.

Examples of the aromatic diamine represented by the general formula (III) include 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene and 1,4- Bis (4-aminophenoxy)
Benzene, 4,4 '-[1,3-phenylenebis (1-
Methylethylidene)] bisaniline, 4,4 ′-[1,
4-phenylenebis (1-methylethylidene)] bisaniline, 3,3 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline and the like.

(C) Examples of the aromatic diamine other than the above (a) and (b) include, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenyl ether, 4,4'-diamino-3,
3 ', 5,5'-tetramethyldiphenylmethane, 4,
4'-diamino-3,3 ', 5,5'-tetraethyldiphenyl ether, 2,2- [4,4'-diamino-
3,3 ', 5,5'-tetramethyldiphenyl] propane, metaphenylenediamine, paraphenylenediamine, 3,3'-diaminodiphenylsulfone and the like,
This can also be used together.

(D) Examples of diamines other than the above (a), (b) and (c) include, for example, piperazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylylenediamine, m-xylylenediamine. There are amines and aliphatic diamines such as 3-methylheptamethylenediamine, which can be used in combination.

The aromatic diamines (b) and (c) are preferably used in combination for improving heat resistance, and the total amount of (b) and (c) is 0.1 with respect to the total amount of diamine.
It is preferable to use it so as to be ˜99.9 mol%.

Next, an example will be shown for the composition of the preferable composition of the diamine. (1) Diaminosiloxane of (a) 0.1-10
0 mol% and diamine of (b), (c) or (d)
Formulated such that the total amount becomes 100 mol% at 99.9 to 0 mol%. (2) Diaminosiloxane of (a) 0.1-9
9.9 mol% (b) or (c) aromatic diamine
0.1 to 99.9 mol% and (d) diamine 9
Formulated such that the total amount becomes 100 mol% at 9.8 to 0 mol%. (3) Diaminosiloxane of (a) 0.1-40
Aromatic diamine 99.9 with mol% (b) or (c)
-60 mol% and (d) diamine 39.9 to 0 mol% so that the total amount becomes 100 mol%. (4) Diaminosiloxane of (a) 0.2 to 15
Aromatic diamine 99.8 with mol% (b) or (c)
˜85 mol% and (d) diamine 14.8 to 0 mol% so that the total amount becomes 100 mol%. (5) Diaminosiloxane of (a) 0.1-40
Aromatic diamine of mol% (b) 99.9 to 60 mol% Aromatic diamine of (c) 39.9 to 0 mol% and diamine of (d) 39.9 to 0 mol%, and the whole is 10.
Formulated to be 0 mol%.

The aromatic dicarboxylic acid in the present invention has two carboxyl groups bound to the aromatic nucleus, and the aromatic tricarboxylic acid has three carboxyl groups bound to the aromatic nucleus, and 3 Two of the carboxyl groups are attached to adjacent carbon atoms. Of course, this aromatic ring may have a hetero atom introduced, or the aromatic rings may be bonded to an alkylene group, oxygen, carbonyl group or the like. Further, a substituent such as an alkoxy group, an allyloxy group, an alkylamino group, or a halogen that does not participate in the condensation reaction may be introduced into the aromatic ring.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid-4,4 ', diphenyl sulfone dicarboxylic acid-
4,4 ', diphenyldicarboxylic acid-4,4', naphthalenedicarboxylic acid-1,5-, and the like can be mentioned, but terephthalic acid and isophthalic acid are preferable because they are easily available and inexpensive. In particular, the use of a mixture of terephthalic acid and isophthalic acid is desirable from the viewpoint of solubility of the resulting polymer. The reactive derivative of an aromatic dicarboxylic acid in the present invention means a dihalide of the above aromatic dicarboxylic acid, for example, dichloride, dibromide, diester or the like.

As the aromatic tricarboxylic acid, trimellitic acid, 3,3,4'-benzophenone tricarboxylic acid, 2,3,4'-diphenyltricarboxylic acid,
2,3,6-pyridinetricarboxylic acid, 3,4,4'-
Benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2'-methoxy-3,4,4'-diphenyl ether tricarboxylic acid, 2'-chlorobenzanilide-3,4,4'-tricarboxylic acid, etc. be able to. The reactive derivative of the aromatic tricarboxylic acid means an acid anhydride, halide, ester, amide, ammonium salt or the like of the aromatic dicarboxylic acid. Examples of these are trimellitic anhydride, trimellitic anhydride monochloride, 1,4-dicarboxy-3-N, N-dimethylcarbamoylbenzene, 1,
4-dicarbomethoxy-3-carboxybenzene, 1,
4-dicarboxy-3-carbophenoxybenzene,
2,6-dicarboxy-3-carbomethoxypyridine,
1,6-dicarboxy-5-carbamoylnaphthalene,
Examples thereof include ammonium salts composed of the above aromatic tricarboxylic acids and ammonia, dimethylamine, triethylamine and the like. Of these, trimellitic anhydride,
Trimellitic anhydride monochloride is preferable because it is easily available and inexpensive.

In the present invention, the aromatic dicarboxylic acid, aromatic tricarboxylic acid or reactive derivative thereof is preferably used in a total amount of 80 to 120 mol% based on the total amount of diamine of 100 mol%, particularly preferably 95 to 100 mol%. It is preferable to use 105 mol%. The highest molecular weight product is obtained when the total amount of these diamines is equimolar to the total amount. If the aromatic dicarboxylic acid, aromatic tricarboxylic acid or their reactive derivative is too much or too little with respect to the diamine, the molecular weight tends to decrease and mechanical strength, heat resistance and the like tend to decrease.

The epoxy resin used in the present invention is 1
A compound having two or more epoxy groups in a molecule is used, and examples thereof include bisphenol A diglycidyl ether, novolac resin polyglycidyl ether, cresol novolac resin polyglycidyl ether, polyhydric alcohol polyglycidyl ether, and polycarboxylic acid. There are polyglycidyl ethers, polyglycidyl amines, and aliphatic cyclic epoxy compounds.

These epoxy resins correspond to polyamide-silicon polymer or polyamide-imide silicone polymer 10
It is used in a proportion of 1 to 100 parts by weight with respect to 0 parts by weight. If the amount of the epoxy resin is too small, the adhesion to the substrate will be poor, and if it is too large, the stress at the time of heat curing will increase, which will cause cracks on the surface of the coating film, and the ease of relaxation of thermal shock tends to decrease.

The polyamide silicon polymer or polyamide imide silicon polymer obtained by polycondensing an aromatic dicarboxylic acid, aromatic tricarboxylic acid or a reactive derivative thereof and a diamine as described above is dimethylformamide 0.2. The reduced viscosity at 30 ° C. in the weight% solution is preferably 0.2 to 2.0 dl / g. If this reduced viscosity is too small, heat resistance and mechanical strength decrease,
If it is too large, the solubility in the solvent tends to decrease.

The conductive powder used in the present invention is
A metal having high conductivity such as silver, copper or nickel can be used, but silver powder is particularly preferable. Further, in order to prevent migration of the metal forming the conductive powder, particularly migration of silver, it is preferable to use a metal oxide having an ion adsorption ability in combination. Examples of such materials include activated alumina, alumina, zirconium oxide, synthetic zeolite, vanadium pentoxide, cuprous oxide, cupric oxide and the like.

These conductive powders are made of polyamide silicone polymer or polyamideimide silicone polymer 100.
It is blended in a ratio of 100 to 2000 parts by weight, preferably 700 to 1800 parts by weight with respect to parts by weight. If the blending amount of the conductive powder is less than 100 parts by weight, the conductivity is remarkably lowered, and if it exceeds 2000 parts by weight, the mechanical strength of the coating film is lowered and the functionality as the coating film is deteriorated.

Further, the metal oxide showing the ion adsorption capacity is
It is preferable to use 5 to 70% by weight, more preferably 30 to 60% by weight, based on the conductive powder. If the compounding amount of the metal oxide showing the ion adsorption capacity is less than 5% by weight,
The ability to adsorb silver ions is remarkably inferior, and if it exceeds 70% by weight, the conductivity is lowered. These metal oxides may be used alone or as a mixture of two or more kinds at any ratio.

Examples of the organic solvent in the present invention include acetamide, N, N-dimethylacetamide, N
-Methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, dimethyl sulfoxide, nitrobenzene, polar solvents such as glycol carbonate, 1,4-dioxane, tetrahydrofuran,
Ether solvents such as 1,2-dimethoxyethane, ethylene glycol ether compounds such as diethylene glycol dimethyl ether and ethylene glycol methyl ether acetate, propylene glycol methyl ether,
Examples thereof include propylene glycol ether compounds such as propylene glycol methyl ether acetate, and alicyclic ketone compounds such as 2-cyclohexanone and 4-methyl-2-cyclohexanone. These may be used alone or in combination of two or more.

The organic solvent is used in the range of 100 to 3500 parts by weight, preferably 200 to 1500 parts by weight, based on 100 parts by weight of the polyamide silicon polymer or the polyamide imide silicon polymer.

If the amount of the above organic solvent used is less than 100 parts by weight, the ratio of the solid content is high, so that the coating property deteriorates and it becomes difficult to keep the thickness of the coating surface constant. Since the viscosity of the resin is remarkably lowered and the conductive powder is apt to settle, the ability to form a coating film is remarkably inferior when formed into a paste.

The conductive paste composition of the present invention comprises, for example, a polyamide-silicon polymer obtained by polycondensing (A) an aromatic dicarboxylic acid or a reactive acid derivative thereof and a diamine containing diaminosiloxane as an essential component, or A polymer obtained by dissolving 100 parts by weight of a polyamideimide silicone polymer obtained by polycondensing an aromatic tricarboxylic acid or its reactive derivative and a diamine containing diaminosiloxane as an essential component in 100 to 3500 parts by weight of an organic solvent. Add 1 to 100 parts by weight of (B) epoxy resin, 100 to 2000 parts by weight of (C) conductive powder and optionally a metal oxide to the varnish, and mix and knead with a rafting machine, three rolls, ball mill, etc. It is particularly preferable to manufacture by dispersing conductive powder in the polymer varnish by a method such as .

The conductive paste composition of the present invention may contain a curing agent for epoxy resin and a curing accelerator. Examples of the curing agent include polycarboxylic acid anhydrides, polyamines, novolac resins, polyvinylphenol resins or salts thereof, diazabicycloundecene (DB
U) and tertiary amines such as imidazole or salts thereof, dicyandiamide, and hydrazide compounds. Examples of the curing accelerator include phenol compounds, tertiary amines, quaternary ammonium salts, quaternary phosphonium salts, metal alkoxides, organic acid metal salts, and Lewis acids.

The curing agent is preferably used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the epoxy resin, and the curing accelerator is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the epoxy resin. It is preferable.

The conductive paste composition of the present invention may contain a coupling agent, and may be used by adding it during mixing and kneading in the above-mentioned production method. As the coupling agent, a silane coupling agent or a titanate coupling agent can be used, and is added in an amount of 30 parts by weight or less relative to 100 parts by weight of the above-mentioned polyamide silicon polymer or polyamide imide silicon polymer.

The conductive paste composition of the present invention comprises
It includes a polyamide-silicon polymer or a polyamide-imide silicone polymer which is a heat-resistant thermoplastic resin. Since the polyamide-silicone polymer or the polyamide-imide-silicone polymer is soluble in a solvent, it can be easily dried to form a coating film by being heated and dried without being accompanied by a curing reaction. Therefore, deformation due to internal stress due to curing shrinkage does not occur, and it is suitable as a material for forming a coating film on the semiconductor surface. The conductive paste composition in the present invention,
By including an epoxy resin which is a thermosetting resin, it is possible to improve the adhesion to the base material.

[0042]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention.

Synthesis Example 1 As a diamine in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube, as a diamine under a nitrogen gas atmosphere.
2-bis [4- (4-aminophenoxy) phenyl] propane 65.6 g (160 mmol)

[Chemical 11] 36 g (40 mmol) of diaminosiloxane of
It was dissolved in 335 g of diethylene glycol dimethyl ether. The solution was cooled to -10 ° C, and at this temperature 40.6 g (200 mmol) of isophthalic acid dichloride was added.
Addition was done so that the temperature did not exceed -5 ° C. Then, 23.2 g of propylene oxide was added, 96 g of diethylene glycol dimethyl ether was added, and stirring was continued at room temperature for 3 hours. The polymer was isolated by pouring the reaction solution into methanol. After drying this, it was again dissolved in dimethylformamide, and this was put into methanol to purify the polyamide-silicon polymer.

Synthesis Example 2 As a diamine in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube, as a diamine,
2-bis [4- (4-aminophenoxy) phenyl] propane 174.3 g (425 mmol)

[Chemical 12] 225 g (75 mmol) (85 mol% / 15 mol% in terms of molar ratio) of the diaminosiloxane of was added and dissolved in 1177 g of diethylene glycol dimethyl ether. This solution was cooled to -10 ° C, and 101.5 g (500 mmol) of isophthalic acid dichloride was added at a temperature of -5 ° C at this temperature.
Was added so as not to exceed the value. After the addition, 87 g of propylene oxide was added, and stirring was continued at room temperature for 3 hours. When the viscosity of the reaction solution increased and the solution became transparent, 841 g of diethylene glycol dimethyl ether was added, and after stirring for another 1 hour, The obtained reaction liquid was put into a large amount of a mixed solvent of n-hexane / methanol = 1/1 (weight ratio) to isolate the polymer. After drying it,
It was dissolved in N, N-dimethylformamide, poured into methanol to purify the polyamide-silicon polymer, and dried under reduced pressure.

Synthesis Example 3 As a diamine in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube, as a diamine under a nitrogen gas atmosphere.
2-bis [4- (4-aminophenoxy) phenyl] propane 174.3 g (425 mmol)

[Chemical 13] 225 g (75 mmol) of diaminosiloxane of 1 was added, and 1177 g of diethylene glycol dimethyl ether was added.
Dissolved in. This solution was cooled to -10 ° C, and at this temperature, 105.3 g of trimellitic anhydride monochloride (5
00 mmol) was added so that the temperature did not exceed -5 ° C. After the addition, 87 g of propylene oxide was added, and stirring was continued at room temperature for 3 hours. When the viscosity of the reaction solution increased and the solution became transparent, 841 g of diethylene glycol dimethyl ether was added, and after stirring for another 1 hour, Add acetic anhydride 128g and pyridine 64g,
Stirring was continued overnight at 0 ° C. The obtained reaction liquid was put into a large amount of a mixed solvent of n-hexane / methanol = 1/1 (weight ratio) to isolate the polymer. After drying it,
It is dissolved in N, N-dimethylformamide and poured into methanol to purify the polyamide-imide silicon polymer,
It was dried under reduced pressure.

Synthesis Example 4 Polyamide polymer according to Synthesis Example 1 except that the diaminosiloxane of Synthesis Example 1 was excluded and 2,2-bis [4- (4-aminophenoxy) phenyl] propane was changed to 100 mol%. Was manufactured.

Examples 1 to 3 100 parts by weight of the polyamide-silicon polymer obtained in Synthesis Example 1 was dissolved in 680 parts by weight of diethylene glycol dimethyl ether to form a varnish, and an epoxy resin (Epocoat 828, Yuka Shell Epoxy Chemical Co., Ltd. ) 9
5 parts by weight and a curing agent (Curesol 2MZ-AZINE,
A mixture with 5 parts by weight of Shikoku Kasei Kogyo Co., Ltd. (hereinafter referred to as an epoxy resin mixture) was added in a compounding amount shown in Table 1. In addition, flaky silver powder (“TC
G1 ") is added in an amount of 540 parts by weight, and further, 360 parts by weight of cuprous oxide (manufactured by Mitsui Mining & Smelting Co., Ltd.) having an average particle size of 2 μm is added, 3
A kneading roll was used to prepare a conductive paste composition.
After defoaming the obtained conductive paste composition, it was thinly spread on a glass plate and dried at 180 ° C. for 1 hour to obtain a cured product. The volume resistivity of the obtained cured product was measured. The conductive paste composition was thinly spread on a Teflon plate and dried under the same drying conditions as above to obtain a film-shaped cured product. The obtained cured product was cut into a certain size and the film strength was measured. Furthermore, after defoaming the conductive paste composition, it is packed in a 50 ml syringe,
A conductive carbon paste was applied on the surface, and the paste was dropped onto a glass plate (hereinafter referred to as carbon glass), a ceramic plate, a gold plate, and an aluminum plate so that the diameter was 5 mm and the thickness was 30 to 100 μm. This was dried under the same drying conditions as above to obtain a cured product. A jig was attached to this cured product using an adhesive, and the adhesion strength was measured using a tensile test air. The results of the characteristic evaluations obtained by these measurements are shown in Table 2.

Example 4 A paste was prepared according to Example 1 except that the polyamide silicon polymer obtained in Synthesis Example 2 was used. The characteristic evaluation results are shown in Table 2.

Example 5 A paste was prepared according to Example 1 except that the polyamide-imide silicon polymer obtained in Synthesis Example 3 was used. The characteristic evaluation results are shown in Table 2.

Comparative Example 1 Example 1 except that no epoxy resin mixture was added.
A conductive paste composition was prepared in the same manner as in. Table 2 shows the evaluation results of the characteristics.

Comparative Example 2 A conductive paste composition was prepared in the same manner as in Example 1 except that the amount of the epoxy resin mixture used was 150 parts by weight. Table 2 shows the evaluation results of the characteristics.

Comparative Example 3 A conductive paste composition was prepared in the same manner as in Example 3 except that the amount of the epoxy resin mixture used was 100 parts by weight. Table 2 shows the evaluation results of the characteristics. Comparative Example 4 A paste was prepared according to Example 3 except that the polyamideimide silicon polymer obtained in Synthesis Example 4 was used and the epoxy resin mixture was not added. The characteristic evaluation results are shown in Table 2.

[0053]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Composition (unit: parts by weight) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Embodiment 1 Embodiment 2 Embodiment 3 ────── ─────────────────────────────── (1) Poly 100 100 100 amide silicon polymer synthesized in Synthesis Example 1 (2 ) Epoxy resin mixture 10 40 80 (3) Conductive powder 900 900 900 900 (4) Organic solvent 680 680 680 ━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━

[0054]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 Specific characteristics Evaluation results ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Volume resistivity Dynamic elastic modulus Cohesion strength (Ω ・ cm ² ) (Kgf / mm ² ) (Kgf / cm ² ) Carbon Cerami Gold Aluminum plate × 10 ^-6 Glass plate ───────────────────────── ──────────── Example 1 4 290 21.9 32.2 15.6 18.0 Example 2 6 430 30.3 40 <28.9 30.0 Example 3 9 680 40 <40 <40 <40 <Example 4 2 230 18.2 27.9 19.3 20.3 Example 5 4 280 25.7 35.2 18.8 12.2 Comparative Example 1 2 190 15.3 22.5 2.3 1.2 Comparative example 2 10 970 4 <40 <40 <40 <Comparative Example 3 3 1130 40 <40 <40 <40 <Comparative Example 4 2 820 26.0 27.0 3.5 5.6 ━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━

[0055]

The conductive paste composition according to the first aspect of the invention has excellent adhesion to a substrate, and the cured product thereof exhibits high heat and humidity resistance, low elasticity, and excellent thermal stress relaxation.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Morinaga 14th Goi South Coast, Ichihara City, Chiba Hitachi Chemical Co., Ltd. Goi Factory

Claims (1)

[Claims] 1. A polyamide-silicon polymer obtained by polycondensing an aromatic dicarboxylic acid or a reactive acid derivative thereof and a diamine containing diaminosiloxane as an essential component, or an aromatic tricarboxylic acid or a reactive derivative thereof and diaminosiloxane. Polyamidoimide silicon polymer 1 obtained by polycondensing diamine as an essential component
00 parts by weight, epoxy resin 1 to 100 parts by weight, conductive powder 100 to 2000 parts by weight and organic solvent 100 to 350
A conductive paste composition containing 0 part by weight.