JPH06116517A - Electrically conductive paste composition and its production - Google Patents

Abstract

PURPOSE:To obtain an electrically conductive paste composition free from sagging after application, giving a coating film having excellent heat and moisture resistance, film strength and uniformity and useful for electronic parts, etc., by mixing specific resin varnish with electrically conductive powder and organic solvent at specific ratios. CONSTITUTION:The composition is produced by dispersing (A) 100-2,000 pts.wt. of electrically conductive powder such as silver powder in (B) a resin varnish produced by dissolving (i) 100 pts.wt. of a polyamide silicone polymer obtained by the polycondensation of an aromatic dicarboxylic acid (or its reactive acid derivative) with a diamine containing a diaminosiloxane as an essential component or a polyamide imide silicone polymer obtained by the polycondensation of an aromatic tricarboxylic acid (or its reactive derivative) with a diamine containing a diaminosiloxane as an essential component in (ii) 90-330 pts.wt. of an organic solvent having a boiling point of >=130 deg.C (e.g. N-methyl-2- pyrrolidone) and adding (C) 5-1,750 pts.wt. of an organic solvent having a boiling point of 50-130 deg.C (e.g. acetone) to the dispersion.

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 no sagging of the paste after coating, and is uniform and has excellent coating strength, and a method for producing the same.

[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-3-350).
66 publication). However, when this is applied to the electrode of a tantalum capacitor, if it is left on the tantalum element after coating, sagging of the paste is seen from the element surface, and the coating thickness after curing becomes uneven, resulting in a coating strength It had the drawback of falling.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems by providing a coating film which prevents sagging after application of a paste and has a uniform film thickness after application and a strong film strength. The present invention provides a high heat resistant conductive paste and a method for producing the same.

[0005]

As a result of various studies to solve the above problems, the inventors of the present invention have found that the composition of the organic solvent to be used has a high volatility as an organic solvent as a part of the organic solvent. By adding, to accelerate the drying property after coating,
It has been found that sagging can be prevented, and as a result, a uniform coating film can be obtained, and the present invention has been completed.

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
100 to 2000 parts by weight of conductive powder, 90 to 3300 parts by weight of organic solvent having a boiling point of 130 ° C or higher, and 50 ° C or higher 1
It contains 5 to 1750 parts by weight of an organic solvent having a boiling point range of less than 30 ° C.

Next, the conductive paste composition of the present invention will be described in detail. First, the (A) polyamide-silicone polymer and polyamide-imide 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 polyamide silicon polymer or polyamide imide silicon polymer obtained by polycondensing an aromatic dicarboxylic acid, an 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 ability 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.

An organic solvent having a boiling point of 130 ° C. or higher, preferably 150 ° C. or higher is used for dissolving the polyamide silicon polymer or the polyamide imide silicon polymer. Examples of such a solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide,
Polar solvents such as N, N-diethylformamide, dimethylsulfoxide, nitrobenzene and glycol carbonate, ethylene glycol ether compounds such as diethylene glycol dimethyl ether and ethylene glycol methyl ether acetate, propylene glycols such as propylene glycol methyl ether and propylene glycol methyl ether acetate Ether compound, 2
Examples thereof include alicyclic ketone compounds such as -cyclohexanone and 4-methyl-2-cyclohexanone, which may be used alone or in combination of two or more kinds.

The organic solvent is used in the range of 90 to 3300 parts by weight, preferably 400 to 1200 parts by weight, based on 100 parts by weight of the polyamide silicone polymer or the polyamideimide silicone polymer.

If the amount of the organic solvent used is less than 90 parts by weight, the resin is difficult to dissolve, and if it exceeds 3300 parts by weight, the viscosity of the resin is remarkably reduced and the conductive powder tends to settle. The film-forming ability is extremely poor.

In order to accelerate the drying property of the coating film and prevent sagging of the coating film, use of an organic solvent having a boiling point of 50 ° C. or higher and lower than 130 ° C., preferably 50 to 120 ° C. (hereinafter referred to as low boiling point solvent) Is mandatory. Examples of such an organic solvent include ketone solvents such as acetone, methyl ethyl ketone and diethyl ketone, ester solvents such as methyl acetate, ethyl acetate and acetic acid-n-butyl, alcohol solvents such as methanol, ethanol, isopropanol and butanol. , 1,4-dioxane, tetrahydrofuran, 1,
Examples thereof include ether solvents such as 2-dimethoxyethane. Further, the low boiling point solvent needs to be mixed with a solvent that dissolves the polyamide silicon polymer or the polyamide imide silicon polymer.

The amount of the low boiling point solvent used is such that the polyamide silicon polymer or the polyamide imide silicon polymer 10 is used.
It is used in the range of 5 to 1750 parts by weight, preferably 10 to 400 parts by weight, based on 0 parts by weight. If the amount of these solvents used is less than 5 parts by weight, the sagging of the coating film at the time of applying the paste is significant, a uniform film thickness cannot be obtained, and the strength of the obtained coating film decreases. On the other hand, the amount of solvent added is 17
If it exceeds 50 parts by weight, on the contrary, the flowability of the coating film deteriorates,
The coating film becomes unnecessarily thick and causes voids during drying.

If the boiling point of the solvent added for preventing sagging of the coating film is less than 50 ° C., drying at room temperature is remarkable, and the surface of the coating material sticks when the paste is applied, which is not preferable because the workability is significantly reduced. On the other hand, when the boiling point of the solvent is 130 ° C. or higher, the drying property at the time of applying the paste is poor, the solvent sags after the application, and a uniform coating film cannot be obtained.

Other low boiling solvents include hydrocarbon solvents such as hexane and benzene, halogenated hydrocarbon solvents such as carbon tetrachloride and chloroform, and these are polyamide silicon polymers or polyamide imide silicon. It is not preferable because it does not mix with the solvent that dissolves the polymer and causes precipitation of the polymer.

The conductive paste composition of the present invention comprises, for example, a polyamide silicon polymer obtained by polycondensing (A) an aromatic dicarboxylic acid or its reactive acid derivative and a diamine containing diaminosiloxane as an essential component, or An organic solvent having a boiling point of 130 ° C. or higher for dissolving 100 parts by weight of a polyamideimide silicone polymer obtained by polycondensing an aromatic tricarboxylic acid or a reactive derivative thereof and a diamine having diaminosiloxane as an essential component 100 to 2000 parts by weight of the conductive powder (B) and, if necessary, a metal oxide are added to a polymer varnish dissolved in 90 to 3300 parts, and a raker machine, three rolls,
It is particularly preferable that the conductive varnish is dispersed in the polymer varnish by a method such as mixing and kneading with a ball mill or the like, and then (C) the low boiling point solvent is added in an amount of 5 to 1750 parts by weight. The low boiling point solvent has a boiling point of 130 ° C.
Although it may be used together with the above organic solvent, it is preferable to cool it during the mixing and kneading so that the low boiling point solvent does not evaporate.

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
A conductive powder is dispersed in an organic solvent solution of 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. That is, the conductive paste composition in the present invention can prevent sagging at the time of application by adding a highly volatile solvent, and can form a uniform and strong conductive coating film having a uniform strength. An excellent coating film can be obtained. Since the cured product has high heat resistance and low elasticity, it is excellent in thermal stress relaxation. Therefore, it is suitable as a conductive coating film for semiconductor products to which heat stress is applied. In addition, since the curing shrinkage is smaller than that of the epoxy resin that has been conventionally used as a conductive paste, there is no stress on the base material, and the miniaturization of electronic parts,
It can be made thin enough.

[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 540 parts by weight of flake silver powder ("TCG1" manufactured by Tokuriki Kagaku Co., Ltd.). Further, 360 parts by weight of cuprous oxide (manufactured by Mitsui Mining & Smelting Co., Ltd.) having an average particle diameter of 2 μm was added, and the mixture was kneaded with a three-roll mill to prepare a conductive paste composition. To this, methyl ethyl ketone was added in different amounts as shown in Table 1. After defoaming the obtained composition, a certain amount of paste was dropped on a glass plate, the glass plate was tilted at 45 °, and the flowability of the paste after a certain period of time was measured. A similar sample 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. Further, the uniformity of the coating film of the conductive paste composition was measured by the following method. That is, after defoaming the sample, a 5 mm square tantalum element was dipped in the paste, pulled up, and left for a certain period of time. Then, it dried at 180 degreeC for 1 hour, and measured the coating film thickness of the bottom face and the side face. Further, in order to measure the strength of the coating film, the cured product was attached to a ceramic substrate with an adhesive and the peel strength was measured with a tensile tester. The results are shown in Table 1.

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 1.

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 1.

Comparative Example 1 Example 1 except that methyl ethyl ketone was not added.
A conductive paste composition was prepared in the same manner as in. Table 1 shows the evaluation results of the characteristics.

Comparative Example 2 A conductive paste composition was prepared in the same manner as in Example 3 except that n-hexane was added instead of methyl ethyl ketone. Table 1 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 carbon tetrachloride was added instead of methyl ethyl ketone. Table 1 shows the evaluation results of the characteristics.

[0053]

[Table 1]

[0054]

The conductive paste composition according to claim 1, claim 2 or claim 3 can form a uniform and strong conductive coating film without sagging during coating.
The conductive paste composition according to claim 1 can be easily manufactured by the manufacturing method according to claim 4.

Claims (4)

[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
A conductive material containing 00 parts by weight, 100 to 2000 parts by weight of conductive powder, 90 to 3300 parts by weight of an organic solvent having a boiling point of 130 ° C. or more, and 5 to 1750 parts by weight of an organic solvent having a boiling point of 50 ° C. or more and less than 130 ° C. Paste composition. 2. The organic solvent having a boiling point in the range of 50 ° C. to 130 ° C. is a ketone organic solvent, an alcohol organic solvent,
The conductive paste composition according to claim 1, which comprises an ester organic solvent or an ether organic solvent. 3. The boiling point of the organic solvent is 50 ° C. to 130 ° C.
The conductive paste composition according to claim 1, wherein the content of the organic solvent in the range is 5 to 50% by weight, and the organic solvent having a boiling point of 130 ° C or higher is 50 to 95% by weight. 4. 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
100 parts by weight of an organic solvent having a boiling point of 130 ° C. or higher 90-330
Conductive powder 10 is added to resin varnish dissolved in 0 parts by weight.
Disperse 0 to 2000 parts by weight, and have a boiling point of 50 ° C or higher 1
A method for producing a conductive paste composition, which comprises adding 5 to 1750 parts by weight of an organic solvent having a temperature lower than 30 ° C.