JPS58188002A - Printing type electroconductive paste - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a baking type paste containing nickel as a component, and more particularly, the present invention relates to a baking type paste containing nickel, and more particularly, the present invention relates to a baking type paste containing nickel as a component, and more particularly, to ceramic conductors such as wiring, terminals, etc. inside or outside of a multilayer ceramic circuit housing. The present invention relates to a baking type conductive paste suitable for forming by co-firing with a green sheet.

In order to increase the degree of integration of multilayer ceramic circuit devices, thick film capacitors, thick film resistors, etc. have been formed on the protruding surface of the multilayer ceramic body. Conventionally, the conductor of such a multi-layer Selancek circuit cover has been formed from a baking-type conductive paste (70''N) containing palladium (30%) as a main component.

However, since the silver-palladium paste also contains palladium t-30%, which has a high specific resistance, when it was sintered into a conductor, the sheet resistance was as high as 02.5 μΩ. Furthermore, silver palladium paste was expensive.

For this reason, attempts have been made to form an electrode using a paste of a base metal such as nickel. However, it has been impossible to form a conductor having the desired characteristics t- by simply making a paste of nickel powder. That is, it is desirable that the paste for forming the internal and external conductors of the multilayer ceramic construction circuit i* satisfies the following conditions.

111 The firing temperature of general-purpose warm body paste for forming thick film capacitors is approximately 850C to 1000C, and the firing temperature of resistance paste for forming film resistors is approximately 700C to 800C, so conductive It is possible to set the firing temperature of the paste to about 1100 to 1400C.

(21 conductive paste was fired at 1100t:' to 1400C, and 10001:l' in a trapped atmosphere of g and 100 g (m atmosphere) to form film capacitors, thick film resistors, etc.
The resistivity of the conductor is small even after heat treatment.

131 Even if the same firing and heat treatment as 12+ is done,
The tensile force g1 degree of the conductor shall be t kg/sit" or more.

However, a conductive paste containing nickel as a main component that satisfies the above conditions does not yet exist.

Therefore, an object of the present invention is to provide a baking type conductive paste that satisfies the above conditions.

The invention No. 12 of the present application for achieving the above object is as follows:
Nickel powder of 70-98% and manganese powder is Mn.
Powder of manganese or manganese compound having a weight of 0.05 to 29% by weight and 0.1 to 201i1%
glass frit, 1 the nickel powder and the Mn
The present invention relates to a baking-type conductive paste characterized in that it contains Q and the glass frit in a total amount of 100% by weight, and also contains an excessive amount of vehicle.

According to the above invention, the stiffness of mangai or this compound is 25μΩm or less, and the tensile strength is 1kg/m at 9M.
It is possible to provide a conductive paste that can hold the above-mentioned conductors.

The second invention of the present application further adds nickel silicide or zirconium silicide to the paste of the 111th invention, so that the resistivity does not increase even when heat treatment is performed at 1050 t:' in an air atmosphere. This is what I did.

Next, embodiments of the present invention will be described.

Example 1 Ni powder with an average particle size of lOμ, MnU powder wood with an average particle size of 5μ, average particle size of 3 p no 8rU -8i0. - PBU-based glass frit (1000C per piece) was mixed with a pestle in the proportions shown in Table 1, and this mixture was 100 weight 1 fl SK to [
, -C ethyl cell a-6, and α-terpineol 33 were added as a vehicle and kneaded with a 3-stage roll and 2 rolls to prepare conductive paste samples, respectively.

Next KAJ, 0. 50 parts by weight of powder, 8i0. @end 20 weight 1
5 parts of OJ powder, 9 parts of Li, 0 parts of powder lVi and 4 parts of MgO powder, a binder consisting of a water-soluble acrylic acid ester polymer, glycerin, phosphate phosphate and water were added, respectively. A slip was prepared by mixing in a ball mill, and a green sheet with a thickness of 50 μm was prepared using a doctor blade method after degassing. After drying, it was punched out into a rectangular shape using a press.

The conductive paste described above was applied to this paste using a 280-mesh screen in the pattern shown in Figure 1, dried at 125C for 10 minutes, stacked in four sheets and heated in a hot press, and then placed in an air atmosphere. The binder was blown off by heat treatment at 0900C, and the mixture was heated in an atmosphere of (98°596)+'l (1,5%) for 12001 hours, and then heated in an atmosphere of 1.5%.
Heat treatment at 100OC for 30 minutes in air was repeated 5 times,
A sample consisting of the porcelain Il+ and the conductor (2) shown in FIGS. 1 and 2 was prepared.

Next, the resistance value of the conductor (2) of each layer between 2a and 2b (width 0.2mm, thickness 15μ, length 20M) is measured with a resistance bridge of 61
11 f! When the average resistivity (ρ) was determined using riJIL, the results shown in Table 1 were returned. Note that the resistance of the inner layer was measured using a previously provided through hole (not shown).

In addition, the same green sheet as above was punched into a square shape,
Print the above-mentioned fathom paste in the center in the same way,
The entire sample was made by firing in the same manner as above, consisting of the turnout (3) and the conductor (4) as shown in Figures 3 and 4. After sintering, the conductor (41 and As shown in the figure, the ring-shaped part of the 0.6-inch steel wire (5) is fixed with 30 mg of solder (61), and the tensile strength (
When I5 was measured, the results shown in Table 1 were obtained. In addition, in Tables 1 to 6, the measurement samples of resistivity ρ and the tensile strength &T
This is a different sample from the measurement sample, but since the porcelain and conductor are the same, the same sample No. 11 is assigned and shown in the same column.

#! Table 1 As is clear from Table 1, 1Mn0 is 0.05 to 29.
By adding within the range of 9% by weight, it becomes possible to form 11&, that is, a conductive T-porcelain with P of 25 μΩ or less and T of 1 kg/μ or more. That is, conventional ill/
It is possible to obtain a conductor with a resistivity significantly lower than that of a radium electrode (62.5 μΩ3).

Note that if MnO is less than 0.05% by weight, oxidation of the Ni particles cannot be prevented, and the tensile strength T becomes less than 1 kg/12.

Moreover, when MnO exceeds 29.9% by weight, the resistivity decreases to 25% by weight.
Exceeds μΩ3i. Therefore, Mn0i0.05~29.9
It is desirable that the content be in the range of weight t%.

Furthermore, since the glass frit content is less than 0.1% by weight, it is desirable that the glass frit content be in the range of O01 to 20% by weight.

Therefore, sample number 1, 10.14 is outside the scope of the present invention.

Example 2 IJI except that the MnU powder in Example 1 was changed to Mn powder.
[When a paste having the composition shown in Table 2 was prepared exactly as in Example 1 and the same measurements as in Example 1 were carried out, the results shown in Table 2 were obtained.

So, there are no nitrous swords or young rice, and it becomes 1 kg/1 kg,
20] [When exceeding violet%, ρ exceeds 25 μΩclR′t−.

ill As is clear from Table 2 of the AA table, even if Mn powder is used, Mn
The same effects as U powder can be obtained. The preferred range of Mn is 0.04 to 24.83% by weight, and if aX is added to iMnU, it falls within the range of 0.05 to 29.9% by weight.

In Table 2, sample number q15.24.26 is outside the scope of the present invention.

Example 3 Ni powder with an average particle size of lμ was used instead of the Ni powder with lOμ in Example 1, and PbU was used as glass 7 liters.
-HaO-SiO, based glass powder (melting point 800C)
A paste having the composition shown in the %3 table was prepared in the same manner as in Example 1, except that 10% was used, and the same measurements were carried out.The results in Table 3 were superior.

As is clear from Table 3, the same effects as in Example 1 can be obtained even if the particle size of the NI powder is changed or the grain size of the glass frit is changed.

In Table 3, samples numbered 29, 37.39 are outside the scope of the present invention.

Example 4 Example 3 and 4 were used except that MnOH powder was used instead of the MnL powder in Example 3, and paste T- was made. ρ and Tft were determined, and the results shown in Table 4 were obtained. was gotten.

Table 4 As is clear from Table 4, even if MnU is used, the same effect 1 as in Examples 1 to 3 can be obtained. The preferred range of MnO is this Mn @ 1kMn
It is 0.05 to 29.9% for OK warriors. Furthermore, sample number 41.4B in Table 4 is outside the scope of the present invention.

Example 5 Ni, MnO, and glass frit in Example IK were used as generated components, and the average particle size was 1 for 100 parts of the main components.
The entire paste was prepared in the same manner as in Example 1 by adding nickel silicide of 0μ as shown in Table 5, and ρ, T
When t-611 was added, the results in Table 5 were superior. However, the heat treatment in a total atmosphere was performed at 100 QC in Example 1.
This process was repeated 5 times for 30 minutes at 1050C, which is 50C higher than the original temperature.

Table 5 (2) Table 5 (6) Table 5 0 As is clear from Table 5, Ni8i is 0.05
If added in the range of ~25 bundles, 10
Even when heat treatment is performed for 50 tl', ρ can be kept at a low value. This is because NiS reacts with oxygen and decomposes to prevent oxidation of Ni particles. However, 0.1
If the amount is less than 1 part by weight, the addition has no effect.

Moreover, if the weight exceeds 25 layers, the sinterability will be poor and a dense conductor will not be excellent. Therefore, the preferred # of Ni8i! The range is 0.05 to 25 parts by weight. For this reason, the fifth
In the table, sample numbers 49-54.60, 66.72.78.
84.85 to 90.96 is outside the scope of the present invention. Also, regarding the sinterability, the measurement of ρ and T was not possible.

Example 6 A paste was prepared in the same manner as in Example 5 by adding ZrH (zirconium chloride) as shown in Table 1iI6 instead of NiSi in Example 5, and adding ρ and T in the same manner.
! The results shown in 6 tables were obtained.

Table 6 As is clear from this Table 6, ZrB is 0.05
The same effect as in Example 5 is obtained even when ~25 times the amount of dopant is added. In addition, sample numbers 97, 101, 102, 106 in Table 6
．． 107.111 is outside the scope of this invention. Furthermore, it was impossible to measure ρ and T for those with poor sinterability.

Example 7 A material in which 1% by weight of clay was added to CaTjO powder,
A ceramic building green sheet was prepared in the same manner as in Example 1, and a conductive paste according to the present invention (Ni' powder 85×fX, Mn powder 7.5111×pb) was prepared.

Prepare a green sheet (7.5% by weight of BaO-S iO glass frit and binder) and paste on a green sheet (paste 71+8) as shown in FIGS. 5 and 6. Screen printed and stacked in 4 layers so that each layer was alternated,
Further, only a green sheet was laminated on top of this, and heated under hot pressure N at 1280C for 4 hours (98.5%) + Ht (1,5%).
It was integrally fired in the reducing atmosphere of No. 1.

Thereafter, heat treatment was carried out at 1000C for 1 hour in an air atmosphere to compensate for the reduced portion of the crocodile electric body, and then the In-Qa11 residue was burned and formed on one surface of the feeding body. Then, the capacitance and -1 were measured using Yokotsutsu Seisakusho model YHk'4270-A, and the specific cast rate (gs) was determined from the measured capacitance. In addition, insulation resistance (
The eyes became dull after applying DClooV and fiosho. As a result, the results shown in Table 7 were obtained.

For comparison, the conductive paste of this example was changed to 4-electroconductive paste 11 palladium, and the firing was performed at 128.0C1.
A specific soft sample was prepared by conducting the experiment for 4 hours in an air atmosphere, and the specific electric constant (S) of this comparative sample was measured in exactly the same manner as in this example.
, (5) δ, and insulation resistance ([4) were determined in milliliter, and the results shown in Table 7 below were obtained.

Table 7: It is certain that it can be used as both poles of the capacitor 4.
Ta.

[Brief explanation of the drawing]

Figure l1g1 is a plan view showing the porcelain and electrodes involved in Example IK of the present invention, Figure 2 is a front view of Figure 1, Figure 3 is a plan view of the sample for measuring T in Example 1, and Figure 4 The figure is a sectional view showing the state of measurement of T, FIG. 5 is a plan view showing the green sheet and base of Example 7, and FIG. 6 is a front view of FIG. In the symbols used in the drawings, (1) indicates porcelain;
(2) is a conductor. Agent: Norihiro Takano Written amendment (voluntary) 1. Indication of the case 1982 Patent Application No. 73181 ¥32 Title of the invention: Baked layer conductive paste 3. Person making the amendment Relationship to the case: Applicant 4 , Agent 5, Date of amendment order f1 Voluntary action 8? Ili positive internal existence As shown in the attached sheet. (1) Page 4 of the specification, line 3 to line 13 of the same expletive “(1)
1 Thick film capacitor **a*hm* Small. ” to the following sentence. (1) Simultaneous firing with the ceramic body (1100~14
00C), it must be possible to sinter at a temperature of approximately 1100 to 1400C. In order to form a thick film capacitor and a thick film resistor on the upper surface of the conductor made into a conductor by T21 11+ treatment, the resistivity should not increase even if heat treatment is performed at 1000C in an atmospheric atmosphere (oxidizing atmosphere). (2) Add "reducing or neutral atmosphere" before "baking mold" on page 5, line 4 of the specification. jl

Claims (1)

[Scope of Claims] Nickel powder with tl+70 to 98% by weight, manganese or manganese compound powder having a manganese content of 0.05 to 29.9% by weight in terms of Mn06c, and 0.1 to 20% by weight. 2% glass frit, 2% nickel powder, the MnU, and the glass 7lits to give a total of 100 tX, and a suitable lid vehicle.
A baking type 4-electroconductive paste. +2170~98% nickel powder, manganese or manganese compound powder with a manganese amount of 0.05~29.9% Mn0K, and 0.1~20di
Violet% glass frit, all the nickel powder and M
nO and the glass frit so that the total amount is 100tfX, and the Pfr+ period nickel powder and the M
0.05 to 25% of nickel silicide or zirconium boride based on 11,100 g of the combined weight of nO and the glass frit, and containing a suitable lid vehicle.
Baking type conductive paste with special characteristics.