JPS6292408A - Resistance material - 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 [Industrial Application Field] The present invention provides a resistor that can form a thick film resistor or a similar resistor by firing in a non-oxidizing atmosphere, and has high moisture resistance. The present invention relates to a pasty resistance material capable of providing a resistance.

[Conventional technology]

Two unfired mixed sheets (110 green sheets) were coated with a conductor paste of base metal such as nickel, and one was coated with a resistor paste containing tungsten silicide, fluoride, and glass, and fired in a non-oxidizing atmosphere. A method of making a multilayer ceramic circuit board having both thick film conductors and thick film wax bodies.

This is disclosed in Japanese Patent Application No. 59-197658 filed by the applicant. In this method, the cost of the multilayer ceramic circuit board can be reduced because 1g4 of prize money is not used for forming the thick film conductor and the thick II resistor.

[The problem that the invention attempts to solve]

However, if it is made of the resistive material related to the above application, “
Thin film resistors do not have sufficient moisture resistance. for example.

Temperature 6. 1000 in an environment of θ℃ and 95% relative humidity.
'Resistance change rate when left for a period of time is +5% to +1
It will be around 0%.

Therefore, one object of the present invention is to provide a resistor material that can be formed into a resistor by firing in a non-oxidizing atmosphere and that can yield a resistor with a resistance change rate of 22% or less in a moisture resistance test. There is a particular thing.

[Tanu's means of solving problems]

The resistance material according to the present invention that achieves the above object is:
25-85% tungsten and 5-65% glass
i1%, calcium carbonate (Ca COm ), strontium carbonate (5rCOs), barium carbonate (Ba
It consists of a powder of a mixture consisting of 10 to 70 weight percent of at least one carbonate of CO, ), an organic binder, and a solvent.

[For production]

If a pasty resistance material having the above composition is printed on a rubber sheet and fired in a non-oxidizing atmosphere, a thick film resistor having a resistance change rate of 223 or less in a moisture resistance test can be obtained. Therefore, it is possible to form a base metal elliptical film resistor simultaneously with the formation of a thick film conductor using a conductor paste of a base metal such as nickel.

[Example 1] Next, a resistor material according to an example of the present invention and a method of forming a multilayer ceramic circuit board using the same will be described.

First, 78.0 parts by weight of silicon dioxide (SjO,), 5.5 parts by weight of zinc oxide (ZnO), and zirconium oxide (ZnO) were added.
rO, ) 12.0 heavy duty, calcium carbonate (CaCOl
) 3.0 parts by weight, and aluminum oxide (AlyOm)
Mix 1.5 parts by weight and place in an aluminum crucible at 1400
The mixture was melted at ℃ for 30 minutes, and the melt was poured into water and rapidly cooled. Take out this rapidly cooled material and put it in an alumina mortar.
The mixture was crushed to a size of approximately 50 μm, and the carbon particles were placed in a polyethylene bot mill together with ethanol, and crushed with alumina balls for 150 hours to obtain powdered glass with a particle diameter of 10 μm or less.

Next, the above glass and tungsten (W) were weighed in the proportions shown in the table, placed in a ball mill, and stirred. Then,
This was heat-treated at 1200°C for 1 hour in an argon gas atmosphere, then placed in a polyethylene bot mill with ethanol, pulverized with alumina balls for 24 hours, and
A powder of a mixture of tungsten and glass below 0 μm J4 was obtained. INO too.

Mixed powders of glass and tungsten in various proportions shown in samples A1 to 70 in the table were obtained.

Next, glass, tungsten, and carbonate (CaCO).

5rCO1, BaC0, etc.] such that the ratio is as shown in the composition column of samples A1 to 70 in the table.

Carbonate was added to the above-mentioned mixed powder of glass and tungsten, and C was mixed to obtain a powder of a resistance material mixture according to the present invention. That is, in sample A1, the composition of the resistance material mixture was 5% by weight of glass and W85i.
(it%, CaC0g 10% by weight), and the remaining samples A2 to A70 also had compositions according to the weight allocation shown in the composition column.

Next, 10 parts by weight of ethyl cellulose as an organic binder was dissolved in 90 parts by weight of butyl calpitol as a solvent in 100 N parts of powder of the resistance material mixture of each sample.
25 parts by weight of an organic binder solution, i.e. vehicle, consisting of C was added and kneaded in a three-roll mill to obtain a resistor paste with about 800 voids.

On the other hand, a green sheet on which the resistor paste was printed was prepared in the following manner. AI, 0. 50 parts by weight of powder, 20 parts by weight of sho powder, 25 parts by weight of SrO powder,
Upper two mix raw material powders consisting of 1 part by weight of Li1O powder and 4 parts by weight of MgO powder, and a binder consisting of an aqueous solution of acrylic acid ester polymer.

Glycerin, a carboxylic acid salt, and water were each placed in a ball mill and mixed to prepare a slip, which was defoamed, and then a long green sheet with a thickness of 200 μm was prepared using a doctor blade method. Then, from this green sheet, 9mm x 9mm and 6mm x 9mm
Two types of green sheet pieces were cut out.

Next, as shown in Fig. 1, the former green sheet piece +1
7, nickel (Ni) powder and organic binder 111
A conductive paste prepared by kneading H[(10 parts by weight of ethyl cellulose dissolved in 90 parts by weight of turpentine oil) in a ratio of 3:1 was printed using a 200 mesh screen,
A Ni conductor film (2) was formed as shown in FIG. 1 by drying at 125° C. for 10 minutes.

Next, a resistor paste according to the present invention is screen printed in the same manner as the conductor paste and dried.
A resistor film (31) was formed as shown in the figure.

Next, 10,000 green sheet pieces (4) of the size indicated by the chain lines were laminated on top of the green sheet pieces (11).

Thermocompression bonding was carried out at 100°C and 150 kg/cm', and this was heat-treated at 500°C in an oxidizing atmosphere to remove the organic binder and solvent (
1100 in a reducing atmosphere of N, (98.5% by volume) + Ht (1.5% by volume).
℃ for 2 hours to form a porcelain layer Ha)E as shown in FIG.
Inside ta) are a thick film conductor (2a) and a thick film resistor (3a).
We have completed a multilayer ceramic circuit board for hybrid integrated circuits. Note that the size of the portion of the resistor (3a) that does not cover the conductor (2a) is 3 mm x 3 mm, and the film thickness is 18 μm. Also.

The composition of the resistor (3a) almost matches the inorganic composition of the resistor material before firing.

Next, the sheet resistance R6 (Ω/hole) of this resistor (3a) at 25° C. was measured using a digital multimeter.

Next, each sample (multilayer ceramic circuit board) was heated to a temperature of 60°C.
℃ and relative humidity of 95% for 1000 hours, and then measured with a digital multimeter to determine the sheet resistance R, (
The thickness of the thick film conductor (2a
) resistance change rate ΔR (R0fta/Ro)
It was determined at 100%. In the characteristic column of the table, the above-mentioned turtle and ΔR are shown. Note that k in the % edge value column means x10.

As is clear from samples A1 to 70 in the table, the composition of the mixture of resistive materials is as follows: Glass 5 to 65% by weight.

By using 25 to 85% by weight of tungsten and 10 to 70% by weight of carbonate, the sheet resistance R0 can be reduced from 27.63Ω/unit to 387.3Ω/unit despite firing in a reducing atmosphere. , resistance change rate ΔR by humidity test is -2.0% ~
Thick film resistors within the range of +2.0% can be provided.

It should be noted that the following has been confirmed with samples not shown in Table 1 that are outside the scope of the present invention.

112 If the amount of tungsten is reduced by as much as 25% by weight, the resistance value becomes too high.

(If the amount of 21 tungsten is increased by more than 85 parts by weight, sintering becomes difficult.

(3) If the amount of glass is reduced by 5% by weight.

Sintering becomes difficult.

(4) When the amount of glass is greater than 65% by weight.

The resistance value is too high.

(5) If the t of the carbonate is reduced by 10% by weight, it becomes difficult to keep the resistance change rate within the range of ΔRt−+2%.

(6) If the amount of carbonate is increased by 70% by weight.

It becomes difficult to keep the resistance change rate Δat within the range of 22%.

[Example 2] To confirm that the same effects as in Example 1 could be obtained even if the composition of the glass was changed, glass powder was exploded as described above. 75.0 parts by weight of silicon dioxide (830,),
13.0 parts by weight of diboron trioxide (B*Om), 10-0 parts by weight of calcium carbonate (CaCo1), and 2-0 parts by weight of aluminum oxide (^'yOa) were mixed.

Powdered glass was obtained in the same manner as in Example 1.

Next, using this glass, a resistive material having the same composition as the sample plate 66 of Example 1 was obtained in the same manner as in Example 1, and a multilayer material having the same structure was obtained by using the same method as in Example 1. When a ceramic circuit board was formed and its electrical characteristics were measured in the same manner as in Example 1, the sheet resistance value was 4.872 kΩ/
The resistance change rate ΔRaη was 100.2%.

As is clear from Example 2, there is no significant difference in resistance characteristics even if the composition of the glass is changed.

Tsumaya 1 The glass used in the present invention is not necessarily limited to one particular composition. Note that SiO, -ZnO-ZrO, -CaO in Example 1
Al 03 series glass, 5i01 Btus of Example 2
-CaO-AI and 01 series glasses both have working points (IX
The glass according to the present invention has a temperature of 900 to 1200"C (temperature at which the
It is not limited to glass with a composition of 971 (PbO, SnO,
Bi.

01, etc.) Any type may be used as long as it does not involve a meeting.

[Modified example]

The present invention is not limited to the embodiments described above.

For example, the following modifications are possible.

(The firing temperature of a green sheet coated with a resistor paste containing tungsten, glass, and carbonate may be varied within the range of 1200°C to 1200°C.

It has been confirmed that the resistance value and the resistance change rate ΔR hardly change. For example, it has the same composition as Sample A66 of Example 1, but only at the firing temperature'? t1000℃.

The resistance value when changing to 1050℃, 1150℃, and 1200℃ is 4.973Ω/0.4.988Ω/mouth.

4.976 kΩ/mouth, 4.987 Ω/mouth, and the resistance change rate ΔR is -0.7%, -0.4%, -
0.5%.

-0.6%. Almost similar results were obtained with other compositions.

[i] The atmosphere when firing the green sheet may be a neutral atmosphere (inert atmosphere).Also.

Before firing the green sheet, the heat treatment temperature in the oxidizing atmosphere of the oxidizing atmosphere for decomposing and scattering organic matter is set to, for example, 400°C.
It may be changed at ~600°C.

(cl) The degree of firing of a mixture of glass and tungsten in an argon atmosphere may be varied, for example, in the range of 900 to 1200°C.Also, this firing may be performed in an inert atmosphere other than argon gas, in a vacuum, or It may be carried out in a neutral atmosphere or a reducing atmosphere.

+d) The organic binder solution (vehicle) for making the resistor pastera may be one in which a resin such as nitrocellulose is dissolved in a high boiling point solvent such as turpentine oil or butyl carpitol acetate.

The amount of the organic binder solution C is preferably about 15 to 35 parts by weight.

〔Effect of the invention〕

As is clear from the above, the paste-like resistive material of the present invention and the conductor paste made of base metal such as nickel can be co-fired in a non-oxidizing atmosphere, and the resistive material of the present invention does not contain any noble metal. . Therefore, it is possible to contribute to miniaturization and cost reduction of multilayer ceramic circuit boards or similar electrical circuit components. Furthermore, the resistive material of the present invention can provide a resistor with better moisture resistance than the resistive material of the patent application mentioned above.

[Brief explanation of drawings]

Figure 1 is a plan view of the above-mentioned pattern of the green sheet, conductor film, and resistor film when fabricating the multilayer ceramic circuit layer and i- according to the embodiment of the present invention, and Figure 2 corresponds to the low n-wire shown in Figure 1. FIG. 3 is a cross-sectional view showing the multilayer ceramic circuit board after firing the portion to be heated. +11... Green sheet piece, (21... Conductor film,
(3)...Resistor film, +41-...Green sheet piece. Agent Nori Takano Figure 1 Figure 2

Claims (2)

[Claims] (1) A powder of a mixture consisting of 25 to 85% by weight of tungsten, 5 to 65% by weight of glass, and 10 to 70% by weight of at least one carbonate of calcium carbonate, strontium carbonate, and barium carbonate, and an organic bond. A paste-like resistance material consisting of an agent and a solvent. (2) The resistance material according to claim 1, wherein the glass has a working point in the range of 900 to 1200°C.