JPS62104001A - 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 which can be formed into a thick film resistor or a similar resistor by firing in a non-oxidizing atmosphere and which has high moisture resistance. The present invention relates to a paste-like resistance material capable of providing a resistor.

[Conventional technology]

An unfired ceramic sheet, i.e., a green sheet, coated with a conductive paste of base metal such as nickel, and coated with a resistor paste containing molybdenum boride, fluoride, glass, and silica, is fired in a non-oxidizing atmosphere. , a method for creating a multilayer ceramic circuit board having both JS film conductor and thick film resistor
No. 655 Specification 1 (1). This method reduces the cost of multilayer ceramic circuit boards because no metal stock is used to form the thick film conductors and thick film resistors. can.

[Problems that the invention helps solve, Q]

However, the thick film resistor formed from the resistive material according to the above application does not have sufficient resistance characteristics. for example.

When left for 1000 hours in an environment with a temperature of 60° C. and a relative humidity of 95%, the rate of change in resistance will be about +5% to about 10%.

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 within ±2% in a moisture test. It is in C.

〔problem? Means to solve]

The resistance material according to the present invention for achieving the above object is as follows:
Tungsten boride 20-70% weight.

10 to 60 μt% per lath and lucium fluoride (CaFt
), strontium chloride (Srl;', ),
and barium fluoride (BaF*) at least 1 within σ
Seed fluoride 5-501% by weight and calcium carbonate ((?a
CUa), carbonate 07teum (5reos),
It consists of a powder of a mixture consisting of at least one carbonate of barium carbonate (BaeC) 10 to 60'BI:% by weight, a double binder, and a bath agent.

[For production]

When a paste-like resistive material having the above composition is printed on a green sheet and fired in a non-oxidizing atmosphere, a thick film resistor having a resistance change rate within ±2% in a moisture resistance test can be obtained. Therefore, at the same time as a thick film conductor is formed using a conductor paste for base metal such as nickel, is it possible to form a base metal thick film resistor? You can form C.

[Embodiment 1] Next, a method for forming a resistor material and a multilayer ceramic circuit base σ) according to an embodiment of the present invention will be described.

First, silicon dioxide (5t(J, ) 78-Oik M
h, zinc oxide (Zn (JJ 5.5 kn part, zirconia oxide A (Zro, ) 12.0 Kame Jt &z,
Flucium 7 carbonate (CaCQ, ) 3. Mix Og bones and 1°51 L parts of aluminum oxide (Alt(Jm)), melt in an aluminum crucible at 1400°C for 30 minutes, pour the molten liquid into water, cool it with a valve. Take out all the quenched material and put it in an alumina mortar.

The powder was ground to a culm size of approximately 5 Q It m, then placed in a polyethylene bot mill with ethanol, and ground with alumina balls for 150 hours until the particle size was 10 μn.
Obtain powdered glass with a particle size of 1 or less.

Next, the above glass and tungsten boride (W, B, we
lw, B, one of them) and fluoride ((?aF,
.

One or more of SrF'O, l1aF, etc.) were weighed in the proportions shown in Table R, and the mixture was placed in a ball mill and stirred. Next (at ゛.

The mixture was heat-treated at 1200°C for 1 hour in a cn2 argon gas atmosphere, then placed in a polyethylene hot mill with ethanol, and ground with alumina balls for 24 hours.
Powdered powder of a mixture of tungsten boride, glass, and fluoride with a diameter of 0 μm or less. That is, mixed powders of glass, tungsten boride, and fluoride in various proportions shown in Samples A1 to 32 in the table were obtained.

Next, the weight ratio of glass and one or more of tungsten chloride, fluoride, and carbonate (CaCC), 8rCCJ, BaC0, is shown in the composition column of Table 1-32. As shown, by adding carbonate to the above-mentioned mixed powder of glass, tungsten boride, and fluoride, and mixing by filtration, a powder of the resistance material Ct) mixture according to the present invention is obtained. That is, at sample point 1 (・
The composition of the mixture of resistance materials is 10% by weight, W
, l:l 207JLt! −%, CaFt l OIi
jjk'lc, C:aCoz was set at 60% by weight, and the remaining sample points 2 to 32 also had the compositions shown in the composition column.

Next, each sample's resistance material σ) powder 100ik of the mixture:
In the h part, 10 m of ethyl cellulose, an organic binder, is added.
ffR1'90"M parts of butyl calpitol as a bath agent was bathed with 110 parts of an organic binder made from sigma, and 25N parts of chitokuru were added thereto and kneaded in a three-roll mill to form a resistor paste with about 800 voids. Obtained.

The above-mentioned resistor paste) was printed on a green sheet by the following method. AI, U, powder 50 mi
fm, Sin, powder 20 m section, SrU powder 25''
I4L-m part, Li, (J powder bed xifLi 1 part, and M
A binder consisting of gO powder 4-fold 11-glow ceramic raw material powder and an aqueous solution of acrylic acid ester polymer.

Glycerin, carboxylic acid salt, water, and grapes were placed in a ball mill and mixed to make a slip.

After degassing treatment, the degree of baseness is 200 by the doctor blade method.
Next, a long green sheet of ρm is prepared.

From this green sheet, 9 mm x 9
Two types of green sheet pieces, 2 mm and 6 mm x 9 mm, were cut out.

Next, as shown in Fig. 1, nickel (Ni) powder and an organic binder bath (g (10 parts by weight of ethyl cellulose dissolved in 907 parts by weight of turpentine oil) were mixed in a 3:1 mixture of nickel (Ni) powder and an organic binder bath (10 parts by weight of ethyl cellulose and 907 parts by weight of turpentine) on top of a stack of the former green sheets. Knead at a ratio of
, C and dry for 10 minutes as shown in Figure 1.
A conductive film (2) was formed.

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

Next, on top of the green sheet piece 111, 100,000 more green sheet pieces (41 pieces) of the size indicated by #J1WM were laminated.

The material was thermocompressed at 100°C and 150 kg/cm'', and then heat treated at 500°C in a cholera oxidizing atmosphere to scatter and decompose the binder and solvent (organic vehicle), resulting in N, (98,
By firing at 1100° C. for 2 hours in a reducing atmosphere of 10 He (1.5 vol. N%), the thick film conductor ( 2a) and a thick film resistor (3a) and σ) multilayer ceramic circuit base for hybrid integrated circuits were completed. Note that the size of the S portion of the resistor (3a) that does not span the conductor (2a) is 3rnm
3 mm, and the film thickness is 18 μm. It was a cabinet.

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

Next, the sheet resistance (tt, tΩ/mouth) of this resistor (3a) at 25° C. was measured using a digital multimeter. Next, each sample (multilayer ceramic circuit board)'! : Leave it for 1000 hours in an environment with a water content of 60% and a relative humidity of 95%.
Measure LEtl (Ω/mouth) and Js from this moisture resistance test.
The resistance of the membrane conductor (2a) is expressed as ΔR (R8-a, /R,
JX 100% wanted. In the characteristics column of the table, the above R
o and Δ are shown. Note that k in the Ro value column indicates: in X10'.

As is clear from Samples A1 to 32 in the table, the composition of the mixture of resistance materials.

Crow 10-60% by weight.

Tungsten boride 20-7clcJ1%.

Fluoride 5-50 weight - J1%.

By setting the carbonate weight to 10 to 60%, the sheet resistance was reduced to 790.6Ω/low to 354.8Ω even though the firing was performed in an IRx atmosphere.
/ mouth, resistance change rate ΔR by humidity test is -2.0% to +
J within 2.0%! #Membrane resistors can be provided.

r(h) The following was confirmed by samples not shown in the table (・) which are outside the scope of the present invention.

III If the amount of tungsten boride t-20%l9 is also reduced, the resistance value becomes too high.

[If the amount of 21 tungsten boride is more than 70% by weight, sintering becomes difficult.

(If it is less than 1kyio heavy view% of 31 glass,
Sintering becomes difficult.

(If it is more than 41 glass weight 60 weight mei.

The resistance value becomes too high.

(When the content of 51 fluoride is less than 5% by weight.

It becomes difficult to keep the resistance change rate Δft' within a range of ±2%.

(6) When the fluoride element is increased to more than 50% by weight.

It becomes difficult to keep the resistance change rate ΔR within ±2% of 9 yen.

(7) If the carbonate content is less than 1011 i%, it becomes difficult to keep the resistance change rate within ±2%.

(8) tk60 weight of carbonate [if it is greater than '9o.

It becomes difficult to keep the resistance change rate Δ[(i±2%).

[Example 2] Even if the composition of the glass changes, Example 1 and l1ii]44
Make sure that the effect is obtained 'fc Nuni 1st glue] I <In the glass powder book? 'Made by E. Silicon dioxide (S
jO*) 75.01kts, diboron trioxide (Bt(J
s) 13.0 heavy tS, calcium carbonate A (CaC(
Js) IO-0 heavy Jlt part and aluminum oxide (Al, U, ) 2.0 East were mixed in the parts and a powdered glass mixture was prepared in the same manner as in Example 1.

Next, use this glass to make glass 207 by weight%.

W, B, 5% by weight, W, 815″ weight%, W820% by weight.

SrF, CaF, and BaF = k 5% by weight each
, CaCUl 10% Toso, 5rCt) 110 heavy J
A mixture of resistive materials consisting of 1% by weight and 15% by weight of BaCO was obtained in the same manner as in Example 1, and used to prepare a multilayer ceramic circuit board 8! of the same structure in the same manner as in Example 1. II- was formed, and the electrical characteristic sound was measured in the same manner as in Example 1, and the sheet resistance m was 2.324 kΩ/hole, and the resistance change rate ΔR was +0.2 ahead.

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

In other words, the glass used in the present invention is not necessarily limited to one specified composition.
-(', a(J Aftυ, thread glass, Example 2-3
iU1-BIC) s-CaO-AI, 03 thread glass layer (・Zunemo production point (temperature at which IXIO' whiz) is 9
It is glass with a temperature of 00 to 1200°C. The glass according to the present invention is not limited to the glass having the composition of Examples 1 and 2, but
The metal oxide tPbO is heated to a working temperature of 900-1200°C and is converted to gold when fired in a reducing atmosphere.
, 8nOt, 5itO1, etc.) Any material may be used as long as it does not contain k.

[Modified example]

The invention is not limited to the embodiments described above.

For example, the following modifications are possible.

lal Even if the firing temperature of a green sheet coated with a resistor paste containing tungsten boride, glass, fluoride, and carbonate is varied in the range of 1000°C to 1200°C, the resistance value R8 and the resistance change rate ΔI ( It has been confirmed that there is almost no change (for example.

Sample A of Example 1 Same composition as 12, only firing temperature 71
Change from 000℃ to 1050℃% to 1150℃% to 1200℃.The resistance value R0 at 9 o'clock is 4.589 kΩ/mouth.

4.574 to Ω/0.4.563 to Ω/mouth, 4.578
is Ω/mouth, and the resistance change rate ΔR is 5%, -0
．． 4%, -0.3%, -Sail 4% and friend. Almost similar results were obtained with other compositions.

(bl Green Sea) k The atmosphere during firing may be a neutral atmosphere (inert atmosphere). The heat treatment temperature in an oxidizing atmosphere for decomposing and scattering organic substances before firing the IL green sheet is, for example, 400°C N 600°C.
You may change it by

(cl) The firing temperature of a mixture of glass, tungsten boride, and fluoride in an argon atmosphere, e.g.
It may be changed within a range of 1200°C. This firing session also uses an inert atmosphere outside the argon gas core.

Alternatively, it may be carried out in Makabe, a neutral atmosphere, or a reducing atmosphere.

+a+ @K The organic binder solution (vehicle) of the tanu produced by body hest can be dissolved in a resin such as nitrocellulose, turpentine oil, or a high boiling point solvent such as butyl carpitol acetate.

The amount of this organic binder solution is preferably about 15 to 35 ttffll.

〔Effect of the invention〕

As is clear from the above η, the paste-like resistive material of the present invention and the conductive paste 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 a noble metal. Not yet. Therefore, it is possible to contribute to miniaturization and cost reduction of multilayer ceramic circuit boards or similar electric circuit components. Second, the resistive material of the present invention can provide a resistor with better moisture resistance than the resistive material of the above-mentioned patent application.

[Brief explanation of drawings]

FIG. 1 is a plan view showing the pattern combination of a green sheet, a conductor film, and a resistor film when manufacturing a multilayer ceramic circuit board according to an embodiment of the present invention, and FIG. 2 corresponds to line 11-1 in FIG. 1. FIG. 3 is a cross-sectional view showing the multilayer ceramic circuit board of the fired bond. ; 11... green sheet piece, (21... conductor film,
(31...Resistor M, +41...Green sheet piece.

Claims (3)

[Claims] (1) Tungsten boride 20-70% by weight, glass 10%
~60% by weight, 5 to 50% by weight of at least one fluoride of calcium fluoride, strontium fluoride, and barium fluoride; at least one carbonate of calcium carbonate, strontium carbonate, and barium carbonate A paste-like resistance material consisting of a powder mixture consisting of 10 to 60% by weight, an organic binder, and a solvent. (2) The tungsten boride is at least one of ditungsten monoboride (W_2B), monotungsten monoboride (WB), and ditungsten pentaboride (W_2B_5). Resistance materials listed in section. (3) The resistance material according to claim 1 or 2, wherein the glass has a working point in the range of 900 to 1200°C.