JPS58117264A - Resistance paint and resistor formed therefrom - Google Patents

Abstract

PURPOSE:To provide a resistance paint having improved resistance characteristics as well as improved temperature coefficient of the resistance in a high resistance region of a thick-film resistor, consisting of ruthenium oxide, glass, lanthanum oxide or neodymium oxide, and an org. vehicle. CONSTITUTION:Ruthenium oxide, glass, lanthanum oxide and/or neodyminum oxide, and an org. vehicle are blended togehter. Lanthanum oxide and/or neodymium oxide have an effect of making the temperature coefficient of resistance close to zero and of increasing resistance when added to a ruthenium oxide/glass resistance film. The particle size of lanthanum oxide and/or neodymium oxide is pref. 0.1-2mu. Lanthanum oxide and/or neodymium oxidd are/is used in an amount of 0.05-7pts.wt. per 100pts.wt. of the combined amount of ruthenium oxide and glass. When the amount is less than 0.05pt.wt., a satisfactory effect can not be obtd., while when the amount exceeds 7pts.wt., the temperature coefficient is shifted to a negative side. Thus, the temperature coefficient can not be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a temperature coefficient (
In addition, the resistance characteristics such as noise and voltage coefficient of resistance value (hereinafter referred to as rVCR1) have been improved.

A thick film resistor made of ruthenium oxide and glass has a resistance value varying from several IN,/mm to 10 MΩ/mm when the ratio of ruthenium oxide to glass is in the range of 60:40 to 5:95, and the desired L/,) resistance. It is desirable that the resistance value of the resistive film does not change depending on the ambient temperature during use, that is, that the TCR is (j). However,
The relationship between resistance value and TOH varies depending on the particle size of ruthenium oxide and the composition and particle size of glass, but although there is a region where TCR is 0 in the medium resistance region, TOR becomes positive as the resistance value decreases beyond this region. As the resistance value increases, the TCR becomes more negative, and the resistance value has the disadvantage that it is easily influenced by the ambient temperature over most of the range of the resistance value.

As a method for improving TCR, for example, U.S. Pat.
No. 324,049 describes separation of manganese oxide and copper oxide. Exactly large TO like low resistance area
By adding manganese oxide to a resistive film having R or using glass containing manganese oxide as a component, TOR, which was previously large, can be brought close to zero. However, when manganese oxide is added to a resistive film in the high resistance range that has a large negative TCR, although T(1!R approaches 0), the resistance value of the resulting resistive film remains low, resulting in It was not possible to obtain a TCR close to 0 in the resistance range.

Also, by adding copper oxide or using glass containing copper oxide as a component, the negative TCR can be made close to 0, but the resulting resistive film will have a low resistance value.
In addition, VOR also deteriorates, which is not preferable. Another method for improving TCH is to coarsen the particle sizes of ruthenium oxide and glass, but this method increases noise and causes large variations in resistance values, making it unsuitable for practical use. in this way,
The conventional method could not be said to be preferable as a TOH improvement method in a high resistance region.

The present inventors conducted research to solve these problems, and by adding lanthanum oxide and/or neodymium oxide to a ruthenium oxide glass resistor that exhibits a high resistance value, TC
In addition to improving R, noise and VOR'ii are also improved.

That is, the present invention provides a resistance paint consisting of ruthenium oxide, glass, lanthanum oxide and/or neodymium oxide, and an organic vehicle; The resistor is made of nium, glass, and a resistive film made of lanthanum oxide and/or neodymium oxide.

Lanthanum oxide and/or neodymium oxide, when added to a ruthenium oxide-glass resistive film, will bring the TOR close to zero, while increasing the resistance value will have special effects. This is an extremely unique performance considering that conventional additives have the disadvantage of reducing resistance. In this way, the present invention not only improves TOR, but also reduces noise and improves vCR because it contains more conductive particles and has less dust compared to conventional resistive films with the same resistance value. This also has the effect of

As described above, the addition of lanthanum oxide and/or neodymium oxide has an unexpectedly excellent effect.The ruthenium oxide, glass, and organic vehicle used in the resistive coating of the present invention are
Any material normally used for resistance paints may be used.

There are no particular restrictions on the particle size of the lanthanum oxide and/or neodymium oxide, but it may be strong, for example, 10 μm or less, and preferably 0.1 to 2 μm. These oxides are used in an amount of 0.05 to 7 parts by weight per 100 parts by weight of ruthenium oxide and glass.
If it is less than 5 parts by weight, the effect of adding it will not be seen much.
If more than 7 parts by weight is used, TOR will become soft on the negative side, and TCR will not be improved. Lanthanum oxide and neodymium oxide may be used alone or in combination, or may be incorporated in glass in advance.

The invention will be explained below with reference to examples, but the invention is not limited thereto.

Table 1 shows Examples 1 to 10 and Comparative Examples 1 to 5. Examples and comparative examples with the same resistance value are shown together for ease of comparison. Each side except Example 4.7 is shown in Table 1, respectively.
After mixing each component shown in, roll mixing is performed,
A uniformly dispersed resistance paint was created. The glass used was pbo 52.0%, BxOa 8.3%, EIiO+ by weight.
+36-5%, Al5O12,3%, and the organic vehicle is ethyl cellulose 75% by weight.
parts, terbiquiol 32.5 parts, dibutyl phthalate 5 parts
．． 0 parts homogeneous mixture.

In Example 4, ruthenium oxide, glass, and lanthanum oxide were placed in a platinum crucible, heated to the melting temperature of glass, then rapidly cooled, and then finely pulverized and uniformly dispersed in an organic vehicle in the same manner as above. did. In Example 7, after glass and lanthanum oxide were treated in the same manner as in Example 4, ? r
This and ruthenium oxide were uniformly dispersed in an organic vehicle to make a resistance paint.

The resistive paint f thus obtained was 1+ma
After screen printing the w+ pattern, it was dried and then fired in a belt furnace at a peak temperature of 850° C. for 10 minutes.

゛ The resistance value, TOR, noise, and VCRf of the obtained resistor were measured, and the results are also shown in Table 1. The resistance value was measured using a digital multimeter manufactured by Takeda Riken Kogyo Co., Ltd.
TR-6855) and converted to a thickness of 12μ. TCR was measured over a temperature range of -25°C to +125°C. The noise is Quan-Tech's Re5is.
torNoi, se Te5t (MODEL -2l
36). The smaller the noise value, the better 0vCR is General Radio's Meg-
ohm Bridge (MODKL 1644
A) was measured at 10-1 onv. VORi is T
Similar to CR, the closer it is to 0, the better (7).

(Left below) Comparison of Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 6 and Comparative Example 6, Examples 4-6 and Comparative Example 4, and Examples 7-10 and Comparative Example 5, respectively. Then, the resistor obtained according to the present invention has T compared to a conventional resistor having the same resistance value.
It can be seen that CR has been improved. Furthermore, noise 1. V
It has been shown that OH is also excellent.Table 2 also shows that the resistance value increases when the blending ratio of ruthenium oxide and glass is changed and lanthanum oxide is added. Ta. Similar comparisons can be made between Examples 9 and 10 and Comparative Example 4 in Table 1. The experimental method and measurement method are the same as described above.

Table 2 (All parts are parts by weight) As described above, the present invention improves the TCR in the high resistance range by adding lanthanum oxide and/or neodymium oxide to the ruthenium oxide-glass resistance film. This makes it possible to bring the noise value close to 0, and also improves noise and vCR, making it extremely practical in practice.

Patent Applicant Shoei Chemical Industry Co., Ltd. Procedural Amendment (Voluntary) Commissioner of the Patent Office Kazuo Wakasugi1, Case Description 1982 Patent Application No. 210.2072, Title of Invention Resistive Paint and Resistor Formed Therefrom゛6 Address of the person making the amendment: 2-2-1-5 Nishi-Shinjuku, Shinjuku-ku, Tokyo 160-91 Details of the amendment (1) Amend "resistance film" to "resistance element" in the highlighted part of the description. .

2nd page, 3rd line from the bottom, 5th page, 2nd line, 8th line, 11th page, 6th line (2) ``TCR...'' from page 3, line 8 to page 4, line 6 of the specification ...It is not suitable for practical use.'' ヲ, correct it as follows.

It is known to incorporate various additives as a method of improving rTOR'i. For example, MnO2, Al2O,
, TiO□, zr02, etc. have the effect of shifting TCRi in the negative direction, and are effective for resistors in the low resistance range that have a large positive TCR. However, in the case of resistors in the high resistance range, for example, U.S. Patent No. 3,324,049 describes adding copper oxide or using glass containing oxidized steel; Then, TCR approaches OVc, but at the same time the resistance value decreases and V
OR also worsens. Further, British Patent No. 1,470,497 describes that addition of colloidal A100Hf causes TOR to change in the positive direction, but in this case, the resistance value also decreases. Therefore, as a result, TOR in the high resistance region
It was not possible to obtain a value close to 0. Another method is to coarsen the grain sizes of ruthenium oxide and glass, but this method increases noise and causes large variations in resistance values, making it unsuitable for practical use. ” (3) “Has a negative TCR” is added in front of “ruthenium oxide” on the second line of page 5 of the specification tube.

(4) In the 5th line from the bottom of page 5 of the specification, the phrase ``ruthenium oxide may be treated in advance and used in the form of being contained in the glass'' is fully added.

(5) The 6th line from the bottom of the 6th page of the Book of Meireisho: “Has...
...The organic vehicle has an average particle size of 6μ with r'lr, and the ruthenium oxide has a specific surface area of 25μ.
rr? /f was used. "Organic vehicle" is corrected.

Claims (1)

[Scope of Claims] 1. A resistance paint consisting of ruthenium oxide, glass, lanthanum oxide and/or neodymium oxide, etc., and an organic vehicle. , 2 Lanthanum oxide and/or neodymium oxide power; Claim 1 previously included in the glass
Resistant paint as described in section. 6 Resistance paint according to claim 1, in which ruthenium oxide and lanthanum oxide and/or neodymium oxide are included in the glass in advance 04 The weight ratio of ruthenium oxide and glass is 60 nia 0 to 5:95 and the lanthanum oxide and/or neodymium oxide is in an amount of 0.05 to 7 parts by weight based on a total of 100 parts by weight of ruthenium oxide and glass. The resistance paint according to items 1 to 6 of the desired scope. 5. A resistor consisting of (a) an insulating substrate, (b) a resistive film made of ruthenium oxide, glass, and lanthanum oxide and/or neodymium oxide closely coated thereon. 6 The weight ratio of ruthenium oxide and crow is 0 to 5.
:95, and the lanthanum oxide and/or neodymium oxide is contained in an amount of 0.05 to 7 parts by weight based on a total of 100 parts by weight of the acid-treated ruthenium and glass.