JP7295973B2 - thick film resistor paste - Google Patents

Description

The present invention relates to conductive pastes and, in particular, to thick film resistor pastes.

Thick-film chip resistors are widely used in thick-film resistor electronic components, thick-film hybrid circuits, etc. Sheet-type thick-film resistors are mainly composed of a composition formed on the surface of an insulating substrate. A thick film resistor is obtained by printing on a conductive wire pattern or electrode and then firing the print at a temperature of 850°C ± 20°C.

Thick film resistor pastes are prepared by dispersing conductive components and inorganic binders in an organic medium (carrier). The thick film resistor paste is then deposited on the insulating substrate by a screen printing method. The electrical performance of thick film resistors is primarily determined by the nature of the inorganic binder and conductive components in the deposited layers. The inorganic binder, whose main component is glass, whose role is mainly to stick the conductive components together into a conductive path, maintain the integrity of the thick film resistor, and improve the adhesion with the substrate. play an important role in the The organic medium is the dispersing medium, which mainly affects the application properties of the paste, especially the rheological properties.

Conventional thick film resistors are available in low resistance ranges with sheet resistances below 100 ohms per square (eg, resistance ranges of 10 ohms/square, 1 ohms/square, 0.1 ohms/square, or 0.1 ohms/square). 01 Ω/square), using Ag, Pd, _RuO2 as the conductive phase, but the challenge is to improve the temperature coefficient of resistance (TCR) performance. , the content of Pd, which is a noble metal, must be increased, resulting in a significant increase in cost.

In conventional formulations in the low resistance range, lead-containing lead silicate glass is mainly used as the inorganic binder, and the three conductive phases of Ag, Pd, and _RuO2 are often used as the conductive component, generally Ag , Pd controls the resistance value and TCR, and the higher the Pd content, the lower the TCR can be obtained, but it becomes difficult to lower the resistance value. Therefore, a low-cost, high-performance resistor paste is required.

Conventional thick film resistors in the low resistance range lower the TCR by increasing the content of Pd powder, which is a noble metal, but increasing the content of Pd powder generally leads to higher resistance values, and It is necessary to increase the Ag content, but in this case the TCR is improved, so the content of the Pd powder can be further increased, and so on until the desired resistance value and TCR performance are achieved. A major problem with such a method is that it is difficult to achieve the desired resistance and TCR performance with such a cumbersome method.

SUMMARY OF THE INVENTION It is an object of the present invention to overcome deficiencies in the prior art and provide a thick film resistor paste with lower resistance and better TCR performance.

To achieve the above object, an embodiment of the present invention includes at least two of Ag powder, Pt powder and Ag—Pt alloy powder, wherein the Pt powder or Ag—Pt alloy powder has a honeycomb spherical shape, flocculate shape, , at least one of a spherical shape and a substantially spherical shape, and in the Pt powder or Ag—Pt alloy powder, the length ratio of the major axis to the minor axis of at least 90 wt% of the Pt powder or Ag—Pt alloy powder is Long Axis: Thick Film Resistor Paste with Minor Axis=1-3.

In conventional formulations, the TCR in the mid-to-low resistance range, especially for resistors with a sheet resistance of less than 100 ohms/square, is primarily related to the content of Pd, a noble metal. Since Pd has the above drawbacks, the present invention employs the means of using Pt instead of Pd. In the periodic table of the elements, Pt is an element of the same main group as Pd, both have very similar physical and chemical properties, and in terms of purity, rarity and durability, both may be substituted with each other. , pure Pt has good high temperature oxidation resistance and chemical stability. At normal temperature, Pt can stably exist in the thick film resistor paste, and after sintering at 850° C., can form Ag and Ag—Pt binary alloy in the paste, so that It exists as a crystalline phase of Ag—Pt binary alloy in thick film resistors. Moreover, the biggest difference between Pt and Pd powder is as follows. Pd undergoes a process of oxidation and decomposition between room temperature and 850°C, begins to oxidize in the temperature range of 300 to 400°C to form PdO, and begins to decompose to form Pd at about 800°C, but PdO is completely decomposed. When the temperature exceeds 850°C, some undecomposed PdO may remain after sintering at 850°C. The higher the amount, the higher the resistance value, the lower the Pd content, and the higher the TCR value. On the other hand, Pt powder does not undergo oxidation/decomposition processes, and can form an Ag—Pt binary alloy directly with Ag when sintered to a certain temperature. A thick film resistor paste with excellent TCR performance can be obtained.

Therefore, the inventors found out the following. Since the use of Pt powder instead of Pd powder results in lower TCR for resistors with a sheet resistance of less than 100 ohms/square, the use of Pt powder can improve TCR performance, thereby reducing cost. And it was found that the object of improving the TCR performance can be achieved. When a Pt powder or Ag--Pt alloy powder having a specific shape is used, the temperature dependence of TCR (influence of sintering temperature on TCR) and the TCR size effect (influence of size) are improved. And when Pt powder is used instead of Pd powder, it is ensured that the short time overload performance of the thick film resistor remains constant or even better.

The morphology of the Pt powder or Ag--Pt alloy powder has a great influence on the electrical performance of the thick film resistor. It can be homogeneously mixed in the organic carrier with other ingredients to exhibit good rheological performance. At the same time, the Pt powder with the above morphology can make good contact with the glass phase and Ag particles, and in the sintering process, it favors the formation of Ag--Pt alloy, and the glass phase is good against it. Similarly, the Ag—Pt alloy powder with the morphology as described above also comes into good contact with the glass phase, which makes the glass phase exhibit good wetting with respect to it. When sheet-like powder is used, the Pt powder/Ag—Pt alloy powder is difficult to disperse in other components, resulting in non-uniform dispersion, which may cause clogging in the screen printing process, and After sintering, thermal stress can cause defects such as cracks and voids on the surface of the thick film resistor.

When the Pt powder or Ag—Pt powder has a length ratio a/b of the major axis (a) to the minor axis (b) of more than 3, the morphology of the powder is close to an acicular morphology. In the case of such a morphology, it is difficult to disperse in the manufacturing process, and a phenomenon of non-uniform dispersion in other conductive phases, glass phases and organic carriers is likely to occur, which affects the electrical performance and other performance of the thick film resistor. influence. Pt powder or Ag—Pt powder with a/b of 1 to 3 can be uniformly mixed with other components in an organic carrier to exhibit good rheological performance, and a thick film resistor with excellent performance can be obtained. can get.

Preferably, in the Pt powder and the Ag—Pt alloy powder, the crystallite size of the (111) crystal face of Pt measured by X-ray diffraction is 7 to 50 nm.

Preferably, the Pt powder has a particle size of 10 nm to 1 μm, the Pt powder has a specific surface area of 0.3 m ² /g to 25 m ² /g, and the Ag—Pt alloy powder has a particle size of 200 nm to 1 μm, and the specific surface area of the Ag—Pt alloy powder is 0.3 m ² /g to 15 m ² /g. If the crystallite size is too high, the larger the particle size, the smaller the specific surface area, and the smaller the volume ratio when the same mass of Pt powder or Ag—Pt alloy powder is added. It directly affects the electrical performance of film resistors. Similarly, if the crystallite size is too low, the smaller the particle size, the larger the specific surface area, the easier it is to form agglomerates in the manufacturing process, and the glass phase wets the powder inside the agglomerates during the sintering process. As a result, during the sintering process, cracks and voids occur on the surface of the thick film resistor due to the action of thermal stress, and such defects directly affect the electrical performance of the thick film resistor. Therefore, when the crystallite diameter of the (111) crystal plane of Pt is 7 to 50 nm, a thick film resistor having excellent performance and free from surface defects such as cracks and voids can be obtained.

Preferably, said thick film resistor paste comprises 30-80wt% solid phase component and 20-70wt% organic component, wherein said solid phase component is 10-70wt% % Ag, 0.1-60 wt % Pt, 0-50 wt % RuO ₂ , 5-60 wt % glass component, and 0-5 wt % inorganic filler.

Preferably, when the solid phase component is 100 wt%, the solid phase component is 30-70 wt% Ag, 5-60 wt% Pt, 0-20 wt% _RuO2 , and 5-35 wt% glass. and 0-5 wt% inorganic filler. In particular, the solid phase component has a resistance range of 0.1 Ω/□ (in the present application, a resistance range of 0.1 Ω/□ substantially means a resistance range of 0.08 to 0.8 Ω/□). ) is applied to the manufacture of thick film resistor pastes.

Preferably, when the solid phase component is 100 wt%, the solid phase component is 20-60 wt% Ag, 5-50 wt% Pt, 0-20 wt% _RuO2 , and 10-40 wt% glass. and 0-5 wt% inorganic filler. The solid phase component is particularly a thick film having a resistance range of 1 Ω/□ (in this application, the resistance range of 1 Ω/□ substantially indicates a resistance range of 0.8 to 10 Ω/□). Applied in the production of resistor paste.

Preferably, when the solid phase component is 100 wt%, the solid phase component is 10-40 wt% Ag, 0.1-20 wt% Pt, 20-50 wt% _RuO2 , 20-60 wt% of the glass component and 0 to 5 wt% of inorganic filler. The solid phase component is, in particular, a thick film resistor paste with a resistance range of 10Ω/□ Applies to the manufacture of

In a resistor with a sheet resistance of less than 100Ω/□, when the content of Pt in the resistor paste exceeds a predetermined upper limit, firstly, the relative content of Ag powder with low resistivity decreases, and the sheet resistance is reduced to meet the predetermined requirement. and the relative content of the glass phase decreases, with too little glass phase to wet out much of the conductive phase, which leads to cracks and voids on the surface of the thick film resistor. , its electrical performance deteriorates further. If the Pt content is less than the predetermined lower limit, the TCR performance, STOL performance and other electrical performance are difficult to meet the requirements, so it is necessary to select an appropriate addition range to meet all requirements.
Preferably, the glass component is at least one of glass composition 1, glass composition 2, glass composition 3 and glass composition 4,

The glass composition 1 contains, in weight percentages, 10-50% PbO, 35-55% SiO ₂ , 5-30% CaO, 1-20% Al ₂ O ₃ , 1-10% B ₂ O ₃ and 0 ZnO. ~10%, wherein the sum of the PbO, _SiO2 , CaO, _Al2O3 , _B2O3 and _ZnO contents in the glass composition 1 in weight percentage is at least ₉₅ %;
The glass composition 2 contains, in weight percentage, SiO ₂ 40-75%, BaO 0-15%, SrO 0-20%, Na ₂ O 0-10%, K ₂ O 0-10%, Al ₂ O ₃ 1-15%, B ₂ O ₃ 1-25% and ZnO 0-10%, and said SiO ₂ , BaO, SrO, Na ₂ O, K ₂ O, Al ₂ O ₃ , B ₂ O ₃ and ZnO the total content in weight percentage in the glass composition 2 is at least 95%;
The glass composition 3 contains, in weight percentage, 50-88% PbO, 10-30% SiO _{2 ,} 1-10% Al ₂ O ₃ , 1-10% B _{2 O} 3 and 0-10% ZnO, the sum of the PbO, SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and ZnO contents in the glass composition 3 in weight percentage is at least 95%;
The glass composition 4 contains, in weight percentages, 60-88% PbO, 10-35% SiO _{2 ,} 1-10% Al ₂ O ₃ , 1-10% B _{2 O} 3 and 0-20% transition metal oxides. and _the transition metal oxide includes at least one of CuO, _MnO2 , _Nb2O5 , _{Ta2O5 , TiO2} and _ZrO2 .
The inorganic filler is at least one of _Nb2O5 , _MnO2 , _CuO , _TiO2 and _{Ta2O5 .}

Preferably, the organic component comprises an organic carrier and an organic solvent, wherein the organic carrier is at least one of ethyl cellulose, methyl cellulose, an acrylic resin and an epoxy resin, and the organic solvent comprises terpineol, At least one of butyl carbitol, butyl carbitol acetate, diethylene glycol dibutyl ether and alcohol ester.

Another object of the present invention is to provide a resistor manufactured with said thick film resistor paste.

Beneficial effects of the present invention are as follows. The present invention provides a thick film resistor paste, the conductive phase component in the thick film resistor paste according to the present invention uses Pt instead of Pd, and utilizes Pt powder or Ag-Pt alloy powder with a specific morphology. After that, the TCR of resistors with a sheet resistance of less than 100 Ω/square is reduced, and the temperature dependence of the TCR (the effect of the sintering temperature on the TCR) and the TCR size effect (the effect of the size of the size) are improved; It can be seen that the Pt powder with a specific morphology can improve the TCR performance, achieving the objectives of lowering the cost and improving the TCR performance. And it is ensured that the short time overload performance of the thick film resistor remains constant or even better after using Pt instead of Pd powder.

注：表の中のＰｔ（１１１）面の粒子径及び粒子の長軸と短軸との比とは、走査電子顕微鏡により測定された写真において８０％以上の粒子の粒子径が当該Ｐｔ（１１１）面の粒子径及び粒子の長軸と短軸との比の範囲内にあることを示す。一般的には、抵抗ペーストに使用される白金粉末の一次粒子径は、基本的にＸ線回折法により測定された結晶子径と同等であるとみなし、結晶子径Ｄ（ｎｍ）は、Ｓｃｈｅｒｒｅｒの式により算出され：Ｄ（ｎｍ）＝（Ｋ・γ）／（Ｂ・ｃｏｓθ）、ここで、ＫはＳｃｈｅｒｒｅｒ定数であり、０．８９とし、γ（ｎｍ）はＸ線の波長であり、Ｂは（１１１）面のピークの半値幅であり、θは回折角である。実施例に係るＰｔ粉末の結晶子径は、Ｘ線回折法により測定された相対強度が最も高いピーク値から算出される。
実施例及び比較例に係るガラス成分は、表２に示し、単位はｗｔ％である。

ここで、遷移金属酸化物はＣｕＯ、ＭｎＯ_２、Ｎｂ_２Ｏ_５、Ｔａ_２Ｏ_５、ＴｉＯ_２及びＺｒＯ_２の混合物であり、前記ＣｕＯ、ＭｎＯ_２、Ｎｂ_２Ｏ_５、Ｔａ_２Ｏ_５、ＴｉＯ_２及びＺｒＯ_２の重量の比は、１：１：１：１：１：１である。 In order to better explain the objects, embodiments and advantages of the present invention, the present invention will now be further described with reference to specific examples.
The types of Pt powder according to Examples and Comparative Examples are shown in Table 1.

Note: The particle size of the Pt (111) plane and the ratio of the long axis to the short axis of the particle in the table are those of the Pt (111 ) within the grain size of the plane and the ratio of the major axis to the minor axis of the particle. In general, the primary particle size of the platinum powder used in the resistor paste is basically considered to be equivalent to the crystallite size measured by the X-ray diffraction method, and the crystallite size D (nm) is determined by Scherrer D (nm) = (K · γ) / (B · cos θ), where K is the Scherrer constant and is set to 0.89, γ (nm) is the wavelength of the X-ray, B is the half width of the peak of the (111) plane, and θ is the diffraction angle. The crystallite size of the Pt powder according to the example is calculated from the peak value with the highest relative intensity measured by the X-ray diffraction method.
Glass components according to Examples and Comparative Examples are shown in Table 2, and the unit is wt %.

Here, the transition metal oxide is a mixture of CuO, _{MnO2 , Nb2O5} , _Ta2O5 , _TiO2 and _{ZrO2 , and the CuO, MnO2 , Nb2O5 , Ta2O5} , TiO ₂ and ZrO ₂ weight ratio is 1:1:1:1:1:1.

In the examples and comparative examples, the organic component comprises the following weight percentage contents: ethyl cellulose and terpineol, weight ratio of ethyl cellulose and terpineol = 1:4.

Formulations for thick film resistor pastes with a resistance range of 0.1 ohms/square are shown in Table 3.

Thick film resistor paste formulations with a resistance range of 1 ohm/square are shown in Table 4.

A thick film resistor paste formulation with a resistance range of 10 ohms/square is shown in Table 5.

により測定したＨ（Ｃ）ＴＣＲ性能が以下のとおりであった：０．１Ω／□＜８００ｐｐｍ、１Ω／□＜５００ｐｐｍ、１０Ω／□が±１００ｐｐｍ範囲内にあった。
ｃ．短時間過負荷（ＳＴＯＬ）性能を測定した。０．８＊０．８サイズの厚膜抵抗器に５ｓの２．５倍の定格電流（１０Ω／□以下）或いは２．５倍の定格電圧（１０Ω／□）を印加し、３０分間放置して、

（ここで、Ｒ_０、Ｒ_１は、それぞれ、印加前後の抵抗値である。）によりその前後の抵抗値の変化を確認し、ΔＲ変化絶対値が１％未満であるものを合格とし、そうしないものを不合格とした。定格電圧が

であり、定格電流が

（Ｒが、対応するチップ抵抗器の抵抗値である。）である。 After the thick film resistor paste was sintered at 850° C. to produce a chip resistor, its performance was measured.
a. 0603 standard was printed and the standard deviation of the resistance values of all chip resistors across the entire surface was measured to be SD<4%.
b. The TCR performance of 0.8*0.8 standard chip resistors was measured. In general, with 25°C as the reference, the resistance value measured by keeping the temperature at 125°C for 10 minutes is defined as _R125 , and the resistance value measured by keeping the temperature at -55°C for 10 minutes is defined as R _-55 .

The H(C)TCR performance as measured by RI was as follows: 0.1 Ω/square <800 ppm, 1 Ω/square <500 ppm, 10 Ω/square within ±100 ppm.
c. Short time overload (STOL) performance was measured. Apply 2.5 times the rated current (10Ω/square or less) or 2.5 times the rated voltage (10Ω/square) of 5s to a 0.8*0.8 size thick film resistor and leave it for 30 minutes. hand,

(Here, R ₀ and R ₁ are the resistance values before and after the application, respectively.) Confirm the change in the resistance value before and after the application, and pass those with an absolute value of ΔR change of less than 1%. Those that did not were rejected. rated voltage

and the rated current is

(R is the resistance value of the corresponding chip resistor).

Performance measurements of thick film resistor pastes with a resistance range of 0.1 ohms/square are shown in Table 6.

Thick film resistor paste performance measurements with a resistance range of 1 ohm/square are shown in Table 7.

Thick film resistor paste performance measurements with a resistance range of 10 ohms/square are shown in Table 8.

Comparative example 5
The difference between this comparative example and Example 5 is that in this Comparative example, Pd is used instead of Pt in Example 5, and the morphology and particle size range of this Pd powder are the same as those of the Pt powder of Example 5. It's all about what happened.

Comparative example 6
The difference between this comparative example and Example 14 is that in this comparative example, Pd is used instead of Pt in Example 14, and the morphology and particle size range of this Pd powder are the same as those of the Pt powder of Example 14. It's all about what happened.

Comparative example 7
The difference between this comparative example and Example 21 is that Pd is used instead of Pt in Example 21 in this comparative example, and the morphology and particle size range of this Pd powder are the same as those of the Pt powder of Example 21. It's just that.

表６～９からわかるように、厚膜抵抗器は、低い抵抗範囲である１Ω／□、０．１Ω／□、或いはより低い抵抗範囲、例えば０．０１Ω／□の場合、Ｐｔ粉末又はＡｇ－Ｐｔ合金のモルフォロジー、比表面積及び粒子径を制御し、Ｐｄ粉末の代わりに同等の質量百分率のＰｔ粉末を使用することにより、より優れたＴＣＲ性能が得られた。１０Ω／□の場合、Ｐｄ粉末の代わりに同等の質量百分率のＰｔ粉末を使用することにより、より優れたＴＣＲ温度依存特性及び小さいＴＣＲサイズ効果が得られた。 Table 9 shows the measurement results of Comparative Examples 5 to 7.

As can be seen from Tables 6-9, the thick film resistors can be either Pt powder or Ag- Better TCR performance was obtained by controlling the morphology, specific surface area and particle size of the Pt alloy and substituting the same mass percentage of Pt powder for Pd powder. In the case of 10 ohms/square, better TCR temperature dependent properties and smaller TCR size effect were obtained by substituting equivalent mass percentage of Pt powder for Pd powder.

Example 25
The only difference from Example 7 is that f-type Pt was used instead of Pt in Example 7 in this example.

Example 26
The only difference from Example 15 is that g-type Pt was used instead of Pt in Example 15 in this example.

Example 27
The only difference from Example 10 is that h-type Pt was used instead of Pt in Example 10 in this example.

Example 28
The only difference from Example 17 is that i-type Pt was used instead of Pt in Example 17 in this example.

Comparative example 8
The only difference from Example 5 is that j-type Pt was used instead of Pt in Example 5 in this comparative example.

Comparative example 9
The only difference from Example 14 is that j-type Pt was used instead of Pt in Example 14 in this comparative example.

Comparative example 10
The only difference from Example 21 is that j-type Pt was used instead of Pt in Example 21 in this comparative example.

The measurement results of Examples 25-28 and Comparative Examples 8-10 are shown in Table 10.

As can be seen from Table 10, when the crystallite diameter of the (111) crystal face of Pt is not within the range of 7 to 50 nm, the concentration of STOL and resistance value is difficult to meet the requirements, and the Pt powder or Ag—Pt alloy powder When the length ratio of the major axis to the minor axis of is greater than 3 (Comparative Example 10), CTCR and SD were difficult to meet the requirements.

After fabricating chip resistors from thick film resistor paste at different sintering temperatures, the TCR performance of 0.8*0.8 standard chip resistors was measured according to the above method. 15.

As can be seen from Tables 11-15, the resistors fabricated with the resistor paste using Pt powder have better TCR temperature dependence than those using Pd powder, indicating that Pt ( 111) The crystallite diameter of the crystal plane is in the range of 7 to 50 nm, the ratio of the length of the major axis to the minor axis of the Pt powder or Ag—Pt alloy powder is in the range of 3, and such a resistor paste has a better TCR temperature dependence.

After manufacturing chip resistors by sintering the thick film resistor paste at 850° C., the TCR performance of different standard chip resistors was measured according to the above method. The measurement results are shown in Tables 16-20.

As can be seen from Tables 16-20, resistors made with resistor pastes using Pt powder have better TCR sizing effects than those using Pd powder, showing that Pt (111 ) The crystallite diameter of the crystal plane is in the range of 7 to 50 nm, the length ratio of the major axis to the minor axis of the Pt powder or Ag-Pt alloy powder is in the range of 3, and such a resistor paste has a better TCR size effect.

It should be noted that the above embodiments are not intended to limit the scope of the present invention, but are for the purpose of explaining the technical means of the present invention, and the present invention has been described in detail with reference to preferred embodiments. , Those skilled in the art will understand that the technical means of the present invention can be modified or replaced with equivalents without departing from the essence and scope of the technical means of the present invention.

Claims (6)

At least two of Ag powder, Pt powder, and Ag—Pt alloy powder, wherein the Pt powder or Ag—Pt alloy powder is at least one of honeycomb spherical, flocculent, spherical, and substantially spherical, and the Pt In the powder or Ag—Pt alloy powder, at least 90 wt% of the Pt powder or Ag—Pt alloy powder has a length ratio of the major axis to the minor axis of major axis: minor axis = 1 to 3,
The thick film resistor paste includes 30-80 wt% solid phase component and 20-70 wt% organic component, where the solid phase component is 100 wt%, the solid phase component is 10-40 wt% Ag , 0.1-20 wt% Pt, 20-50 wt% RuO2 _, 20-60 wt% glass component, and 0-5 wt% inorganic filler. paste. In the Pt powder and Ag—Pt alloy powder, the crystallite size of the (111) crystal face of Pt measured by X-ray diffraction is 7 to 50 nm, The thickness according to claim 1 Membrane resistor paste. The Pt powder has a particle size of 10 nm to 1 μm, the Pt powder has a specific surface area of 0.3 m ² /g to 25 m ² /g, and the Ag—Pt alloy powder has a particle size of 200 nm to 1 μm. , and the specific surface area of the Ag—Pt alloy powder is 0.3 m ² /g to 15 m ² /g. the glass component is at least one of glass composition 1, glass composition 2, glass composition 3 and glass composition 4;
The glass composition 1 contains, in weight percentages, 10-50% PbO, 35-55% SiO ₂ , 5-30% CaO, 1-20% Al ₂ O ₃ , 1-10% B ₂ O ₃ and 0 ZnO. ~10%, wherein the sum of the PbO, _SiO2 , CaO, _Al2O3 , _B2O3 and _ZnO contents in the glass composition 1 in weight percentage is at least ₉₅ %;
The glass composition 2 contains, in weight percentage, SiO ₂ 40-75%, BaO 0-15%, SrO 0-20%, Na ₂ O 0-10%, K ₂ O 0-10%, Al ₂ O ₃ 1-15%, B ₂ O ₃ 1-25% and ZnO 0-10%, and said SiO ₂ , BaO, SrO, Na ₂ O, K ₂ O, Al ₂ O ₃ , B ₂ O ₃ and ZnO the total content in weight percentage in the glass composition 2 is at least 95%;
The glass composition 3 contains, in weight percentage, 50-88% PbO, 10-30% SiO _{2 ,} 1-10% Al ₂ O ₃ , 1-10% B _{2 O} 3 and 0-10% ZnO, the sum of the PbO, SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and ZnO contents in the glass composition 3 in weight percentage is at least 95%;
The glass composition 4 contains, in weight percentages, 60-88% PbO, 10-35% SiO _{2 ,} 1-10% Al ₂ O ₃ , 1-10% B _{2 O} 3 and 0-20% transition metal oxides. wherein the transition metal oxide _comprises at least one of CuO, _MnO2 , _Nb2O5 , _Ta2O5 , _TiO2 and _{ZrO2 ;}
The thick film resistor paste according to any one of claims 1 to 3 , characterized in that: The organic component includes an organic carrier and an organic solvent, wherein the organic carrier is at least one of methyl cellulose, ethyl cellulose, acrylic resin and epoxy resin, and the organic solvent is terpineol, butyl carbitol, butyl carbitol. Thick film resistor paste according to any one of claims 1 to 3, characterized in that it is at least one of tall acetate, diethylene glycol dibutyl ether and alcohol ester system. A resistor manufactured from the thick film resistor paste according to any one of claims 1-5 .