Resistance paste and preparation method thereof

Abstract

The invention relates to the technical field of resistance paste, and provides resistance paste and a preparation method thereof, and the resistance paste comprises 70-112 parts of a conductive phase material, 0.1-3 parts of a temperature coefficient regulator, 0.1-2 parts of a thermal expansion coefficient regulator, 0.1-5 parts of a sintering activator, 2-5 parts of glass powder, and 14-41 parts of an organic carrier. According to the resistance paste provided by the invention, the conductive phase material serves as a core component and is used for forming a continuous and compact conductive network; the temperature coefficient regulator controls the resistance temperature coefficient of the resistance paste, so that the resistance paste can keep the resistance value stable in a wider temperature range; the thermal expansion coefficient regulator reduces the thermal expansion coefficient of the resistance paste, so that the resistance paste is compatible with a base material, and the problem of cracking after sintering caused by overlarge thermal expansion coefficient is avoided; the sintering activator reduces the sintering temperature of the resistance paste, promotes diffusion and rearrangement among particles, improves the sintering density, improves the combination between the paste and a base material, and improves the stability and reliability of a resistor body.

Description

Technical Field

[0001] The present application belongs to the technical field of resistor pastes, and in particular, relates to a resistor paste and a preparation method thereof. Background Art

[0002] Chip resistors, as an indispensable electronic component in modern electronic devices, undertake key functions such as voltage division, current limiting and signal processing. With the rapid development of electronic technology, chip resistors are gradually developing in the direction of high precision, miniaturization and high reliability to meet the needs of increasingly complex electronic systems. As one of the key materials of chip resistors, the performance of resistor paste is directly related to the electrical properties, durability and consistency of the resistor, so it is particularly important.

[0003] Ruthenium resistor paste, with its excellent electrical conductivity, outstanding chemical stability and outstanding high temperature resistance, occupies a pivotal position in the manufacture of chip resistors. Its core conductive component is ruthenium dioxide (RuO2). Although RuO2 has high temperature stability as a conductive phase, it is difficult for RuO2 to form a dense sintering network under low temperature conditions, resulting in a higher sintering temperature for ruthenium resistor paste to achieve close bonding between particles. High sintering temperature not only increases production costs, but may also cause thermal damage to the substrate, thereby limiting the widespread use of ruthenium resistor paste in certain temperature-sensitive application scenarios. In addition, the existing ruthenium resistor paste often has a mismatch problem in the thermal expansion coefficients of the substrate (such as Al2O3 substrate). During the sintering process, due to temperature changes, large thermal stress will be generated between the paste and the substrate, resulting in microcracks after sintering, which will not only damage the electrical properties of the resistor, but also affect its long-term stability.

[0004] Therefore, there is an urgent need to develop a resistor paste with low sintering temperature, stable performance and good compatibility with the substrate. Summary of the invention

[0005] The purpose of the present application is to provide a resistor paste and a preparation method thereof, aiming to solve the problems of the existing ruthenium-based resistor paste, such as high sintering temperature, unstable performance, and mismatch in thermal expansion coefficient with the substrate.

[0006] In order to achieve the above application purpose, the technical solution adopted in this application is as follows: In a first aspect, the present application provides a resistor paste comprising the following components in weight proportions: 70 to 112 parts of a conductive phase material, 0.1 to 3 parts of a temperature coefficient regulator, 0.1 to 2 parts of a thermal expansion coefficient regulator, 0.1 to 5 parts of a sintering activator, 2 to 5 parts of a glass powder, and 14 to 41 parts of an organic carrier.

[0007] In a second aspect, the present application provides a method for preparing a resistor paste, comprising the following steps: Premixing the conductive phase material, the thermal expansion coefficient regulator and the sintering activator to obtain a mixed powder; Adding a temperature coefficient regulator into an organic carrier and performing a mixing treatment to obtain a suspension; The mixed powder and glass powder are added into the suspension to be dispersed, then three-roller milled, and filtered to obtain resistor slurry.

[0008] Compared with the prior art, this application has the following beneficial effects: The resistor paste provided in the first aspect of the present application, the conductive phase material is used as the core component of the resistor paste to form a continuous and dense conductive network; the added temperature coefficient regulator can accurately control the resistance temperature coefficient of the resistor paste, so that the resistor paste can maintain a stable resistance value in a wider temperature range, thereby improving the thermal stability and reliability of the resistor body made of the resistor paste; the added thermal expansion coefficient regulator can reduce the thermal expansion coefficient of the resistor paste, making it compatible with the substrate, avoiding the cracking problem after sintering caused by excessive thermal expansion coefficient; the added sintering activator can reduce the sintering temperature of the resistor paste and increase the sintering activity of the paste, thereby promoting the diffusion and rearrangement between particles, increasing the sintering density, and improving the interface bonding between the resistor paste and the substrate, thereby reducing the interface defects and thermal stress caused by problems such as thermal expansion coefficient mismatch, and improving the stability and reliability of the resistor body. Therefore, under the synergistic effect of the temperature coefficient regulator, the thermal expansion coefficient regulator and the sintering activator, the resistor paste of the present application is endowed with a lower sintering temperature and excellent substrate compatibility, so that the performance of the resistor body formed by sintering is stable.

[0009] The second aspect of the present application provides a method for preparing a resistor paste. First, a ruthenium-containing mixture powder, a thermal expansion coefficient regulator and a sintering activator are pre-mixed to make the components initially mixed evenly to form a mixed powder, and the temperature coefficient regulator is added to an organic carrier to form a suspension. The mixed powder and glass powder are then added to the suspension for dispersion treatment to ensure that the powder is completely wetted and evenly dispersed to prevent agglomeration. After three-roll ball milling treatment, the resistor paste of the target fineness can be obtained after filtration. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0011] Figure 1 This is a SEM image of the resistor paste provided in Example 1 of the present application. DETAILED DESCRIPTION In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0012] A first aspect of an embodiment of the present application provides a resistor paste, comprising the following components in parts by weight: 70 to 112 parts of a conductive phase material, 0.1 to 3 parts of a temperature coefficient regulator, 0.1 to 2 parts of a thermal expansion coefficient regulator, 0.1 to 5 parts of a sintering activator, 2 to 5 parts of a glass powder, and 14 to 41 parts of an organic carrier.

[0013] The resistor paste provided in the embodiment of the present application, the conductive phase material is used as the core component of the resistor paste to form a continuous and dense conductive network; the added temperature coefficient regulator can accurately control the resistance temperature coefficient of the resistor paste, so that the resistor paste can maintain a stable resistance value in a wider temperature range, thereby improving the thermal stability and reliability of the resistor body made of the resistor paste; the added thermal expansion coefficient regulator can reduce the thermal expansion coefficient of the resistor paste, making it compatible with the substrate, avoiding the cracking problem after sintering caused by excessive thermal expansion coefficient; the added sintering activator can reduce the sintering temperature of the resistor paste and increase the sintering activity of the paste, thereby promoting the diffusion and rearrangement between particles, increasing the sintering density, improving the interface bonding between the resistor paste and the substrate, thereby reducing the interface defects and thermal stress caused by problems such as thermal expansion coefficient mismatch, and improving the stability and reliability of the resistor body. Therefore, under the synergistic effect of the temperature coefficient regulator, the thermal expansion coefficient regulator and the sintering activator, the resistor paste of the present application is endowed with a lower sintering temperature and excellent substrate compatibility, so that the performance of the resistor body formed by sintering is stable.

[0014] In the embodiment, the temperature coefficient adjuster includes a positive temperature coefficient adjuster and a negative temperature coefficient adjuster in a mass ratio of (1-9): (1-9). By adding the positive temperature coefficient adjuster and the negative temperature coefficient adjuster and controlling the ratio of the two, the resistance temperature coefficient of the resistor paste is reduced and stabilized within the range of ±50ppm / ℃, so that the manufactured resistor body can maintain a stable resistance value within a wide temperature range and has excellent thermal stability and reliability.

[0015] In an embodiment, the positive temperature coefficient regulator includes LaMnO3, MoO3 and ZrO2; further, the mass ratio of LaMnO3, MoO3 and ZrO2 is (1-10): (20-50): (1-10). By synthesizing LaMnO3, MoO3 and ZrO2 into a composite oxide with a specific composite perovskite structure, the linear control capability of the resistance temperature coefficient can be optimized and the long-term stability of the resistor can be improved.

[0016] In a specific embodiment, the positive temperature coefficient regulator also includes ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate, and the mass ratio of LaMnO3, MoO3, ZrO2, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate is (1~10):(20~50):(1~10):(1~10):(1~10):(10~30).

[0017] In an embodiment, the negative temperature coefficient regulator includes NiMn2O4, SnO2 and Fe2O3; further, the mass ratio of NiMn2O4, SnO2 and Fe2O3 is (10-20): (1-10): (20-50). By synthesizing NiMn2O4, SnO2 and Fe2O3 into a composite oxide with a specific composite spinel structure, the linear control capability of the resistance temperature coefficient can be optimized and the long-term stability of the resistor can be improved.

[0018] In a specific embodiment, the negative temperature coefficient regulator also includes ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate, and the mass ratio of NiMn2O4, SnO2, Fe2O3, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate is (10~20): (1~10): (20~50): (1~10): (1~10): (10~30).

[0019] The positive temperature coefficient regulator and the negative temperature coefficient regulator can avoid the temperature drift problem caused by adding MnO2, Co2O3 and CuO separately by forming a single composite perovskite or composite spinel phase.

[0020] In an embodiment, the thermal expansion coefficient regulator includes Al2O3, Si3N4 and B2O3 in a mass ratio of (75-95): (5-10): (0.1-5); Al2O3 and Si3N4 have extremely low thermal expansion coefficients, and adding them to the resistor paste can significantly reduce the thermal expansion coefficient of the resistor body, improve compatibility with the substrate, and avoid cracking problems after sintering caused by excessive thermal expansion coefficients. Adding B2O3 can reduce carbon residue after resin sintering, thereby further reducing the thermal expansion coefficient. Therefore, under the synergistic effect of the ultra-low thermal expansion coefficient ceramic oxides Al2O3, Si3N4 and B2O3, the resistor paste is given a very small thermal expansion coefficient, which is compatible with the substrate.

[0021] In an embodiment, the sintering activator is selected from at least one of nano-grade RuO2 powder, nano-grade ZrO2 powder and nano-grade CuO powder. These sintering activators can significantly reduce the sintering temperature of the resistor paste, reducing the sintering temperature from 850°C to below 750°C, thereby increasing the sintering density and interface bonding, and improving the stability and reliability of the resistor.

[0022] In the embodiment, the particle size of the nano-sized RuO2 powder, the nano-sized ZrO2 powder and the nano-sized CuO powder is 10 to 300 nm.

[0023] In an embodiment, the conductive phase material includes a ruthenium-containing mixture powder; specifically, the ruthenium-containing mixture powder includes 45 to 68 parts of ruthenium dioxide powder, 15 to 24 parts of bismuth ruthenate powder and 10 to 20 parts of lead ruthenate powder.

[0024] In the embodiment, the particle size of the ruthenium dioxide powder, the bismuth ruthenate powder and the lead ruthenate powder is 0.1-5 μm.

[0025] In an embodiment, the organic vehicle includes 5-10 parts of ethyl cellulose, 2-8 parts of terpineol, 2-8 parts of ethylene glycol butyl ether and 5-15 parts of ethylene glycol butyl ether acetate.

[0026] In the embodiment, the fineness of the resistor paste is ≤10 μm, the viscosity is 50-300 Pa·s, and the temperature coefficient is within the range of ±50 ppm / °C.

[0027] In the embodiment, the particle size of the glass powder is 0.5-3 μm.

[0028] In an embodiment, the glass powder includes Bi2O3, SiO2, B2O3, ZnO, Al2O3 and ZrO2 in a mass ratio of (40-60): (15-25): (5-15): (5-10): (2-5): (1-5).

[0029] The second aspect of the embodiment of the present application provides a method for preparing the above resistor paste. The method for preparing the resistor paste of the present application comprises the following steps: S01: premixing a conductive phase material, a thermal expansion coefficient regulator and a sintering activator to obtain a mixed powder; S02: adding a temperature coefficient regulator to an organic carrier for mixing to obtain a suspension; S03: adding the mixed powder and glass powder into the suspension for dispersion treatment, then performing a three-roller ball milling treatment, and filtering to obtain a resistor slurry.

[0030] The preparation method of the resistor paste provided in the embodiment of the present application is to pre-mix the conductive phase material, the thermal expansion coefficient regulator and the sintering activator, so that the components are initially mixed evenly to form a mixed powder, and the temperature coefficient regulator is added to the organic carrier to form a suspension, and then the mixed powder and the glass powder are added to the suspension for dispersion treatment, which can ensure that the powder is completely wetted and evenly dispersed to prevent agglomeration. After three-roll ball milling treatment, the resistor paste with the target fineness can be obtained after filtration.

[0031] The specific components and contents of the conductive phase material, thermal expansion coefficient regulator, sintering activator, temperature coefficient regulator, organic carrier and glass powder in the above steps S01~S03 are the same as the conductive phase material, thermal expansion coefficient regulator, sintering activator, temperature coefficient regulator, organic carrier and glass powder included in the resistor paste of the above text application embodiment, and are not repeated here.

[0032] In the above step S01, in the embodiment, the step of premixing the conductive phase material, the thermal expansion coefficient regulator and the sintering activator comprises: according to the above component ratios, weighing appropriate amounts of the conductive phase material, the thermal expansion coefficient regulator and the sintering activator and adding them into a high-speed mixer and stirring them evenly to obtain a mixed powder.

[0033] In the above step S02, in the embodiment, the step of preparing a positive temperature coefficient regulator includes: weighing appropriate amounts of LaMnO3 powder, MoO3 powder, ZrO2 powder, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate according to the mass ratio of LaMnO3, MoO3, ZrO2, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate of (1~10): (20~50): (1~10): (1~10): (10~30); calcining the LaMnO3 powder, MoO3 powder and ZrO2 powder at 400~600℃ for 2~6h to form a first composite oxide; mixing the first composite oxide, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate to obtain a positive temperature coefficient regulator.

[0034] In an embodiment, the steps of preparing a negative temperature coefficient regulator include: weighing appropriate amounts of NiMn2O4 powder, SnO2 powder, Fe2O3 powder, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate according to a mass ratio of NiMn2O4, SnO2, Fe2O3, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate of (10~20): (1~10): (20~50): (1~10): (1~10): (10~30); calcining the NiMn2O4 powder, SnO2 powder and Fe2O3 powder at 400~600°C for 2~6h to form a second composite oxide; mixing the second composite oxide, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate to obtain a negative temperature coefficient regulator.

[0035] In an embodiment, the step of adding the temperature coefficient regulator into the organic carrier for mixing includes: adding the positive temperature coefficient regulator and the negative temperature coefficient regulator into the organic carrier and stirring evenly to obtain a suspension.

[0036] In the above step S03, in the embodiment, the step of adding the mixed powder and the glass powder into the suspension for dispersion treatment includes: adding the mixed powder into the suspension, fully dispersing the mixed material by ultrasonic-assisted ball milling equipment, and then adding the glass for full dispersion.

[0037] The following describes the invention in conjunction with specific embodiments.

[0038] Example 1 This embodiment provides a resistor paste and a preparation method thereof.

[0039] A resistor paste comprising the following components in parts by weight: 57 parts of ruthenium dioxide powder, 20 parts of bismuth ruthenate powder, 15 parts of lead ruthenate powder, 0.8 parts of a positive temperature coefficient regulator, 0.7 parts of a negative temperature coefficient regulator, 1 part of a thermal expansion coefficient regulator, 2.5 parts of nano-grade RuO2 powder, 3.5 parts of glass powder, 7.5 parts of ethyl cellulose, 5 parts of pine alcohol, 5 parts of ethylene glycol butyl ether and 10 parts of ethylene glycol butyl ether acetate; The positive temperature coefficient regulator is composed of LaMnO3, MoO3, ZrO2, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate in a mass ratio of 6:35:6:5:6:20; The negative temperature coefficient regulator is composed of NiMn2O4, SnO2, Fe2O3, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate in a mass ratio of 15:6:35:5:6:20; The thermal expansion coefficient regulator is composed of Al2O3 powder, Si3N4 powder and B2O3 powder in a mass ratio of 85:7.5:2.5; The glass powder is composed of Bi2O3, SiO2, B2O3, ZnO, Al2O3 and ZrO2 in a mass ratio of 50:20:10:7.5:3.5:3; The D50 particle size of the glass powder is 2 μm; The D50 particle size of ruthenium dioxide powder, bismuth ruthenate powder and lead ruthenate powder is 2.5 μm; The D50 particle size of nano-scale RuO2 powder is 150nm.

[0040] The method for preparing the resistor paste comprises the following steps: S11: according to the proportion of each component of the resistor paste of this embodiment, weigh appropriate amounts of raw materials of each component; S12: adding ruthenium dioxide powder, bismuth ruthenate powder, lead ruthenate powder, Al2O3 powder, Si3N4 powder, B2O3 powder and nano-grade RuO2 powder into a high-speed mixer and stirring evenly to obtain a mixed powder; S13: calcining LaMnO3 powder, MoO3 powder and ZrO2 powder at 500°C for 4 hours to form a first composite oxide; uniformly mixing the first composite oxide, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate to obtain a positive temperature coefficient regulator; The NiMn2O4 powder, SnO2 powder and Fe2O3 powder are calcined at 500°C for 4 hours to form a second composite oxide; the second composite oxide, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate are mixed to obtain a negative temperature coefficient regulator; The positive temperature coefficient regulator and the negative temperature coefficient regulator are added into the organic carrier of ethyl cellulose, pineol, ethylene glycol butyl ether and ethylene glycol butyl ether acetate and stirred evenly to obtain a suspension; S14: adding the mixed powder to the suspension, fully dispersing the mixed powder by ultrasonic-assisted ball milling equipment, then adding glass powder and continuing ball milling to fully disperse the mixed powder, and then going through a three-roller ball milling process, grinding 12 times, and filtering to obtain a resistor slurry.

[0041] Example 2 This embodiment provides a resistor paste and a preparation method thereof, which is different from Embodiment 1 in that: The resistor paste does not contain a positive temperature coefficient adjuster.

[0042] Example 3 This embodiment provides a resistor paste and a preparation method thereof, which is different from Embodiment 1 in that: The resistor paste does not contain a negative temperature coefficient adjuster.

[0043] Example 4 This embodiment provides a resistor paste and a preparation method thereof, which is different from Embodiment 1 in that: The resistor paste and the thermal expansion coefficient regulator are composed of Al2O3 powder and Si3N4 powder in a mass ratio of 85:7.5.

[0044] Example 5 This embodiment provides a resistor paste and a preparation method thereof, which is different from Embodiment 1 in that: Resistor paste, thermal expansion coefficient regulator is B2O3 powder.

[0045] Example 6 This embodiment provides a resistor paste and a preparation method thereof, which is different from Embodiment 1 in that: The resistor paste uses 1 part of nano-grade ZrO2 powder and 0.5 part of nano-grade CuO powder to replace 2.5 parts of nano-grade RuO2 powder, and the D50 particle size of the nano-grade ZrO2 powder and the nano-grade CuO powder is 150 nm.

[0046] Example 7 This embodiment provides a resistor paste and a preparation method thereof, which is different from Embodiment 1 in that: The preparation method of the resistor paste, step S13 is to directly mix LaMnO3 powder, MoO3 powder, ZrO2 powder, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate to obtain a positive temperature coefficient regulator; directly mix NiMn2O4 powder, SnO2 powder, Fe2O3 powder, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate to obtain a negative temperature coefficient regulator.

[0047] Comparative Example 1 This comparative example provides a resistor paste and a preparation method thereof.

[0048] A resistor paste comprising the following components in parts by weight: 57 parts of ruthenium dioxide powder, 20 parts of bismuth ruthenate powder, 15 parts of lead ruthenate powder, 3.5 parts of glass powder, 7.5 parts of ethyl cellulose, 5 parts of pineneol, 5 parts of ethylene glycol butyl ether and 10 parts of ethylene glycol butyl ether acetate; The glass powder is composed of PbO, SiO2, B2O3, Al2O3 and ZnO in a mass ratio of 60:15:10:3.5:6; the D50 particle size of the glass powder is 2.0 μm; The D50 particle size of the ruthenium dioxide powder, the bismuth ruthenate powder and the lead ruthenate powder is 2.5 μm.

[0049] The method for preparing the resistor paste comprises the following steps: S11: according to the proportion of each component of the resistor paste of this embodiment, weigh appropriate amounts of raw materials of each component; S12: adding ruthenium dioxide powder, bismuth ruthenate powder and lead ruthenate powder into a high-speed mixer and stirring them evenly to obtain a mixed powder; S13: mixing ethyl cellulose, pinene alcohol, ethylene glycol butyl ether and ethylene glycol butyl ether acetate to obtain an organic carrier solution; S14: adding the mixed powder into the organic carrier solution, fully dispersing the mixed powder by ultrasonic-assisted ball milling equipment, then adding glass powder and continuing ball milling to fully disperse the mixed powder, and then performing a three-roller ball milling process, grinding 12 times, and filtering to obtain a resistor paste.

[0050] Comparative Example 2 This comparative example provides a resistor paste and a preparation method thereof, which is different from Example 1 in that: The resistor paste does not contain a positive temperature coefficient adjuster and a negative temperature coefficient adjuster.

[0051] The method for preparing the resistor paste comprises step S13 of uniformly stirring ethyl cellulose, pinene alcohol, ethylene glycol butyl ether and ethylene glycol butyl ether acetate to obtain an organic carrier solution; and step S14 of replacing the suspension with the organic carrier solution.

[0052] Comparative Example 3 This comparative example provides a resistor paste and a preparation method thereof, which is different from Example 1 in that: Resistor paste without CTE modifier.

[0053] The method for preparing the resistor slurry, step S12 is to add ruthenium dioxide powder, bismuth ruthenate powder, lead ruthenate powder and RuO2 powder into a high-speed mixer and stir them evenly to obtain a mixed powder.

[0054] Comparative Example 4 This comparative example provides a resistor paste and a preparation method thereof, which is different from Example 1 in that: Resistor paste, does not contain sintering activator (RuO2 powder).

[0055] The method for preparing the resistor slurry, step S12 is to add ruthenium dioxide powder, bismuth ruthenate powder, lead ruthenate powder, Al2O3 powder, Si3N4 powder and B2O3 powder into a high-speed mixer and stir them evenly to obtain a mixed powder.

[0056] Related performance test analysis: 1. The fineness of the resistor pastes provided in Examples 1 to 7 and Comparative Examples 1 to 4 was tested using a scraper fineness method.

[0057] 2. The viscosity of the resistor pastes provided in Examples 1 to 7 and Comparative Examples 1 to 4 was tested using a rotational viscometer.

[0058] 3. The resistor pastes provided in Examples 1 to 7 and Comparative Examples 1 to 4 were printed on substrates respectively, and then sintered in air at 800° C. to form resistors.

[0059] (1) Use a resistance tester to test the temperature coefficient of resistance (HTCR) of a resistor in the high temperature range and the temperature coefficient of resistance (CTCR) in the low temperature or below room temperature range.

[0060] (2) Short-time overload test, that is, to detect the stability and damage resistance of the resistor when it is subjected to power exceeding the rated power for a short period of time. Specifically, a load of 6.25 times the rated power is applied to the resistor, and the overload time is 5s. After the overload test is completed, it is placed in a standard environment for 1h to detect the resistance change; the resistance change ΔR / R is calculated and it is determined whether it is within the range of ±0.5% to ±1%; (3) High temperature storage test, that is, to detect the performance stability and reliability of the resistor in a long-term high temperature environment. Specifically, the sample is placed in a high temperature environment of 125℃ or 175℃ for 1000 hours, and the resistance value is sampled and detected every 250 hours during the storage process; after the storage is completed, the sample is placed at room temperature for 1~2 hours, and the resistance change is detected; the resistance change ΔR / R is calculated and it is determined whether it is within the range of ±0.5% to ±2%. (4) Power load test, that is, testing the aging and stability of the resistor under long-term rated power load conditions. Specifically, at an ambient temperature of 70°C or 85°C, continuously apply a load of rated power or close to rated power; use a periodic on-off test method, such as 1.5 hours of power on, 0.5 hours of power off, and repeat the cycle for a cumulative test of 1000 hours; after the test, let it stand at room temperature for 1 to 2 hours and detect the resistance change. Calculate the resistance change ΔR / R and determine whether it is within the range of ±1% to ±3%.

[0061] The test results are shown in Table 1 below: Table 1 It can be seen from Table 1 that the fineness, viscosity, HTCR, CTCR, short-term overload, high-temperature storage and power load of the resistor slurries provided in Examples 1 to 7 of the present application all meet the national standards or even exceed the national standards, indicating that the resistor slurries in the embodiments of the present application can meet the application requirements.

[0062] The HTCR, CTCR, short-term overload, high-temperature storage and power load of the resistor paste provided in Example 1 are significantly better than those of Comparative Examples 1 to 4, indicating that under the synergistic effect of the temperature coefficient regulator, the thermal expansion coefficient regulator and the sintering activator, the resistor formed by sintering the resistor paste in the embodiment of the present application has strong damage resistance and good long-term high-temperature stability, better reliability and a wider range of applications.

[0063] The HTCR and CTCR of the resistor paste provided in Example 1 are significantly better than the national standard, and are significantly better than Examples 2, 3 and Comparative Examples 1, 2, indicating that the positive temperature coefficient regulator and negative temperature coefficient regulator added to the resistor paste in the example of the present application can significantly reduce the resistance temperature coefficient of the resistor paste.

[0064] The short-term overload and power load of the resistor paste provided in Example 1 are significantly better than those in Examples 4 and 5, indicating that the resistor paste in the embodiment of the present application can better reduce the thermal expansion coefficient of the resistor paste in cooperation with Al2O3 powder, Si3N4 powder and B2O3 powder, and has better compatibility with the substrate, thereby having better damage resistance and long-term stability.

[0065] The HTCR, CTCR, short-term overload, high-temperature storage and power load of the resistor paste provided in Example 1 are better than those in Example 7, indicating that in the process of preparing the resistor paste in the embodiment of the present application, LaMnO3 powder, MoO3 powder and ZrO2 powder are first calcined to synthesize a composite oxide with a specific composite perovskite structure, and NiMn2O4 powder, SnO2 powder and Fe2O3 powder are calcined to synthesize a composite oxide with a specific composite spinel structure, and then mixed with the organic system, which can optimize the linear control ability of the resistance temperature coefficient and improve the long-term stability of the resistor.

[0066] from Figure 1 It can be seen from the SEM that the resistor paste provided in Example 1 is evenly dispersed, and the size of all solid phase particles is less than 10 microns, without obvious agglomeration, indicating that the resistor paste provided in the embodiment of the present application can form a dense and stable resistor after sintering.

[0067] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A resistor paste, characterized in that: The invention comprises the following components in parts by weight: 70-112 parts of conductive phase material, 0.1-3 parts of temperature coefficient regulator, 0.1-2 parts of thermal expansion coefficient regulator, 0.1-5 parts of sintering activator, 2-5 parts of glass powder and 14-41 parts of organic carrier.

2. The resistor paste according to claim 1, characterized in that The temperature coefficient regulator includes a positive temperature coefficient regulator and a negative temperature coefficient regulator in a mass ratio of (1-9):(1-9).

3. The resistor paste according to claim 2, characterized in that: The positive temperature coefficient regulator includes LaMnO3, MoO3 and ZrO2; And / or, the negative temperature coefficient modifier includes NiMn2O4, SnO2 and Fe2O3.

4. The resistor paste according to claim 3, characterized in that The positive temperature coefficient regulator also includes ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate, and the mass ratio of LaMnO3, MoO3, ZrO2, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate is (1-10): (20-50): (1-10): (1-10): (1-10): (10-30); And / or, the negative temperature coefficient regulator also includes ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate, and the mass ratio of NiMn2O4, SnO2, Fe2O3, ethylene glycol, N-vinyl pyrrolidone and diethylene glycol butyl ether acetate is (10~20): (1~10): (20~50): (1~10): (1~10): (10~30).

5. The resistor paste according to claim 1, characterized in that: The sintering active agent is selected from at least one of nano-grade RuO2 powder, nano-grade ZrO2 powder and nano-grade CuO powder; And / or, the thermal expansion coefficient regulator includes Al2O3, Si3N4 and B2O3 in a mass ratio of (75-95): (5-10): (0.1-5).

6. The resistor paste according to claim 5, characterized in that The conductive phase material includes ruthenium-containing mixture powder.

7. The resistor paste according to claim 6, characterized in that: The ruthenium-containing mixed powder comprises 45-68 parts of ruthenium dioxide powder, 15-24 parts of bismuth ruthenate powder and 10-20 parts of lead ruthenate powder; And / or, the organic carrier comprises 5-10 parts of ethyl cellulose, 2-8 parts of terpineol, 2-8 parts of ethylene glycol butyl ether and 5-15 parts of ethylene glycol butyl ether acetate.

8. The resistor paste according to claim 7, characterized in that: The particle sizes of the ruthenium dioxide powder, bismuth ruthenate powder and lead ruthenate powder are 0.1-5 μm; And / or, the particle size of the nano-scale RuO2 powder, nano-scale ZrO2 powder and nano-scale CuO powder is 10 to 300 nm.

9. The resistor paste according to any one of claims 1 to 8, characterized in that: The resistor slurry has a fineness of ≤10 μm, a viscosity of 50-300 Pa·s, and a temperature coefficient within the range of ±50 ppm / °C; And / or, the particle size of the glass powder is 0.5-3 μm.

10. A method for preparing a resistor paste according to any one of claims 1 to 9, characterized in that: The following steps are involved: Premixing the conductive phase material, the thermal expansion coefficient regulator and the sintering activator to obtain a mixed powder; Adding a temperature coefficient regulator into an organic carrier and performing a mixing treatment to obtain a suspension; The mixed powder and glass powder are added into the suspension to be dispersed, then three-roller milled, and filtered to obtain resistor slurry.

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