TW202236309A - Resistor paste, use thereof, and method for producing resistor - Google Patents

Abstract

The present invention relates to a resistor paste, a use thereof, and a method for manufacturing a resistor. The present invention prepares a resistor paste containing an inorganic component and an organic vehicle. The inorganic component comprises a metal component, low-melting-point glass and high-melting-point glass. The metal component includes copper and nickel. The softening point Ths of the high-melting-point glass is 600 DEG C or more and is 100 DEG C or more higher than the softening point Tls of the low-melting-point glass. The softening point Tls of the low melting point glass may be 350 to 750 DEG C. The softening point Ths of the high melting point glass may be 650 to 1,150 DEG C. The glass transition temperature Thg of the high-melting-point glass may be 600 to 900 DEG C. In the inorganic component, the proportion of the low-melting-point glass may be 3-25 vol%, and the proportion of the high-melting-point glass may be 3-80 vol%.

Description

Resistive element paste, its use and manufacturing method of resistive element

The present invention relates to a resistance element paste with copper and nickel as conductive components, its application and the manufacturing method of the resistance element.

As resistor element pastes for forming resistor elements of resistors used in electronic circuits and power circuits of various electronic devices, resistor element pastes containing copper (Cu) and nickel (Ni)-based metals as conductive components are known.

A chip resistor is disclosed in Japanese Patent Application Laid-Open No. 9-275002 (Patent Document 1), which has: an insulating substrate; a resistance layer formed on at least one side of the insulating substrate and containing a copper/nickel alloy; and end faces An electrode, which is arranged on a pair of opposite ends of the above-mentioned insulating substrate in a manner of connecting the above-mentioned resistance layer; the resistance layer includes an alloy layer, and the alloy layer is a thick-film resistor composed of copper powder, glass frit, and organic vehicle components Component paste is printed onto copper/nickel alloy powder and fired. According to this document, the glass frit component is 0.5 to 10% by weight relative to the metal component. Also, it is stated that the purpose is to provide a thick film resistance element with low resistance below 1Ω, especially below 100mΩ. Resistive elements with a resistance value of ~50 mΩ.

Japanese Patent Application Laid-Open No. 2010-129896 (Patent Document 2) discloses a resistor element paste, which contains at least conductive metal powder including copper powder and nickel powder, glass powder, and resin and solvent In the paste of the vehicle, the glass powder includes: a first glass powder containing bismuth at least 70% by mass in terms of oxides; and a second glass powder substantially free of lead and cadmium. It is described in this document that the compounding quantity of the 1st glass powder is preferably in the range of 0.5-10 mass parts with respect to 100 mass parts of electroconductive metal powders, and 2-5 mass parts were compounded in the Example. Also, according to reports, the blending amount of the second glass powder is preferably in the range of 2 to 10 parts by mass relative to 100 parts by mass of the conductive metal powder, and in the examples, 1 to 10 parts by mass of borosilicate is blended Lead glass or borosilicate glass is used as the second glass powder. Furthermore, it is stated that the volume resistivity of the resistive element film obtained by firing the above-mentioned resistive element paste is 20-200 μΩ·cm, and a resistive element film of 37-126 μΩ·cm was produced in the examples.

Japanese Patent Application Laid-Open No. 2015-046567 (Patent Document 3) discloses a resistor element paste with a specific resistance of 200 μΩ·cm or more, which is based on the deployment of alumina powder in the resistor element paste that uses copper and nickel as conductive components. , silicon dioxide powder, titanium oxide powder and other non-conductive inorganic particles that will not melt at the firing temperature are obtained as resistance value adjustment components. This method can adjust the specific resistance to a wide range by adjusting the amount of non-conductive inorganic particles that do not melt under firing conditions. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 9-275002 [Patent Document 2] Japanese Patent Laid-Open No. 2010-129896 [Patent Document 3] Japanese Patent Laid-Open No. 2015-046567

[Problem to be solved by the invention]

However, the resistive element film formed from the resistive element pastes of Patent Documents 1 and 2 has a low resistance value and cannot be used for low and medium resistance applications above 200 μΩ·cm.

Also, in Patent Document 3, although the non-conductive inorganic particles can also increase the resistance value of the resistance element, the non-conductive inorganic particles themselves will not soften, melt, or sinter during the firing process, so they are formed by firing. Voids and pores are generated inside the resistive element film to form a porous structure. Moreover, in the environment of high temperature, high humidity or oxidative environment, oxygen or moisture will invade the inside of the resistance element film, which will oxidize or corrode the resistance element film with a porous structure, resulting in a change in resistance value. As a result, improvements in reliability such as heat resistance and moisture resistance of resistor element films have been demanded.

Furthermore, it is preferable that the resistance value adjustment component has a function of continuously and freely adjusting the resistance value (volume resistivity) within a wide range of 100 μΩ·cm to 10,000 μΩ·cm (easiness of adjustment).

Therefore, an object of the present invention is to provide a resistor element paste capable of forming a resistor element having excellent resistance value adjustment ease and high reliability, its use, and a method for manufacturing a resistor element. [Technical means to solve the problem]

The inventors of the present invention conducted diligent research to achieve the above-mentioned problems, and as a result found that by combining a metal component including copper and nickel, a low-melting-point glass, and a high-melting-point glass, and adjusting the relationship between the above-mentioned low-melting-point glass and the above-mentioned high-melting-point glass The relationship between the softening point provides a resistance element paste capable of forming a resistance element having excellent ease of adjustment of resistance value and high reliability, thereby completing the present invention.

That is, the resistance element paste of the present invention contains inorganic components and organic vehicles, The above-mentioned inorganic components include metal components, low melting point glass and high melting point glass, The above metal components include copper and nickel, The softening point Ths of the above-mentioned high-melting-point glass is 600°C or more, and is 100°C or more higher than the softening point Tls of the above-mentioned low-melting-point glass.

The softening point Tls of the above-mentioned low-melting glass may be 350-750°C. The softening point Ths of the above-mentioned high melting point glass may be 650-1150°C. The glass transition point Thg of the above-mentioned high melting point glass may be 600-900°C. The metal component mentioned above may be metal particles with a central particle diameter (D50) of 0.05-15 μm. The above-mentioned low-melting-point glass can be low-melting-point glass particles with a central particle diameter (D50) of 1-5 μm, and the above-mentioned high-melting-point glass can be high-melting-point glass particles with a central particle diameter (D50) of 1-8 μm. In the said inorganic component, the ratio of the said low melting point glass may be 3-25 volume%, and the ratio of the said high melting point glass may be 3-80 volume%.

The present invention also includes a method of manufacturing a resistor element by firing the above-mentioned resistor element paste. In this method, the firing temperature Tf can be higher than the softening point Tls of the lower melting point glass by more than 150°C. The above-mentioned firing temperature Tf may be higher than the glass transition point Thg of the higher melting point glass and be equal to or lower than the softening point Ths of the high melting point glass + 100°C.

The present invention also includes a resistance element comprising an inorganic component and having a volume resistivity of 100 μΩ·cm or more, The above-mentioned inorganic components include metal components, low melting point glass and high melting point glass, The above metal components include copper and nickel, The softening point Ths of the above-mentioned high-melting-point glass is 600°C or more, and is 100°C or more higher than the softening point Tls of the above-mentioned low-melting-point glass.

The volume resistivity of the above-mentioned resistive element may also be 10,000 μΩ·cm or less.

The present invention also includes a method for adjusting the volume resistivity of a resistance element obtained by firing the above-mentioned resistor element paste. It is in the range of 100～10,000 μΩ・cm. [Effect of Invention]

The present invention combines metal components including copper and nickel, low-melting-point glass and high-melting-point glass and adjusts the relationship between the softening points of the above-mentioned low-melting-point glass and the above-mentioned high-melting-point glass. It is excellent in the function (easiness of adjustment) to freely adjust the resistance value (volume resistivity), and is a resistive element paste for a resistive element with high reliability such as heat resistance and moisture resistance by forming a dense resistive element film. Furthermore, since a dense resistive element film can be formed, shape retention is excellent, and even a resistive element film having a relatively high resistance value can be improved in adhesion to a base material.

[Resistor element paste] In the resistance element paste (resistor element composition) of the present invention, a low-melting-point glass as an inorganic binder component and a high-melting-point glass as a resistance value adjusting component are blended with a metal component as a conductive component, and the above-mentioned low-melting-point glass and The relationship between the softening point of the above-mentioned high-melting point glass can take into account the ease of adjustment and reliability of the resistance value. The mechanism by which such an effect is exhibited is presumed to be as follows.

That is, in order to increase the resistance value of a resistor element containing a conductive component, it is necessary to prepare a non-conductive component in the resistor element paste. If the non-conductive component is uniformly and stably distributed in the conductive component, the volume ratio of the conductive component will decrease, and the conductivity will decrease. Not only that, it also has the effect of making the conductive channel thinner and longer due to the presence of non-conductive components in the conductive phase, so it can reduce conductivity by far exceeding the effect of the volume ratio of the non-conductive components formulated. However, if glass is used in the non-conductive components to be melted during firing, then during the firing process of the resistor element film, the non-conductive components will melt and flow, and the non-conductive components and conductive components will segregate and separate during the firing process instead of The conductive component cannot be uniformly dispersed in the conductive component. As a result, the conductivity cannot be effectively reduced. Not only that, but also it is difficult to control the state of segregation and separation, so the resistance value becomes unstable, and the control of conductivity becomes difficult, so the non-conductive component cannot effectively and stably increase the volume resistance rate (specific resistance).

As in Patent Document 3, high-melting inorganic particles such as alumina powder and silicon dioxide powder, which are non-conductive components that do not melt at the firing temperature, are used as resistance value adjustment components, thereby increasing the resistance value of the resistance element. However, the inorganic particles themselves are not softened or sintered during the firing process, so voids and pores are generated inside the resistance element film formed by firing to become porous. The more the amount of high-melting-point inorganic particles is added (when a relatively high resistance value is required), the more prominent the degree of porosity (porosity) becomes. If the resistance element film becomes porous, there is a possibility that the strength of the resistance element film will decrease, resulting in a decrease in thermal shock resistance. In addition, in reliability tests such as heat resistance tests or high-temperature and high-humidity tests of resistance element films, oxygen Or moisture intrudes into the hole to oxidize the resistance element film to increase the resistance value, thereby reducing the reliability of the resistance element film.

On the other hand, in the resistance element paste of the present invention, the low-melting glass as the inorganic binder component and the resistance value adjustment component of the resistance element paste (resistor element composition) have the properties of softening, deforming, and melting at the firing temperature. The high-melting-point glass that is sintered but not melted is combined with the metal component as the conductive component, so that a dense resistance element film can be formed regardless of the amount of compounding, and the resistance value can be continuously and freely adjusted in a wide range ( Volume resistivity) function. Furthermore, since a dense resistive film can be formed, reliability (heat resistance, moisture resistance) can also be improved.

(metal component) The resistor element paste of the present invention contains a metal component as a conductive component. The metal component may be in the form of particles (metal particles), and forms a conductive path in the resistance element (resistor element film) formed by firing. In order to obtain lower temperature dependence of resistance (TCR), the metal particles include at least copper and nickel.

The said metal particles may further contain other metals other than copper and nickel. Examples of other metals include: transition metals (for example, metals of Group 4A of the periodic table such as titanium and zirconium; metals of Group 5A of the periodic table such as vanadium and niobium; metals of Group 6A of the periodic table such as molybdenum and tungsten; metals of Group 6A of the periodic table such as manganese; Metals of group 7A; metals of group 8 of the periodic table such as iron, cobalt, ruthenium, rhodium, palladium, rhenium, iridium, platinum; metals of group 1B of the periodic table such as silver and gold, etc.), metals of group 2B of the periodic table (such as zinc , cadmium, etc.), metals of group 3B of the periodic table (such as aluminum, gallium, indium, etc.), metals of group 4B of the periodic table (such as germanium, tin, lead, etc.), metals of group 5B of the periodic table (such as antimony, bismuth, etc.) Wait. These metals may be used alone or in combination of two or more, and may also be alloys. The ratio of other metals in the metal particles may be 50% by mass or less (for example, 0 to 50% by mass), such as 30% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less (for example, 0.1% by mass or less). ~5% by mass). Metal particles are generally formed of only copper and nickel because they are inexpensive and have excellent electrical conductivity.

The metal particles consisting only of copper and nickel may be copper and nickel alloy particles or at least two types selected from the group consisting of copper particles, nickel particles, and copper and nickel alloy particles (such as a combination of copper particles and nickel particles , copper particles and/or combinations of nickel particles and the above-mentioned alloy particles, etc.), in terms of simplicity, etc., it is usually a combination of copper particles and nickel particles.

In the metal component, the mass ratio of copper to nickel is, for example, copper/nickel=90/10-30/70, preferably 80/20-40/60, further preferably 70/30-50/50, and more preferably It is 65/35～55/45. When the mass ratio of copper to nickel is too large or too small, the temperature dependence of resistance (TCR) may increase. Within this range, the temperature dependence (TCR) of the resistance value of the copper-nickel alloy resistance element can be controlled within a sufficiently low range. In the present invention, it is also assumed that, in addition to the inorganic binder component made of low melting point glass, a large amount of resistance value adjustment components made of high melting point glass are added, so TCR will be changed from the original copper due to these components. The TCR of the nickel alloy resistance element changes, but the TCR of the original copper-nickel alloy resistance element is maintained in the present invention. It can be presumed that the reason is that since the inorganic binder component and the resistance value adjustment component are electrically insulating, they will have an electrical influence on the conduction path formed by the sintered network of the metal, and are thermochemically stable before reaching a high temperature. There is no influence on the composition, therefore, in fact, the TCR of the copper-nickel alloy resistance element is hardly affected and shows the original lower TCR.

In this application, the so-called relatively low TCR means that the absolute value is about 300 ppm/°C or less and can be practically used as a resistor level TCR, which can be measured by the method described in the following examples. Also, in this application, the absolute value is 200 ppm/°C or less, further 100 ppm/°C or less as a preferable range of TCR.

Furthermore, in this application, the so-called ppm/°C means that the numerical value represented by the unit "/°C" is magnified by 10 ⁶ times.

The shape of the metal particles is not particularly limited, and it can be spherical (true spherical or roughly spherical), ellipsoid (ellipsoid), polyhedral (triangular pyramid, regular hexahedron or cube, cuboid, eight Surface shape, etc.), plate shape (flat, scale or flake shape, etc.), rod shape or rod shape, fiber shape, indeterminate shape, etc. The shape of metal particles is generally spherical, ellipsoidal, polyhedral, indeterminate, etc.

The particle size of the metal particles is not particularly limited. Since a large amount of non-conductive components (inorganic binder components and resistance value adjustment components) are prepared, when copper particles and nickel particles are used as separate metal particles, it is difficult to In terms of uniform dispersion and alloying during firing, it is advantageous to use metal particles with small particle diameters. On the other hand, when alloy particles of copper and nickel are used, there is no problem with the uniformity of alloying, but in terms of dispersibility, it is also advantageous to use alloy particles with a small particle size.

The central particle diameter (D50) of the metal particles can be selected from the range of about 0.05-15 μm. Especially for copper particles or copper-nickel alloy particles, the central particle diameter (D50) is, for example, 0.05-15 μm, preferably 0.08-10 μm, further preferably 0.1-5 μm, more preferably 0.2-4 μm (for example, 1 to 4 μm), preferably 2 to 3.5 μm. Regarding nickel particles, the central particle diameter (D50) is, for example, 0.05-5 μm, preferably 0.08-2 μm, further preferably 0.1-1 μm, more preferably 0.2-0.7 μm, most preferably 0.3-0.5 μm. Since the melting point (1455° C.) of nickel particles is higher than that of copper particles, the use of small particles is advantageous in terms of sinterability. If the particle size of the metal particles is too small, the economic efficiency will decrease, and the dispersibility in the resistor element paste and the fluidity of the resistor element composition as a whole may also decrease. If it is too large, the dispersibility of the resistor element paste and printing Resistance, sinterability of resistance elements, and uniformity of alloying may decrease.

Furthermore, in this application, the central particle diameter of the metal particles (including the following glass particles) means the particle diameter distribution and the central particle diameter (volume basis) measured using a laser diffraction scattering particle size distribution measuring device .

The volume fraction of the metal component can be selected from the range of about 5 to 90% by volume relative to the total volume of the metal component, the inorganic binder component, and the resistance adjustment component. For example, it is 10-85 volume%, Preferably it is 15-80 volume%. By adjusting the volume fraction of the metal component, it is possible to obtain a resistive element with a volume resistivity of less than 100 μΩ·cm and a high resistance of more than 100,000 μΩ·cm. If the volume occupied by the metal component is too large, the volume resistivity of the resistance element may become too low, and if it is too small, it may be difficult to obtain stable conductivity.

(low melting point glass) The resistor element paste of the present invention further includes low-melting glass as an inorganic binder component. The low-melting point glass can also be in granular form (low-melting point glass particles), and it is formulated for the following: it melts during firing to improve the wettability of the metal particles and the substrate, thereby improving the adhesion, and melting throughout the resistance element film as a whole Curing, thereby forming a strong resistance element. Because it is insulating, it also has a certain adjustment function of resistance value.

The low-melting-point glass used as an inorganic binder component is a low-melting-point glass particle that can melt and flow during firing. Low-melting-point glass (low-melting-point glass particles) can function as a bonding component as long as it has a softening point that is 150°C or more lower than the firing temperature Tf, but in terms of forming a highly reliable resistance element such as heat resistance The softening point Tls of the low-melting glass particles may be in the range of 350-750°C, preferably 400-700°C, and more preferably 450-650°C. If the softening point Tls of the low-melting glass particles is too high, the melt fluidity will be lowered, which may lower the film forming property (uniformity) and the adhesiveness and denseness of the resistance element film. Especially when the difference between the softening point Tls of the low-melting glass particles and the firing temperature Tf is less than 150°C, the flow of the glass will not be sufficient and the conductive components and the resistance adjustment components cannot be closely connected to each other, so the resistance element formed The membrane becomes porous and brittle, and the stability and reliability as a resistance element decrease. On the other hand, if the softening point Tls of the low-melting-point glass particles is too low, the melt fluidity at the time of firing may be too high and may ooze out from the resistor element film.

Low-melting-point glass (low-melting-point glass particles) only needs to have the above-mentioned softening point, and usually contains other oxides other than silicon oxide. As other oxides, for example, other metal oxides (for example, alkali metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, and barium oxide; titanium oxide, Metal oxides of group 4A of the periodic table such as zirconia; metal oxides of group 6A of the periodic table such as chromium oxide; metal oxides of group 8 of the periodic table such as iron oxide; metal oxides of group 2B of the periodic table such as zinc oxide; oxides of group 3B of the periodic table such as aluminum oxide Group metal oxides; tin oxide, lead oxide and other periodic table 4B metal oxides; periodic table 5B metal oxides such as bismuth oxide, etc.), boron oxide, etc. These other oxides can be used alone or in combination of two or more. Among these oxides, barium oxide, zinc oxide, bismuth oxide, boron oxide and the like are often contained. The low-melting glass may also be glass that does not contain silicon oxide.

As the low-melting-point glass particles formed from the above-mentioned oxides, conventional low-melting-point glass particles, such as borosilicate-based glass particles, borosilicate-zinc-based glass particles, zinc-based glass particles, bismuth-based glass particles, lead-based glass particles etc. These low-melting glass particles can be used alone or in combination of two or more. Among these low-melting-point glass particles, zinc borosilicate-based glass particles, bismuth-based glass particles, and the like are generally used. Preferably, it does not contain harmful substances such as lead and cadmium.

The shape of the low-melting glass particles can be selected from the shapes exemplified as the shape of the above-mentioned metal particles. The shape of low-melting glass particles is usually spherical, ellipsoidal, polyhedral, or indeterminate.

The central particle diameter (D50) of the low-melting point glass particles is not particularly limited, for example, it is 0.1-20 μm, preferably 0.5-10 μm, further preferably 1-5 μm, and more preferably 2-4 μm. If the particle size of the low-melting-point glass particles is too small, the economical efficiency and the dispersibility in the resistor element paste may decrease. If it is too large, it may become difficult to uniformly mix with the metal component and the high-melting-point glass, and the resistance value may vary. risk of reduced reproducibility and reliability.

The volume fraction of the low melting point glass can be selected from the range of about 3 to 25% by volume relative to the total volume of the inorganic components including the metal component, low melting point glass and high melting point glass, for example, 5 to 20% by volume. Preferably it is 6-15 volume%, More preferably, it is 8-12 volume%. If the volume occupied by the low-melting-point glass is too large, the amount of melt-flowing components during firing may become too large, making it difficult to maintain the shape of the resistor element film, and the metal component and the low-melting-point glass may be separated from each other, resulting in a significant increase in conductivity. There is a risk of not being able to obtain a stable resistance value due to deviation. On the other hand, if the volume occupied by the low-melting glass is too small, it may be difficult to ensure the strength and compactness of the resistance element film, and the adhesion between the resistance element film and the base material.

In addition, in this application, a volume fraction is a volume fraction at 25 degreeC and atmospheric pressure.

The thermal expansion coefficient of the low-melting point glass is preferably equal to or lower than that of the base material used to form the resistance element. The base material of the resistance element is usually a ceramic substrate, so the thermal expansion coefficient of the low-melting point glass is, for example, 2-10 ppm/°C, preferably 3-8 ppm/°C, and more preferably 3.5-7 ppm/°C. When the coefficient of thermal expansion of the low-melting glass is too high or too low, the bonding reliability with the base material may decrease.

Furthermore, in this application, the so-called "thermal expansion coefficient" refers to the average expansion coefficient (average linear expansion coefficient) measured by using a thermomechanical analysis device (Thermomechanical Analysis: TMA) in the temperature range of 50°C to 350°C , means the value obtained by dividing the change in the length of the sample relative to the initial length of the sample by the temperature difference. In addition, in this application, a thermal expansion coefficient can be measured based on JISR 3102 (1995).

(high melting point glass) The resistance element paste of the present invention further includes high melting point glass as a resistance value adjustment component. The high-melting-point glass can also be granular (high-melting-point glass particles), which reduces the content of metal components in the resistance element film formed by firing to increase the resistance value, and also sinters itself to densify the resistance element film as a whole. That is, it is preferable that the high-melting-point glass as a resistance value adjustment component has a glass transition point Thg below the firing temperature Tf. If the glass transition point Thg of the high melting point glass is higher than the firing temperature Tf, the high melting point glass cannot be softened and deformed during firing, and the high melting point glass can hardly be sintered, so there is a possibility that the resistive element film cannot be densified. Also, the high melting point glass is preferably one that does not melt and flow during firing. If melt flow occurs, the glass components may segregate and the resistance value may not be improved efficiently and stably.

The specific glass transition point Thg of high melting point glass can be above 550°C, and can be selected from the range of 550-900°C, for example, 600-900°C, preferably 650-880°C, and more preferably 700-850°C °C, more preferably 750-830 °C.

In order to prevent melting and flowing together with the low melting point glass, the softening point Ths of the high melting point glass (high melting point glass particles) must be higher than the softening point Tls of the lower melting point glass by 100°C or more, preferably 150°C or more (for example, 150 to 700°C About), more preferably higher than 200°C (for example, about 200-600°C), more preferably higher than 250°C (for example, about 250-500°C). If the difference between the softening point Ths of the high melting point glass and the softening point Tls of the low melting point glass is less than 100° C., the ease of adjustment and reliability of the resistance value will decrease.

The softening point Ths of the high-melting point glass should be 600°C or higher, and can be selected from the range of 650-1150°C, for example, 700-1150°C, preferably 750-1050°C, and more preferably 800-1000°C. More preferably, it is 850-950°C. If the softening point Ths is too small, the glass will flow or be excessively sintered during firing, resulting in compositional segregation and failing to obtain a stable resistance element film. If the softening point Ths is too large, the sinterability will decrease, and there may be a possibility that a sufficiently dense resistor element film cannot be obtained.

The softening point Ths of the high melting point glass can be within the range of ±100°C of the firing temperature Tf. Even if the softening point Ths of the high melting point glass is higher than the firing temperature Tf, as long as the temperature difference is below 100°C, it will be sintered together with other components during firing. Even if the softening point Ths of the high melting point glass is lower than the firing temperature Tf, as long as the temperature difference is below 100°C, significant segregation of the high melting point glass will not occur. The temperature difference between the softening point Ths of the high melting point glass and the firing temperature Tf may also be more preferably within the range of ±80°C, further preferably within the range of ±50°C. If the softening point Ths of the high melting point glass is higher than the firing temperature Tf by more than 100°C, the high melting point glass cannot be fully sintered during firing, and a large number of voids remain inside the resistance element film, resulting in heat resistance and moisture resistance of the resistance element, etc. risk of reduced reliability. On the other hand, if the softening point Ths of the high melting point glass is lower than the firing temperature Tf by more than 100°C, there is a possibility that the resistance value may not be controlled due to segregation of components due to melt flow or excessive sintering of the high melting point glass during firing.

The high melting point glass (high melting point glass particle) should just have the said softening point, and usually contains other oxides other than silicon oxide. Examples of other oxides include: alkali metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, and barium oxide; oxides of Group 3A metals such as yttrium oxide; Metal oxides of group 4A of the periodic table such as titanium oxide and zirconia; metal oxides of group 5A of the periodic table such as tantalum oxide and niobium oxide, metal oxides of group 6A of the periodic table such as titanium oxide and chromium oxide; metal oxides of group 6A of the periodic table such as iron oxide Group 2B metal oxides of the periodic table such as zinc oxide; metal oxides of group 3B of the periodic table such as boron oxide and aluminum oxide; metal oxides of group 4B of the periodic table such as tin oxide and lead oxide; 5B of the periodic table such as bismuth oxide metal oxides etc. These other oxides can be used alone or in combination of two or more. Among these oxides, barium oxide, yttrium oxide, zinc oxide, aluminum oxide, magnesium oxide, boron oxide, and the like are often contained in order to obtain a high softening point.

As the high-melting-point glass particles made of the above-mentioned oxides, conventional high-melting-point glass particles, such as borosilicate-based glass particles, borosilicate-zinc-based glass particles, aluminosilicate-based glass, zinc-based glass particles, Bismuth-based glass particles, lead-based glass particles, and the like. These high-melting-point glass particles can be used alone or in combination of two or more. Among these high-melting-point glass particles, borosilicate-based glass particles, zinc borosilicate-based glass particles, aluminosilicate-based glass, and the like are generally used. Preferably, it does not contain harmful substances such as lead and cadmium.

The shape of the high-melting-point glass particles can be selected from the shapes exemplified as the shape of the above-mentioned metal particles. The shape of the high melting point glass particles is usually spherical, ellipsoidal, polyhedral, indeterminate, etc.

The central particle size (D50) of the high-melting point glass particles is not particularly limited, for example, it is 0.1-20 μm, preferably 0.5-10 μm, further preferably 1-8 μm, more preferably 1.5-5 μm, most preferably 1.8-3 μm. If the particle size of the high melting point glass particles is too small, the economical efficiency and the dispersibility in the resistor element paste may decrease. If it is too large, the composition of the resistor element film may become uneven and the resistance value may be stable and reliable. Risk of sexual decline.

The volume fraction of the high melting point glass can be selected from the range of about 3 to 80% by volume relative to the total volume of the inorganic components including the metal component, low melting point glass and high melting point glass, for example, 5 to 75% by volume. Preferably it is 8-70 volume%, More preferably, it is 10-68 volume%. The function of the resistance value adjustment component is to adjust the resistance value. Therefore, by adjusting the volume fraction of the resistance value adjustment component, it is possible to obtain a low resistance with a volume resistivity below 100 μΩ·cm to a high resistance with a volume resistivity as high as 20,000 μΩ·cm element. If the volume occupied by the resistance value adjustment component is too small, the volume resistivity of the resistance element will become too low, and if it is too large, the volume resistivity will become too high, making it difficult to obtain a stable resistance value.

Regarding the volume ratio of the high-melting point glass to the low-melting point glass, the volume of the high-melting point glass may be less than 10 times the volume of the low-melting point glass, such as 0.1 to 10 times, preferably 0.3 to 9 times, and more preferably 0.5 to 9 times. 7 times. When the volume ratio of the high-melting-point glass to the low-melting-point glass is too large, the reliability of the resistance element may decrease.

The thermal expansion coefficient of the high melting point glass can be selected so that the thermal expansion coefficient of the resistance element formed by firing becomes similar to the thermal expansion coefficient of the base material. If the coefficient of thermal expansion of the resistor element is similar to that of the base material, the adhesion between the resistor element and the base material can be maintained even in severe environments such as thermal shock, thereby ensuring excellent reliability. Generally, the coefficient of thermal expansion of a ceramic substrate used as a base material is low compared to that of metal components (copper, nickel). Therefore, in order to make the average coefficient of thermal expansion of the resistance element approximate to that of the substrate, the resistance adjusting component can be selected to have a coefficient of thermal expansion lower than that of the substrate. The thermal expansion coefficient of the high melting point glass is, for example, -2 to 8 ppm/°C, preferably -1 to 7 ppm/°C, and more preferably 0 to 6 ppm/°C. When the coefficient of thermal expansion of the high melting point glass is too high or too low, the reliability of bonding with the base material may decrease.

Furthermore, in this application, the coefficient of thermal expansion of the resistance element formed by firing the resistance element paste can be calculated using the following formula.

Thermal expansion coefficient of resistance element = (thermal expansion coefficient of metal component) × (volume fraction of metal component) + (thermal expansion coefficient of low melting point glass) × (volume fraction of low melting point glass) + (thermal expansion coefficient of high melting point glass) × (volume fraction of high melting point glass).

(organic medium) The organic vehicle may be a conventional organic vehicle used as an organic vehicle for a resistor element paste containing metal particles, such as an organic binder and/or an organic solvent. The organic vehicle may be any one of an organic binder and an organic solvent, and is usually a combination of an organic binder and an organic solvent (a solubilized product of an organic binder in an organic solvent).

The organic binder is not particularly limited, and examples thereof include thermoplastic resins (olefin-based resins, vinyl resins, acrylic resins, styrene-based resins, polyether-based resins, polyester-based resins, polyamide-based resins , cellulose derivatives, etc.), thermosetting resins (thermosetting acrylic resins, epoxy resins, phenol resins, unsaturated polyester resins, polyurethane resins, etc.), etc. These organic binders can be used individually or in combination of 2 or more types. Among these organic binders, resins that are easy to burn and have less ash in the roasting process are usually used, such as acrylic resins (polymethyl methacrylate, polybutyl methacrylate, etc.), cellulose derivatives (nitrocellulose cellulose, ethyl cellulose, butyl cellulose, cellulose acetate, etc.), polyethers (polyoxymethylene, etc.), rubbers (polybutadiene, polyisoprene, etc.) In terms of thermal decomposability in the environment, etc., poly(meth)acrylate C _1-10 alkyl esters such as polymethyl(meth)acrylate and polybutyl(meth)acrylate are preferable.

The organic solvent is not particularly limited, as long as it is an organic compound that imparts moderate viscosity to the resistor element paste and can be easily volatilized by drying treatment after the resistor element paste is applied to the substrate. It may be an organic solvent with a high boiling point. . Examples of such organic solvents include aromatic hydrocarbons (p-xylene, etc.), esters (ethyl lactate, etc.), ketones (isophorone, etc.), amides (dimethylformamide, etc.), etc.), aliphatic alcohols (octyl alcohol, decyl alcohol, diacetone alcohol, etc.), cellolytics (methyl cellolytic, ethyl cellolytic, etc.), cellolytic acetates (ethyl cellolytic cellulose acetate, butyl cellulose acetate, etc.), carbitols (carbitol, methyl carbitol, ethyl carbitol, etc.), carbitol acetates (ethyl carbitol ethyl ester, butyl carbitol acetate), aliphatic polyols (ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, triethylene glycol, glycerin, etc.), alicyclic alcohols[ For example, cycloalkanols such as cyclohexanol; terpene alcohols such as pinoresinol and dihydropinoresinol (monoterpene alcohol, etc.), etc.], aromatic alcohols (m-cresol, etc.), aromatic carboxylic acid esters ( Dibutyl phthalate, dioctyl phthalate, etc.), nitrogen-containing heterocyclic compounds (dimethylimidazole, dimethylimidazolidinone, etc.), etc. These organic solvents can be used alone or in combination of two or more. Among these organic solvents, alicyclic alcohols such as pinoresinol and C _1-4 alkyl cellosolve acetates such as butyl carbitol acetate are preferable in terms of paste fluidity and the like.

The volume fraction of the organic vehicle is, for example, 30 to 70% by volume, preferably 40 to 60% by volume, and more preferably 45 to 55% by volume relative to the entire volume of the resistor element paste.

The mass fraction of the organic vehicle is, for example, 5 to 50% by mass, preferably 7 to 40% by mass, and more preferably 10 to 25% by mass relative to the entire mass of the resistor element paste. When combining an organic binder and an organic solvent, the ratio of the organic binder is 3 to 60% by mass, preferably 5 to 50% by mass, more preferably 10 to 40% by mass, relative to the entire organic vehicle, More preferably, it is 20-30 mass %.

(other additives) Resistor element paste may also contain commonly used additives, such as hardeners (acrylic resin hardeners, etc.), adhesion promoters (copper oxide powder, etc.), colorants (dye pigments, etc.), hue improvers, metal corrosion inhibitors , stabilizers (antioxidants, ultraviolet absorbers, etc.), surfactants or dispersants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.), dispersion stabilizers, Viscosity modifier or rheology modifier, humectant, thixotropy imparting agent, leveling agent, defoamer, fungicide, filler, etc. These additives may be used alone or in combination of two or more.

The method of preparing resistor element paste is not particularly limited as long as a paste containing the above-mentioned components can be prepared. Generally, it can be prepared by dispersing metal components, low-melting point glass and high-melting point glass in an organic vehicle by a conventional method.

[Resistive element and its manufacturing method] The resistance element of the present invention is obtained by a production method of firing the resistance element paste, preferably by a production method including the following steps: a coating step of applying the resistance element paste to the base material by printing or the like forming a coating film; a drying step of drying the formed coating film to form a dry film; and a firing step of baking the dry film under an inert gas environment to form a resistor element film.

The base material is not particularly limited as long as it is a material that can handle the firing temperature. Generally, various ceramic or glass materials, ceramic green sheets, and other plate-shaped base materials (substrates) are commonly used, and they are excellent in adhesion to the resistance element film. For this purpose, a ceramic substrate is preferred.

As the material of the ceramic substrate, for example, metal oxide (alumina or aluminum, zirconia, sapphire, ferrite, zinc oxide, niobium oxide, mullite, beryllium oxide, etc.), silicon oxide (quartz, bismuth, etc.) silicon oxide, etc.), metal nitrides (aluminum nitride, titanium nitride, etc.), silicon nitride, boron nitride, carbon nitride, metal carbides (titanium carbide, tungsten carbide, etc.), silicon carbide, boron carbide, metal Multiple oxides [metal titanate (barium titanate, strontium titanate, lead titanate, niobium titanate, calcium titanate, magnesium titanate, etc.), zirconate metal salt (barium zirconate, calcium zirconate, zirconate lead, etc.) etc.] etc. These ceramics can be used alone or in combination of two or more. The ceramic may also be a low temperature co-fired ceramic (LTCC).

Among these ceramic substrates, alumina substrates, alumina-zirconia substrates, aluminum nitride substrates, silicon nitride substrates, and silicon carbide substrates are preferred in terms of high reliability in the electrical and electronic fields, Furthermore, an alumina substrate, an aluminum nitride substrate, and a silicon nitride substrate are preferable, and an alumina substrate is most preferable from the point of view of excellent adhesion with the resistor element film.

The thickness of the substrate may be appropriately selected according to the application, for example, it may be 0.001 to 10 mm, preferably 0.01 to 5 mm, further preferably 0.05 to 3 mm, and more preferably 0.1 to 1 mm.

Examples of coating methods for resistor element paste include flow coating, spin coating, spray coating, screen printing, flexographic printing, casting, rod coating, and curtain coating. Coating method, roll coating method, gravure coating method, dipping method, slit coating method, photolithography method, inkjet method, etc. Coating can be formed on the entire surface of the substrate, but it is usually formed on a part of the entire surface of the substrate such as in a pattern. When forming (drawing) a pattern in the coating film, a sintered pattern (sintered film, metal film, sintered body layer, conductor layer) can be formed by firing the formed pattern (drawn pattern). The drawing method (or printing method) for drawing a pattern (coating layer) is not particularly limited as long as it is a printing method capable of forming a pattern, for example, screen printing method, inkjet printing method, gravure printing method, etc. Printing method (such as gravure printing method, etc.), process printing method, gravure process printing method, flexographic printing method, etc. Among these methods, the screen printing method and the like are preferable.

In the drying step of drying the formed coating film to form a dry film, natural drying or heat drying may be used. The heating temperature can be selected according to the type of organic solvent, for example, it is 50-200°C, preferably 60-150°C, and more preferably about 80-120°C. The heating time is, for example, 1 minute to 3 hours, preferably 5 minutes to 2 hours, and more preferably about 10 to 30 minutes.

The formed dried film is subjected to a firing step of heating (baking or heat treatment) at a specific temperature, whereby a resistance element film is obtained.

In the firing step, the firing temperature Tf is preferably at least 150°C (for example, 150-500°C) higher than the softening point Tls of the lower melting point glass, and more preferably at least 200°C (for example, 200-450°C) higher temperature , more preferably a temperature higher than 250°C (for example, 250-400°C), most preferably a temperature higher than 300°C (for example, 300-350°C).

The firing temperature Tf is preferably above the glass transition point Thg of high-melting glass [for example, Thg~(Thg+250)°C], more preferably (Thg+30)~(Thg+200)°C, more preferably (Thg+50)~(Thg+150)°C.

The firing temperature Tf is preferably below the softening point Ths of the high-melting glass + 100°C, more preferably within ±100°C of the softening point of the high-melting glass, more preferably within ±50°C of the softening point of the high-melting glass.

The specific firing temperature Tf can be above 500°C, for example, 500-1100°C, preferably 700-1050°C, further preferably 800-1000°C, more preferably 850-950°C, most preferably 850-900°C .

The heat treatment time (heating time at the above-mentioned calcination temperature) corresponds to the heat treatment temperature and the like, and is, for example, 1 minute to 5 hours, preferably 5 minutes to 3 hours, and more preferably 10 to 60 minutes.

The calcination is preferably carried out in an inert gas (such as nitrogen, argon, helium, etc.) environment or a vacuum environment, especially preferably in a nitrogen environment.

The average thickness of the resistance element film formed by firing can be appropriately selected in the range of about 0.5-500 μm corresponding to the application, for example, 1-100 μm, preferably 5-50 μm, and more preferably 10-30 μm. μm.

The resistive element (resistive element film) of the present invention has a value of 100 μΩ·cm or more, for example, 100 to 10,000 μΩ·cm (area resistance of 100 mΩ/□ to 10 Ω/□ when the film thickness is 10 μm), which has been relatively high in recent years. The volume resistivity of low and medium resistance is especially effective in the range of 200-5,000 μΩ·cm, which is more useful. In particular, the resistor element of the present invention can continuously and freely adjust the resistance value (volume resistivity) in such a wide range by changing the composition ratio (especially the ratio of the high-melting point glass to the metal component).

Furthermore, the absolute value of the resistance temperature dependence (TCR) of the resistance element of the present invention is, for example, 300 ppm/°C or less, preferably 200 ppm/°C or less, further preferably 100 ppm/°C or less. Therefore, the resistance element of the present invention has less temperature dependence and excellent stability.

Furthermore, in this application, the volume resistivity and TCR can be measured by the methods described in the following examples. [Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. In the following examples, the materials used in the examples and the evaluation methods of the resistance elements obtained in the examples are shown below.

[Materials used] (metal component) Cu powder 1: Copper particles, central particle size (D50) 3 μm Cu powder 2: Copper particles, central particle size (D50) 5 μm Cu powder 3: Copper particles, central particle size (D50) 8 μm Ni powder 1: nickel particles, central particle size (D50) 0.4 μm Ni powder 2: nickel particles, central particle size (D50) 1 μm Ni powder 3: nickel particles, central particle diameter (D50) 3 μm.

(Glass particles) Glass powder 1: composition system Bi ₂ O ₃ · ZnO · B ₂ O ₃ , central particle diameter (D50) 3 μm, glass transition point (Tg) 385°C, softening point (Ts) 440°C Glass powder 2 -1: Composition system ZnO·SiO ₂ ·B ₂ O ₃ , central particle size (D50) 3 μm, glass transition point (Tg) 510°C, softening point (Ts) 580°C Glass frit 2-2: Composition system ZnO· SiO ₂・B ₂ O ₃ , central particle size (D50) 1 μm, glass transition point (Tg) 510°C, softening point (Ts) 580°C Glass powder 2-3: composition system ZnO・SiO ₂・B ₂ O ₃ , central particle size (D50) 5 μm, glass transition point (Tg) 510°C, softening point (Ts) 580°C Glass powder 2-4: composition system ZnO·SiO ₂ ·B ₂ O ₃ , central particle size (D50) 7 μm, glass transition point (Tg) 510°C, softening point (Ts) 580°C Glass frit 3: Composition system SiO ₂ B ₂ O ₃ ·RO, central particle size (D50) 3 μm, glass transition point (Tg) 590°C, softening point (Ts) 700°C Glass frit 4: composition system SiO ₂ ·B ₂ O ₃ ·ZrO ₂ ·R ₂ O, central particle size (D50) 3 μm, glass transition point (Tg) 620°C, softening Point (Ts) 740°C Glass frit 5: composition system SiO ₂ · B ₂ O ₃ · RO, central particle size (D50) 3 μm, glass transition point (Tg) 700°C, softening point (Ts) 830°C Glass frit 6 -1: Composition system SiO ₂・Al ₂ O ₃・Y ₂ O ₃ , central particle size (D50) 2 μm, glass transition point (Tg) 810°C, softening point (Ts) 920°C Glass frit 6-2: Composition System SiO ₂ ·Al ₂ O ₃ ·Y ₂ O ₃ , central particle size (D50) 1 μm, glass transition point (Tg) 810°C, softening point (Ts) 920°C Glass frit 6-3: composition system SiO ₂ · Al ₂ O ₃・Y ₂ O ₃ , central particle size (D50) 7 μm, glass transition point (Tg) 810°C, softening point (Ts) 920°C Glass frit 6-4: Composition system SiO ₂・Al ₂ O ₃・Y ₂ O ₃ , central particle size (D50) 12 μm, glass transition point (Tg) 810°C, softening point (Ts) 920°C Glass frit 7: composition system SiO ₂・Al ₂ O ₃・Y ₂ O ₃ , The central particle size (D50) is 2 μm, the glass transition point (Tg) is 890°C, and the softening point (Ts) is 1000°C.

In addition, "RO" in glass frit 3 and 5 refers to the description collectively referring to alkaline earth metal components (MgO, CaO, BaO, SrO), and "R ₂ O" in glass frit 4 refers to the description of alkali metal components (Li ₂ O, Na ₂ O, K ₂ O) collectively referred to as records.

(Other ingredients) Al ₂ O ₃ powder: alumina powder, center particle size (D50) 1 μm Copper oxide (Cu ₂ O) powder: center particle size (D50) 3 μm Organic vehicle: acrylic resin dissolved in rosin 30% by mass solution of acrylic resin prepared in a mixed solvent of alcohol and butyl carbitol acetate (mass ratio 1/1) Alumina substrate: 96% alumina substrate Aluminum nitride substrate: 170 W/m・K aluminum nitride substrate.

(A) Characteristics of resistance element (resistor element film) [shape maintenance properties] The appearance of the resistor element film formed by firing was observed with a microscope (20 times magnification).

(Measure to judge) a: The resistance element film is uniform and there is no shrinkage, deformation, and shape collapse (qualified) b: There is some uniform shrinkage of the resistance element film, but there is no shape collapse and flow (qualified) c: Significant shrinkage, shape collapse, or flow exists in the resistance element film (unacceptable).

[closeness] The edge part of the pattern of the resistive element film formed by baking was peeled off with metal tweezers, and it was confirmed whether the resistive element film peeled off.

(Measure to judge) a: The resistive element film is not peeled off from the substrate at all (passed) b: A part of the resistance element film is slightly peeled off (pass) c: Most or all of the resistance element film peeled off (unacceptable).

[Volume resistivity] After the resistance element film formed by firing was left to stand for more than 30 minutes in an environment with a temperature of 25±3°C and a humidity of 65±10%RH, the resistance value of the resistance element film was measured by the four-terminal method. Also, the thickness of the resistance element film was measured with a stylus film thickness meter ("DEKTAK 6M" manufactured by ULVAC Co., Ltd.), and the volume resistivity (average value of 10 samples) was obtained. In the case where the volume resistivity became infinite, it was judged as unacceptable.

In addition, for a specific resistance value adjustment component, it was confirmed whether the volume resistivity of the formed resistive element film can be adjusted continuously and freely within a wide range of 100 μΩ·cm to 10,000 μΩ·cm by adjusting its blending ratio ( adjustment function). And when there is no adjustment function in this wide range, it was set as unacceptable.

[TCR] The resistance element film formed by firing was placed in a constant temperature bath at 125°C and left to stand for more than 30 minutes, and the resistance value (volume resistivity) of the resistance element film was measured by the four-probe method. The resistance value and the rate of change with respect to the resistance value measured at the above-mentioned 25° C. were obtained and judged according to the following criteria.

TCR＝[{average resistance (125℃)－average resistance (25℃)}/{average resistance (25℃)×(125℃－25℃)}]×10 ⁶ (ppm/℃)

(Measure to judge) a: TCR is above -100 ppm/°C and below 100 ppm/°C (pass) b: TCR is above -200 ppm/°C and less than -100 ppm/°C or over 100 ppm/°C and below 200 ppm/°C (pass) c: TCR does not reach -200 ppm/°C or exceeds 200 ppm/°C (unacceptable).

(B) Initial judgment Regarding the above-mentioned evaluation items, as an initial judgment, judgments were made based on the following criteria, and grades were given.

Grade A: The judgments of shape retention, adhesion, volume resistivity, and TCR are all qualified, and the judgments of shape retention, adhesion, and TCR are all a (passed) Grade B: All judgments of shape retention, adhesion, volume resistivity, and TCR pass, and the judgment of shape retention, adhesion, and TCR includes b (pass) Rank C: Any one of shape retention, adhesiveness, volume resistivity, and TCR was unacceptable (unacceptable).

(C) Reliability test of resistance element film [Heat resistance test] The resistance element film formed by firing was placed in a hot air dryer at a temperature of 155° C. and left for 500 hours. After that, the sample was left to stand for more than 30 minutes in an environment of 25±3°C and humidity 65±10%RH, and the resistance value (volume resistivity) of the resistance element film was measured by the four-terminal method to obtain the heat resistance test The change rate of the resistance value before and after.

(Measure to judge) a: The change rate of resistance value is less than 1% (qualified) b: The change rate of the resistance value exceeds 1% and is less than 2% (qualified) c: The change rate of the resistance value exceeds 2% (unqualified).

[Moisture resistance test] The resistance element film formed by firing was placed in a constant temperature and humidity chamber at a temperature of 85° C. and a humidity of 85% RH, and left for 500 hours. After that, the sample was left to stand at 25±3°C and humidity 65±10%RH for more than 30 minutes, and the resistance value of the resistance element film was measured by the four-terminal method, and the resistance value before and after the humidity resistance test was obtained. rate of change.

(Measure to judge) a: The change rate of resistance value is less than 1% (qualified) b: The change rate of the resistance value exceeds 1% and is less than 2% (qualified) c: The change rate of the resistance value exceeds 2% (unqualified).

(D) Comprehensive judgment (labeled grade) Regarding the results of the above-mentioned evaluation tests, as a comprehensive judgment, the following criteria are used to judge and mark the grade.

Grade A: The initial judgment is A and the judgment of heat resistance and/or moisture resistance is a Grade B: The initial judgment is qualified and the judgment of heat resistance and moisture resistance is both b or the initial judgment is B and the judgment of heat resistance and/or moisture resistance is a Grade C: Passed the initial judgment but failed the judgment of heat resistance and/or moisture resistance Rank D: Initial judgment failed.

[Example 1] A resistor element (resistor element film) was produced by the method shown below.

(Preparation of resistor element paste) 64 parts by mass of copper powder (Cu powder 1: central particle diameter 3 μm), 36 parts by mass of nickel powder (Ni powder 1: central particle diameter 0.4 μm) were used as metal components, and low-melting glass (glass frit 2-1: softening point 580°C), high melting point glass (glass frit 6-1: glass transition point 810°C, softening point 920°C) for adjusting the resistance value as the glass component, and then add an organic vehicle and pass through the mixer After mixing, the mixture was uniformly mixed with three rolls (manufactured by EXAKT (Germany)), whereby a resistor element paste (resistor element composition) was prepared.

In this composition, as shown in Table 1, the volume fraction of the low-melting glass in the inorganic component is fixed at about 10% by volume and the volume fraction of the metal component in the inorganic component is 24.4 to 83.7% by volume. Compositions in which the blending amount of high melting point glass (resistance value adjustment component) was varied in 11 levels were referred to as Examples 1-1 to 1-11.

(Manufacturing of resistor elements) For the prepared resistive element paste, use the screen printing method to apply a rectangular resistive element pattern of 1 mm×10 mm on the 96% alumina substrate with thick film copper electrodes formed in advance in a way that can perform 4-terminal measurement to form a coating film. Dry the coating film in an air dryer at 100°C for 20 minutes to remove the solvent, then bake it in a belt-type continuous baking furnace in a nitrogen atmosphere with a peak temperature of 900°C and a peak temperature holding time of 10 minutes , forming a resistance element (resistor element film). The total time before expulsion was set at 60 minutes.

In this embodiment, the softening point of glass powder 2-1 (low melting point glass) is 320°C lower than the firing temperature, the glass transition point of glass powder 6-1 (high melting point glass) is 90°C lower than the firing temperature, and the softening point is lower than The firing temperature is 20°C higher. The difference between the softening points of glass frit 2-1 and glass frit 6-1 was 340°C.

The verification results of the obtained resistance element (resistor element film) are shown in Table 1 and FIG. 1 . In addition, FIG. 2 is a scanning electron microscope (SEM) image of a cross section of the resistance element of Examples 1-4.

[Table 1] Table 1 Example 1 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass Glass powder 2-1 4.5 5.4 6.3 8.2 10.0 11.4 12.4 13.6 15.0 15.7 16.4 high melting point glass Glass powder 6-1 3.0 11.2 19.4 34.8 50.2 61.8 69.8 80.3 91.9 97.7 103.5 organic medium 13.5 16.4 19.2 25.3 31.4 36.0 39.1 43.3 47.9 50.2 52.5 Volume fraction (volume%) Ratio of metal components in inorganic components 83.7% 69.9% 60.1% 47.4% 39.1% 34.6% 32.0% 29.2% 26.6% 25.4% 24.4% Ratio of low melting point glass in inorganic components 9.9% 9.9% 9.9% 10.1% 10.2% 10.3% 10.4% 10.4% 10.4% 10.5% 10.5% Ratio of high melting point glass in inorganic components 6.5% 20.2% 30.0% 42.5% 50.7% 55.1% 57.6% 60.4% 63.0% 64.1% 65.1% Ratio of organic vehicle in paste 50.1% 50.4% 50.7% 51.6% 52.2% 52.6% 52.7% 52.9% 53.1% 53.2% 53.3% Mass fraction (mass%) Ratio of metal components in inorganic components 93.0% 85.8% 79.6% 70.0% 62.4% 57.7% 54.9% 51.6% 48.3% 46.9% 45.5% Ratio of low melting point glass in inorganic components 4.2% 4.6% 5.0% 5.7% 6.2% 6.6% 6.8% 7.0% 7.3% 7.4% 7.5% Ratio of high melting point glass in inorganic components 2.8% 9.6% 15.4% 24.3% 31.3% 35.7% 38.3% 41.4% 44.4% 45.8% 47.1% Ratio of organic vehicle in paste 11.2% 12.3% 13.3% 15.0% 16.4% 17.2% 17.7% 18.3% 18.8% 19.0% 19.3% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a a a Closeness a a a a a a a a a a a Volume resistivity (μΩ・cm) 77 123 193 401 830 1,586 2,627 6,093 18,040 39,240 113,880 Can realize continuous adjustment in a wide range TCR(ppm/℃) -12 -12 -10 -10 -8 -12 -6 -5 1 -5 -2 determination a a a a a a a a a a a initial judgment A A A A A A A A A A A Reliability of Resistive Elements heat resistance rate of change 0.30% 0.90% 0.90% 1.15% 1.24% 0.54% 0.38% 0.55% 0.50% 0.26% 0.25% (155℃, 500hrs) determination a a a b b a a a a a a Moisture resistance rate of change 0.76% 0.59% 0.61% 0.68% 0.66% 0.56% 0.80% 0.61% 0.82% 0.79% 0.68% (85℃, 85%RH, 500hrs) determination a a a a a a a a a a a Comprehensive judgment A A A A A A A A A A A

(Verification of characteristics and reliability of resistance elements) In the resistive element of Example 1-1 in which the volume fraction of the metal component in the inorganic component was 83.7 vol%, the volume resistivity was 77 μΩ·cm, and the shape retention, adhesion, and TCR were good. In addition, in the reliability (heat resistance, humidity resistance) test, the change rate of the volume resistivity is small, and the durability reliability is also excellent.

Also, in Examples 1-2 to 1-9, compared to Example 1-1, if the volume fraction of the high melting point glass in the inorganic component is gradually increased and the volume fraction of the metal component is gradually decreased, the volume The resistivity increases slowly in the range of 123-18,040 μΩ·cm. In Examples 1-10 and 1-11 in which the volume fraction of the metal component was further reduced, the volume resistivity increased sharply and could be adjusted to a maximum of 113,880 μΩ·cm. In this way, the function of continuously and freely adjusting the resistance value (volume resistivity) in a wide range from low resistance to high resistance by high melting point glass is obtained (Fig. 1).

In addition, the resistance elements of Examples 1-2 to 1-11 were good in shape retention, adhesion, and TCR, and were also excellent in durability reliability (rank A in the comprehensive evaluation).

According to the above results, it is verified that in Example 1 using the composition comprising glass frit 2-1 (low melting point glass) and glass frit 6-1 (high melting point glass), the glass powder with the ability to continuously and freely adjust in a wide range is obtained. Resistive elements that have a function of resistance value (volume resistivity) and have excellent heat resistance and humidity resistance reliability.

Generally, since copper and nickel as base metals are easily oxidized, they are easily oxidized in a high-temperature and high-humidity environment such as 85°C and 85%RH, resulting in an increase in resistance value. The volume resistivity changes very little under the environment and the reliability is excellent. The cross-section of the resistance element (resistor element film) of Examples 1-4 was observed with a scanning electron microscope (SEM). As a result (FIG. 2), the resistance element was very densely sintered. It is considered that by densely sintering the resistance element, the intrusion of oxygen and moisture into the resistance element is prevented, and a resistance element excellent in heat resistance and moisture resistance is obtained.

[Comparative Example 1] Alumina powder (Al ₂ O ₃ powder) that does not soften and melt at the firing temperature is used as a resistance adjustment component, and the ratio of low-melting glass in the inorganic component is set to about 9% by volume. In addition, verification was performed by the method according to Example 1. The composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test are shown in Table 2 and FIG. 3 as Comparative Examples 1-1 to 1-9. In addition, a cross-sectional SEM image of the resistance element in Comparative Example 1-4 is shown in FIG. 4 .

[Table 2] Table 2 Comparative example 1 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass Glass powder 2-1 4.5 6.7 7.5 8.4 9.6 11.2 13.5 14.6 16.8 Resistor Value Adjustment Components Al ₂ O ₃ powder 10.0 36.0 45.0 56.3 70.5 90.0 117.0 131.0 157.0 organic medium 22.0 32.0 36.0 40.0 46.0 54.0 65.0 70.0 81.0 Volume fraction (volume%) Ratio of metal components in inorganic components 74.3% 50.1% 45.0% 39.9% 35.0% 29.9% 24.9% 22.9% 19.9% Ratio of low melting point glass in inorganic components 8.8% 8.8% 8.8% 8.8% 8.8% 8.8% 8.8% 8.7% 8.8% Ratio of high melting point glass in inorganic components 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Ratio of resistance adjustment components in inorganic components 17.0% 41.1% 46.2% 51.3% 56.3% 61.4% 66.4% 68.4% 71.3% Ratio of organic vehicle in paste 59.3% 58.8% 59.0% 58.7% 58.9% 58.9% 59.0% 58.8% 58.9% Mass fraction (mass%) Ratio of metal components in inorganic components 87.3% 70.1% 65.6% 60.7% 55.5% 49.7% 43.4% 40.7% 36.5% Ratio of low melting point glass in inorganic components 3.9% 4.7% 4.9% 5.1% 5.3% 5.6% 5.9% 5.9% 6.1% Ratio of high melting point glass in inorganic components 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Ratio of resistance adjustment components in inorganic components 8.7% 25.2% 29.5% 34.2% 39.1% 44.7% 50.8% 53.3% 57.3% Ratio of organic vehicle in paste 16.1% 18.3% 19.1% 19.5% 20.3% 21.2% 22.0% 22.2% 22.8% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a Closeness a a a b b b b b b Volume resistivity (μΩ・cm) 135 265 363 550 826 1,522 7,260 21,680 123,500 Can realize continuous adjustment in a wide range TCR(ppm/℃) -3 2 -5 -8 -5 -4 -1 -9 -5 determination a a a a a a a a a initial judgment A A A B B B B B B Reliability of Resistive Elements heat resistance rate of change 1.80% 3.20% 3.60% 3.50% 2.94% 3.20% 4.30% 4.52% 4.68% (155℃, 500hrs) determination b c c c c c c c c Moisture resistance rate of change 6.50% 13.60% 14.50% 18.40% ∞ ∞ ∞ ∞ ∞ (85℃, 85%RH, 500hrs) determination c c c c c c c c c Comprehensive judgment C C C C C C C C C

In Comparative Example 1-1 in which the volume fraction of the metal component in the inorganic component was 74.3% by volume, the volume resistivity of the resistance element was 135 μΩ·cm, and the shape retention, adhesion, and TCR were good. However, in the reliability test, the humidity resistance was unacceptable, and the heat resistance was acceptable but lower than that of Example 1.

In Comparative Examples 1-2 to 1-8, compared with Comparative Example 1-1, if the volume fraction of alumina powder in the inorganic component is gradually increased and the volume fraction of the metal component is gradually decreased, the volume resistivity Slowly rise to 265～21,680 μΩ·cm. In Comparative Examples 1-9 in which the volume fraction of the metal component was further reduced, the volume resistivity increased sharply and could be adjusted to a maximum of 123,500 μΩ·cm. Thus, the function of continuously and freely adjusting the resistance value (volume resistivity) in a wide range from low resistance to high resistance is obtained (Fig. 3).

However, although the resistance elements of Comparative Examples 1-2 to 1-9 were acceptable in terms of shape retention, adhesion, and TCR, when the volume fraction of alumina powder in the inorganic component was 50% by volume or more, the adhesion was slightly inferior. reduce. Also, in the reliability test, both the heat resistance and the moisture resistance were unacceptable. In particular, with regard to moisture resistance, the rate of change in resistance value tends to increase as the volume fraction of alumina powder increases, and the volume resistivity becomes infinitely large when it becomes 56.3% by volume or more.

Based on the above results, it has been verified that Comparative Example 1, which uses alumina powder as a resistance value adjustment component, has the function of continuously and freely adjusting the resistance value (volume resistivity) in a wide range, but cannot obtain sufficient heat resistance and humidity resistance. Reliability (grade C in comprehensive judgment).

It is considered that if the volume fraction of the non-sinterable resistance adjustment component (aluminum oxide powder) increases, the resistance element film will become porous with voids and voids, and the low melting point glass as a bonding component will remain inside the resistance element film. , and the amount moved to the interface between the resistive element film and the substrate is reduced, thereby reducing the adhesion to the substrate.

When observing the SEM image ( FIG. 4 ) obtained by photographing the section of the resistance element (resistor element film) of Comparative Examples 1-4, it can be known that there are a large number of pores and voids inside the resistance element film. Since the resistance value adjustment component (alumina powder) will not soften, sinter, and melt during the firing process, it will hinder the sintering of the bonding component (low melting point glass) and conductive component (copper, nickel powder) to produce pores and voids, resulting in Resistive elements cannot be sintered densely. It is considered that such a porous resistive element film is under high temperature and high humidity conditions, oxygen, moisture, corrosive gases, etc. invade the interior of the resistive element film through the pore structure, so that the conductive components are corroded and the resistance value increases.

[Comparative example 2] The verification was carried out by the method according to Example 1 except that the low melting point glass (glass frit 2-1) was used as the glass component without using the high melting point glass as the resistance value adjustment component. The composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test are shown in Table 3 and FIG. 5 as Comparative Examples 2-1 to 2-7.

[Table 3] Table 3 Comparative example 2 2-1 2-2 2-3 2-4 2-5 2-6 2-7 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass Glass powder 2-1 7.5 16.4 25.3 42.3 59.6 92.0 128.0 organic medium 13.5 16.4 19.2 25.3 31.4 43.3 56.7 Volume fraction (volume%) Ratio of metal components in inorganic components 83.6% 70.0% 60.2% 47.5% 39.1% 29.3% 23.0% Ratio of low melting point glass in inorganic components 16.4% 30.0% 39.8% 52.5% 60.9% 70.7% 77.0% Ratio of high melting point glass in inorganic components 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Ratio of organic vehicle in paste 50.1% 50.4% 50.7% 51.7% 52.2% 53.1% 53.7% Mass fraction (mass%) Ratio of metal components in inorganic components 93.0% 85.9% 79.8% 70.3% 62.7% 52.1% 43.9% Ratio of low melting point glass in inorganic components 7.0% 14.1% 20.2% 29.7% 37.3% 47.9% 56.1% Ratio of high melting point glass in inorganic components 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Ratio of organic vehicle in paste 11.2% 12.3% 13.3% 15.1% 16.4% 18.4% 19.9% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a b c c c c c Closeness a a a a a a a Volume resistivity (μΩ・cm) 63 106 153 218 258 339 ∞ Unable to achieve a wide range of adjustments (unqualified) TCR(ppm/℃) -6 -2 -5 -1 -4 0 - determination a a a a a a a initial judgment C C C C C C C Comprehensive judgment D. D. D. D. D. D. D.

In Comparative Example 2-1 in which the volume fraction of the metal component in the inorganic component was 83.6% by volume, the volume resistivity of the resistance element was 63 μΩ·cm, and the shape retention, adhesion, and TCR were good.

In Comparative Examples 2-2 to 2-6, compared with Comparative Example 2-1, if the volume fraction of the low-melting glass in the inorganic component was gradually increased and the volume fraction of the metal component was gradually decreased, the adhesion, The TCR was good, but the volume resistivity only increased to 339 μΩ·cm. In Comparative Example 2-7 in which the volume fraction of the metal component was further reduced, the resistance value became infinite. As shown by comparison in FIG. 5 , compared with Example 1, which can continuously and freely adjust the volume resistivity in a wide range from low resistance to high resistance, the range of adjustable volume resistivity in Comparative Example 2 is narrowed.

Also, if the volume fraction of the metal component in the inorganic component is 60% by volume or less, the shape of the resistor element film will collapse during firing, and the shape retention property will be unacceptable. It is believed that the reason is that if the volume fraction of the low-melting glass increases, the low-melting glass melts and flows and separates from the metal component during firing, so the glass component does not enter the metal phase, and cannot make the conductive channel thinner and increase the resistance value. The effect. In addition, since the low-melting-point glass melted and flowed excessively, the shape of the resistor element film could not be maintained. Furthermore, if the ratio of the low-melting-point glass increases, the low-melting-point glass melts and flows and segregates locally during firing. The deformation of the resistive element film or the segregation of glass components is an unstable state, so the shape or segregation state is easy to change, and the volume resistivity is also unstable and the deviation increases.

Based on the above results, Comparative Example 2, which did not use the high-melting-point glass as the resistance value adjusting component, failed the initial evaluation, so the reliability test was not performed. It was verified that the composition of Comparative Example 2 was not suitable as a resistance element (rank D in the comprehensive judgment).

[Comparative example 3] The verification was carried out by the method according to Example 1 except that low-melting-point glass as an inorganic binder component was not used, and only high-melting-point glass (glass frit 6-1) was used as a glass component.

The composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test are shown in Table 4 as Comparative Examples 3-1 to 3-7.

[Table 4] Table 4 Comparative example 3 3-1 3-2 3-3 3-4 3-5 3-6 3-7 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 high melting point glass Glass powder 6-1 7.5 16.8 25.7 43.0 60.0 93.5 130.0 organic medium 13.5 16.4 19.2 25.3 31.4 43.3 56.7 Volume fraction (volume%) Ratio of metal components in inorganic components 83.8% 69.8% 60.1% 47.4% 39.2% 29.3% 23.0% Ratio of low melting point glass in inorganic components 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Ratio of high melting point glass in inorganic components 16.2% 30.2% 39.9% 52.6% 60.8% 70.7% 77.0% Ratio of organic vehicle in paste 50.2% 50.4% 50.7% 51.6% 52.3% 53.0% 53.7% Mass fraction (mass%) Ratio of metal components in inorganic components 93.0% 85.6% 79.6% 69.9% 62.5% 51.7% 43.5% Ratio of low melting point glass in inorganic components 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% Ratio of high melting point glass in inorganic components 7.0% 14.4% 20.4% 30.1% 37.5% 48.3% 56.5% Ratio of organic vehicle in paste 11.2% 12.3% 13.3% 15.0% 16.4% 18.3% 19.8% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a Closeness c c c b b b b Volume resistivity (μΩ・cm) 92 155 246 522 1,271 13,104 236,000 Can realize continuous adjustment in a wide range TCR(ppm/℃) 1 -3 -2 -6 5 -3 -3 determination a a a a a a a initial judgment C C C A A A A Reliability of Resistive Elements heat resistance rate of change - - - 4.80% 4.50% 3.80% 2.80% (155℃, 500hrs) determination - - - c c c c Moisture resistance rate of change - - - peel off peel off peel off peel off (85℃, 85%RH, 500hrs) determination - - - c c c c Comprehensive judgment D. D. D. C C C C

In Comparative Examples 3-1 to 3-7, compared with Comparative Example 3-1, if the volume fraction of the high melting point glass in the inorganic component is gradually increased and the volume fraction of the metal component is gradually decreased, the volume resistivity It rises slowly in the range of 92～236,000 μΩ·cm, and has the function of continuously and freely adjusting the volume resistivity in a wide range from low resistance to high resistance.

In Comparative Examples 3-1 to 3-3 in which the volume fraction of the refractory glass in the inorganic component was 40% by volume or less, the shape retention and TCR were good, but the adhesion was unacceptable. In Comparative Examples 3-4 to 3-7 in which the volume fraction of the high-melting point glass was 40% by volume or more, the shape retention, adhesion, and TCR were good and passed the initial judgment, but the heat resistance and moisture resistance It became a failure during the test.

From the above results, it was verified that Comparative Example 3, which did not use low-melting-point glass as an inorganic binder component, had the function of continuously and freely adjusting the resistance value (volume resistivity) over a wide range, but due to adhesion, heat resistance, The moisture resistance reliability is not sufficient, so it is not suitable as a resistance element (rank C or D in the comprehensive judgment).

Because the glass transition point of high melting point glass is lower than the firing temperature, it will be softened and deformed to some extent during firing, but because the softening temperature is higher than the firing temperature, there will be no melt flow and segregation during firing, and it will be uniformly dispersed in the metal component In this way, the effect of stably increasing the resistance value can be exerted. However, since there is no low-melting-point glass as an inorganic binder component, sufficient adhesion cannot be obtained between the resistor element film and the base material, and the film will peel off during the moisture resistance evaluation even if the initial judgment is passed.

[Example 2] The inorganic binder component (low melting point glass) was verified by the method based on Example 1 except that glass frit 1 (softening point: 440° C.) was used. The composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film) and the results of the reliability test are shown in Table 5 and FIG. 6 as Examples 2-1 to 2-7.

[Table 5] Table 5 Example 2 2-1 2-2 2-3 2-4 2-5 2-6 2-7 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass glass powder 1 8.8 12.3 19.4 22.2 26.4 29.2 31.9 high melting point glass Glass powder 6-1 3.0 19.4 50.2 61.8 80.3 91.9 103.5 organic medium 13.5 19.2 31.4 36.0 43.3 47.9 52.5 Volume fraction (volume%) Ratio of metal components in inorganic components 83.7% 60.1% 39.1% 34.6% 29.2% 26.6% 24.4% Ratio of low melting point glass in inorganic components 9.9% 9.9% 10.2% 10.3% 10.4% 10.4% 10.5% Ratio of high melting point glass in inorganic components 6.5% 30.0% 50.7% 55.1% 60.4% 63.0% 65.1% Ratio of organic vehicle in paste 50.1% 50.7% 52.2% 52.6% 52.9% 53.1% 53.3% Mass fraction (mass%) Ratio of metal components in inorganic components 89.5% 76.0% 58.9% 54.4% 48.4% 45.2% 42.5% Ratio of low melting point glass in inorganic components 7.8% 9.3% 11.5% 12.1% 12.8% 13.2% 13.5% Ratio of high melting point glass in inorganic components 2.7% 14.7% 29.6% 33.6% 38.8% 41.6% 44.0% Ratio of organic vehicle in paste 10.8% 12.7% 15.6% 16.4% 17.3% 17.8% 18.2% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a Closeness a a a a a a a Volume resistivity (μΩ・cm) 71 174 774 1,484 5,616 16,796 107,040 Can realize continuous adjustment in a wide range TCR(ppm/℃) -4 -5 -5 -8 -2 0 2 determination a a a a a a a initial judgment A A A A A A A Reliability of Resistive Elements heat resistance rate of change 0.25% 0.70% 0.98% 0.48% 0.45% 0.34% 0.21% (155℃, 500hrs) determination a a a a a a a Moisture resistance rate of change 0.78% 0.72% 0.80% 0.56% 0.49% 0.68% 0.53% (85℃, 85%RH, 500hrs) determination a a a a a a a Comprehensive judgment A A A A A A A

In Example 2, the softening point of glass powder 1 (low melting point glass) is 460°C lower than the firing temperature, the glass transition point of glass powder 6-1 (high melting point glass) is 90°C lower than the firing temperature, and the softening point is lower than the firing temperature 20°C higher. The difference between the softening points of glass frit 1 and glass frit 6-1 is 480°C.

In Example 2, the same tendency as in Example 1 appeared. That is, in Examples 2-2 to 2-6, compared with Example 2-1, if the volume fraction of the high-melting glass in the inorganic component is gradually increased, and the volume fraction of the metal component is gradually decreased, it is good. The shape retention, adhesion, and TCR are maintained, and the volume resistivity rises slowly to 71-16,796 μΩ·cm. In Examples 2-7, where the volume fraction of the metal component is further reduced, it can be adjusted to a maximum of 107,040 μΩ· cm.

According to the above results, it was verified that in Example 2 (2-1 to 2-7) using a composition comprising glass frit 1 (low melting point glass) and glass frit 6-1 (high melting point glass) It is a resistance element with the function of continuously and freely adjusting the resistance value (volume resistivity) in a wide range from resistance to high resistance and having excellent heat resistance and humidity resistance reliability. (Rate A in the comprehensive judgment).

[Example 3] Glass frit 5 (glass transition point 700°C, softening point 830°C) was used as the resistance adjustment component (high melting point glass), and the firing temperature was changed from 900°C to 850°C. method to verify. The composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test are shown in Table 6 and FIG. 7 as Examples 3-1 to 3-7.

[Table 6] Table 6 Example 3 3-1 3-2 3-3 3-4 3-5 3-6 3-7 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass Glass powder 2-1 4.5 6.0 7.0 8.0 10.5 13.0 14.0 high melting point glass glass powder 5 3.0 18.0 27.0 36.0 59.0 80.0 90.0 organic medium 13.5 18.5 21.5 24.5 33.0 40.0 43.0 Volume fraction (volume%) Ratio of metal components in inorganic components 83.4% 60.9% 52.3% 45.9% 34.9% 28.6% 26.4% Ratio of low melting point glass in inorganic components 9.8% 9.6% 9.6% 9.6% 9.6% 9.7% 9.7% Ratio of high melting point glass in inorganic components 6.7% 29.6% 38.1% 44.5% 55.5% 61.7% 64.0% Ratio of organic vehicle in paste 50.1% 50.1% 50.0% 50.0% 50.6% 50.4% 50.2% Mass fraction (mass%) Ratio of metal components in inorganic components 93.0% 80.6% 74.6% 69.4% 59.0% 51.8% 49.0% Ratio of low melting point glass in inorganic components 4.2% 4.8% 5.2% 5.6% 6.2% 6.7% 6.9% Ratio of high melting point glass in inorganic components 2.8% 14.5% 20.1% 25.0% 34.8% 41.5% 44.1% Ratio of organic vehicle in paste 11.2% 13.0% 13.8% 14.5% 16.3% 17.2% 17.4% Roasting temperature 850°C Characteristics of Resistive Elements shape maintenance a a a a a a a Closeness b b b a a a a Volume resistivity (μΩ・cm) 88 253 450 846 3,460 14,300 42,510 Can realize continuous adjustment in a wide range TCR(ppm/℃) -4 -3 -5 -12 -9 1 3 determination a a a a a a a initial judgment B B B A A A A Reliability of Resistive Elements heat resistance rate of change 0.42% 0.65% 0.88% 0.84% 0.95% 0.52% 0.31% (155℃, 500hrs) determination a a a a a a a Moisture resistance rate of change 0.65% 0.59% 0.45% 0.66% 0.62% 0.55% 0.68% (85℃, 85%RH, 500hrs) determination a a a a a a a Comprehensive judgment B B B A A A A

In Example 3, the softening point of glass powder 2-1 (low melting point glass) is 270°C lower than the firing temperature, the glass transition point of glass powder 5 (high melting point glass) is 150°C lower than the firing temperature, and the softening point is lower than the firing temperature 20°C lower. The difference between the softening points of glass frit 2-1 and glass frit 5 is 250°C.

In Example 3, in Examples 3-2 to 3-7, if compared with Example 3-1, the volume fraction of the high melting point glass in the inorganic component is gradually increased, and the volume fraction of the metal component is gradually increased. Decrease, the volume resistivity rises to 88~42,510 μΩ·cm. However, in Examples 3-1 to 3-3, the judgment of adhesiveness became b (slight peeling), which is presumed to be because the difference between the softening point and firing temperature of the low-melting glass is relatively small at 270°C. In Example 3, the same tendency as in Example 1 appeared except that the adhesiveness was slightly lowered.

According to the above results, it was verified that in Example 3 (3-1 to 3-7) using a composition comprising glass frit 2-1 (low melting point glass) and glass frit 5 (high melting point glass) A resistance element with the function of continuously and freely adjusting the resistance value (volume resistivity) in a wide range from resistance to high resistance and having excellent heat resistance and humidity resistance reliability. (A grade of A or B in the comprehensive judgment).

[Example 4] Glass frit 7 (glass transition point 890°C, softening point 1000°C) was used as the resistance adjustment component (high melting point glass), and the firing temperature was changed from 900°C to 950°C. method to verify. The composition of the resistive element paste used for verification, the characteristics of the resistive element (resistor element film), and the results of the reliability test are shown in Table 7 and FIG. 8 as Examples 4-1 to 4-10.

[Table 7] Table 7 Example 4 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass Glass powder 2-1 4.5 5.4 6.3 8.2 10.0 12.4 13.6 15.0 15.7 16.4 high melting point glass Glass Powder 7 3.0 11.2 19.4 34.8 50.2 69.8 80.3 91.9 97.7 103.5 organic medium 13.5 16.4 19.2 25.3 31.4 39.1 43.3 47.9 50.2 52.5 Volume fraction (volume%) Ratio of metal components in inorganic components 83.7% 70.1% 60.3% 47.7% 39.4% 32.3% 29.4% 26.8% 25.7% 24.6% Ratio of low melting point glass in inorganic components 9.9% 9.9% 9.9% 10.2% 10.3% 10.5% 10.5% 10.5% 10.6% 10.6% Ratio of high melting point glass in inorganic components 6.4% 20.0% 29.7% 42.2% 50.3% 57.3% 60.1% 62.7% 63.8% 64.8% Ratio of organic vehicle in paste 50.2% 50.5% 50.8% 51.8% 52.4% 52.9% 53.1% 53.3% 53.4% 53.5% Mass fraction (mass%) Ratio of metal components in inorganic components 93.0% 85.8% 79.6% 70.0% 62.4% 54.9% 51.6% 48.3% 46.9% 45.5% Ratio of low melting point glass in inorganic components 4.2% 4.6% 5.0% 5.7% 6.2% 6.8% 7.0% 7.3% 7.4% 7.5% Ratio of high melting point glass in inorganic components 2.8% 9.6% 15.4% 24.3% 31.3% 38.3% 41.4% 44.4% 45.8% 47.1% Ratio of organic vehicle in paste 11.2% 12.3% 13.3% 15.0% 16.4% 17.7% 18.3% 18.8% 19.0% 19.3% Roasting temperature 950°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a a Closeness a a a a a a a a a a Volume resistivity (μΩ・cm) 65 103 175 380 866 2,893 6,860 20,130 46,210 132,500 Can realize continuous adjustment in a wide range TCR(ppm/℃) 2 5 -3 4 12 twenty three 19 4 6 twenty one determination a a a a a a a a a a initial judgment A A A A A A A A A A Reliability of Resistive Elements heat resistance rate of change 0.52% 0.85% 0.46% 0.55% 0.43% 0.40% 0.52% 0.63% 0.46% 0.36% (155℃, 500hrs) determination a a a a a a a a a a Moisture resistance rate of change 0.94% 0.66% 0.63% 0.54% 0.38% 0.54% 0.66% 0.49% 0.57% 0.62% (85℃, 85%RH, 500hrs) determination a a a a a a a a a a Comprehensive judgment A A A A A A A A A A

In Example 4, the softening point of glass powder 2-1 (low melting point glass) is 370°C lower than the firing temperature, the glass transition point of glass powder 7 (high melting point glass) is 60°C lower than the firing temperature, and the softening point is lower than the firing temperature 50°C higher. The difference between the softening points of glass frit 2-1 and glass frit 7 was 420°C.

In Example 4, the same tendency as in Example 1 appeared. That is, in Examples 4-2 to 4-8, compared with Example 4-1, if the volume fraction of the high melting point glass in the inorganic component is gradually increased, and the volume fraction of the metal component is gradually decreased, it is good. The shape retention, adhesion, and TCR are maintained, and the volume resistivity slowly rises to 65-20,130 μΩ·cm. In Examples 4-9-4-10, the volume fraction of the metal component is further reduced, and the maximum can be adjusted. to 132,500 μΩ・cm.

According to the above results, it was verified that in Example 4 (4-1 to 4-10) using a composition comprising glass frit 2-1 (low melting point glass) and glass frit 7 (high melting point glass) It is a resistance element with the function of continuously and freely adjusting the resistance value (volume resistivity) in a wide range from resistance to high resistance and having excellent heat resistance and humidity resistance reliability. (Rate A in the comprehensive judgment).

[Comparative example 4] Comparative Example 4 is a verification of an example in which the difference between the softening points of the low-melting point glass and the high-melting point glass is small (90° C.). Specifically, glass frit 4 (softening point 740°C) was used as an inorganic binder component (low melting point glass), and glass frit 5 (glass transition point 700°C, softening point 830°C) was used as a resistance adjustment component (high melting point glass). Glass), and the verification of the case where the firing temperature is varied in three levels (850°C, 900°C, 950°C).

In this comparative example, when the firing temperature is 850°C, the softening point of glass frit 4 is 110°C lower than the firing temperature, the glass transition point of glass frit 5 is 150°C lower than the firing temperature, and the softening point is 20°C lower than the firing temperature. ℃. When the firing temperature is 900°C, the softening point of glass powder 4 (low melting point glass) is 160°C lower than the firing temperature, the glass transition point of glass powder 5 (high melting point glass) is 200°C lower than the firing temperature, and the softening point is lower than The firing temperature is 70°C lower. When the firing temperature is 950°C, the softening point of glass frit 4 is 210°C lower than the firing temperature, and for glass frit 5, the glass transition point is 250°C lower than the firing temperature, and the softening point is 120°C lower than the firing temperature.

Table 8 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Comparative Examples 4-1 to 4-6.

[Table 8] Table 8 Comparative example 4 4-1 4-2 4-3 4-4 4-5 4-6 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 Ni powder 1 36.0 36.0 low melting point glass glass powder 4 7.9 10.8 high melting point glass glass powder 5 48.0 76.8 organic medium 31.4 43.3 Volume fraction (volume%) Ratio of metal components in inorganic components 39.1% 29.2% Ratio of low melting point glass in inorganic components 10.2% 10.4% Ratio of high melting point glass in inorganic components 50.7% 60.4% Ratio of organic vehicle in paste 52.2% 52.9% Mass fraction (mass%) Ratio of metal components in inorganic components 64.1% 53.3% Ratio of low melting point glass in inorganic components 5.1% 5.8% Ratio of high melting point glass in inorganic components 30.8% 40.9% Ratio of organic vehicle in paste 16.8% 18.7% Roasting temperature 850 900 950 850 900 950 Characteristics of Resistive Elements shape maintenance b c c b c c Closeness c b b c b b Volume resistivity (μΩ・cm) 1,120 910 826 7,120 6,330 6,180 TCR(ppm/℃) -5 2 -3 4 -1 -2 determination a a a a a a initial judgment C C C C C C Comprehensive judgment D. D. D. D. D. D.

When the firing temperature was 850° C. (Comparative Examples 4-1 and 4-4), the shape retention and TCR were acceptable, but the adhesiveness was unacceptable. When the firing temperature is 900°C and 950°C (Comparative Examples 4-2, 4-3, 4-5, 4-6), the adhesion and TCR are at the acceptable level, but the resistance element film shrinks and deforms greatly, so the shape Sustainability becomes unqualified. When the difference between the softening point of the low-melting point glass and the high-melting point glass is as small as 90°C and the firing temperature is 850°C, since the difference between the softening point of the low-melting point glass and the firing temperature is also small, the joint components (low melting point Glass) does not melt and flow sufficiently and the adhesion is insufficient. When the firing temperature is above 900°C, the low-melting point glass melts and flows, so the adhesion is improved, but because the softening point of the high-melting point glass is 70°C lower than the firing temperature, the high-melting point glass also melts and flows, so the resistance element film The shape retention is insufficient, and the volume resistivity becomes stable.

Based on the above results, Comparative Example 4, in which the difference between the softening points of the low-melting point glass and the high-melting point glass was small, failed the initial evaluation, so the reliability test was not performed. It was verified that the composition of Comparative Example 4 was not suitable as a resistance element (rank D in the comprehensive judgment).

[Comparative Example 5] Comparative Example 5 is a verification of the case of using high-melting-point glass with low glass transition point and softening point. Specifically, glass frit 1 (softening point 440°C) was used as an inorganic binder component (low melting point glass), and glass frit 2-1 (glass transition point 510°C, softening point 580°C) was used as a resistance value adjustment component ( High-melting point glass), when the firing temperature is varied in three levels (650°C, 700°C, 750°C).

In this comparative example, when the firing temperature is 650°C, the softening point of glass powder 1 is 210°C lower than the firing temperature, the glass transition point of glass powder 2-1 is 140°C lower than the firing temperature, and the softening point is lower than the firing temperature 70°C lower. When the firing temperature is 700°C, the softening point of glass powder 1 is 260°C lower than the firing temperature, the glass transition point of glass powder 2-1 is 190°C lower than the firing temperature, and the softening point is 120°C lower than the firing temperature. When the firing temperature is 750°C, the softening point of glass frit 1 is 310°C lower than the firing temperature, the glass transition point of glass frit 2-1 is 240°C lower than the firing temperature, and the softening point is 170°C lower than the firing temperature. The difference between the softening points of glass frit 1 and glass frit 2-1 was 140°C.

Table 9 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Comparative Examples 5-1 to 5-6.

[Table 9] Table 9 Comparative Example 5 5-1 5-2 5-3 5-4 5-5 5-6 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 Ni powder 1 36.0 36.0 low melting point glass glass powder 1 19.3 26.4 high melting point glass Glass powder 2-1 49.5 79.1 organic medium 31.4 43.3 Volume fraction (volume%) Ratio of metal components in inorganic components 39.1% 29.2% Ratio of low melting point glass in inorganic components 10.2% 10.4% Ratio of high melting point glass in inorganic components 50.7% 60.4% Ratio of organic vehicle in paste 52.2% 52.9% Mass fraction (mass%) Ratio of metal components in inorganic components 59.2% 48.7% Ratio of low melting point glass in inorganic components 11.4% 12.8% Ratio of high melting point glass in inorganic components 29.3% 38.5% Ratio of organic vehicle in paste 15.7% 17.4% Roasting temperature 650 700 750 650 700 750 Characteristics of Resistive Elements shape maintenance a c c a c c Closeness b b b b b b Volume resistivity (μΩ・cm) 8,600 2,100 1,130 ∞ 15,420 12,200 TCR(ppm/℃) 890 180 25 - 165 15 determination c b a - b a initial judgment C C C C C C Comprehensive judgment D. D. D. D. D. D.

When the firing temperature is 650°C (Comparative Examples 5-1 and 5-4), the shape retention and adhesion become good, but if the volume fraction of the metal component in the inorganic component in Example 1 is Comparing examples of the same degree, the volume resistivity and TCR increase in Comparative Examples 5-1 and 5-4 (for example, Example 1-5 is 830 μΩ·cm, compared to this, Comparative Example 5-1 is 8,600 μΩ·cm). It is discussed that when the firing temperature is 650°C, the metal components cannot be fully sintered and alloyed, so sufficient conductive channels cannot be formed and low TCR can not be achieved by alloying copper and nickel. When the firing temperature is 700°C and 750°C (Comparative Examples 5-2, 5-3, 5-5, 5-6), the metal components are sintered and alloyed, so the volume resistivity decreases, and the TCR also decreases to become passing grade. However, the resistive element film was greatly shrunk and deformed, and the shape could not be maintained. It is considered that the softening point of the high melting point glass is 120°C or more lower than the firing temperature, so the high melting point glass melts and flows during firing, making it difficult to maintain the shape. Therefore, in order to sinter the metal component, the firing temperature must be set at 700°C or higher. In order to prevent excessive flow of the high melting point glass, it is preferable to set the difference between the softening point of the high melting point glass and the firing temperature within 100°C. That is, it can be said that the softening point of the high melting point glass is preferably 600°C or higher.

Based on the above results, Comparative Example 5, which used high-melting-point glass with a relatively small glass transition point and softening point, failed the initial evaluation, so the reliability test was not performed. It was verified that the composition of Comparative Example 5 was not suitable as a resistance element (rank D in the comprehensive judgment).

[Example 5] In Example 5, the result of Comparative Example 5 was taken into consideration, and the case of using a high-melting glass whose softening point was slightly higher than that of Comparative Example 5 was verified. Specifically, glass frit 1 (softening point 440°C) was used as an inorganic binder component (low melting point glass), and glass frit 3 (glass transition point 590°C, softening point 700°C) was used as a resistance adjustment component (high melting point glass). Glass), the verification was performed when the firing temperature was varied in three levels (700°C, 750°C, 800°C).

In this embodiment, when the firing temperature is 700°C, the softening point of glass powder 1 is 260°C lower than the firing temperature, the glass transition point of glass powder 3 is 110°C lower than the firing temperature, and the softening point is the same as the firing temperature. When the firing temperature is 750°C, the softening point of glass powder 1 is 310°C lower than the firing temperature, the glass transition point of glass powder 3 is 160°C lower than the firing temperature, and the softening point is 50°C lower than the firing temperature. When the firing temperature is 800°C, the softening point of glass powder 1 is 360°C lower than the firing temperature, the glass transition point of glass powder 3 is 210°C lower than the firing temperature, and the softening point is 100°C lower than the firing temperature. The difference between the softening points of glass frit 1 and glass frit 3 is 260°C.

Table 10 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Examples 5-1 to 5-6.

[Table 10] Table 10 Example 5 5-1 5-2 5-3 5-4 5-5 5-6 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 Ni powder 1 36.0 36.0 low melting point glass glass powder 1 19.3 26.4 high melting point glass glass powder 3 43.7 69.8 organic medium 31.4 43.3 Volume fraction (volume%) Ratio of metal components in inorganic components 39.1% 29.2% Ratio of low melting point glass in inorganic components 10.2% 10.4% Ratio of high melting point glass in inorganic components 50.7% 60.4% Ratio of organic vehicle in paste 52.2% 52.9% Mass fraction (mass%) Ratio of metal components in inorganic components 61.3% 51.0% Ratio of low melting point glass in inorganic components 11.8% 13.5% Ratio of high melting point glass in inorganic components 26.8% 35.6% Ratio of organic vehicle in paste 16.2% 18.1% Roasting temperature 700 750 800 700 750 800 Characteristics of Resistive Elements shape maintenance a a b a a b Closeness a a a a a a Volume resistivity (μΩ・cm) 2,430 1,210 980 21,340 13,150 8,540 TCR(ppm/℃) 168 32 25 172 18 12 determination b a a b a a initial judgment B A B B A B Reliability of Resistive Elements heat resistance rate of change 1.95% 1.22% 0.84% 1.64% 0.98% 0.42% (155℃, 500hrs) determination b b a b a a Moisture resistance rate of change 1.02% 0.89% 0.75% 0.82% 0.75% 0.55% (85℃, 85%RH, 500hrs) determination b a a a a a Comprehensive judgment B A B B A B

When the firing temperature was 700° C. (Examples 5-1, 5-4), shape retention and adhesiveness became favorable. Although the sintering is slightly insufficient or the volume resistivity and TCR are slightly high, and the change rate of the volume resistivity in the reliability test is more than 1%, it is still a qualified level (level B in the comprehensive judgment). When the firing temperature was 750°C (Examples 5-2, 5-5), the shape retention, adhesion, and TCR were good, and the reliability test was also a pass level (level A in the comprehensive judgment). When the firing temperature was 800°C (Example 5-3, 5-6), although the shape retention was slightly lowered, it was still at the acceptable level, and the adhesion, TCR, and reliability also became good (in the comprehensive evaluation, it was grade B).

[Example 6] Example 6 is about using glass frit 2-1 (softening point 580°C) as an inorganic binder component (low melting point glass), and glass frit 6-1 (glass transition point 810°C, softening point 920°C) as resistance value Example 1 of adjusting the composition (high melting point glass), making the composition of Examples 1-5 into a paste, setting the volume fraction (39.1%) of the metal component in the inorganic component to be fixed, and making the low melting point glass and the high melting point Verification in the case of variable glass volume ratios. Except for these changes, verification was performed using the method according to Example 1. Table 11 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Examples 6-1 to 6-6. Furthermore, Example 6-3 is the same verification as Example 1-5.

[Table 11] Table 11 Example 6 6-1 6-2 6-3 (1-5) 6-4 6-5 6-6 6-7 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass Glass powder 2-1 3.0 5.0 10.0 15.0 20.0 25.0 30.0 high melting point glass Glass powder 6-1 57.3 55.3 50.2 45.1 40.0 34.9 29.8 organic medium 31.4 31.4 31.4 31.4 31.4 31.4 31.4 Volume fraction (volume%) Ratio of metal components in inorganic components 39.1% 39.1% 39.1% 39.1% 39.1% 39.1% 39.2% Ratio of low melting point glass in inorganic components 3.1% 5.1% 10.2% 15.4% 20.5% 25.6% 30.7% Ratio of high melting point glass in inorganic components 57.8% 55.8% 50.7% 45.5% 40.4% 35.2% 30.1% Ratio of organic vehicle in paste 52.2% 52.2% 52.2% 52.2% 52.2% 52.2% 52.2% Mass fraction (mass%) Ratio of metal components in inorganic components 62.4% 62.4% 62.4% 62.5% 62.5% 62.5% 62.6% Ratio of low-melting glass components in inorganic components 1.9% 3.1% 6.2% 9.4% 12.5% 15.6% 18.8% Ratio of high melting point glass components in inorganic components 35.7% 34.5% 31.3% 28.2% 25.0% 21.8% 18.6% Ratio of organic vehicle in paste 16.4% 16.4% 16.4% 16.4% 16.4% 16.4% 16.4% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a b b Closeness b a a a a a a Volume resistivity (μΩ・cm) 884 856 830 1,586 2,627 6,093 18,040 Can realize continuous adjustment in a wide range TCR(ppm/℃) -6 -5 -8 -10 -12 -10 -16 determination a a a a a a a initial judgment B A A A A B B Reliability of Resistive Elements heat resistance rate of change 1.65% 1.26% 1.24% 0.99% 0.95% 0.83% 0.61% (155℃, 500hrs) determination b b b a a a a Moisture resistance rate of change 0.82% 0.68% 0.66% 0.62% 0.66% 0.48% 0.51% (85℃, 85%RH, 500hrs) determination a a a a a a a Comprehensive judgment B A A A A B B

In Examples 6-2 to 6-5 in which the volume fraction of the low-melting point glass in the inorganic component was 5.1 to 20.5% by volume, good results were obtained in all judgment items (rank A in the comprehensive judgment). In Example 6-1 in which the volume fraction of the low-melting point glass was small (3.1 volume %), although the adhesiveness was slightly reduced, it was still a pass level in all judgment items (rank B in the comprehensive judgment). In Examples 6-6 and 6-7, in which the volume fraction of the low-melting point glass was relatively large (25% by volume or more), although the shape retention was slightly lowered, it was still a pass level in all judgment items (in the comprehensive judgment, it was grade B).

According to the above results, it was verified that the volume fraction of the low-melting glass in the inorganic component can be applied to about 30 volume%.

[Example 7] Except changing the calcination temperature from 900° C. to 950° C., verification was performed by the method based on Example 1. The composition of the resistance element paste used for the verification, and the characteristics of the resistance element (resistor element film) and the results of the reliability test are shown in Table 12 and FIG. 9 as Examples 7-1 to 7-11.

[Table 12] Table 12 Embodiment 7 (the firing temperature of embodiment 1 changes) 7-1 7-2 7-3 7-4 7-5 7-6 7-7 7-8 7-9 7-10 7-11 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.0 low melting point glass Glass powder 2-1 4.5 5.4 6.3 8.2 10.0 11.4 12.4 13.6 15.0 15.7 16.4 high melting point glass Glass powder 6-1 3.0 11.2 19.4 34.8 50.2 61.8 69.8 80.3 91.9 97.7 103.5 organic medium 13.5 16.4 19.2 25.3 31.4 36.0 39.1 43.3 47.9 50.2 52.5 Volume fraction (volume%) Ratio of metal components in inorganic components 83.7% 69.9% 60.1% 47.4% 39.1% 34.6% 32.0% 29.2% 26.6% 25.4% 24.4% Ratio of low melting point glass in inorganic components 9.9% 9.9% 9.9% 10.1% 10.2% 10.3% 10.4% 10.4% 10.4% 10.5% 10.5% Ratio of high melting point glass in inorganic components 6.5% 20.2% 30.0% 42.5% 50.7% 55.1% 57.6% 60.4% 63.0% 64.1% 65.1% Ratio of organic vehicle in paste 50.1% 50.4% 50.7% 51.6% 52.2% 52.6% 52.7% 52.9% 53.1% 53.2% 53.3% Mass fraction (mass%) Ratio of metal components in inorganic components 93.0% 85.8% 79.6% 70.0% 62.4% 57.7% 54.9% 51.6% 48.3% 46.9% 45.5% Ratio of low melting point glass in inorganic components 4.2% 4.6% 5.0% 5.7% 6.2% 6.6% 6.8% 7.0% 7.3% 7.4% 7.5% Ratio of high melting point glass in inorganic components 2.8% 9.6% 15.4% 24.3% 31.3% 35.7% 38.3% 41.4% 44.4% 45.8% 47.1% Ratio of organic vehicle in paste 11.2% 12.3% 13.3% 15.0% 16.4% 17.2% 17.7% 18.3% 18.8% 19.0% 19.3% Roasting temperature 950°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a a a Closeness a a a a a a a a a a a Volume resistivity (μΩ・cm) 71 110 170 345 697 1,269 1,997 4,387 12,267 25,506 70,606 Can realize continuous adjustment in a wide range TCR(ppm/℃) -6 -9 -11 -8 -1 -4 -5 -3 -2 -4 -5 determination a a a a a a a a a a a initial judgment A A A A A A A A A A A Reliability of Resistive Elements heat resistance rate of change 0.25% 0.77% 0.73% 0.83% 0.79% 0.58% 0.32% 0.51% 0.55% 0.34% 0.21% (155℃, 500hrs) determination a a a a a a a a a a a Moisture resistance rate of change 0.66% 0.52% 0.60% 0.61% 0.56% 0.50% 0.71% 0.42% 0.63% 0.64% 0.55% (85℃, 85%RH, 500hrs) determination a a a a a a a a a a a Comprehensive judgment A A A A A A A A A A A

In Example 7, relative to the firing temperature of 950°C, the softening point of glass powder 2-1 is 370°C lower than the firing temperature, the glass transition point of glass powder 6-1 is 140°C lower than the firing temperature, and the softening point is lower than the firing temperature 30°C lower.

In Example 7 in which the firing temperature was changed to 950° C., in the same manner as in Example 1, in Examples 7-1 to 7-10, the volume fraction of the high-melting glass in the inorganic component was gradually increased, so that The volume fraction of the metal component is gradually reduced, and the shape retention, adhesion, and TCR are well maintained, and the volume resistivity rises slowly to 71-25,506 μΩ·cm. In Example 7, the volume fraction of the metal component is further reduced In -11, it can be adjusted up to 70,606 μΩ・cm (Fig. 9).

In particular, the heat resistance and moisture resistance in the reliability test were superior to those of the resistance element film of Example 1 (rank A in the comprehensive judgment). It is considered that by increasing the firing temperature, the sintering of the resistance element film becomes more dense, thereby preventing the penetration of oxygen and moisture into the inside of the resistance element film, so that the heat resistance and moisture resistance are improved.

[Example 8] Regarding the resistor element pastes of Examples 1-2 (low resistance), 1-6 (medium resistance), and 1-9 (high resistance) in Example 1, the high melting point glass (glass frit 6-1: center particle size 2 μm) to glass powder 6-2 (central particle size 1 μm), glass powder 6-3 (central particle size 7 μm), glass powder 6-4 (central particle size 12 μm) with different particle sizes Resistive element paste, and use the method according to embodiment 1 to verify. Table 13 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Examples 8-1 to 8-12. In addition, in order to compare the verification results, the verification results in Examples 1-2, 1-6, and 1-9 are described as Examples 8-2, 8-6, and 8-10.

[Table 13] Table 13 Example 8 8-1 8-2 (1-2) 8-3 8-4 8-5 8-6 (1-6) 8-7 8-8 8-9 8-10 (1-9) 8-11 8-12 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 low melting point glass Glass powder 2-1 5.4 11.4 15.0 high melting point glass Glass powder 6-2 (1 μm) 11.2 61.8 91.9 Glass powder 6-1 (2 μm) 11.2 61.8 91.9 Glass powder 6-3 (7 μm) 11.2 61.8 91.9 Glass powder 6-4 (12 μm) 11.2 61.8 91.9 organic medium 16.4 36.0 47.9 Volume fraction (volume%) Ratio of metal components in inorganic components 69.9% 34.6% 26.6% Ratio of low melting point glass in inorganic components 9.9% 10.3% 10.4% Ratio of high melting point glass in inorganic components 20.2% 55.1% 63.0% Ratio of organic vehicle in paste 50.4% 52.6% 53.1% Mass fraction (mass%) Ratio of metal components in inorganic components 85.8% 57.7% 48.3% Ratio of low melting point glass in inorganic components 4.6% 6.6% 7.3% Ratio of high melting point glass in inorganic components 9.6% 35.7% 44.4% Ratio of organic vehicle in paste 12.3% 17.2% 18.8% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a a a a Closeness a a a a a a a a a a a a Volume resistivity (μΩ・cm) 128 123 116 109 1,626 1,586 1,539 1,478 18,438 18,040 17,833 17,240 TCR(ppm/℃) -5 -12 -8 -11 -9 -12 -13 -12 -5 1 -8 -11 determination a a a a a a a a a a a a initial judgment A A A A A A A A A A A A Reliability of Resistive Elements heat resistance rate of change 0.62% 0.90% 0.86% 1.43% 0.42% 0.54% 0.56% 1.03% 0.45% 0.50% 0.49% 0.86% (155℃, 500hrs) determination a a a b a a a b a a a a Moisture resistance rate of change 0.46% 0.59% 0.64% 1.08% 0.50% 0.56% 0.61% 1.10% 0.62% 0.82% 0.75% 1.21% (85℃, 85%RH, 500hrs) determination a a a b a a a b a a a b Comprehensive judgment A A A B A A A B A A A A

Embodiment 8-1～8-4 is the comparison that utilizes the low-resistance resistance element film to carry out, even if the high-melting point glass (glass frit 6-1: central particle diameter) in embodiment 1-2 (i.e. embodiment 8-2) 2 μm) to glass frit 6-2 (central particle diameter 1 μm), glass frit 6-3 (central particle diameter 7 μm), glass frit 6-4 (central particle diameter 12 μm) with different particle sizes, also appeared The same tendency, but when the particle size becomes larger, the reliability decreases slightly. The reason for this is considered to be that the uniformity and sinterability of the resistor element paste decrease as the particle size of the high melting point glass increases.

Similarly, Examples 8-5 to 8-8 are the results of comparative verification using a medium-resistance resistance element film, and Examples 8-9 to 8-12 are the results of comparative verification using a high-resistance resistance element film. In embodiment 1-6 (i.e. embodiment 8-6) and embodiment 1-9 (i.e. embodiment 8-10), even if the high melting point glass (glass frit 6-1: central particle diameter 2 μ m) is changed to Glass powder 6-2 (central particle diameter 1 μm), glass powder 6-3 (central particle diameter 7 μm), and glass powder 6-4 (central particle diameter 12 μm) with different particle sizes also showed the same tendency, but When the particle size becomes larger, the reliability slightly decreases.

From the above results, it has been verified that the high melting point glass has the function of freely adjusting the resistance value (volume resistivity) in a wide range from low resistance to high resistance even if the particle size of the high melting point glass is different. In order to ensure excellent heat resistance and humidity resistance reliability, the particle size (central particle size) of high melting point glass is preferably around 1-7 μm.

[Example 9] Regarding the resistor element pastes of Examples 1-2 (low resistance), 1-6 (medium resistance), and 1-9 (high resistance) in Example 1, the low melting point glass (glass frit 2-1: center particle size 3 μm) to glass powder 2-2 (central particle size 1 μm), glass powder 2-3 (central particle size 5 μm), glass powder 2-4 (central particle size 7 μm) with different particle sizes The resistor element paste was verified by the method according to Example 1. Table 14 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Examples 9-1 to 9-12. In addition, in order to compare the verification results, the verification results in Examples 1-2, 1-6, and 1-9 are described as Examples 9-2, 9-6, and 9-10.

[Table 14] Table 14 Example 9 9-1 9-2 (1-2) 9-3 9-4 9-5 9-6 (1-6) 9-7 9-8 9-9 9-10 (1-9) 9-11 9-12 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 low melting point glass Glass powder 2-2 (1 μm) 5.4 11.4 15.0 Glass powder 2-1 (3 μm) 5.4 11.4 15.0 Glass powder 2-3 (5 μm) 5.4 11.4 15.0 Glass powder 2-4 (7 μm) 5.4 11.4 15.0 high melting point glass Glass powder 6-1 11.2 61.8 91.9 organic medium 16.4 36.0 47.9 Volume fraction (volume%) Ratio of metal components in inorganic components 69.9% 34.6% 26.6% Ratio of low melting point glass in inorganic components 9.9% 10.3% 10.4% Ratio of high melting point glass in inorganic components 20.2% 55.1% 63.0% Ratio of organic vehicle in paste 50.4% 52.6% 53.1% Mass fraction (mass%) Ratio of metal components in inorganic components 85.8% 57.7% 48.3% Ratio of low melting point glass in inorganic components 4.6% 6.6% 7.3% Ratio of high melting point glass in inorganic components 9.6% 35.7% 44.4% Ratio of organic vehicle in paste 12.3% 17.2% 18.8% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a a a a Closeness a a a a a a a a a a a a Volume resistivity (μΩ・cm) 109 123 132 139 1,526 1,586 1,638 1,673 16,950 18,040 18,332 18,950 TCR(ppm/℃) -9 -12 -12 -12 -11 -12 -9 -10 -13 1 -10 -12 determination a a a a a a a a a a a a initial judgment A A A A A A A A A A A A Reliability of Resistive Elements heat resistance rate of change 0.78% 0.90% 0.96% 1.28% 0.45% 0.54% 0.71% 1.08% 0.42% 0.50% 0.66% 0.83% (155℃, 500hrs) determination a a a b a a a b a a a a Moisture resistance rate of change 0.52% 0.59% 0.71% 1.13% 0.47% 0.56% 0.63% 0.79% 0.70% 0.82% 0.91% 0.89% (85℃, 85%RH, 500hrs) determination a a a b a a a a a a a a Comprehensive judgment A A A B A A A A A A A A

Embodiment 9-1～9-4 is the comparison that utilizes low-resistance resistance element film to carry out, even if the low-melting point glass in embodiment 1-2 (i.e. embodiment 9-2) (glass frit 2-1: central particle diameter 3 μm) to glass frit 2-2 (central particle diameter 1 μm), glass frit 2-3 (central particle diameter 5 μm), and glass frit 2-4 (central particle diameter 7 μm) with different particle sizes. The same tendency, but when the particle size becomes larger, the reliability decreases slightly. The reason for this is considered to be that the uniformity and sinterability of the resistor element paste decrease as the particle size of the low-melting glass increases.

Similarly, Examples 9-5 to 9-8 are the results of comparative verification using a medium-resistance resistance element film, and Examples 9-9 to 9-12 are the results of comparative verification using a high-resistance resistance element film. In embodiment 1-6 (i.e. embodiment 9-6) and embodiment 1-9 (i.e. embodiment 9-10), even if the low-melting point glass (glass powder 2-1: central particle diameter 3 μ m) is changed to Glass powder 2-2 (central particle diameter 1 μm), glass powder 2-3 (central particle diameter 5 μm), and glass powder 2-4 (central particle diameter 7 μm) with different particle sizes also showed the same tendency, but When the particle size becomes larger, the reliability slightly decreases.

From the above results, it has been verified that the low-melting point glass has the function of freely adjusting the resistance value (volume resistivity) in a wide range from low resistance to high resistance even if the particle size of the low-melting point glass is different. In order to ensure excellent heat resistance and humidity resistance reliability, the particle size (central particle size) of the low-melting point glass is preferably about 1-5 μm.

[Example 10] With respect to the resistor element pastes of Examples 1-2 (low resistance), 1-6 (medium resistance), and 1-9 (high resistance) in Example 1, copper particles (Cu powder 1: center particle diameter 3 μm ) was changed to Cu powder 2 (central particle diameter 5 μm) and Cu powder 3 (central particle diameter 8 μm) with different particle sizes to obtain a resistor element paste. For the obtained resistor element paste, use the method according to Example 1. verify. Table 15 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Examples 10-1 to 10-9. In addition, in order to compare the verification results, the verification results in Examples 1-2, 1-6, and 1-9 are described as Examples 10-1, 10-4, and 10-7.

[Table 15] Table 15 Example 10 10-1 (1-2) 10-2 10-3 10-4 (1-6) 10-5 10-6 10-7 (1-9) 10-8 10-9 Composition (parts by mass) metal composition Cu powder 1 (3 μm) 64.0 64.0 64.0 Cu powder 2 (5 μm) 64.0 64.0 64.0 Cu powder 3 (8 μm) 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 low melting point glass Glass powder 2-1 5.4 11.4 15.0 high melting point glass Glass powder 6-1 11.2 61.8 91.9 organic medium 16.4 36.0 47.9 Volume fraction (volume%) Ratio of metal components in inorganic components 69.9% 34.6% 26.6% Ratio of low melting point glass in inorganic components 9.9% 10.3% 10.4% Ratio of high melting point glass in inorganic components 20.2% 55.1% 63.0% Ratio of organic vehicle in paste 50.4% 52.6% 53.1% Mass fraction (mass%) Ratio of metal components in inorganic components 85.8% 57.7% 48.3% Ratio of low melting point glass in inorganic components 4.6% 6.6% 7.3% Ratio of high melting point glass in inorganic components 9.6% 35.7% 44.4% Ratio of organic vehicle in paste 12.3% 17.2% 18.8% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a Closeness a a a a a a a a a Volume resistivity (μΩ・cm) 123 108 86 1,586 1,377 1,420 18,040 17,330 15,680 TCR(ppm/℃) -12 38 126 -12 46 142 1 65 178 determination a a b a a b a a b initial judgment A A B A A B A A B Reliability of Resistive Elements heat resistance rate of change 0.90% 0.63% 0.97% 0.54% 0.59% 0.79% 0.50% 0.66% 0.86% (155℃, 500hrs) determination a a a a a a a a a Moisture resistance rate of change 0.59% 0.53% 0.78% 0.56% 0.48% 0.82% 0.82% 0.71% 1.05% (85℃, 85%RH, 500hrs) determination a a a a a a a a b Comprehensive judgment A A B A A B A A B

Examples 10-1 to 10-3 are comparisons using low-resistance resistance element films, even if the copper particles (Cu powder 1: central particle diameter 3 μm) in Example 1-2 (i.e. Example 10-1) Changing to Cu powder 2 (central particle diameter 5 μm) and Cu powder 3 (central particle diameter 8 μm) with different particle sizes also shows the same tendency, but when the particle size becomes larger, the resistance value decreases and the TCR increases. The reason for this is considered to be that the uniformity in the alloying of the copper particles and the nickel particles decreases as the particle size of the copper particles increases.

Similarly, Examples 10-4 to 10-6 are the results of comparative verification using a medium-resistance resistance element film, and Examples 10-7 to 10-9 are the results of comparative verification using a high-resistance resistance element film. In Examples 1-6 (i.e., Example 10-4) and Examples 1-9 (i.e., Example 10-7), even if the copper particles (Cu powder 1: central particle diameter 3 μm) are changed to have different particle sizes Cu powder 2 (central particle size 5 μm) and Cu powder 3 (central particle size 8 μm) have the same tendency, but when the particle size becomes larger, the resistance value decreases and the TCR increases.

From the above results, it has been verified that the copper particles have the function of freely adjusting the resistance value (volume resistivity) in a wide range from low resistance to high resistance even if the particle diameters of the copper particles are different. In order to ensure a relatively low TCR, the particle size (central particle size) of the copper particles is preferably about 3-5 μm.

[Example 11] With respect to the resistor element pastes of Examples 1-2 (low resistance), 1-6 (medium resistance), and 1-9 (high resistance) in Example 1, nickel particles (Ni powder 1: central particle diameter 0.4 μm ) was changed to Ni powder 2 (central particle diameter 1 μm) and Ni powder 3 (central particle diameter 3 μm) with different particle sizes to obtain a resistor element paste. For the obtained resistor element paste, use the method according to Example 1. verify. Table 16 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Examples 11-1 to 11-9. In addition, in order to compare the verification results, the verification results in Examples 1-2, 1-6, and 1-9 are described as Examples 11-1, 11-4, and 11-7.

[Table 16] Table 16 Example 11 11-1 (1-2) 11-2 11-3 11-4 (1-6) 11-5 11-6 11-7 (1-9) 11-8 11-9 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 Ni powder 1 (0.4 μm) 36.0 36.0 36.0 Ni powder 2 (1 μm) 36.0 36.0 36.0 Ni powder 3 (3 μm) 36.0 36.0 36.0 low melting point glass Glass powder 2-1 5.4 11.4 15.0 high melting point glass Glass powder 6-1 11.2 61.8 91.9 organic medium 16.4 36.0 47.9 Volume fraction (volume%) Ratio of metal components in inorganic components 69.9% 34.6% 26.6% Ratio of low melting point glass in inorganic components 9.9% 10.3% 10.4% Ratio of high melting point glass in inorganic components 20.2% 55.1% 63.0% Ratio of organic vehicle in paste 50.4% 52.6% 53.1% Mass fraction (mass%) Ratio of metal components in inorganic components 85.8% 57.7% 48.3% Ratio of low melting point glass in inorganic components 4.6% 6.6% 7.3% Ratio of high melting point glass in inorganic components 9.6% 35.7% 44.4% Ratio of organic vehicle in paste 12.3% 17.2% 18.8% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a a a a a a a Closeness a a a a a a a a a Volume resistivity (μΩ・cm) 123 106 115 1,586 1,360 1,280 18,040 16,300 15,630 TCR(ppm/℃) -12 twenty three 153 -12 38 168 1 55 149 determination a a b a a b a a b initial judgment A A B A A B A A B Reliability of Resistive Elements heat resistance rate of change 0.90% 0.83% 1.04% 0.54% 0.86 1.23% 0.50% 0.79% 1.27% (155℃, 500hrs) determination a a b a a b a a b Moisture resistance rate of change 0.59% 0.67% 0.97% 0.56% 0.72% 1.17% 0.82% 0.88% 1.35% (85℃, 85%RH, 500hrs) determination a a a a a b a a b Comprehensive judgment A A B A A B A A B

Examples 11-1 to 11-3 are comparisons using low-resistance resistance element films, even if the nickel particles (Ni powder 1: central particle diameter 0.4 μm) in Example 1-2 (i.e. Example 11-1) Changing to Ni powder 2 (center particle size 1 μm) and Ni powder 3 (center particle size 3 μm) with different particle sizes also shows the same tendency, but when the particle size becomes larger, the resistance value decreases and the TCR increases. The reason for this is considered to be that the uniformity in the alloying of the copper particles and the nickel particles decreases as the particle size of the nickel particles increases.

Similarly, Examples 11-4 to 11-6 are the results of comparative verification using medium resistance resistance element films, and Examples 11-7 to 11-9 are the results of comparative verification using high resistance resistance element films. In Examples 1-6 (i.e. Example 11-4) and Examples 1-9 (i.e. Example 11-7), even if the nickel particles (Ni powder 1: central particle diameter 0.4 μm) are changed to have different particle sizes Ni powder 2 (central particle size 1 μm) and Ni powder 3 (central particle size 3 μm) also showed the same tendency, but when the particle size became larger, the resistance value decreased and the TCR increased.

From the above results, it has been verified that even if the particle diameters of the nickel particles are different, the resistance value (volume resistivity) can be freely adjusted in a wide range from low resistance to high resistance. In order to ensure a relatively low TCR, the particle size (central particle size) of the nickel particles is preferably about 0.4-1 μm.

[Example 12] Change the ceramic substrate to an aluminum nitride substrate, in addition, use the method according to embodiment 1 to make the equivalent of embodiment 1-2 (low resistance), 1-6 (medium resistance), 1-9 (high resistance) resistor element and verify. Table 17 shows the composition of the resistance element paste used for verification, the characteristics of the resistance element (resistor element film), and the results of the reliability test as Examples 12-1 to 12-3.

[Table 17] Table 17 Embodiment 12 (change the substrate of Embodiment 1) 12-1 12-2 12-3 Composition (parts by mass) metal composition Cu powder 1 64.0 64.0 64.0 Ni powder 1 36.0 36.0 36.0 low melting point glass Glass powder 2-1 5.4 11.4 15.0 high melting point glass Glass powder 6-1 11.2 61.8 91.9 Copper oxide powder 5.0 5.0 5.0 organic medium 17.0 36.0 47.9 Volume fraction (volume%) Ratio of metal components in inorganic components 66.5% 33.7% 26.1% Ratio of low melting point glass in inorganic components 9.4% 10.1% 10.2% Ratio of high melting point glass in inorganic components 19.2% 53.7% 61.8% Ratio of organic vehicle in paste 50.1% 51.9% 52.6% Mass fraction (mass%) Ratio of metal components in inorganic components 85.8% 56.1% 47.2% Ratio of low melting point glass in inorganic components 4.6% 6.4% 7.1% Ratio of high melting point glass in inorganic components 9.6% 34.7% 43.4% Ratio of organic vehicle in paste 12.3% 16.8% 18.4% Roasting temperature 900°C Characteristics of Resistive Elements shape maintenance a a a Closeness a a a Volume resistivity (μΩ・cm) 113 1,402 16,540 TCR(ppm/℃) 6 19 16 determination a a a initial judgment A A A Reliability of Resistive Elements heat resistance rate of change 0.89% 0.65% 0.68% (155℃, 500hrs) determination a a a Moisture resistance rate of change 0.65% 0.69% 0.86% (85℃, 85%RH, 500hrs) determination a a a Comprehensive judgment A A A

From the results of Examples 12-1 to 12-3, the same tendencies as those of Examples 1-2 (low resistance), 1-6 (medium resistance), and 1-9 (high resistance) were obtained. It has been verified that even if the alumina substrate is changed to an aluminum nitride substrate, the function of freely adjusting the resistance value (volume resistivity) in a wide range from low resistance to high resistance and excellent heat resistance and humidity resistance reliability can be obtained. The resistance element. (Rate A in the comprehensive judgment).

Table 18 clearly summarizes the relationship between the temperature characteristics of the glass particles used in Examples 1-12 and Comparative Examples 1-5 and the firing temperature.

[Table 18] Table 18 (Unit: °C) low melting point glass high melting point glass Firing temperature Tf Ths-Tls Tf-Tls Tf-Thg Tf-Ths type Softening point Tls type Softening point Ths Glass transition point Thg Example 1 Examples 10-12 Glass powder 2-1 580 Glass powder 6-1 920 810 900 340 320 90 -20 Example 8 Glass powder 2-1 Glass powder 6-2 Glass powder 6-3 Glass powder 6-4 Example 9 Glass powder 2-2 Glass powder 6-1 Glass powder 2-3 Glass powder 2-4 Example 2 glass powder 1 440 Glass powder 6-1 920 810 900 480 460 90 -20 Example 3 Glass powder 2-1 580 glass powder 5 830 700 850 250 270 150 20 Example 4 Glass powder 2-1 580 Glass Powder 7 1000 890 950 420 370 60 -50 Example 5 glass powder 1 440 glass powder 3 700 590 700 260 260 110 0 750 310 160 50 800 360 210 100 Example 6 Glass powder 2-1 580 Glass powder 6-1 920 810 900 340 320 90 -20 Example 7 Glass powder 2-1 580 Glass powder 6-1 920 810 950 340 370 140 30 Comparative example 1 Glass powder 2-1 580 Alumina powder - - 900 - 320 - - Comparative example 2 Glass powder 2-1 580 - - - 900 - 320 - - Comparative example 3 - - Glass powder 6-1 920 810 900 - - 90 -20 Comparative example 4 glass powder 4 740 glass powder 5 830 700 850 90 110 150 20 900 160 200 70 950 210 250 120 Comparative Example 5 glass powder 1 440 Glass powder 2-1 580 510 650 140 210 140 70 700 260 190 120 750 310 240 170

Although this invention was demonstrated in detail with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention. This application is based on Japanese Patent Application No. 2021-38738 filed on March 10, 2021, the contents of which are incorporated herein by reference. [Industrial availability]

The resistance element paste of the present invention can be used for thick film resistance elements such as chip resistors, resistance built-in modules, resistance built-in substrates, ceramic heaters, and resistors equipped with the thick film resistance elements (such as resistors equipped with resistance elements and copper electrodes, etc. ) or electronic parts, etc.

FIG. 1 is a graph showing the change in the volume resistivity of the metal component in the inorganic component of Example 1 with respect to the volume fraction. Fig. 2 is a scanning electron micrograph of a cross section of a resistive element film obtained in Examples 1-4. 3 is a graph showing the change in volume resistivity of the metal component in the inorganic component of Comparative Example 1 with respect to the volume fraction. Fig. 4 is a scanning electron micrograph of a section of a resistive element film obtained in Comparative Examples 1-4. 5 is a graph comparing the change of the volume resistivity of the metal component in the inorganic component of Comparative Example 2 relative to the volume fraction with that of Example 1. 6 is a graph showing changes in volume resistivity of metal components in inorganic components in Example 2 with respect to volume fraction. FIG. 7 is a graph showing the change in volume resistivity of the metal component in the inorganic component of Example 3 with respect to the volume fraction. 8 is a graph showing changes in volume resistivity of metal components in inorganic components in Example 4 with respect to volume fraction. FIG. 9 is a graph showing changes in volume resistivity of metal components in inorganic components in Example 7 with respect to volume fraction.

Claims (11)

A resistor element paste, which contains inorganic components and organic agents, The above-mentioned inorganic components include metal components, low melting point glass and high melting point glass, The above metal components include copper and nickel, The softening point Ths of the above-mentioned high-melting-point glass is 600°C or more, and is 100°C or more higher than the softening point Tls of the above-mentioned low-melting-point glass. The resistance element paste according to claim 1, wherein the softening point Tls of the above-mentioned low-melting-point glass is 350-750°C, and the softening point Ths of the above-mentioned high-melting-point glass is 650-1150°C. The resistance element paste according to claim 1 or 2, wherein the glass transition point Thg of the above-mentioned high-melting glass is 600-900°C. The resistance element paste according to any one of claims 1 to 3, wherein the above-mentioned metal components are metal particles with a central particle diameter (D50) of 0.05-15 μm, and the above-mentioned low melting point glass is a metal particle with a central particle diameter (D50) of 1-5 μm The low-melting-point glass particles, the above-mentioned high-melting-point glass are high-melting-point glass particles with a central particle diameter (D50) of 1-8 μm. The resistor element paste according to any one of claims 1 to 4, wherein in the inorganic component, the ratio of the low-melting glass is 3-25% by volume, and the ratio of the high-melting glass is 3-80% by volume. A method of manufacturing a resistance element, which is to manufacture the resistance element by firing the resistance element paste according to any one of claims 1 to 5. The method of claim 6, wherein the firing temperature Tf is higher than the softening point Tls of the melting point glass by more than 150°C. The method according to claim 6 or 7, wherein the above-mentioned firing temperature Tf is higher than the glass transition point Thg of the melting point glass, and is equal to or lower than the softening point Ths of the high melting point glass + 100°C. A resistive element comprising an inorganic component and having a volume resistivity of 100 μΩ·cm or more, The above-mentioned inorganic components include metal components, low melting point glass and high melting point glass, The above metal components include copper and nickel, The softening point Ths of the above-mentioned high-melting-point glass is 600°C or more, and is 100°C or more higher than the softening point Tls of the above-mentioned low-melting-point glass. As in the resistance element of claim 9, the volume resistivity is 10,000 μΩ·cm or less. A method for adjusting the volume resistivity of a resistance element. The resistance element is obtained by firing the resistance element paste according to any one of claims 1 to 5. The method is obtained by adjusting the ratio of the metal component to the high melting point glass Adjust the above-mentioned volume resistivity to the range of 100 to 10,000 μΩ·cm.

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