WO2016039108A1 - 厚膜抵抗体及びその製造方法 - Google Patents
厚膜抵抗体及びその製造方法 Download PDFInfo
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- WO2016039108A1 WO2016039108A1 PCT/JP2015/073358 JP2015073358W WO2016039108A1 WO 2016039108 A1 WO2016039108 A1 WO 2016039108A1 JP 2015073358 W JP2015073358 W JP 2015073358W WO 2016039108 A1 WO2016039108 A1 WO 2016039108A1
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- glass
- thick film
- film resistor
- resistance
- ruthenium
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- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
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- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
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Definitions
- the present invention relates to a thick film resistor that does not substantially contain a lead component and a manufacturing method thereof.
- the present invention relates to a thick film resistor formed in a thick film circuit, a multilayer circuit board, various laminated composite parts, and the like, and a manufacturing method thereof.
- a thick film resistor (hereinafter sometimes simply referred to as a resistor) is formed by forming a film made of a resistance composition mainly composed of a conductive component and glass on various insulating substrates, and firing the film.
- the resistance composition is printed in a predetermined shape mainly on the alumina substrate on which the electrode is formed, a ceramic composite part, or the like in the form of a paste or paint, and fired at a high temperature of about 600 to 900 ° C. Then, after forming a protective film with overcoat glass if necessary, the resistance value is adjusted by laser trimming or the like as necessary.
- the required resistor characteristics are that the temperature coefficient of resistance (TCR) is small, the current noise is small, the withstand voltage characteristic and the process stability are good (for example, the resistance value changes due to process variations). Small).
- a resistance composition using a ruthenium-based oxide powder as a conductive component (hereinafter also referred to as a ruthenium-based resistance composition) has been widely used.
- This ruthenium-based resistor composition can be fired in air, and a resistor having a wide range of resistance values can be easily obtained by changing the ratio of the conductive component and glass.
- Examples of the conductive component of the ruthenium-based resistor composition include ruthenium dioxide (hereinafter sometimes referred to as ruthenium (IV) oxide), pyrochlore structure bismuth ruthenate, lead ruthenate, and the like, and perovskite structure barium ruthenate and ruthenium.
- Ruthenium complex oxides such as calcium acid and ruthenium precursors such as ruthenium resinate are used.
- a ruthenium composite oxide such as bismuth ruthenate described above is preferably used rather than ruthenium dioxide.
- resistivity of ruthenium composite oxide is generally one digit higher than that of ruthenium dioxide, and it can be blended in a larger amount than ruthenium dioxide, so there is little variation in resistance value, and resistance characteristics such as current noise characteristics and TCR. This is because a stable resistor is easily obtained.
- a glass containing lead oxide is mainly used as a glass used as a component constituting the thick film resistor.
- the glass containing lead oxide has a low softening point, good fluidity, good wettability with conductive components, excellent adhesion to the substrate, and a thermal expansion coefficient compatible with ceramics, especially alumina substrates. This is because it has excellent characteristics suitable for the formation of thick film resistors.
- the lead component is toxic and undesirable from the viewpoint of human influence and pollution.
- electronic products are required to comply with the WEEE (Waste Electrical and Electronic Equipment Directive and Electronic Equipment) and the RoHS (Restriction of the Use of the Certificate of the Hazardous Resistant) requirement.
- WEEE Wired Electrical and Electronic Equipment Directive and Electronic Equipment
- RoHS Restriction of the Use of the Certificate of the Hazardous Resistant
- the lead component since the lead component has very good wettability with respect to alumina, it may spread too much on the alumina substrate during firing, resulting in an unintended shape of the finally obtained resistor.
- thick film resistors using lead-free glass still have excellent characteristics over a wide resistance range comparable to conventional thick film resistors using lead-containing glass.
- the above-described decomposition can be suppressed to some extent by using a ruthenium composite oxide powder having a large particle size (for example, an average particle size of 1 ⁇ m or more).
- a ruthenium composite oxide powder having a large particle size for example, an average particle size of 1 ⁇ m or more.
- current noise and load characteristics deteriorate, and good resistance characteristics cannot be obtained.
- a conductive layer in a resistance composition using a combination of a conventional ruthenium composite oxide and lead-free glass, the above-described network structure (hereinafter referred to as a conductive layer) is stable particularly in a high resistance region where the content of conductive particles is small. It was extremely difficult to create a network. For this reason, a thick film resistor that does not contain lead and has excellent characteristics such as TCR characteristics, current noise characteristics, and variations has not yet been put into practical use in industry.
- the present invention eliminates harmful lead components from conductive components and glass, and has excellent resistance values, TCR characteristics, current noise characteristics, withstand voltage characteristics, etc. in a wide resistance range, which are equal to or better than those of the prior art.
- An object of the present invention is to provide a thick film resistor having characteristics.
- Another object of the present invention is to provide a thick film resistor that has a small variation and variation in resistance value, TCR, and the like due to firing, and thus can obtain a thick film resistor having stable characteristics even in a high resistance region. It is to provide a manufacturing method.
- the thick film resistor of the present invention that achieves the above object is a thick film resistor made of a fired product of a resistance composition, and is a glass containing substantially no ruthenium-based conductive particles containing ruthenium dioxide and a lead component.
- a thick film resistor having a resistance value in a range of 100 ⁇ / ⁇ to 10 M ⁇ / ⁇ and a resistance temperature coefficient of ⁇ 100 ppm / ° C. or less.
- the method for producing a thick film resistor of the present invention is a ruthenium-based conductive particle containing ruthenium dioxide and a glass frit substantially free of a lead component, which is a mixture of glass frit and ruthenium dioxide.
- a resistance composition containing a glass frit and an organic vehicle such that the temperature coefficient of resistance of the fired product exhibits a positive range is provided on the printed material.
- the thick film resistor is baked at 600 to 900 ° C.
- the thick film resistor of the present invention has a resistance value in the range of 100 ⁇ / ⁇ to 10 M ⁇ / ⁇ , and has a temperature coefficient of resistance of ⁇ 100 ppm / ° C. or less even though it does not substantially contain lead.
- the thick film resistor of the present invention is extremely useful as a resistor having a medium resistance range to a high resistance range of 1 k ⁇ / ⁇ or more, particularly as a resistor having a high resistance range of 100 k ⁇ / ⁇ or more.
- the ruthenium-based conductive particles in the present invention preferably contain 50% by mass or more of ruthenium dioxide (RuO 2 ), and more preferably consist only of ruthenium dioxide (RuO 2 ).
- RuO 2 ruthenium dioxide
- the resistive composition of the present invention can form a stable conductive network more easily after firing at a high temperature, has little variation, and has good resistance characteristics even in a high resistance range. A thick film resistor having good process stability can be obtained.
- the ruthenium-based conductive particles may be a mixture or composite of ruthenium dioxide and other conductive particles described later.
- the ruthenium-based conductive particles are substantially composed only of ruthenium dioxide.
- the ruthenium-based conductive particles in the present invention are substantially free of a lead component and further substantially free of a bismuth component.
- the terms “consisting essentially of” and “substantially free of” allow “a trace amount” such as an unintended impurity. This refers to the case of 1000 ppm or less, and is particularly desirable to be 100 ppm or less.
- a ruthenium-based conductive particle having a fine particle diameter For example, a mass-based integrated fraction 50% value (hereinafter referred to as a particle size distribution measurement using a laser-type particle size distribution measuring apparatus)
- the average particle diameter D 50 is preferably in the range of 0.01 to 0.2 ⁇ m.
- the average particle diameter D 50 of the ruthenium-based conductive particles is 0.01 ⁇ m or more, easily quenched to glass easily obtained stable characteristics. Further, by the average particle diameter D 50 is 0.2 ⁇ m or less, they tend to easily improve the current noise and load life characteristics.
- the ruthenium conductive particles preferably have an average particle diameter D 50 of 0.03 to 0.1 ⁇ m.
- Glass frit In the present invention, as the glass frit, when the fired product of the mixture of glass frit and ruthenium dioxide takes a value in the range of 1 k ⁇ / ⁇ to 1 M ⁇ / ⁇ , the temperature coefficient of resistance (TCR) of the fired product shows a positive range. Such glass frit is used. When the glass frit having such characteristics is used, the inventors have adjusted the blending ratio with the ruthenium-based conductive particles or added an inorganic additive as will be described later, etc. It has been found that the TCR can be reduced even in the resistance region. For example, the thick film resistor of the present invention can control the TCR to be ⁇ 100 ppm / ° C. or less in a wide resistance range of 100 ⁇ / ⁇ to 10 M ⁇ / ⁇ .
- the glass frit has a TCR of 0 ppm / ° C. or more and 500 ppm / ° C. or less when the fired product of the mixture of glass frit and ruthenium dioxide exhibits a resistance value of 1 k ⁇ / ⁇ to 1 M ⁇ / ⁇ .
- the glass frit is preferably 400 ppm / ° C. or less, more preferably 300 ppm / ° C. or less.
- a glass composition having a high resistance region and a positive TCR those containing 20 to 45 mol% BaO, 20 to 45 mol% B 2 O 3 , and 25 to 55 mol% SiO 2 in terms of oxides. preferable.
- the TCR in the high resistance region can be set in a plus range, and when it is 45 mol% or less, the film shape after firing can be easily maintained.
- the SiO 2 content is 25 mol% or more, the film shape after baking can be easily kept good, and when it is 55 mol% or less, a dense fired film can be easily obtained.
- the glass frit More preferably, the glass frit, BaO 23 ⁇ 42 mol% in terms of oxide, B 2 O 3 23 ⁇ 42 mol%, and SiO 2 35 ⁇ 52 mol%.
- the glass transition point Tg of the glass frit is preferably in the range of 450 to 700 ° C.
- Tg is preferably in the range of 580 to 680 ° C.
- Tg is preferably (baking temperature ⁇ 200) ° C. or lower, and in this case, the following formula (1) is satisfied.
- Tg ⁇ (calcination temperature ⁇ 200) [° C.]
- D 50 of the glass frit is 5 ⁇ m or less. When D 50 is 5 ⁇ m or less, it is easy to adjust the resistance value in the high resistance region, but when D 50 is too small, voids tend to be generated in the resistor.
- a particularly preferred range of D 50 is 0.5 to 3 ⁇ m.
- the glass frit further includes a metal oxide capable of adjusting TCR and other resistance characteristics, such as ZnO, Al 2 O 3 , Li 2 O, Na 2 O, K 2 O, Nb 2 O 5 , Ta 2 O 5. , TiO 2 , CuO, MnO 2 , La 2 O 3, or one or more components may be contained. These components can provide a high effect even in a small amount, but for example, they can be contained in a total amount of about 0.1 to 10 mol% in a glass frit, and can be appropriately adjusted according to the intended characteristics. .
- a metal oxide capable of adjusting TCR and other resistance characteristics
- other resistance characteristics such as ZnO, Al 2 O 3 , Li 2 O, Na 2 O, K 2 O, Nb 2 O 5 , Ta 2 O 5.
- TiO 2 , CuO, MnO 2 , La 2 O 3, or one or more components may be contained. These components can provide a high effect even in a small amount, but for example, they can be contained in a total
- the resistance composition forming the thick film resistor of the present invention preferably contains a functional filler (hereinafter sometimes simply referred to as filler) in addition to the above-described inorganic components.
- a functional filler hereinafter sometimes simply referred to as filler
- the functional filler in the present invention apart from the glass frit described above, glass particles having low fluidity during firing are prepared, and the ruthenium-based conductive particles described above are formed on the surface of the glass particles or in the vicinity thereof.
- composite particles prepared by adhering and fixing other conductive particles hereinafter referred to as conductive particles) prepared separately are preferable.
- the term “glass frit” and the term “glass particle” are used separately.
- the glass component derived from the glass frit is referred to as “first glass component”
- the glass component derived from the glass particles is referred to as “second glass component”.
- the glass particles can be used regardless of the composition as long as the fluidity during firing is low.
- the glass transition point Tg ′ is 500 ° C. or higher, and in particular, the glass has a glass transition point Tg ′ higher than the glass transition point Tg of the glass frit described above (that is, Tg ⁇ Tg ′ is satisfied).
- the glass composition having a high glass transition point Tg ′ include borosilicate zinc-based glass, lead borosilicate glass, borosilicate alkaline earth metal glass such as borosilicate barium and calcium borosilicate. The invention is not limited to these.
- Tg ′ is preferably (baking temperature ⁇ 150) ° C. or more, and in this case, the following formula (2) is satisfied.
- conductive particles to be combined with glass particles in the functional filler silver (Ag), gold (Au), platinum (Pt), palladium (Pd), copper (Cu), nickel (Ni), aluminum (Al)
- silver Au
- gold Au
- platinum Pt
- palladium Pd
- copper Cu
- nickel Ni
- aluminum Al
- alloy particles containing these metals ruthenium-based conductive particles can also be used.
- Ruthenium-based conductive particles include ruthenium dioxide, neodymium ruthenate (Nd 2 Ru 2 O 7 ), samarium ruthenate (Sm 2 Ru 2 O 7 ), neodymium calcium ruthenate (NdCaRu 2 O 7 ), ruthenic acid.
- Ruthenium composite oxides having a perovskite structure having a perovskite structure; other ruthenium composite oxides such as cobalt ruthenate (Co 2 RuO 4 ) and strontium ruthenate (Sr 2 RuO 4 ); and mixtures thereof .
- the conductive particles one or two or more of those exemplified above may be used. Further, they may be used in combination with a precursor compound such as silver oxide or palladium oxide.
- ruthenium-based conductive particles mainly composed of ruthenium dioxide as the conductive particles combined with the glass particles in the functional filler.
- the conductive particles preferably have a fine particle diameter, and the average particle diameter D 50 is preferably in the range of 0.01 to 0.2 ⁇ m.
- the method for producing the functional filler is not limited.
- the conductive particles described above are deposited on the surface of glass particles prepared in advance by a known method such as substitution deposition, electroless plating, or electrolysis. You may make it.
- the glass particles prepared in advance and the conductive particles are stirred and mixed by a known stirring means such as a media mill, heat treated (for example, 850 to 900 ° C.), and then pulverized, whereby the surface of the glass particles and / or It is desirable to manufacture by a so-called mechanochemical method in which conductive particles are fixed inside.
- the resistance composition according to the present invention can easily adjust the TCR and other resistance characteristics, a good resistor can be obtained even by using an inorganic additive described later, but contains the above-described functional filler. Accordingly, it is possible to obtain a resistor which is stable with little variation in resistance value in the high resistance region and improved in various characteristics such as withstand voltage characteristics, electrostatic characteristics and resistance value changes.
- the average particle diameter D 50 of the filler is desirably in the range of 0.5 to 5 ⁇ m.
- the average particle diameter D 50 of the filler is 0.5 ⁇ m or more, easy dense fired film can be obtained, withstand voltage characteristic is hardly degraded by at 5 ⁇ m or less.
- the average particle diameter D 50 is preferably 1 to 3 ⁇ m.
- the average particle diameter D 50 of the filler is, for example, when producing in the preceding mechanochemical technique can be controlled by adjusting milling conditions.
- the content of the conductive particles contained in the filler is preferably 20 to 35% by mass with respect to the filler. When it is 20% by mass or more, it is easy to adjust / control the resistance value of the thick film resistor obtained after firing, and when it is 35% by mass or less, STOL characteristics (voltage resistance characteristics) are improved. .
- glass particles containing substantially no lead component are included, and the glass transition point Tg of the glass frit is (calcination temperature ⁇ 200) ° C. or less.
- the glass in the resistor forms a sea-island structure.
- This sea-island structure is a structure in which glass (first glass component) derived from glass frit forms the sea (matrix), and glass derived from glass particles (second glass component) forms islands. .
- Such a structure is formed not only when a functional filler is added as a component of the resistance composition, but also when glass particles are used instead of the functional filler.
- Such a structure is a structure that is not found in a conventional resistor.
- the resistance composition according to the present invention is variously used for the purpose of improving and adjusting resistance characteristics such as TCR, current noise, ESD characteristics, and STOL, as long as the effects of the present invention are not impaired.
- Inorganic additives such as Nb 2 O 5 , Ta 2 O 5 , TiO 2 , CuO, MnO 2 , ZnO, ZrO 2 , La 2 O 3 , Al 2 O 3 , V 2 O 5 , glass (hereinafter referred to as additive glass).
- additive glass is another glass component different from said 1st glass component and 2nd glass component.) Etc. may be added individually or in combination.
- the amount of addition is appropriately adjusted according to the purpose of use.
- the total amount of inorganic solids in the resistance composition is 100.
- the total amount is about 0.1 to 10 parts by mass with respect to parts by mass.
- it may add exceeding 10 mass parts.
- the ruthenium-based conductive particles and glass frit are suitable for a method of applying a resistance composition such as screen printing by being mixed with an organic vehicle together with a functional filler and additives blended as necessary. It becomes a paste-like, paint-like, or ink-like resistance composition having rheology.
- the organic vehicle is not particularly limited, and terpineol (hereinafter referred to as TPO), carbitol, butyl carbitol, cellosolve, butyl cellosolve and their esters, toluene, xylene, etc., which are generally used in resistance compositions.
- TPO terpineol
- carbitol butyl carbitol
- cellosolve butyl cellosolve and their esters
- toluene xylene, etc.
- a solution prepared by dissolving a resin such as ethyl cellulose, nitrocellulose, acrylic acid ester, methacrylic acid ester, or rosin.
- a plasticizer, a viscosity modifier, a surfactant, an oxidizing agent, a metal organic compound, or the like may be added.
- the blending amount of the organic vehicle may be within a range generally blended in the resistance composition, and is appropriately adjusted according to an application method such as printing for forming the resistor.
- the inorganic solid content is preferably about 50 to 80% by mass and the organic vehicle is about 50 to 20% by mass.
- the resistance composition according to the present invention is produced by mixing and kneading with an organic vehicle and dispersing uniformly with a ruthenium-based conductive particle, glass frit, and a functional filler or additive blended as necessary according to a conventional method.
- the composition is not limited to a paste form, and may be a paint form or an ink form.
- the resistance composition in the present invention is printed / coated in a predetermined shape by a printing method or the like on an insulating substrate such as an alumina substrate or a glass-ceramic substrate or a laminated electronic component according to a conventional method, and after drying, for example, 600 Baking at a high temperature of about 900 ° C.
- the thick film resistor thus formed is usually formed with a protective film by baking overcoat glass, and the resistance value is adjusted by laser trimming or the like as necessary.
- a combination of two or more resistance compositions forming resistors having different resistance values is often sold and distributed as a set.
- the resistance composition of the present invention is suitable for this, and by providing two or more types of the resistance composition of the present invention as a set, the user appropriately mixes a plurality of resistance compositions to obtain a desired resistance value. It is possible to prepare a resistance composition capable of producing a resistor having a resistance value, and thereby a wide range of resistance regions can be covered by a plurality of resistance compositions having similar compositions.
- the measurement of the physical property value about each sample produced in the Example was performed with the following measuring instruments and measuring methods.
- [Rs (sheet resistance)] It measured using the digital multimeter "3458A” made from Agilent, and converted into the fired film thickness of 8 micrometers. 20 samples were measured and the average value was taken.
- [TCR] Using the digital multimeter, +25 to + 125 ° C. (H-TCR) and ⁇ 55 to + 25 ° C. (C-TCR) were measured. 20 samples were measured and the average value was taken.
- Tg, Tg ′, TMA] A thermomechanical measuring device “TMA4000S” manufactured by Bruker AXS was used. 20 samples were measured and the average value was taken.
- a resistance value Rs is measured for each of the fired patterns, and a fired pattern having a resistance value of about 1 k ⁇ / ⁇ or higher is further expressed as a TCR (hereinafter, H-TCR) of + 25 ° C. to + 125 ° C.
- H-TCR a TCR of + 25 ° C. to + 125 ° C.
- C-TCR a TCR of ⁇ 55 ° C. to + 25 ° C.
- a glass frit (samples 43 to 50 in Table 2) containing SiO 2 , B 2 O 3 , and BaO as main components in the same manner as the sample 13 is newly added in the same manner as described above. Then, a paste having a mass ratio of ruthenium dioxide to each glass frit of 30:70, 20:80, 10:90 was prepared. Next, a firing pattern was obtained using each paste, and a glass transition point Tg, a thermal expansion coefficient ⁇ , and a resistance value Rs, H-TCR, and C-TCR of the firing pattern were measured.
- the glass frit of the samples 13, 43, 44, 45, 46, 47, and 49 used in Experimental Examples 13, 43, 44, 45, 46, 47, and 49 is the glass frit.
- the fired product of the mixture of ruthenium dioxide has a value in the range of 1 k ⁇ / ⁇ to 1 M ⁇ / ⁇ , it can be said to be a glass frit in which the temperature coefficient of resistance of the fired product shows a positive range.
- a resistor is prepared from a resistor composition containing glass frit of Sample 13 will be described.
- ruthenium dioxide (Ru-109) is prepared as the conductive particles contained in the filler, so that the content of the conductive particles in the filler is 20% by mass, 30% by mass, and 40% by mass, respectively.
- Three kinds of fillers were prepared by pulverizing until.
- the content of the conductive particles in the filler is preferably in the range of 20 to 35% by mass in the present invention.
- Example 1 This example is an example in the case where the resistance composition contains a functional filler as a component.
- a functional filler as a component.
- Ru-109 Ruthenium dioxide
- a composition in which 30 parts by mass of an organic vehicle was added was kneaded with three rolls to prepare pastes of Examples 1-1 to 2-6.
- the organic vehicle used was 15 parts by mass of ethyl cellulose and the remaining TPO as a solvent.
- the sheet resistance value Rs, H-TCR, C-TCR, resistance value variation CV, noise, and STOL were measured for each resistor.
- CV is a value obtained from 20 resistors.
- Table 4 The measured results are also shown in Table 4.
- Table 4 measurement is omitted for those that are difficult to measure due to overrange with respect to noise, and is indicated by “ ⁇ ” in the table.
- the resistance value Rs set as the target value for each paste is also shown in Table 4 for reference.
- FIG. 1 shows the result of analyzing the obtained resistor by a scanning microscope-energy dispersive X-ray analysis (SEM-EDX).
- FIG. 1A is a SEM image of a resistor
- FIG. 1B is a diagram showing a result of mapping for a Ba element
- FIG. 1C is a diagram showing a result of mapping for a Ru element.
- the resistor obtained in Example 1 has a discontinuous body (hereinafter referred to as an island) not including Ba in a continuous body region (hereinafter referred to as a matrix) including Ba.
- a discontinuous body hereinafter referred to as an island
- a continuous body region hereinafter referred to as a matrix
- the resistor of the present invention is included in the glass frit matrix. It is presumed that the glass particles having low fluidity at the time of firing remain in the shape of islands, and such a sea-island structure is formed.
- RuO 2 particles are not uniformly dispersed in the resistor of the present invention. It is inferred that a part of the resistor has a network structure with a soap bubble-like bias.
- Example 2 This example is an example in the case where the resistance composition does not contain a functional filler.
- Example 2-1 to Example 2-6 As a glass frit having a composition close to that of the sample 13, a sample 51 (SiO 2 38.1 mol%, B 2 O 3 26.1 mol%, BaO 27.2 mol%, Al 2 O 3 0. 8 mol%, SrO 0.5 mol%, ZnO 3.6 mol%, Na 2 O 3.2 mol% was prepared K 2 O 0.5 mol%). Sample 51 had a Tg of 629.4 ° C.
- an additive glass was added to the paste for the purpose of adjusting the TCR.
- the doped glass SiO 2 43.0 mol% in terms of oxide, B 2 O 3 18.2 mol%, Al 2 O 3 13.0 mol%, CaO 2.8 mol%, MgO 3.2 mol% SnO 2 1.3 mol%, Co 2 O 3 1.9 mol%, K 2 O 6.6 mol%, Li 2 O 10.0 mol%).
- the glass transition point of the added glass was 494.0 ° C.
- the TCR could be adjusted to ⁇ 100 ppm / ° C. or less in a wide resistance range.
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Abstract
Description
特に本発明の厚膜抵抗体は、1kΩ/□以上の中抵抗域~高抵抗域の抵抗体、とりわけ100kΩ/□以上の高抵抗域の抵抗体として極めて有用である。
本発明におけるルテニウム系導電性粒子としては、二酸化ルテニウム(RuO2)を50質量%以上含むことが好ましく、二酸化ルテニウム(RuO2)のみからなるものが更に好ましい。これにより本発明の抵抗組成物は、高温で焼成した後も、安定な導電ネットワークがより容易に形成され、ばらつきが小さく、高抵抗域においても良好な抵抗特性が得られ、その他の電気特性及びプロセス安定性の良好な厚膜抵抗体を得ることができる。
本発明においてガラスフリットとしては、ガラスフリット及び二酸化ルテニウムの混合物の焼成物が1kΩ/□~1MΩ/□の範囲の値をとるとき、前記焼成物の抵抗温度係数(TCR)がプラスの範囲を示すようなガラスフリットを用いる。
本発明者等は、このような特性のガラスフリットを用いた場合に、ルテニウム系導電性粒子との配合比率を調整したり、後述する無機添加剤を適宜加える等によって、100kΩ/□以上の高抵抗域においてもTCRを小さくすることができることを見出した。例えば本発明の厚膜抵抗体は、100Ω/□~10MΩ/□の広い抵抗域において、TCRを±100ppm/℃以下にコントロールすることができる。
Tg≦(焼成温度-200)〔℃〕・・・式(1)
また、ガラスフリットの平均粒径D50は5μm以下であることが好ましい。D50が5μm以下であることにより高抵抗域での抵抗値の調整が容易になるが、D50が小さすぎると抵抗体にボイドが発生しやすくなる傾向がある。特に好ましいD50の範囲は0.5~3μmである。
本発明の厚膜抵抗体を形成する抵抗組成物は、上述した無機成分の他、機能性フィラー(以下、単にフィラーと記すこともある)を含むことが好ましい。
また、本発明においては厚膜抵抗体を構成するガラス成分については、ガラスフリットに由来するガラス成分を「第1のガラス成分」といい、ガラス粒子に由来するガラス成分を「第2のガラス成分」ということもある。
Tg’≧(焼成温度-150)〔℃〕・・・式(2)
本発明に係る抵抗組成物には、本発明の効果を損なわない範囲であれば、TCR、電流雑音、ESD特性、STOL等の抵抗特性の改善や調整の目的で一般的に使用される種々の無機添加剤、例えばNb2O5、Ta2O5、TiO2、CuO、MnO2、ZnO、ZrO2、La2O3、Al2O3、V2O5、ガラス(以下添加ガラスという。なお、「添加ガラス」は、前記の第1のガラス成分、第2のガラス成分とは異なる別のガラス成分である。)等を単独で又は組み合わせて添加してもよい。このような添加剤を配合することにより、広い抵抗値範囲に亘ってより優れた特性の抵抗体を製造することができる。添加量は、その使用目的に応じて適宜調整されるが、例えばNb2O5等の金属酸化物系の添加剤の場合は、一般的には、抵抗組成物中の無機固形分の合計100質量部に対して合計で0.1~10質量部程度である。また添加ガラスを添加する場合は、10質量部を超えて添加する場合もある。
本発明においてルテニウム系導電性粒子、ガラスフリットは、必要に応じて配合される機能性フィラーや添加剤と共に有機ビヒクルと混合されることにより、スクリーン印刷等の抵抗組成物を適用する方法に適したレオロジーを備えるペースト状、塗料状、又はインク状の抵抗組成物となる。
本発明における抵抗組成物は常法に従って、ルテニウム系導電性粒子、ガラスフリット及び必要に応じて配合される機能性フィラーや添加剤と共に、有機ビヒクルと混合・混練され、均一に分散させることによって製造されるが、本発明において組成物はペースト状に限られるものではなく、塗料状またはインク状でも良い。
本発明における抵抗組成物は常法に従ってアルミナ基板、ガラスセラミック基板等の絶縁性基板や積層電子部品等の被印刷物上に、印刷法等により所定の形状に印刷/塗布され、乾燥後、例えば600~900℃程度の高温で焼成される。このようにして形成された厚膜抵抗体には、通常オーバーコートガラスを焼付けることにより保護被膜が形成され、必要に応じてレーザートリミング等により抵抗値の調整が行われる。
本発明の抵抗組成物はこれに適したものであり、本発明の抵抗組成物の2種以上をセットで提供することにより、使用者において適宜複数の抵抗組成物を配合して所望の抵抗値を有する抵抗体を作製することが可能な抵抗組成物を調製することができる、これにより、類似した組成の複数の抵抗組成物によって広い範囲の抵抗領域をカバーすることができる。
[Rs(シート抵抗)]
Agilent社製デジタルマルチメーター「3458A」を使用し測定し焼成膜厚8μmに換算した。試料20個について測定しその平均値をとった。
[TCR]
上記デジタルマルチメーターを使用して、+25~+125℃(H-TCR)、-55~+25℃(C-TCR)を測定した。試料20個について測定しその平均値をとった。
[Tg,Tg’,TMA]
Bruker AXS社製熱機械測定装置「TMA4000S」を使用した。試料20個について測定しその平均値をとった。
[STOL]
1/4W定格電圧の2.5倍(但し最大400V)を5秒間かけた後の抵抗値変化率を測定した。試料20個について測定しその平均値をとった。
[平均粒径D50]
HORIBA社製レーザー回折/散乱式粒子径分布測定装置「LA950V2」を使用した。試料20個について測定しその平均値をとった。
まず、ガラスフリット及び二酸化ルテニウムの混合物の焼成物が1kΩ/□~1MΩ/□の範囲の値をとるとき、焼成物の抵抗温度係数がプラスの範囲を示すガラスフリットを得るための実験を行った。
表1に示すガラス組成で、平均粒径D50が2μmのガラスフリットを作製し、それぞれを試料1~42とした。
また、表1において、Rsが1kΩ/□に満たなかったものについては、H-TCR及びC-TCRの測定を省略し、表中に“-”の符号を記した。
後述する実施例では試料13のガラスフリットを含む抵抗組成物から抵抗体を作製した実施例を示す。
次に、耐電圧特性、静電気特性、抵抗値変化等の諸特性を改善するための機能性フィラーについての予備実験を行った。
なお、表3において、抵抗値が大きく値が安定しないためにSTOLの測定が困難であったものについては測定を省略し、表中に“-”で記した。
本実施例は抵抗組成物が機能性フィラーを成分として含有する場合についての実施例である。
(実施例1-1~実施例1-6)
二酸化ルテニウム(Ru-109)、予備実験Bで作製した導電粒子含有量が30質量%のフィラー、及び、予備実験Aで作製した試料13のガラスフリットを、表4に示す質量部で配合し、これに対して有機ビヒクルを30質量部加えた組成物を3本ロールで混練して実施例1-1~実施例2-6のペーストを作製した。なお、有機ビヒクルとしてはエチルセルロースを15質量部、溶剤としてTPOを残部加えたものを用いた。
なお、表4において、ノイズに関してオーバーレンジのため、測定が困難なものについては測定を省略し、表中に“-”で記した。
また各ペースト毎に目標値として設定した抵抗値Rsについても、参考程度に表4に併記した。
本実施例は抵抗組成物が機能性フィラーを含有しない場合についての実施例である。
(実施例2-1~実施例2-6)
組成が試料13に近いガラスフリットとして、新たに試料51(酸化物換算でSiO238.1モル%、B2O3 26.1モル%、BaO 27.2モル%、Al2O30.8モル%、SrO 0.5モル%、ZnO 3.6モル%、Na2O 3.2モル%、K2O 0.5モル%)を準備した。なお試料51のTgは629.4℃であった。
各抵抗体に対し、シート抵抗値Rs、H-TCR、C-TCR、抵抗値のバラツキCV、ノイズ、を測定した。
測定した結果を表5に併記する。
使用するルテニウム系導電性粒子を平均粒径D50=0.20μmの二酸化ルテニウム(昭栄化学工業株式会社製、製品名:Ru-108)、及び、D50=0.02μmの二酸化ルテニウム(昭栄化学工業株式会社製、製品名:Ru-105)にそれぞれ変更した他は予備実験A、予備実験B、実施例1及び実施例2と同様の実験を行ったところ、ほぼ同様の結果が得られた。
Claims (21)
- 抵抗組成物の焼成物からなる厚膜抵抗体であって、
二酸化ルテニウムを含むルテニウム系導電性粒子と、鉛成分を実質的に含まないガラス成分とを含み、
100Ω/□~10MΩ/□の範囲内の抵抗値を有し、抵抗温度係数が±100ppm/℃以下である厚膜抵抗体。 - 1kΩ/□~10MΩ/□の範囲内の抵抗値を有する請求項1に記載の厚膜抵抗体。
- 10kΩ/□~10MΩ/□の範囲内の抵抗値を有する請求項2に記載の厚膜抵抗体。
- 100kΩ/□~10MΩ/□の範囲内の抵抗値を有する請求項3に記載の厚膜抵抗体。
- 1MΩ/□~10MΩ/□の範囲内の抵抗値を有する請求項4に記載の厚膜抵抗体。
- 前記ガラス成分が、ガラスフリット及び二酸化ルテニウムの混合物の焼成物が1kΩ/□~1MΩ/□の範囲の値をとるとき、前記焼成物の抵抗温度係数がプラスの範囲を示すガラスフリットに由来するガラス成分を含む請求項1乃至5の何れかに記載の厚膜抵抗体。
- 前記ガラスフリットが、酸化物換算でBaO 20~45モル%、B2O3 20~45モル%、SiO2 25~55モル%を含む請求項6に記載の厚膜抵抗体。
- 抵抗組成物の焼成物からなる厚膜抵抗体であって、
二酸化ルテニウムを含むルテニウム系導電性粒子と、鉛成分を実質的に含まないガラス成分を含み、
前記ガラス成分が少なくとも、第1のガラス成分、及び、当該第1のガラス成分よりもガラス転移点の高い第2のガラス成分を含み、前記第1のガラス成分のマトリクスに対して、第2のガラス成分が島状に点在する海島構造を備えており、100Ω/□~10MΩ/□の範囲内の抵抗値を有し、抵抗温度係数が±100ppm/℃以下である厚膜抵抗体。 - 前記二酸化ルテニウムの一部が、島状に点在する前記第2のガラス成分の表面及びその近傍に偏在した構造を備える請求項8に記載の厚膜抵抗体。
- 前記ルテニウム系導電性粒子が、平均粒径D50が0.01~0.2μmの粒子である請求項8又は9に記載の厚膜抵抗体。
- 二酸化ルテニウムを含むルテニウム系導電性粒子と、鉛成分を実質的に含まないガラスフリットであって、ガラスフリット及び二酸化ルテニウムの混合物の焼成物が1kΩ/□~1MΩ/□の範囲の値をとるとき、前記焼成物の抵抗温度係数がプラスの範囲を示すガラスフリットと、有機ビヒクルとを含む抵抗組成物を被印刷物上に印刷した後、600~900℃で焼成する厚膜抵抗体の製造方法。
- 前記抵抗組成物として、前記ルテニウム系導電性粒子と前記ガラスフリットとの含有率が異なる2以上の抵抗組成物を用い、前記2以上の抵抗組成物のそれぞれの配合割合を調整して、100Ω/□~10MΩ/□の範囲内の抵抗値を有する厚膜抵抗体を製造する請求項11に記載の厚膜抵抗体の製造方法。
- 前記ガラスフリットが、酸化物換算でBaO 20~45モル%、B2O320~45モル%、SiO2 25~55モル%を含む請求項11又は12に記載の厚膜抵抗体の製造方法。
- 前記ルテニウム系導電性粒子の平均粒径D50が0.01~0.2μmである請求項11乃至13の何れかに記載の厚膜抵抗体の製造方法。
- 前記抵抗組成物が更に機能性フィラーを含み、
当該機能性フィラーが鉛成分を実質的に含まないガラス粒子に対して当該ガラス粒子よりも粒径が小さく鉛成分を実質的に含まない導電粒子とからなる複合粒子である請求項11乃至14の何れかに記載の厚膜抵抗体の製造方法。 - 前記ガラス粒子のガラス転移点Tg’が、前記ガラスフリットのガラス転移点Tgに対して、Tg<Tg’を満たす請求項15に記載の厚膜抵抗体の製造方法。
- Tgが450~700℃であり、Tg’が500℃以上である請求項16に記載の厚膜抵抗体の製造方法。
- 前記機能性フィラーが前記導電粒子を20~35質量%含む請求項15乃至17の何れかに記載の厚膜抵抗体の製造方法。
- 前記導電粒子が二酸化ルテニウムを含むルテニウム系の導電粒子である請求項15乃至18の何れかに記載の厚膜抵抗体の製造方法。
- 前記導電粒子の平均粒径D50が0.01~0.2μmである請求項15乃至19の何れかに記載の厚膜抵抗体の製造方法。
- 前記機能性フィラーの平均粒径D50が0.5~5μmである請求項15乃至20の何れかに記載の厚膜抵抗体の製造方法。
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