TWI795545B - Composition for thick film resistors, paste for thick film resistors, and thick film resistors - Google Patents

Composition for thick film resistors, paste for thick film resistors, and thick film resistors Download PDF

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TWI795545B
TWI795545B TW108110721A TW108110721A TWI795545B TW I795545 B TWI795545 B TW I795545B TW 108110721 A TW108110721 A TW 108110721A TW 108110721 A TW108110721 A TW 108110721A TW I795545 B TWI795545 B TW I795545B
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thick film
ruthenium oxide
film resistors
mass
glass
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TW201942265A (en
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川久保勝弘
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日商住友金屬礦山股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • 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
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C01G55/004—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—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
    • H01C7/003—Thick film resistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—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
    • H01C7/003—Thick film resistors
    • H01C7/005—Polymer thick films

Abstract

提供一種能夠形成電阻溫度系數良好的厚膜電阻，且不含鉛成份的電阻用組成物。該厚膜電阻用組成物包括不含鉛成份之氧化釕粉末及不含鉛成份之玻璃，氧化釕粉末中根據（110）晶面之峰值計算出的微晶徑D1為25nm以上80nm以下，比表面積徑D2為25nm以上114nm以下，且，微晶徑D1（nm）與比表面積徑D2（nm）之比滿足以下公式（1）， 0.70≦D1/D2≦1.00 （1） 玻璃包含SiO2 、B2 O3 及RO（R是從Ca、Sr及Ba中選擇的1種以上的元素），在SiO2 與B2 O3 與RO的合計量為100質量份之情形下，SiO2 之含有比率為10質量份以上50質量份以下，B2 O3 之含有比率為8質量份以上30質量份以下，RO之含有比率為40質量份以上65質量份以下。Provided is a composition for resistors capable of forming a thick film resistor having a good temperature coefficient of resistance and containing no lead. The composition for thick film resistors includes lead-free ruthenium oxide powder and lead-free glass. The crystallite diameter D1 calculated from the peak value of the (110) crystal plane in the ruthenium oxide powder is not less than 25nm and not more than 80nm. The surface area diameter D2 is not less than 25nm and not more than 114nm, and the ratio of the crystallite diameter D1 (nm) to the specific surface area diameter D2 (nm) satisfies the following formula (1), 0.70≦D1/D2≦1.00 (1) The glass contains SiO 2 , B 2 O 3 and RO (R is one or more elements selected from Ca, Sr and Ba), when the total amount of SiO 2 and B 2 O 3 and RO is 100 parts by mass, the content of SiO 2 The ratio is 10 to 50 parts by mass, the content of B 2 O 3 is 8 to 30 parts by mass, and the content of RO is 40 to 65 parts by mass.

Description

厚膜電阻用組成物、厚膜電阻用膏體及厚膜電阻Composition for thick film resistors, paste for thick film resistors, and thick film resistors

本發明涉及一種厚膜電阻用組成物、厚膜電阻用膏體及厚膜電阻。The invention relates to a composition for thick film resistors, a paste for thick film resistors and thick film resistors.

一般而言，藉由在陶瓷基板上印刷厚膜電阻用膏體並進行燒成，可形成芯片電阻、混合IC及電阻網絡等的厚膜電阻。厚膜電阻用組成物廣泛使用以釕類導電粒子及玻璃作為主成份之材料，釕類導電粒子係以氧化釕為代表之導電粒子。In general, thick film resistors such as chip resistors, hybrid ICs, and resistor networks can be formed by printing and firing a paste for thick film resistors on a ceramic substrate. Compositions for thick film resistors are widely used with ruthenium-based conductive particles and glass as the main components. Ruthenium-based conductive particles are conductive particles represented by ruthenium oxide.

關於厚膜電阻使用釕類導電粒子及玻璃的理由，除了可在空氣中進行燒成，可使電阻溫度系數（TCR）接近0之外，還能舉出可形成廣域電阻值等理由。The reason for using ruthenium-based conductive particles and glass for thick film resistors is that they can be fired in air to bring the temperature coefficient of resistance (TCR) close to zero, and that they can form a wide range of resistance values.

在此，電阻溫度系數係根據-55℃及125℃時的電阻值相對於25℃時的電阻值求出的溫度系數，可由以下公式求出。根據-55℃及25℃之電阻值求出的電阻溫度系數稱為低溫側TCR（COLD-TCR），根據25℃及125℃之電阻值求出的電阻溫度系數稱為高溫側TCR（HOT-TCR）。 COLD-TCR（ppm/℃）＝（R-55 -R25 ）/R25 /（-80）×106 HOT-TCR（ppm/℃）＝（R125 -R25 ）/R25 /（100）×106 Here, the temperature coefficient of resistance is a temperature coefficient obtained from the resistance value at -55°C and 125°C relative to the resistance value at 25°C, and can be obtained by the following formula. The temperature coefficient of resistance obtained from the resistance values at -55°C and 25°C is called the low-temperature side TCR (COLD-TCR), and the temperature coefficient of resistance obtained from the resistance values at 25°C and 125°C is called the high-temperature side TCR (HOT- TCR). COLD-TCR (ppm/°C) = (R -55 -R 25 )/R 25 /(-80)×10 6 HOT-TCR (ppm/°C) = (R 125 -R 25 )/R 25 /(100 )×10 6

厚膜電阻中，要求使COLD-TCR與HOT-TCR兩者都接近0。In thick film resistors, both COLD-TCR and HOT-TCR are required to be close to 0.

作為歷來厚膜電阻中使用最多的釕類導電粒子，可以舉出具有金紅石（rutile）型晶體結構的氧化釕（RuO2 ）、具有焦綠石（Pyrochlore）型晶體結構的釕酸鉛（Pb2 Ru2 O6.5 ）。該些均為顯示金屬導電性之氧化物。Ruthenium oxide (RuO 2 ) with a rutile crystal structure, lead ruthenate (Pb 2 Ru 2 O 6.5 ). These are all oxides showing metal conductivity.

厚膜電阻之玻璃，一般使用軟化點低於厚膜電阻用膏體之燒成溫度低的玻璃，歷來使用包含氧化鉛（PbO）的玻璃。作為其理由可以舉出，氧化鉛（PbO）具有降低玻璃軟化點之效果，藉由變更其含有率，可在廣範圍內變更軟化點，可制作成化學耐性較高的玻璃，絕緣性高且耐壓性良好。Glass for thick film resistors generally uses glass with a softening point lower than the firing temperature of the paste for thick film resistors, and glass containing lead oxide (PbO) has traditionally been used. The reason for this is that lead oxide (PbO) has the effect of lowering the softening point of glass, and by changing its content, the softening point can be changed in a wide range, and it can be made into glass with high chemical resistance, high insulation and Good pressure resistance.

在包含釕類導電粒子與玻璃的厚膜電阻用組成物中，要求低電阻值時藉由配合較多釕類導電粒子及較少玻璃，要求高電阻值時藉由配合較少釕類導電粒子及較多玻璃，來調整電阻值。在釕類導電粒子配合較多的低電阻值區域，可見電阻溫度系數容易正向增大，在釕類導電粒子配合較少的高電阻值區域，可見電阻溫度系數容易成為負值之特征。In the thick-film resistor composition containing ruthenium-based conductive particles and glass, when low resistance is required, more ruthenium-based conductive particles and less glass are required, and when high resistance is required, less ruthenium-based conductive particles are required. And more glass to adjust the resistance value. In the low-resistance region with more ruthenium-based conductive particles, it can be seen that the temperature coefficient of resistance tends to increase positively. In the high-resistance region with less ruthenium-based conductive particles, it can be seen that the temperature coefficient of resistance tends to become negative.

如上所述，電阻溫度系數表示溫度變化所致的電阻值變化，其為厚膜電阻的重要特性之一。藉由厚膜電阻用組成物中加入以金屬氧化物為主之添加劑，可調整電阻溫度系數。電阻溫度系數較容易調整為負值，作為添加劑可以舉出錳氧化物、鈮氧化物、鈦氧化物等。然而，電阻溫度系數較難調整成正值，實質上無法將具有負電阻溫度系數的厚膜電阻的電阻溫度系數調整至0附近。因此，在電阻溫度系數容易成為負值的高電阻值區域，優選組合電阻溫度系數正向增大的導電粒子及玻璃。As mentioned above, the temperature coefficient of resistance represents the change in resistance value due to temperature change, which is one of the important characteristics of thick film resistors. The temperature coefficient of resistance can be adjusted by adding additives mainly composed of metal oxides to the composition for thick film resistors. It is relatively easy to adjust the temperature coefficient of resistance to a negative value, and examples of additives include manganese oxide, niobium oxide, and titanium oxide. However, it is difficult to adjust the temperature coefficient of resistance to a positive value, and it is virtually impossible to adjust the temperature coefficient of resistance of a thick film resistor with a negative temperature coefficient of resistance to near zero. Therefore, in a high-resistance region where the temperature coefficient of resistance tends to become a negative value, it is preferable to combine conductive particles and glass whose temperature coefficient of resistance increases positively.

釕酸鉛（Pb2 Ru2 O6.5 ）相比於氧化釕（RuO2 ）電阻率更高，具有可提高厚膜電阻之電阻溫度系數的特征。因此，在電阻值高的區域，作為導電粒子歷來使用釕酸鉛（Pb2 Ru2 O6.5 ）。Lead ruthenate (Pb 2 Ru 2 O 6.5 ) has a higher resistivity than ruthenium oxide (RuO 2 ), and has the feature of improving the temperature coefficient of resistance of thick film resistors. Therefore, lead ruthenate (Pb 2 Ru 2 O 6.5 ) has conventionally been used as conductive particles in a region with a high resistance value.

如上所述，歷來的厚膜電阻用組成物中，導電粒子及玻璃的兩者均含鉛成份。然而，鉛成份從其對人體的影響及公害之觀點而論，不受歡迎，對於不含鉛的厚膜電阻用組成物的開發需求較強。As described above, in conventional compositions for thick film resistors, both conductive particles and glass contain lead components. However, the lead component is not popular from the viewpoint of its influence on the human body and public hazards, and there is a strong demand for the development of compositions for thick film resistors that do not contain lead.

因此，現在已有不含鉛的厚膜電阻用組成物的提案（專利文獻1～5）。Therefore, there have been proposals for lead-free thick-film resistor compositions (Patent Documents 1 to 5).

專利文獻1公開了一種至少包含實質上不含鉛的玻璃組成物及實質上不含鉛且具有規定的平均粒徑的導電材料，並將該些材料與機載體混合而成的電阻膏體。且，作為導電材料舉出了釕酸鈣、釕酸鍶、釕酸鋇。Patent Document 1 discloses a resistor paste comprising at least a substantially lead-free glass composition and a substantially lead-free conductive material having a predetermined average particle size, and mixing these materials with a carrier. In addition, examples of the conductive material include calcium ruthenate, strontium ruthenate, and barium ruthenate.

根據專利文獻1，藉由將使用的導電材料的粒徑設在規定範圍，以確保反應相之外的導電材料的實質性粒徑，從而可獲得預期效果。然而，專利文獻1公開的技術並不能說其能夠改善電阻溫度系數。另外，當使用粒徑較大的導電粒子時，形成的電阻的電流噪聲會較大，從而存在無法獲得良好的負載特性的問題。According to Patent Document 1, by setting the particle size of the conductive material to be used within a predetermined range, a substantial particle size of the conductive material outside the reaction phase can be ensured, thereby obtaining a desired effect. However, the technique disclosed in Patent Document 1 cannot be said to be able to improve the temperature coefficient of resistance. In addition, when conductive particles having a large particle size are used, the current noise of the formed resistor becomes large, and there is a problem that good load characteristics cannot be obtained.

專利文獻2公開了一種電阻膏體的制造方法，其特征在於包括：藉由將包含有用於賦予導電性的金屬元素的第1導電性材料預先溶解於玻璃組成物中來形成玻璃材料的工序；對該玻璃材料、包含該金屬元素的第2導電性材料及載體進行混煉的工序，且該玻璃組成物及該第1、第2導電性材料不含鉛。另外，作為第1、第2導電性材料舉出了Ru2 O等。然而，溶解於玻璃中的氧化釕量根據制造條件會有較大變動，存在電阻值不穩定之問題。Patent Document 2 discloses a method for manufacturing a resistor paste, which is characterized by comprising: a step of forming a glass material by pre-dissolving a first conductive material containing a metal element for imparting conductivity in a glass composition; The process of kneading the glass material, the second conductive material containing the metal element, and the carrier, and the glass composition and the first and second conductive materials do not contain lead. Moreover, Ru2O etc. are mentioned as a 1st, 2nd electroconductive material. However, the amount of ruthenium oxide dissolved in the glass varies greatly depending on the manufacturing conditions, and there is a problem that the resistance value is not stable.

專利文獻3公開了一種厚膜膏體組成物，其特征在於包含（a）釕類導電性材料與（b）不含規定組成的鉛及鎘的玻璃組成物的基本固體物，（a）及（b）全部分散於有機介質中。並且，作為釕類導電性材料舉出了釕酸鉍。然而，根據該組成物，電阻溫度系數會負向增大，而無法使電阻溫度系數接近0。Patent Document 3 discloses a thick-film paste composition, which is characterized in that it contains (a) a ruthenium-based conductive material and (b) a basic solid material that does not contain lead and cadmium of a specified composition, (a) and (b) All dispersed in an organic medium. In addition, bismuth ruthenate is mentioned as the ruthenium-based conductive material. However, according to this composition, the temperature coefficient of resistance increases negatively, and the temperature coefficient of resistance cannot be brought close to zero.

專利文獻4公開了一種電阻組成物，其特征在於包括不含鉛成份之釕類導電性成份、玻璃堿度（Po值）為0.4～0.9且不含鉛成份之玻璃及有機載體，在高溫下對上述材料進行燒成後獲得的厚膜電阻中存在MSi2 Al2 O8 結晶（M：Ba及/或Sr）。根據專利文獻4，由於玻璃堿度接近釕復合氧化物堿度，因此認為釕復合氧化物的分解抑制效果較大。另外，認為藉由玻璃中析出規定結晶相，而能夠形成導電網絡。Patent Document 4 discloses a resistance composition, which is characterized in that it includes ruthenium-based conductive components without lead components, glass with a glass pH (Po value) of 0.4 to 0.9 and no lead components, and an organic carrier. MSi 2 Al 2 O 8 crystals (M: Ba and/or Sr) exist in thick film resistors obtained by firing the above materials. According to Patent Document 4, since the alkalinity of the glass is close to that of the ruthenium composite oxide, it is considered that the decomposition suppression effect of the ruthenium composite oxide is large. In addition, it is considered that a conductive network can be formed by precipitating a predetermined crystal phase in the glass.

然而，專利文獻4中，以作為導電粒子使用釕復合氧化物為前提，關於相比於釕復合氧化物而言工業上更容易獲取的氧化釕並無具體探討。另外，關於玻璃組成對電阻的電阻溫度系數造成的影響也未進行探討。 ＜先前技術文獻＞ ＜專利文獻＞However, Patent Document 4 presupposes the use of a ruthenium composite oxide as the conductive particle, and does not specifically consider ruthenium oxide, which is industrially easier to obtain than the ruthenium composite oxide. In addition, the influence of the glass composition on the temperature coefficient of resistance of the resistor was not considered. ＜Prior Technical Documents＞ ＜Patent Document＞

專利文獻1：特開2005-129806號公報 專利文獻2：特開2003-7517號公報 專利文獻3：特開平8-253342號公報 專利文獻4：特開2007-103594號公報Patent Document 1: JP-A-2005-129806 Patent Document 2: JP-A-2003-7517 Patent Document 3: JP-A-8-253342 Patent Document 4: JP-A-2007-103594

＜發明所欲解決之問題＞＜The problem that the invention intends to solve＞

鑒於解決上述歷來技術中的問題，本發明之一形態其目的在於提供一種能夠形成電阻溫度系數良好的厚膜電阻且不含鉛成份的電阻用組成物。 ＜用於解決問題之手段＞In view of solving the above-mentioned problems in the prior art, an aspect of the present invention aims to provide a composition for resistors that can form a thick film resistor having a good temperature coefficient of resistance and does not contain lead. <Means used to solve problems>

為了解決上述課題，本發明提供一種包括不含鉛的氧化釕粉末及不含鉛的玻璃的厚膜電阻用組成物，該氧化釕粉末中，根據採用X射線繞射法測定的（110）晶面的峰值計算出的微晶徑（crystallite diameter）D1為25nm以上80nm以下，根據比表面積計算出的比表面積徑（specific surface area diameter）D2為25nm以上114nm以下，並且，該微晶徑D1（nm）與該比表面積徑D2（nm）之比滿足以下公式（1）， 0.70≦D1/D2／D2≦1.00 （1）In order to solve the above-mentioned problems, the present invention provides a composition for thick film resistors comprising lead-free ruthenium oxide powder and lead-free glass, wherein the ruthenium oxide powder contains (110) crystal The crystallite diameter (crystallite diameter) D1 calculated from the peak of the surface is not less than 25nm and not more than 80nm, and the specific surface area diameter (specific surface area diameter) D2 calculated from the specific surface area is not less than 25nm and not more than 114nm, and the crystallite diameter D1 ( nm) and the ratio of the specific surface area diameter D2 (nm) satisfies the following formula (1), 0.70≦D1/D2／D2≦1.00 (1)

該玻璃包含SiO2 、B2 O3 及RO（R是從Ca、Sr及Ba中選擇的1種以上的元素），在SiO2 與B2 O3 與RO的合計量為100質量份（parts by mass）之情形下，SiO2 的含有比率為10質量份以上50質量份以下，B2 O3 的含有比率為8質量份以上30質量份以下，RO的含有比率為40質量份以上65質量份以下。 ＜發明之功效＞The glass contains SiO 2 , B 2 O 3 and RO (R is one or more elements selected from Ca, Sr and Ba), and the total amount of SiO 2 , B 2 O 3 and RO is 100 parts by mass (parts In the case of by mass), the content ratio of SiO 2 is 10 to 50 parts by mass, the content ratio of B 2 O 3 is 8 to 30 parts by mass, and the content ratio of RO is 40 to 65 parts by mass servings or less. ＜Efficacy of Invention＞

根據本發明之一形態，可提供能夠形成電阻溫度系數良好的厚膜電阻，且不含鉛成份的電阻用組成物。According to one aspect of the present invention, it is possible to provide a composition for resistors that can form a thick film resistor having a good temperature coefficient of resistance and does not contain lead.

以下，關於本發明的厚膜電阻用組成物、厚膜電阻用膏體及厚膜電阻之一實施方式進行說明。 [厚膜電阻用組成物]Hereinafter, an embodiment of the composition for thick film resistors, the paste for thick film resistors, and the thick film resistors of the present invention will be described. [Compositions for Thick Film Resistors]

本實施方式的厚膜電阻用組成物可以包括不含鉛成份之氧化釕粉末及不含鉛成份之玻璃。The composition for thick film resistors of this embodiment may include lead-free ruthenium oxide powder and lead-free glass.

且優選為，氧化釕粉末中，根據採用X射線繞射法測定的（110）晶面的峰值計算出的微晶徑D1為25nm以上80nm以下，根據比表面積計算出的比表面積徑D2為25nm以上114nm以下。And preferably, in the ruthenium oxide powder, the crystallite diameter D1 calculated from the peak of the (110) crystal plane measured by X-ray diffraction method is 25 nm to 80 nm, and the specific surface area diameter D2 calculated from the specific surface area is 25 nm Above 114nm and below.

另外優選，微晶徑D1（nm）與比表面積徑D2（nm）之比滿足以下公式（1）。 0.70≦D1/D2≦1.00 （1）In addition, preferably, the ratio of the crystallite diameter D1 (nm) to the specific surface area diameter D2 (nm) satisfies the following formula (1). 0.70≦D1/D2≦1.00 (1)

另一方面，玻璃可以包含SiO2 、B2 O3 及RO（R是從Ca、Sr及Ba中選擇的1種類以上的元素）。並且，在SiO2 與B2 O3 與RO的合計量為100質量份之情形下，SiO2 的含有比率可為10質量份以上50質量份以下、B2 O3 的含有比率可為8質量份以上30質量份以下、RO的含有比率可為40質量份以上65質量份以下。On the other hand, the glass may contain SiO 2 , B 2 O 3 , and RO (R is one or more elements selected from Ca, Sr, and Ba). In addition, when the total amount of SiO 2 , B 2 O 3 , and RO is 100 parts by mass, the content ratio of SiO 2 may be 10 parts by mass or more and 50 parts by mass or less, and the content ratio of B 2 O 3 may be 8 parts by mass. The content rate of RO may be 40 to 65 parts by mass, and 30 to 30 parts by mass.

本發明的發明者發現，藉由使用包含微晶徑與比表面積徑之比滿足規定範圍的氧化釕粉末、及含有規定成份之玻璃的電阻用組成物，可使該電阻用組成物經燒成後獲得的厚膜電阻的電阻溫度系數接近0，從而完成了本發明。根據本實施方式的厚膜電阻用組成物，能夠提供一種在使用歷來的氧化釕時電阻溫度系數會成為負值的電阻值區域也具有接近0的電阻溫度系數的電阻。The inventors of the present invention have found that by using a composition for resistance comprising ruthenium oxide powder having a ratio of crystallite size to specific surface area within a predetermined range and glass containing a predetermined composition, the composition for resistance can be fired. The temperature coefficient of resistance of the obtained thick film resistor was close to 0, thus completing the present invention. According to the composition for thick film resistors of this embodiment, it is possible to provide a resistor having a temperature coefficient of resistance close to zero even in a resistance region where the temperature coefficient of resistance becomes negative when conventional ruthenium oxide is used.

以下，對本實施方式中包含的各成份進行說明。 （氧化釕粉末）Hereinafter, each component contained in this embodiment is demonstrated. (ruthenium oxide powder)

不含鉛的厚膜電阻用組成物中無法使用正電阻溫度系數大的釕酸鉛（Pb2 Ru2 O6.5 ）導電粒子，因此，重要的是電阻溫度系數容易成為正值的導電粉末與玻璃之組合。Lead ruthenate (Pb 2 Ru 2 O 6.5 ) conductive particles with a large positive temperature coefficient of resistance cannot be used in lead-free thick film resistor compositions. Therefore, it is important to use conductive powder and glass with a positive temperature coefficient of resistance. combination.

如上所述，即使使用添加劑，也難以將電阻溫度系數調整成正值。因此，電阻溫度系數的負值過大時，難以調整成0附近，例如，±100ppm/℃。然而，電阻溫度系數為正值時，即使其值較高，藉由利用調整劑等添加劑，能夠將電阻溫度系數調整至0附近。As described above, even with additives, it is difficult to adjust the temperature coefficient of resistance to a positive value. Therefore, when the negative value of the temperature coefficient of resistance is too large, it is difficult to adjust to near 0, for example, ±100 ppm/°C. However, when the temperature coefficient of resistance is positive, even if the value is high, the temperature coefficient of resistance can be adjusted to near zero by using additives such as regulators.

作為不含鉛的厚膜電阻用組成物的導電物，適合使用氧化釕粉末，可使厚膜電阻用組成物經燒成後獲得的厚膜電阻具有穩定的電阻值。然而，本發明的發明者的研究表明，根據氧化釕粉末的微晶徑及比表面積徑，電阻溫度系數會成為過大負值。Ruthenium oxide powder is suitably used as the conductor of the lead-free thick-film resistor composition, and the thick-film resistor obtained by firing the thick-film resistor composition can have a stable resistance value. However, studies by the inventors of the present invention have revealed that the temperature coefficient of resistance becomes an excessively negative value depending on the crystallite diameter and specific surface area diameter of the ruthenium oxide powder.

並且，以氧化釕粉末及玻璃作為主要含有成份的厚膜電阻的導電機構，被視為依靠電阻溫度系數為正值的氧化釕粉末的金屬性導電，及電阻溫度系數為負值的氧化釕粉末與玻璃的反應相的半導體性導電之組合。因此，在氧化釕粉末的比率較多的低電阻值區域，電阻溫度系數容易成為正值，而在氧化釕粉末的比率較少的高電阻值區域，電阻溫度系數容易成為負值。由此，在高電阻值區域難以使電阻溫度系數接近0。In addition, the conductive mechanism of thick film resistors mainly composed of ruthenium oxide powder and glass is considered to rely on the metallic conduction of ruthenium oxide powder with a positive temperature coefficient of resistance, and the ruthenium oxide powder with a negative temperature coefficient of resistance. Combination of semiconducting conduction with reactive phase of glass. Therefore, the temperature coefficient of resistance tends to be positive in a low-resistance region where the ratio of ruthenium oxide powder is large, and the temperature coefficient of resistance tends to become negative in a high-resistance region where the ratio of ruthenium oxide powder is small. Accordingly, it is difficult to bring the temperature coefficient of resistance close to zero in a high resistance value region.

對此，本發明的發明者對使用包含氧化釕粉末及玻璃的厚膜電阻用組成物制成的厚膜電阻進行了進一步研究。並發現，在使用包含氧化釕粉末及玻璃的厚膜電阻用組成物來制作厚膜電阻之情形下，所使用的氧化釕粉末的微晶徑及比表面積徑不同時，即使厚膜電阻用組成物的組成相同，所獲得的厚膜電阻的面積電阻值及電阻溫度系數也會不同。In view of this, the inventors of the present invention conducted further studies on thick film resistors produced using a composition for thick film resistors containing ruthenium oxide powder and glass. And found that in the case of using a composition for thick film resistors including ruthenium oxide powder and glass to produce thick film resistors, when the crystallite diameter and specific surface area diameter of the ruthenium oxide powder used are different, even if the composition for thick film resistors If the composition of the material is the same, the area resistance value and temperature coefficient of resistance of the obtained thick film resistors will also be different.

基於上述發現，本實施方式的厚膜電阻用組成物包含的氧化釕粉末中，可將上述微晶徑D1、比表面積徑D2、及微晶徑與比表面積之比D1/D2設為規定範圍。藉由使用該氧化釕粉末，形成厚膜電阻時，可使電阻溫度系數不易成為負值。Based on the above findings, in the ruthenium oxide powder contained in the composition for thick film resistors according to this embodiment, the crystallite diameter D1, the specific surface area diameter D2, and the ratio D1/D2 of the crystallite diameter to the specific surface area can be set within a predetermined range. . By using this ruthenium oxide powder, it is possible to make the temperature coefficient of resistance less likely to become negative when forming a thick film resistor.

通常，由於厚膜電阻中使用的氧化釕粉末的一次粒子的粒徑小，微晶也變小，可完全滿足Bragg條件的晶格會減少，從而照射X射線時的繞射線輪廓會擴展。在可視為無晶格畸變之情形下，在微晶徑為D1（nm）、X射線波長為λ（nm）、（110）晶面之繞射線輪廓的擴展為β、繞射角為θ時，可根據以下公式（2）所示的Scherrer公式，測定計算微晶徑。在此，計算（110）晶面的繞射線輪廓的擴展β時，例如，可以在波形分離成Kα1、Kα2之後，對測定設備的光學系統所致的擴展加以校正，使用Kα1的繞射峰值的半峰全幅值。 D1（nm）＝（K·λ）/（β・cosθ） （2）In general, since the primary particle size of ruthenium oxide powder used in thick film resistors is small, the crystallites are also small, and the number of crystal lattices that can fully satisfy Bragg's conditions decreases, and the diffraction profile when irradiated with X-rays expands. In the case of no lattice distortion, when the crystallite diameter is D1 (nm), the X-ray wavelength is λ (nm), the extension of the diffraction line profile of the (110) crystal plane is β, and the diffraction angle is θ , the crystallite diameter can be determined and calculated according to the Scherrer formula shown in the following formula (2). Here, when calculating the spread β of the diffraction ray profile of the (110) crystal plane, for example, after the waveform is separated into Kα1 and Kα2, the spread caused by the optical system of the measurement device can be corrected, and the diffraction peak value of Kα1 can be used. Full amplitude at half maximum. D1 (nm) = (K·λ)/(β·cosθ) (2)

式（2）中，K是Scherrer常數，可以採用0.9。In formula (2), K is the Scherrer constant, which can be 0.9.

氧化釕（RuO2 ）粉末，在可視為其一次粒子基本為單晶體之情形下，藉由X射線繞射法測定的微晶徑與一次粒子粒徑基本相等。因此，也可以說微晶徑D1即一次粒子之粒徑。就具有金紅石型晶體結構之氧化釕（RuO2 ）而言，繞射峰值中，晶體結構的（110）、（101）、（211）、（301）、（321）晶面之繞射峰值較大，而關於本實施方式的厚膜電阻用組成物中使用的氧化釕粉末，如上所述，可將根據相對強度最高、適於進行測定的（110）晶面的峰值計算出的微晶徑設為25nm以上80nm以下。In ruthenium oxide (RuO 2 ) powder, the primary particle is considered to be basically a single crystal, and the crystallite diameter measured by X-ray diffraction method is basically equal to the primary particle diameter. Therefore, it can also be said that the crystallite diameter D1 is the particle diameter of the primary particles. For ruthenium oxide (RuO 2 ) with a rutile crystal structure, among the diffraction peaks, the diffraction peaks of (110), (101), (211), (301), (321) crystal planes of the crystal structure As for the ruthenium oxide powder used in the thick film resistor composition of this embodiment, as described above, the crystallite calculated from the peak value of the (110) crystal plane with the highest relative intensity and suitable for measurement The diameter is not less than 25 nm and not more than 80 nm.

另一方面，氧化釕粉末的粒徑變小時，比表面積會增大。並且，在氧化釕粉末的粒徑為D2（nm），密度為ρ（g/cm3 ），比表面積為S（m2 /g），將粉末視為真球之情形下，以下公式（3）所示的關系可成立。以根據該D2計算出的粒徑作為比表面積徑。 D2（nm）＝6×103 /（ρ·S） （3）On the other hand, the smaller the particle size of the ruthenium oxide powder, the larger the specific surface area. And, when the particle size of the ruthenium oxide powder is D2 (nm), the density is ρ (g/cm 3 ), the specific surface area is S (m 2 /g), and the powder is regarded as a true sphere, the following formula (3 ) The relationship shown can be established. The particle diameter calculated from this D2 was used as the specific surface area diameter. D2 (nm) = 6×10 3 /(ρ·S) (3)

在本實施方式中，將氧化釕的密度設為7.05g／cm3 ，可將由公式（3）計算出的比表面積徑設定為25nm以上114nm以下。In the present embodiment, the density of ruthenium oxide is set at 7.05 g/cm 3 , and the specific surface area diameter calculated by the formula (3) can be set at 25 nm or more and 114 nm or less.

藉由將氧化釕粉末的微晶徑D1設為25nm以上，能夠抑制厚膜電阻的電阻溫度系數成為負值。另外，藉由將氧化釕粉末的微晶徑D1設為80nm以下，可提高耐電壓特性。By setting the crystallite diameter D1 of the ruthenium oxide powder to be 25 nm or more, it is possible to suppress the temperature coefficient of resistance of the thick film resistor from becoming a negative value. In addition, by setting the crystallite diameter D1 of the ruthenium oxide powder to be 80 nm or less, withstand voltage characteristics can be improved.

另外，藉由將比表面積徑D2設為25nm以上，在為了使用氧化釕粉末來制造厚膜電阻而對包含氧化釕粉末及玻璃粉末的厚膜電阻用膏體進行燒成時，能夠抑制氧化釕粉末與玻璃粉末的反應過度進展。如上所述，氧化釕粉末與玻璃粉末的反應相的電阻溫度系數為負值。因此，藉由抑制氧化釕粉末與玻璃粉末的反應過度所致的該反應相的比率增大，能夠抑制獲得的厚膜電阻的電阻溫度系數成為負值。In addition, by setting the specific surface area diameter D2 to be 25 nm or more, when firing a paste for thick-film resistors containing ruthenium oxide powder and glass powder in order to manufacture thick-film resistors using ruthenium oxide powder, it is possible to suppress the ruthenium oxide The reaction of the powder with the glass powder is excessively advanced. As described above, the temperature coefficient of resistance of the reaction phase of ruthenium oxide powder and glass powder is a negative value. Therefore, by suppressing an increase in the ratio of the reaction phase due to excessive reaction between the ruthenium oxide powder and the glass powder, it is possible to suppress the temperature coefficient of resistance of the obtained thick film resistor from becoming a negative value.

然而，氧化釕粉末的比表面積徑過大時，作為導電粒子的氧化釕粒子之間的接觸點會減少，導致導電路徑減少，從而在噪聲等電氣特性方面可能無法獲得充分的特性。因此，比表面積徑D2優選為114nm以下。However, when the specific surface area diameter of the ruthenium oxide powder is too large, the contact points between the ruthenium oxide particles as conductive particles are reduced, resulting in a reduction of the conductive path, and it may not be possible to obtain sufficient characteristics in terms of electrical characteristics such as noise. Therefore, the specific surface area diameter D2 is preferably 114 nm or less.

藉由將微晶徑D1與比表面積徑D2之比D1/D2設為0.70以上，能夠提高氧化釕的結晶性。然而，D1/D2超過1.00時，粗大粒子與微細粒子會混合存在。藉由將D1/D2設為0.70以上1.00以下，能夠抑制包含該氧化釕的厚膜電阻之電阻溫度系數成為負值。The crystallinity of ruthenium oxide can be improved by setting the ratio D1/D2 of the crystallite diameter D1 to the specific surface area diameter D2 to be 0.70 or more. However, when D1/D2 exceeds 1.00, coarse particles and fine particles are mixed. By making D1/D2 into 0.70-1.00, the temperature coefficient of resistance of the thick-film resistor containing this ruthenium oxide can be suppressed from becoming a negative value.

在此，作為本實施方式的厚膜電阻用組成物中使用的氧化釕粉末，使用不含鉛成份的氧化釕粉末。不含鉛成份的氧化釕粉末是指，無意圖添加鉛，鉛含量為0之情形。然而，並不排除在制造工序等中以雜質成份、不可避免成份形式混入之情形。Here, as the ruthenium oxide powder used in the thick film resistor composition of the present embodiment, ruthenium oxide powder not containing a lead component is used. The lead-free ruthenium oxide powder refers to the case where no lead is added intentionally and the lead content is zero. However, it does not exclude the case that it is mixed in the form of impurity components or unavoidable components in the manufacturing process and the like.

接下來，對本實施方式的厚膜電阻用組成物中使用的氧化釕粉末的制造方法之一構成例進行說明。Next, a configuration example of a method for producing ruthenium oxide powder used in the composition for thick film resistors of this embodiment will be described.

在此，藉由以下氧化釕粉末之制造方法，能夠制造出上述氧化釕粉末，因此，關於已說明過的部分事項，省略贅述。Here, the above-mentioned ruthenium oxide powder can be produced by the following production method of the ruthenium oxide powder, and therefore, the description of some matters already described will be omitted.

關於氧化釕粉末之制造方法並無特別限定，是能夠制造出上述氧化釕粉末之方法即可。The method for producing the ruthenium oxide powder is not particularly limited, and any method capable of producing the above-mentioned ruthenium oxide powder may be used.

作為氧化釕粉末之制造方法，例如，優選採用對濕式合成的氧化釕水合物進行熱處理的制造方法。在這種制造方法中，藉由其合成方法及熱處理的條件等，能夠改變比表面積徑及微晶徑等。As a method for producing ruthenium oxide powder, for example, a production method of heat-treating wet-synthesized ruthenium oxide hydrate is preferably employed. In such a production method, the specific surface area diameter, the crystallite diameter, and the like can be changed by the synthesis method, heat treatment conditions, and the like.

即，氧化釕粉末的制造方法，例如可以包括以下工序。That is, the method for producing ruthenium oxide powder may include, for example, the following steps.

藉由濕式法來合成氧化釕水合物的氧化釕水合物生成工序。A ruthenium oxide hydrate formation process for synthesizing ruthenium oxide hydrate by a wet method.

對溶液中的氧化釕水合物進行分離回收的氧化釕水合物回收工序。A ruthenium oxide hydrate recovery process for separating and recovering the ruthenium oxide hydrate in the solution.

對氧化釕水合物進行幹燥的幹燥工序。A drying step for drying ruthenium oxide hydrate.

對氧化釕水合物進行熱處理的熱處理工序。A heat treatment process of heat-treating ruthenium oxide hydrate.

在此，藉由歷來常用的氧化釕粉末制造方法，即，在制造成粒徑較大的氧化釕之後對該氧化釕進行粉碎的方法，難以使粒徑變小，粒徑差距較大，不適合作為本實施方式的厚膜電阻用組成物中使用的氧化釕粉末的制造方法。Here, it is difficult to reduce the particle size by the conventionally used method of producing ruthenium oxide powder, that is, the method of pulverizing the ruthenium oxide after producing ruthenium oxide with a large particle size, and the difference in particle size is large, so it is not suitable. It is a method for producing ruthenium oxide powder used in the composition for thick film resistors of this embodiment.

在氧化釕水合物生成工序中，對於合成氧化釕水合物的方法並無特別限定，例如可以舉出在含釕水溶液中使氧化釕水合物析出、沈澱之方法。具體而言，例如可以舉出在K2 RuO4 水溶液中加入乙醇來獲得氧化釕水合物的沈澱物的方法，或利用KOH等RuCl3 水溶液進行中和來獲得氧化釕水合物的沈澱物的方法等。In the ruthenium oxide hydrate forming step, the method for synthesizing the ruthenium oxide hydrate is not particularly limited, and examples thereof include a method of depositing and precipitating ruthenium oxide hydrate in an aqueous solution containing ruthenium. Specifically, for example, a method of obtaining a precipitate of ruthenium oxide hydrate by adding ethanol to an aqueous K 2 RuO 4 solution, or a method of obtaining a precipitate of ruthenium oxide hydrate by neutralizing with an aqueous solution of RuCl 3 such as KOH wait.

然後，如上所述，藉由氧化釕水合物的回收工序及幹燥工序，對氧化釕水合物的沈澱物進行固液分離，根據需要進行洗凈之後，加以幹燥而可獲得氧化釕水合物的粉末。Then, as described above, the precipitate of ruthenium oxide hydrate is subjected to solid-liquid separation through the recovery step of ruthenium oxide hydrate and the drying step, washed as necessary, and then dried to obtain a powder of ruthenium oxide hydrate .

關於熱處理工序條件並無特別限定，例如，藉由在氧化氛圍中，以400℃以上的溫度對氧化釕水合物粉末進行熱處理，除去結晶水，可獲得結晶性高的氧化釕粉末。在此，氧化氛圍是指包含10容積%以上的氧的氣體，例如可以使用空氣。The conditions of the heat treatment step are not particularly limited. For example, ruthenium oxide hydrate powder with high crystallinity can be obtained by heat-treating the ruthenium oxide hydrate powder at a temperature of 400° C. or higher in an oxidizing atmosphere to remove crystal water. Here, the oxidizing atmosphere refers to a gas containing 10% by volume or more of oxygen, for example, air can be used.

對氧化釕水合物粉末進行熱處理時的溫度，如上所述，優選在400℃以上，由此能夠獲得結晶性尤其良好的氧化釕（RuO2 ）粉末。關於熱處理溫度的上限值並無特別限定，然而設定過度的高溫會使獲得的氧化釕粉末的微晶徑及比表面積徑過度增大，從而導致釕形成6價或8價的氧化物（RuO3 或RuO4 ），有時揮發比率會增高。因此，例如優選在1000℃以下的溫度進行熱處理。The temperature at the time of heat-treating the ruthenium oxide hydrate powder is preferably 400° C. or higher as described above, whereby ruthenium oxide (RuO 2 ) powder having particularly good crystallinity can be obtained. The upper limit of the heat treatment temperature is not particularly limited, but setting an excessively high temperature will cause the crystallite diameter and specific surface area diameter of the obtained ruthenium oxide powder to increase excessively, thereby causing ruthenium to form a hexavalent or eight-valent oxide (RuO 3 or RuO 4 ), sometimes the volatile ratio will increase. Therefore, for example, heat treatment is preferably performed at a temperature of 1000° C. or lower.

尤其是，對氧化釕水合物粉末進行熱處理的溫度優選為500℃以上1000℃以下。In particular, the temperature at which the ruthenium oxide hydrate powder is heat-treated is preferably not less than 500°C and not more than 1000°C.

如上所述，根據制造氧化釕水合物時的合成條件及熱處理條件等，能夠使獲得的氧化釕粉末的比表面積徑及結晶性發生變化。因此，例如優選事先進行預備試驗等，來選定可獲得具有期望的微晶徑、比表面積徑的氧化釕粉末的條件。As described above, the specific surface area diameter and crystallinity of the obtained ruthenium oxide powder can be changed depending on the synthesis conditions and heat treatment conditions when producing ruthenium oxide hydrate. Therefore, for example, it is preferable to conduct a preliminary test in advance to select conditions under which ruthenium oxide powder having a desired crystallite diameter and specific surface area diameter can be obtained.

氧化釕粉末的制造方法中，除上述工序之外亦可包括任意的工序。In the manufacturing method of the ruthenium oxide powder, arbitrary processes other than the said process may be included.

如上所述，在氧化釕水合物回收工序中對氧化釕水合物的沈澱物進行固液分離，並在幹燥工序中進行幹燥之後，在進行熱處理工序之前，還可以對獲得的氧化釕水合物進行機械性粉碎，獲得被粉碎的氧化釕水合物粉末（粉碎工序）。As mentioned above, in the ruthenium oxide hydrate recovery process, the precipitate of ruthenium oxide hydrate is subjected to solid-liquid separation, and after drying in the drying process, before the heat treatment process, the obtained ruthenium oxide hydrate can also be subjected to Mechanical pulverization to obtain pulverized ruthenium oxide hydrate powder (crushing process).

然後，將粉碎後的氧化釕水合物粉末提供給熱處理工序，藉由在氧化氛圍下，以400℃以上的溫度進行熱處理，如上所述能夠除去結晶水，提高氧化釕粉末的結晶性。藉由實施上述之粉碎工序，能夠抑制、降低將被提供給熱處理工序的氧化釕水合物粉末的凝集程度。並且，藉由對粉碎後的氧化釕水合物粉末進行熱處理，能夠抑制熱處理導致生成粗大粒子或粘連粒子。因此，藉由選擇粉碎工序中的條件，也能夠獲得具有所期望的微晶徑及比表面積徑的氧化釕粉末。Then, the pulverized ruthenium oxide hydrate powder is subjected to a heat treatment step, and by heat treatment at a temperature of 400° C. or higher in an oxidizing atmosphere, the crystallization water can be removed as described above, and the crystallinity of the ruthenium oxide powder can be improved. By carrying out the pulverization step described above, the degree of aggregation of the ruthenium oxide hydrate powder to be supplied to the heat treatment step can be suppressed and reduced. Furthermore, by heat-treating the pulverized ruthenium oxide hydrate powder, it is possible to suppress generation of coarse particles or cohesive particles due to heat treatment. Therefore, ruthenium oxide powder having a desired crystallite diameter and specific surface area diameter can also be obtained by selecting the conditions in the pulverization step.

在此，關於粉碎工序中的粉碎條件並無特別限定，為獲得目標氧化釕粉末，可藉由進行預備試驗等，任意選擇。Here, the pulverization conditions in the pulverization step are not particularly limited, and can be arbitrarily selected by conducting preliminary tests and the like in order to obtain the target ruthenium oxide powder.

另外，氧化釕粉末的制造方法中，熱處理工序之後，還可以對獲得的氧化釕粉末進行分級（分級工序）。藉由實施上述分級工序，可選擇性地回收具有期望的比表面積徑的氧化釕粉末。 （玻璃）In addition, in the production method of the ruthenium oxide powder, after the heat treatment step, the obtained ruthenium oxide powder may be classified (classification step). Ruthenium oxide powder having a desired specific surface area diameter can be selectively recovered by implementing the above-mentioned classification step. (Glass)

本實施方式的厚膜電阻用組成物可以包含不含鉛成份之玻璃（玻璃粉末）。在此，不含鉛成份之玻璃是指，無意圖添加鉛，鉛含量為0。然而，並不排除在制造工序等中以雜質成份、不可避免成份形式混入之情形。The composition for thick film resistors of this embodiment may contain glass (glass powder) that does not contain a lead component. Here, the lead-free glass means that no lead is added intentionally, and the lead content is zero. However, it does not exclude the case that it is mixed in the form of impurity components or unavoidable components in the manufacturing process and the like.

在不含鉛成份的電阻用組成物的玻璃中，藉由配合作為骨骼的SiO2 之外的金屬氧化物，能夠調整燒成時的流動性。作為SiO2 之外的金屬氧化物，可以使用B2 O3 及RO（R表示從Ca、Sr、Ba中選擇的1種以上的堿土元素）等。Fluidity at the time of firing can be adjusted by blending metal oxides other than SiO 2 as the skeleton in the glass of the resistor composition that does not contain lead. As metal oxides other than SiO 2 , B 2 O 3 and RO (R represents one or more earth elements selected from Ca, Sr, and Ba) and the like can be used.

本實施方式的厚膜電阻用組成物包含的玻璃中，在玻璃組成中的SiO2 、B2 O3 、RO的合計量為100質量份之情形下，各成份的含有比率優選為SiO2 占10質量份以上50質量份以下、B2 O3 占8質量份以上30質量份以下、RO占40質量份以上65質量份以下。根據本發明的發明者的研究，藉由使用各成份滿足上述含有比率的玻璃，制作成厚膜電阻時，電阻溫度系數不易成為負值。In the glass contained in the composition for thick film resistors according to this embodiment, when the total amount of SiO 2 , B 2 O 3 , and RO in the glass composition is 100 parts by mass, the content ratio of each component is preferably such that SiO 2 10 to 50 parts by mass, B 2 O 3 to 8 to 30 parts by mass, and RO to 40 to 65 parts by mass. According to the study of the inventors of the present invention, when a thick film resistor is manufactured by using glass whose components satisfy the above content ratio, the temperature coefficient of resistance is less likely to become a negative value.

在玻璃組成中的SiO2 、B2 O3 、RO的合計量為100質量份之情形下，藉由將SiO2 的含有比率設為50質量份以下，能夠充分提高流動性。然而，SiO2 的含有比率低於10質量份時，有時難以形成玻璃，因此，SiO2 的含有比率優選為10質量份以上50質量份以下。When the total amount of SiO 2 , B 2 O 3 , and RO in the glass composition is 100 parts by mass, fluidity can be sufficiently improved by making the content ratio of SiO 2 50 parts by mass or less. However, when the content ratio of SiO 2 is less than 10 parts by mass, glass formation may be difficult, so the content ratio of SiO 2 is preferably not less than 10 parts by mass and not more than 50 parts by mass.

另外，藉由將B2 O3 設為8質量份以上，能夠充分提高流動性，且，藉由設為30質量份以下，能夠提高耐候性。Moreover, fluidity | liquidity can fully be improved by making B2O3 into 8 mass parts or more, and weather resistance can be improved by making it into 30 mass parts or less.

藉由將RO的含有比率設為40質量份以上，能夠充分抑制所獲得的厚膜電阻的電阻溫度系數成為負值。另外，藉由將RO的含有比率設為65質量份以下，能夠抑制結晶化，容易形成玻璃。By setting the content ratio of RO to 40 parts by mass or more, it is possible to sufficiently suppress the temperature coefficient of resistance of the obtained thick film resistor from becoming a negative value. Moreover, crystallization can be suppressed by making the content rate of RO into 65 mass parts or less, and glass formation becomes easy.

根據本發明的發明者的研究，在單獨使用電阻溫度系數不易成為負值的氧化釕粉末，或電阻溫度系數不易成為負值的玻璃之情形下，難以制作成電阻溫度系數接近0的厚膜電阻。然而，藉由組合兩者，能夠制作出電阻溫度系數接近0的厚膜電阻。根據本實施方式的厚膜電阻用組成物，使用該厚膜電阻用組成物形成的厚膜電阻，其電阻溫度系數在歷來困難的面積電阻值高於80kΩ的電阻區域也能夠接近0，從而能夠發揮出尤其高的效果。According to research by the inventors of the present invention, it is difficult to produce a thick film resistor having a temperature coefficient of resistance close to zero when ruthenium oxide powder whose temperature coefficient of resistance is less likely to become negative or glass whose temperature coefficient of resistance is less likely to become negative is used alone. . However, by combining the two, it is possible to manufacture a thick film resistor with a temperature coefficient of resistance close to zero. According to the composition for thick film resistors of this embodiment, the temperature coefficient of resistance of the thick film resistors formed using the composition for thick film resistors can be close to 0 even in the resistance region where the area resistance value is higher than 80 kΩ, which has been difficult in the past, so that exert a particularly high effect.

本實施方式的厚膜電阻用組成物中包含的玻璃的組成，除了上述SiO2 與B2 O3 與RO之外，出於調整玻璃的耐候性及燒成時的流動性之目的，還可以包含其它成份。作為任意的添加成份之例，可以舉出Al2 O3 、ZrO2 、TiO2 、SnO2 、ZnO、Li2 O、Na2 O、K2 O等，可以在玻璃中添加從這些化合物中選擇的1種以上。The composition of the glass contained in the composition for thick film resistors of this embodiment may be, in addition to the aforementioned SiO 2 , B 2 O 3 , and RO, for the purpose of adjusting the weather resistance of the glass and the fluidity during firing. Contains other ingredients. Examples of optional additives include Al 2 O 3 , ZrO 2 , TiO 2 , SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O, etc., which can be added to the glass and selected from these compounds. more than 1 species.

Al2 O3 具有易於抑制玻璃的相分離之作用，ZrO2 、TiO2 具有提高玻璃耐候性之作用。另外，SnO2 、ZnO、Li2 O、Na2 O、K2 O等具有提高玻璃流動性之作用。Al 2 O 3 has the function of easily suppressing the phase separation of glass, and ZrO 2 and TiO 2 have the function of improving the weather resistance of glass. In addition, SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O, etc. can improve glass fluidity.

作為影響玻璃燒成時的流動性之一尺度，有軟化點。一般而言，制造厚膜電阻時，厚膜電阻用組成物的燒成溫度為800℃以上900℃以下。As one of the scales that affect the fluidity of glass when it is fired, there is a softening point. Generally, when producing a thick film resistor, the firing temperature of the composition for a thick film resistor is 800° C. or higher and 900° C. or lower.

如上所述，在制造厚膜電阻時的厚膜電阻用組成物的燒成溫度為800℃以上900℃以下之情形下，本實施方式的厚膜電阻用組成物中使用的玻璃的軟化點優選為600℃以上800℃以下，更優選為600℃以上750℃以下。As described above, when the firing temperature of the composition for thick film resistors in the production of thick film resistors is 800°C to 900°C, the softening point of the glass used in the composition for thick film resistors of this embodiment is preferable It is 600°C or more and 800°C or less, more preferably 600°C or more and 750°C or less.

在此，軟化點是指，採用差熱分析法（TG-DTA）於大氣中以10℃/min對玻璃進行升溫、加熱而獲得的差熱曲線中，相比於最低溫側的表示差熱曲線降低之溫度而言位於高溫側的下一個差熱曲線降低的峰值之溫度。Here, the softening point refers to the differential thermal curve obtained by heating and heating the glass at 10°C/min in the air by differential thermal analysis (TG-DTA), compared to the temperature indicated on the lowest temperature side. The temperature at which the next differential thermal curve falls on the high temperature side is the temperature at which the curve falls.

一般而言，藉由按照目標配比來混合規定的成份或其前驅體，並對獲得的混合物進行熔融及急速冷卻，能夠制造成玻璃。對熔融溫度並無特別限定，例如可以設為1400℃左右。此外，關於急速冷卻的方法也無特別限定，可以將熔融物放入冷水中或置於冷帶上流動來進行冷卻。In general, glass can be manufactured by mixing predetermined components or their precursors according to a target ratio, melting and rapidly cooling the obtained mixture. The melting temperature is not particularly limited, and may be, for example, about 1400°C. In addition, there is no particular limitation on the method of rapid cooling, and the melt can be cooled by putting it in cold water or placing it on a cold belt to flow.

粉碎玻璃時可以使用球磨機、行星式軋機、珠磨機等，為了使粒度鮮明，優選濕式粉碎法。A ball mill, a planetary mill, a bead mill, etc. can be used for pulverizing the glass, and a wet pulverization method is preferable in order to make the particle size clear.

對玻璃粒徑並無限定，然而，利用激光繞射的粒度分布儀測定出的玻璃的50%體積累計粒度優選為5μm以下，更優選為3μm以下。玻璃粒度過大是造成厚膜電阻的電阻值偏差增大及負載特性降低的原因。另一方面，玻璃粒度過小時，會導致生產性降低，雜質等的混入也會增多，因此玻璃的50%體積累計粒度優選為0.1μm以上。 （關於厚膜電阻用組成物之組成）The glass particle size is not limited, however, the 50% volume cumulative particle size of the glass measured by a laser diffraction particle size analyzer is preferably 5 μm or less, more preferably 3 μm or less. Excessively large glass grains are the cause of increased resistance value variation and lower load characteristics of thick film resistors. On the other hand, if the glass particle size is too small, productivity will decrease and contamination of impurities will increase. Therefore, the 50% volume cumulative particle size of glass is preferably 0.1 μm or more. (Regarding the composition of the composition for thick film resistors)

關於本實施方式的厚膜電阻用組成物中包含的氧化釕粉末與玻璃之混合比並無特別限定。例如，可以根據期望的電阻值等，改變氧化釕粉末與玻璃的混合比率。氧化釕粉末的質量：玻璃的質量，例如可以是5：95以上50：50以下。即，在氧化釕粉末與玻璃中，氧化釕粉末的比率優選為5質量%以上50質量%以下。The mixing ratio of the ruthenium oxide powder and the glass contained in the composition for thick film resistors of this embodiment is not specifically limited. For example, the mixing ratio of ruthenium oxide powder and glass can be changed according to a desired resistance value or the like. The mass of ruthenium oxide powder: the mass of glass may be, for example, 5:95 or more and 50:50 or less. That is, the ratio of the ruthenium oxide powder in the ruthenium oxide powder and the glass is preferably not less than 5% by mass and not more than 50% by mass.

其理由在於，在本實施方式的厚膜電阻用組成物包含的氧化釕粉末與玻璃的合計量為100質量%之情形下，氧化釕粉末的比率若小於5質量%，所獲得的厚膜電阻的電阻值可能會過高而不穩定。The reason for this is that when the total amount of ruthenium oxide powder and glass contained in the composition for thick film resistors of this embodiment is 100% by mass, if the ratio of ruthenium oxide powder is less than 5% by mass, the obtained thick film resistor The resistor value may be too high and unstable.

另外，在本實施方式的厚膜電阻用組成物包含的氧化釕粉末與玻璃的合計量為100質量%之情形下，藉由將氧化釕粉末的比率設為50質量%以下，可充分提高所獲得的厚膜電阻之強度，尤其能夠確實地防止其變脆。In addition, when the total amount of ruthenium oxide powder and glass contained in the composition for thick film resistors according to this embodiment is 100% by mass, the ratio of the ruthenium oxide powder can be sufficiently increased by making the ratio of the ruthenium oxide powder to be 50% by mass or less. The strength of the obtained thick film resistors, in particular, can reliably prevent them from becoming brittle.

本實施方式的厚膜電阻用組成物中的氧化釕粉末與玻璃之混合比率，優選氧化釕粉末的質量：玻璃的質量在5：95以上40：60以下之範圍。即，在氧化釕粉末與玻璃中，優選將氧化釕粉末的比率設為5質量%以上40質量%以下。The mixing ratio of the ruthenium oxide powder and glass in the composition for thick film resistors of this embodiment is preferably in the range of 5:95 or more and 40:60 or less by mass of ruthenium oxide powder:mass of glass. That is, in the ruthenium oxide powder and the glass, it is preferable to make the ratio of the ruthenium oxide powder into 5 mass % or more and 40 mass % or less.

在此，本實施方式的厚膜電阻用組成物，作為主成份優選包含如上所述的氧化釕粉末及玻璃，亦可僅由氧化釕粉末與玻璃構成。在本實施方式的厚膜電阻用組成物中，上述氧化釕粉末與玻璃的混合粉末之含有比率，例如優選為80量%以上100質量%以下，更優選為85質量%以上100質量%以下。Here, the composition for thick film resistors according to the present embodiment preferably contains the above-mentioned ruthenium oxide powder and glass as main components, and may consist of only ruthenium oxide powder and glass. In the thick film resistor composition of the present embodiment, the content ratio of the mixed powder of the ruthenium oxide powder and glass is, for example, preferably 80% by mass or more and 100% by mass or less, more preferably 85% by mass or more and 100% by mass or less.

本實施方式的厚膜電阻用組成物，還可以根據需要包含任意成份。The composition for thick film resistors according to this embodiment may contain optional components as necessary.

出於改善、調整電阻的電阻值或電阻溫度系數或負載特性、微調性之目的，亦可在本實施方式之電阻用組成物中添加通常使用的添加劑。作為具代表性之添加劑，可以舉出Nb2 O5 、Ta2 O5 、TiO2 、CuO、MnO2 、ZrO2 、Al2 O3 、SiO2 、ZrSiO4 等。藉由加入這些添加劑，能夠制成特性良好的電阻。可根據目的調整添加量，但相對於氧化釕粉末與玻璃的合計量100質量份，優選設在20質量份以下。For the purpose of improving and adjusting the resistance value, temperature coefficient of resistance, load characteristics, and fine-tunability of resistors, generally used additives may be added to the composition for resistors of this embodiment. Typical additives include Nb 2 O 5 , Ta 2 O 5 , TiO 2 , CuO, MnO 2 , ZrO 2 , Al 2 O 3 , SiO 2 , ZrSiO 4 , and the like. By adding these additives, a resistor with good characteristics can be obtained. The addition amount can be adjusted depending on the purpose, but it is preferably 20 parts by mass or less with respect to 100 parts by mass of the total amount of the ruthenium oxide powder and glass.

另外，亦可不添加這些成份。即，本實施方式的厚膜電阻用組成物亦可僅由氧化釕粉末與玻璃構成。因此，相對於氧化釕粉末與玻璃的合計量100質量份，這些添加劑的添加量可為0以上。 [厚膜電阻用膏體]In addition, these components may not be added. That is, the composition for thick film resistors of this embodiment may consist only of ruthenium oxide powder and glass. Therefore, the addition amount of these additives may be 0 or more with respect to 100 parts by mass of the total amount of the ruthenium oxide powder and the glass. [Paste for thick film resistors]

關於本實施方式的厚膜電阻用膏體的一構成例進行說明。A configuration example of the paste for thick film resistors according to this embodiment will be described.

本實施方式的厚膜電阻用膏體，可以包含上述厚膜電阻用組成物及有機載體。本實施方式的厚膜電阻用膏體優選具有上述厚膜電阻用組成物被分散於有機載體中之結構。The paste for thick film resistors according to this embodiment may contain the above-mentioned composition for thick film resistors and an organic vehicle. The paste for thick film resistors according to the present embodiment preferably has a structure in which the above-mentioned composition for thick film resistors is dispersed in an organic vehicle.

如上所述，作為本實施方式的厚膜電阻用膏體，藉由在溶解有被稱為有機載體的樹脂成份的溶劑中分散上述厚膜電阻用組成物，可形成厚膜電阻用膏體。As described above, the paste for thick film resistors according to this embodiment can be formed by dispersing the composition for thick film resistors in a solvent in which a resin component called an organic vehicle is dissolved.

關於有機載體的樹脂及溶劑的種類、配合並無特別限定。作為有機載體的樹脂成份，例如可以使用從乙基纖維素、丙烯酸酯、甲基丙烯酸酯、松香、馬來酸酯（maleic ester）等中選擇的1種以上。There are no particular limitations on the types and blends of the resin and solvent of the organic vehicle. As the resin component of the organic vehicle, for example, one or more selected from ethyl cellulose, acrylate, methacrylate, rosin, maleic ester, and the like can be used.

另外，作為溶劑，例如可以使用從松油醇（Terpineol）、丁基卡必醇（Butyl carbitol）、丁基卡必醇醋酸酯（Butyl carbitol acetate）等中選擇的1種以上。在此，出於延緩厚膜電阻用膏體幹燥之目的，亦可加入沸點高的溶劑。另外，可以根據需要，加入分散劑或可塑劑等。Moreover, as a solvent, one or more types selected from terpineol, butyl carbitol, butyl carbitol acetate, etc. can be used, for example. Here, for the purpose of delaying the drying of the paste for thick film resistors, a solvent with a high boiling point may be added. In addition, a dispersant, a plasticizer, etc. can be added as needed.

可以根據獲得的厚膜電阻用膏體被要求的粘度等，調整樹脂成份及溶劑的配合比。關於有機載體相對於厚膜電阻用組成物的比率並無特別限定，在厚膜電阻用組成物為100質量份之情形下，有機載體的比率例如可以在20質量份以上200質量份以下。The mixing ratio of resin components and solvents can be adjusted according to the required viscosity of the thick film resistor paste to be obtained. The ratio of the organic vehicle to the composition for thick film resistors is not particularly limited, and the ratio of the organic vehicle may be, for example, 20 parts by mass or more and 200 parts by mass or less when the composition for thick film resistors is 100 parts by mass.

關於制造本實施方式的厚膜電阻用膏體的方法並無特別限定，例如，能夠使用從三輥機（3輥式研磨機）、行星式軋機、珠磨機等中選擇的1種以上，將上述厚膜電阻用組成物分散於有機載體中。另外，例如亦可使用球磨機或粉碎機（grinder）對上述厚膜電阻用組成物進行混合之後，分散於有機載體中。The method for producing the thick film resistor paste of this embodiment is not particularly limited, and for example, one or more types selected from a three-roll mill (three-roll mill), a planetary mill, and a bead mill can be used, The above composition for thick film resistors is dispersed in an organic vehicle. In addition, for example, the composition for thick film resistors may be dispersed in an organic vehicle after being mixed using a ball mill or a grinder.

在厚膜電阻用膏體中，優選分解無機原料粉末的凝集，分散於溶解有樹脂成份的溶劑，即有機載體中。一般而言，隨著粉末粒徑變小，凝集會增強，容易形成二次粒子。因此，本實施方式的厚膜電阻用膏體中，為了能容易地分解二次粒子，分散於一次粒子，還可以作為分散劑添加脂肪酸等。 [厚膜電阻]In the paste for thick film resistors, it is preferable to decompose the aggregation of the inorganic raw material powder and disperse it in a solvent in which the resin component is dissolved, that is, an organic vehicle. Generally speaking, as the particle size of the powder becomes smaller, the aggregation becomes stronger and secondary particles are easily formed. Therefore, in order to easily decompose the secondary particles and disperse them in the primary particles to the paste for thick film resistors according to the present embodiment, a fatty acid or the like may be added as a dispersant. [Thick film resistors]

關於本實施方式的厚膜電阻的一構成例進行說明。A configuration example of the thick film resistor of this embodiment will be described.

能夠使用上述厚膜電阻用組成物、厚膜電阻用膏體來制造本實施方式的厚膜電阻。因此，本實施方式的厚膜電阻可以包含上述厚膜電阻用組成物，即，可以包含上述氧化釕粉末與玻璃成份。The thick film resistor of this embodiment can be manufactured using the composition for thick film resistors and the paste for thick film resistors mentioned above. Therefore, the thick film resistor of this embodiment may contain the above-mentioned composition for thick film resistors, that is, may contain the above-mentioned ruthenium oxide powder and glass components.

在此，如上所述，厚膜電阻用組成物中，在氧化釕粉末與玻璃中，氧化釕粉末之比率優選為5質量%以上50質量%以下。並且，能夠使用該厚膜電阻用組成物來制造本實施方式的厚膜電阻，所獲得的厚膜電阻內的玻璃成份來自厚膜電阻用組成物的玻璃。因此，本實施方式的厚膜電阻與厚膜電阻用組成物同樣，在氧化釕粉末與玻璃成份中，氧化釕粉末的比率優選為5質量%以上50質量%以下，更優選為5質量%以上40質量%以下。Here, as described above, in the composition for thick film resistors, the ratio of the ruthenium oxide powder to the glass is preferably not less than 5% by mass and not more than 50% by mass. Furthermore, the thick film resistor of this embodiment can be manufactured using this composition for thick film resistors, and the glass component in the obtained thick film resistor comes from the glass of the composition for thick film resistors. Therefore, in the thick film resistor of the present embodiment, the ratio of the ruthenium oxide powder in the ruthenium oxide powder and the glass component is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more, like the composition for thick film resistors. 40% by mass or less.

關於本實施方式的厚膜電阻之制造方法並無特別限定，例如，可藉由在陶瓷基板上對上述厚膜電阻用組成物進行燒成，來形成厚膜電阻。另外，亦可將上述厚膜電阻用膏體塗敷在陶瓷基板上之後，進行燒成來形成厚膜電阻。 [實施例]The method of manufacturing the thick film resistor of this embodiment is not particularly limited, and for example, the thick film resistor can be formed by firing the above composition for thick film resistor on a ceramic substrate. Alternatively, the above-mentioned paste for thick film resistors may be applied on a ceramic substrate and then fired to form a thick film resistor. [Example]

以下，舉出具體的實施例、比較例來進行說明，但本發明並不限定於該些實施例。 （評價方法）Hereinafter, specific examples and comparative examples are given and described, but the present invention is not limited to these examples. (Evaluation method)

首先，關於以下實施例、比較例中使用的氧化釕粉末的評價方法進行說明。 1.氧化釕粉末之評價First, the evaluation method of the ruthenium oxide powder used in the following Examples and Comparative Examples will be described. 1. Evaluation of ruthenium oxide powder

為了評價氧化釕粉末的形狀・物性，採用X射線繞射法計算微晶徑，及採用BET法計算了比表面積徑。 （1）微晶徑In order to evaluate the shape and physical properties of ruthenium oxide powder, the crystallite diameter was calculated by the X-ray diffraction method, and the specific surface area diameter was calculated by the BET method. (1) Crystalline diameter

可根據X射線繞射模式的峰值之擴展來計算微晶徑。在此，藉由X射線繞射獲得的金紅石型結構的峰值被波形分離成Kα1、Kα2之後，作為測定設備的光學系統為因的擴展被校正後的Kα1的峰值的擴展，測定了半峰全幅值，並根據Scherrer公式進行了計算。The crystallite diameter can be calculated from the spread of the peak of the X-ray diffraction pattern. Here, after the peak of the rutile structure obtained by X-ray diffraction is waveform-separated into Kα1 and Kα2, the spread of the peak of Kα1 corrected for the spread due to the spread of the optical system of the measurement device was measured to measure the half-peak full-amplitude and were calculated according to the Scherrer formula.

具體而言，在微晶徑為D1（nm）、X射線的波長為λ（nm）、繞射線輪廓的擴展為β、繞射角為θ之情形下，根據以下公式（2）所示的Scherrer公式，計算了微晶徑。 D1（nm）＝（K·λ）/（β·cosθ） （2）Specifically, in the case where the crystallite diameter is D1 (nm), the wavelength of X-rays is λ (nm), the expansion of the diffraction ray profile is β, and the diffraction angle is θ, according to the following formula (2) The Scherrer formula, calculated the crystallite diameter. D1 (nm) = (K·λ)/(β·cosθ) (2)

在公式（2）中，K為Scherrer常數，可採用0.9。 （2）比表面積徑In formula (2), K is the Scherrer constant, which can be 0.9. (2) specific surface area diameter

可根據比表面積與密度，算出比表面積徑。比表面積採用了容易進行測定的BET單點法。在比表面積徑為D2（nm）、密度為ρ（g/cm3 ）、比表面積為S（m2 /g），粉末被視為真球之情形下，以下公式（3）所示的關系可成立。將根據該D2算出的粒徑作為比表面積徑。 D2（nm）＝6×103 ／（ρ·S） （3）The specific surface area diameter can be calculated according to the specific surface area and density. The BET single-point method which is easy to measure was used for the specific surface area. When the specific surface area diameter is D2 (nm), the density is ρ (g/cm 3 ), the specific surface area is S (m 2 /g), and the powder is regarded as a true ball, the relationship shown in the following formula (3) can be established. Let the particle diameter calculated from this D2 be a specific surface area diameter. D2 (nm) = 6×10 3 /(ρ·S) (3)

本實施方式中，氧化釕之密度設為7.05g／cm3 。 2.玻璃的評價In this embodiment, the density of ruthenium oxide is set to 7.05 g/cm 3 . 2. Evaluation of glass

準備玻璃粉末A～H，在下述實施例、比較例中制作了厚膜電阻用組成物等。 （50%體積累計粒度）Glass powders A to H were prepared, and compositions for thick film resistors and the like were prepared in the following Examples and Comparative Examples. (50% volume cumulative particle size)

使用球磨機粉碎玻璃粉末，使其均達到50%體積累計粒度為1.3μm以上1.5μm以下。在此，藉由利用激光繞射的粒度分布儀測定了50%體積累計粒度。 （軟化點）Use a ball mill to pulverize the glass powder so that the cumulative particle size of 50% volume is 1.3 μm or more and 1.5 μm or less. Here, the 50% volume cumulative particle size was measured by a particle size analyzer using laser diffraction. (Softening Point)

玻璃粉末的軟化點是，在採用差熱分析法（TG-DTA）在大氣中以每分鐘10℃對玻璃粉末進行升溫、加熱而獲得的差熱曲線中，相比於最低溫側的表示差熱曲線降低之溫度而言位於高溫側的下一個差熱曲線降低的峰值之溫度。 3.厚膜電阻之評價The softening point of glass powder is expressed as a difference from the lowest temperature side in a differential thermal curve obtained by heating glass powder at 10°C per minute in the air by differential thermal analysis (TG-DTA). The temperature at which the thermal curve decreases is the temperature at the peak of the next differential thermal curve decrease on the high temperature side. 3. Evaluation of thick film resistors

對獲得的厚膜電阻，對膜厚、面積電阻值、25℃至-55℃的電阻溫度系數（COLD-TCR）、25℃至125℃的電阻溫度系數（HOT-TCR）進行了評價。在此，表1中將COLD-TCR記為C-TCR、將HOT-TCR記為H-TCR。 （1）膜厚The obtained thick film resistors were evaluated in terms of film thickness, area resistance value, temperature coefficient of resistance (COLD-TCR) from 25°C to -55°C, and temperature coefficient of resistance (HOT-TCR) from 25°C to 125°C. Here, in Table 1, COLD-TCR is referred to as C-TCR, and HOT-TCR is referred to as H-TCR. (1) Film thickness

藉由對各實施例、比較例中按照同樣方式制作的5個厚膜電阻，使用探針型厚度粗糙度儀（東京精密社制造 型號：SURFCOM 480B）測定膜厚，並求出測定值之平均的方法，算出膜厚。 （2）面積電阻值For each of the five thick film resistors produced in the same manner in each of the examples and comparative examples, the film thickness was measured using a probe type thickness roughness meter (manufactured by Tokyo Seiki Co., Ltd.: SURFCOM 480B), and the average of the measured values was obtained. method to calculate the film thickness. (2) Area resistance value

另外，藉由對各實施例、比較例中按照同樣方式制作的25個厚膜抵抗體，使用數字萬用表（KEITHLEY公司制造，2001號）測定電阻值並求出平均值的方法，算出面積電阻值。 （3）電阻溫度系數In addition, the area resistance value was calculated by measuring the resistance value with a digital multimeter (manufactured by KEITHLEY Co., Ltd., No. 2001) with respect to 25 thick-film resistors produced in the same manner in each of the Examples and Comparative Examples and calculating the average value. . (3) Temperature coefficient of resistance

測定電阻溫度系數時，將各實施例、比較例中按照同樣方式制作的5個厚膜電阻，分別在-55℃、25℃、125℃下保持15分鐘後分別測定電阻值，將-55℃的電阻值表示為R-55 、25℃的電阻值表示為R25 、125℃的電阻值表示為R125 。然後，根據以下公式（4）、公式（5），計算各厚膜電阻在各溫度區域的電阻溫度系數。然後對算出的各溫度區域的電阻溫度系數的5個厚膜電阻進行平均值計算，以此作為各實施例、比較例中獲得的厚膜電阻在各溫度區域的電阻溫度系數（COLD-TCR、HOT-TCR）。單位均為ppm/℃。優選電阻溫度系數接近0，以電阻溫度系數≦±100ppm/℃作為良好電阻之基準。 COLD-TCR＝（R-55 -R25 ）/R25 /（-80）×106 （4） HOT-TCR＝（R125 -R25 ）/R25 ／（100）×106 （5） ［實施例1］When measuring the temperature coefficient of resistance, the five thick film resistors made in the same way in each example and comparative example were kept at -55°C, 25°C, and 125°C for 15 minutes, and then the resistance values were measured respectively. The resistance value at 25°C is expressed as R -55 , the resistance value at 25°C is expressed as R 25 , and the resistance value at 125°C is expressed as R 125 . Then, according to the following formula (4) and formula (5), the temperature coefficient of resistance of each thick film resistor in each temperature range is calculated. Then the average value of 5 thick-film resistors of the calculated temperature coefficient of resistance in each temperature range is calculated as the temperature coefficient of resistance (COLD-TCR, COLD-TCR, HOT-TCR). The unit is ppm/°C. The temperature coefficient of resistance is preferably close to 0, and the temperature coefficient of resistance ≦±100ppm/℃ is used as the benchmark for good resistance. COLD-TCR＝(R -55 -R 25 )/R 25 /(-80)×10 6 (4) HOT-TCR＝(R 125 -R 25 )/R 25 /(100)×10 6 (5) [Example 1]

如表1所示，對18質量份的氧化釕粉末a及82質量份的玻璃粉末A進行混合，調制成厚膜電阻用組成物。在此，以獲得的厚膜電阻的面積電阻值大致達到100kΩ為準，調整了氧化釕粒子與玻璃粉末的比率。另外，氧化釕粉末a的特性及玻璃粉末A中包含的各成份，分別如表2、表3所示。As shown in Table 1, 18 parts by mass of ruthenium oxide powder a and 82 parts by mass of glass powder A were mixed to prepare a composition for thick film resistors. Here, the ratio of the ruthenium oxide particles to the glass powder was adjusted so that the area resistance value of the obtained thick film resistor was approximately 100 kΩ. In addition, the properties of the ruthenium oxide powder a and the components contained in the glass powder A are shown in Table 2 and Table 3, respectively.

然後，使用三輥機對厚膜電阻用組成物100質量份及有機載體43質量份進行混煉，制作成有機載體中分散有厚膜電阻用組成物的厚膜電阻用膏體。Then, 100 parts by mass of the composition for thick film resistors and 43 parts by mass of the organic vehicle were kneaded using a three-roll machine to prepare a paste for thick film resistors in which the composition for thick film resistors was dispersed in the organic vehicle.

在預先藉由燒成而形成於氧化鋁基板上的、包含1質量%的Pd與99質量%的Ag的電極上，印刷上述制作的厚膜電阻用膏體。接下來，在150℃下進行5分鐘幹燥之後，按照峰值溫度850℃下9分鐘，及包括升溫時間及降溫時間在內的合計時間為30分鐘進行燒成，形成了厚膜電阻。在此，將厚膜電阻的尺寸設為電阻寬度1.0mm、電阻長度（電極之間）為1.0mm。The above-produced paste for thick film resistors was printed on an electrode containing 1% by mass of Pd and 99% by mass of Ag formed on an alumina substrate by firing in advance. Next, after drying at 150° C. for 5 minutes, firing was performed at a peak temperature of 850° C. for 9 minutes and a total time of 30 minutes including a heating time and a cooling time to form a thick film resistor. Here, the dimensions of the thick film resistors were set to a resistor width of 1.0 mm and a resistor length (between electrodes) of 1.0 mm.

對獲得的厚膜電阻進行了評價。結果如表1所示。 [實施例2～實施例12]The obtained thick film resistors were evaluated. The results are shown in Table 1. [Example 2 to Example 12]

作為氧化釕粉末及玻璃粉末使用了表1所示的材料，並按照表1所示的比率進行混合，調制成厚膜電阻用組成物，此外採用與實施例1相同的方式，制作了厚膜電阻用組成物、厚膜電阻用膏體、厚膜電阻。The materials shown in Table 1 were used as ruthenium oxide powder and glass powder, and they were mixed in the ratio shown in Table 1 to prepare a composition for thick film resistors. In addition, in the same manner as in Example 1, thick film resistors were fabricated. Compositions for film resistors, pastes for thick film resistors, thick film resistors.

在此，各氧化釕粉末的特性及玻璃粉末中包含的各成份，分別如表2、表3所示。Here, the characteristics of each ruthenium oxide powder and each component contained in the glass powder are shown in Table 2 and Table 3, respectively.

另外，在實施例11、12中，調制厚膜電阻用組成物時，如表1所示，除了氧化釕粉末、玻璃粉末之外，還添加了TiO2 或Nb2 O5 。In addition, in Examples 11 and 12, when preparing the composition for thick film resistors, as shown in Table 1, TiO 2 or Nb 2 O 5 was added in addition to ruthenium oxide powder and glass powder.

獲得的厚膜電阻的評價結果如表1所示。Table 1 shows the evaluation results of the obtained thick film resistors.

[比較例1～比較例9][Comparative Example 1 to Comparative Example 9]

作為氧化釕粉末及玻璃粉末使用了表1所示的材料，並按照表1所示的比率進行混合，調制成厚膜電阻用組成物，此外採用與實施例1相同的方式，制作了厚膜電阻用組成物、厚膜電阻用膏體、厚膜電阻。The materials shown in Table 1 were used as ruthenium oxide powder and glass powder, and they were mixed in the ratio shown in Table 1 to prepare a composition for thick film resistors. In addition, in the same manner as in Example 1, thick film resistors were fabricated. Compositions for film resistors, pastes for thick film resistors, thick film resistors.

在此，各氧化釕粉末的特性及玻璃粉末中包含的各成份，分別如表2、表3所示。Here, the characteristics of each ruthenium oxide powder and each component contained in the glass powder are shown in Table 2 and Table 3, respectively.

獲得的厚膜電阻的評價結果如表1所示。 [表1]

Figure 02_image001
[表2]
Figure 02_image003
[表3]
Figure 02_image005
Table 1 shows the evaluation results of the obtained thick film resistors. [Table 1]
Figure 02_image001
[Table 2]
Figure 02_image003
[table 3]
Figure 02_image005

根據表1所示結果，實施例2～實施例12的電阻溫度系數在±100ppm／℃以內，確認到可獲得良好電阻。From the results shown in Table 1, it was confirmed that the temperature coefficients of resistance of Examples 2 to 12 were within ±100 ppm/°C, and good resistance was obtained.

實施例1的電阻溫度系數中，雖然H-TCR超過100ppm/℃，但容易利用添加劑對電阻溫度系數進行負值調整。例如實施例11、12所示，確認到藉由在實施例1的厚膜電阻用組成物中分別添加TiO2 、Nb2 O5 ，能夠將電阻溫度系數調整為±100ppm/℃以內。In the temperature coefficient of resistance of Example 1, although the H-TCR exceeds 100 ppm/°C, it is easy to adjust the temperature coefficient of resistance to a negative value by using an additive. For example, as shown in Examples 11 and 12, it was confirmed that by adding TiO 2 and Nb 2 O 5 to the composition for thick film resistors in Example 1, it was confirmed that the temperature coefficient of resistance could be adjusted within ±100 ppm/°C.

相對而言，比較例1～比較例9中，確認到電阻溫度系數成為低於-100ppm/℃的負值。因此，即使添加TiO2 、Nb2 O5 等添加劑也無法調整成±100ppm/℃。In contrast, in Comparative Examples 1 to 9, it was confirmed that the temperature coefficient of resistance was a negative value lower than -100 ppm/°C. Therefore, even if additives such as TiO 2 and Nb 2 O 5 are added, it cannot be adjusted to ±100 ppm/°C.

由以上實施例、比較例可看出，針對歷來的難題，藉由使用包括不含鉛成份的氧化釕粉末及玻璃的厚膜電阻用組成物，能夠容易地將厚膜電阻的電阻溫度系數調整為±100ppm/℃以內，能夠形成良好的厚膜電阻。It can be seen from the above examples and comparative examples that the temperature coefficient of resistance of the thick film resistor can be easily adjusted by using a composition for thick film resistors including ruthenium oxide powder and glass that does not contain lead in order to solve the traditional problems. Within ±100ppm/°C, a good thick film resistor can be formed.

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Claims (5)

一種厚膜電阻用組成物，包括不含鉛成份之氧化釕粉末及不含鉛成份之玻璃， 該氧化釕粉末中，根據採用X射線繞射法測定的（110）晶面之峰值計算出的微晶徑D1為25nm以上80nm以下， 根據比表面積計算出的比表面積徑D2為25nm以上114nm以下， 並且，該微晶徑D1（nm）與該比表面積徑D2（nm）之比滿足以下公式（1）， 0.70≦D1/D2≦1.00 （1） 該玻璃包含SiO2 、B2 O3 及RO（R是從Ca、Sr及Ba中選擇的1種以上的元素），在SiO2 與B2 O3 與RO的合計量為100質量份之情形下，SiO2 的含有比率為10質量份以上50質量份以下，B2 O3 的含有比率為8質量份以上30質量份以下，RO的含有比率為40質量份以上65質量份以下。A composition for thick-film resistors, comprising lead-free ruthenium oxide powder and lead-free glass, in the ruthenium oxide powder, calculated from the peak of the (110) crystal plane measured by X-ray diffraction method The crystallite diameter D1 is not less than 25nm and not more than 80nm, and the specific surface area diameter D2 calculated from the specific surface area is not less than 25nm and not more than 114nm, and the ratio of the crystallite diameter D1 (nm) to the specific surface area diameter D2 (nm) satisfies the following formula (1), 0.70≦D1/D2≦1.00 (1) The glass contains SiO 2 , B 2 O 3 and RO (R is one or more elements selected from Ca, Sr and Ba), and SiO 2 and B When the total amount of 2 O 3 and RO is 100 parts by mass, the content ratio of SiO 2 is 10 parts by mass to 50 parts by mass, the content ratio of B 2 O 3 is 8 parts by mass to 30 parts by mass, and the content of RO is The content ratio is not less than 40 parts by mass and not more than 65 parts by mass. 根據申請專利範圍第1項之厚膜電阻用組成物，其中， 在該氧化釕粉末與該玻璃中，該氧化釕粉末的比率為5質量%以上50質量%以下。The composition for thick film resistors according to claim 1, wherein the ratio of the ruthenium oxide powder in the ruthenium oxide powder to the glass is not less than 5% by mass and not more than 50% by mass. 根據申請專利範圍第1或第2項之厚膜電阻用組成物，其中， 該玻璃的50%體積累計粒度為5μm以下。The composition for thick film resistors according to claim 1 or 2, wherein the 50% volume cumulative particle size of the glass is 5 μm or less. 一種厚膜電阻用膏體， 其包含根據申請專利範圍第1至第3中的任一項之厚膜電阻用組成物及有機載體。A paste for thick film resistors, which includes the composition for thick film resistors according to any one of the first to third patent claims and an organic vehicle. 一種厚膜電阻， 其包含根據申請專利範圍第1至第3中的任一項之厚膜電阻用組成物。A thick-film resistor, which includes the composition for thick-film resistors according to any one of claims 1 to 3.
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