TWI686358B - Thick film resistor composition and thick film resistor paste containing same - Google Patents
Thick film resistor composition and thick film resistor paste containing same Download PDFInfo
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Abstract
本發明之課題在於提供可藉脈衝修整法有效率地調整厚膜電阻之電阻值的厚膜電阻組成物。 An object of the present invention is to provide a thick film resistor composition that can efficiently adjust the resistance value of a thick film resistor by a pulse trimming method.
本發明之解決手段為一種厚膜電阻組成物，係包含玻璃料與釕化合物粉末的電阻組成物，其特徵在於，上述玻璃料包含：軟化點為550℃以上且650℃以下的玻璃料LM、與顯示在較上述玻璃料LM之軟化點高出200℃以上且350℃以下之範圍內的高溫軟化點的玻璃料HM；相對於上述玻璃料LM與上述玻璃料HM的合計量，含有15質量%以上且50質量%以下的上述玻璃料LM；上述釕化合物粉末的比表面積粒徑為30nm以上且100nm以下。 The solution of the present invention is a thick film resistor composition comprising a glass frit and a ruthenium compound powder. The glass frit includes a glass frit LM having a softening point of 550°C or higher and 650°C or lower. Contains 15% by mass of glass frit HM showing a high-temperature softening point that is higher than the softening point of the glass frit LM by 200°C or more and 350°C or less; relative to the total amount of the glass frit LM and the glass frit HM % Or more and 50% by mass or less of the glass frit LM; the specific surface area particle diameter of the ruthenium compound powder is 30 nm or more and 100 nm or less.
Description
本案發明關於製作片式電阻或厚膜電阻基板、厚膜電阻加熱器等時使用的厚膜電阻組成物。 The present invention relates to a thick film resistor composition used when manufacturing a chip resistor, thick film resistor substrate, thick film resistor heater, or the like.
一般而言，片式電阻器或厚膜電阻、厚膜電阻加熱器等係例如將氧化鋁基板用於基板，將厚膜電極用於電極，將厚膜電阻或薄膜電阻用於電阻。此等電阻器根據其用途、特性而有各式各樣的種類，隨著裝置的小型化，電阻器相關零件的小型化亦急速發展。 In general, chip resistors, thick film resistors, thick film resistor heaters, and the like use, for example, alumina substrates for the substrates, thick film electrodes for the electrodes, and thick film resistors or thin film resistors for the resistors. There are various types of these resistors according to their uses and characteristics. With the miniaturization of devices, miniaturization of resistor-related parts has also been rapidly developed.
進而，片式電阻器的特性亦存在著例如耐電湧、可調節品、高精度品等各種製品。 Furthermore, characteristics of chip resistors include various products such as surge resistance, adjustable products, and high-precision products.
片式電阻器的電阻值之調整一般係藉由雷射光將厚膜電阻的一部分切除的雷射修整所進行。但是，以雷射修整所進行之電阻值調整，係在厚膜電阻的表面殘留切除痕跡。因此，作為不殘留切除痕跡的厚膜電阻的電阻值調整方法，有如藉由利用雷射照射而引起厚膜電阻之特性變化而降低電阻值的方法，或將脈衝電壓施加於厚膜電阻而降低電阻值的方法等。 The adjustment of the resistance value of the chip resistor is generally performed by laser trimming of a part of the thick film resistor by laser light. However, the adjustment of the resistance value by laser trimming leaves a cut mark on the surface of the thick film resistor. Therefore, as a method of adjusting the resistance value of the thick film resistor without leaving a cut mark, there is a method of reducing the resistance value by changing the characteristics of the thick film resistor by laser irradiation, or applying a pulse voltage to the thick film resistor to reduce Method of resistance value, etc.
此等藉由雷射引起特性變化的方法、或將脈衝電壓施加於厚膜電阻而降低電阻值的方法，係利用施加對厚膜電阻的外觀不致造成物理性破壞之程度的能量的雷射光或脈衝電壓而使電阻 值變低的調整方法。 These methods of changing characteristics by laser, or applying a pulse voltage to a thick film resistor to reduce the resistance value, use laser light or energy that can impart energy to the extent that the appearance of the thick film resistor does not cause physical damage The method of adjusting the resistance value by pulse voltage.
其中，將高電壓脈衝施加於厚膜電阻而降低電阻值的方法，作為脈衝修整法而為已知。在專利文獻1及2中揭示了有關脈衝修整法的技術。 Among them, a method of applying a high voltage pulse to a thick film resistor to reduce the resistance value is known as a pulse trimming method.
由於今後進一步之零件之小型化等，認為此種不伴隨物理性破壞之電阻值的調整方法將變得比目前更為必要。 Due to the further miniaturization of parts in the future, it is believed that this method of adjusting the resistance value without physical damage will become more necessary than at present.
專利文獻1：日本專利特開2002-067366號公報 Patent Document 1: Japanese Patent Laid-Open No. 2002-067366
專利文獻2：日本專利特開2002-127483號公報 Patent Document 2: Japanese Patent Laid-Open No. 2002-127483
然而，由於厚膜電阻組成物的組成不同，即使對得到的厚膜電阻採用脈衝修整法而嘗試電阻值調整，有時電阻值之調整、即電阻值的變化亦不充足。 However, due to the difference in the composition of the thick film resistor composition, even if a pulse trimming method is used to adjust the resistance value of the obtained thick film resistor, the adjustment of the resistance value, that is, the change in the resistance value may not be sufficient.
有鑒於此種狀況，本發明課題在於提供能夠藉由脈衝修整法有效率地調整厚膜電阻之電阻值的厚膜電阻組成物。 In view of this situation, an object of the present invention is to provide a thick film resistor composition that can efficiently adjust the resistance value of the thick film resistor by the pulse trimming method.
為了解決上述課題，發現可提供如下電阻糊，本申請發明人等遂完成本發明，該電阻糊為在導電材料中將二氧化釕粉末及玻璃料有機載體混合而成的電阻糊，藉由適當地調整為了滿足耐電湧特性而使軟化點較糊之燒成溫度高的玻璃料與為了在施加了脈衝電壓時得到適當之電阻變化量的厚膜電阻而使其軟化點較糊 之燒成溫度低的玻璃料與比表面積粒徑為30nm以上且100nm以下的釕化合物粉末的比率，從而同時具有耐電湧、耐脈衝特性的電阻糊。 In order to solve the above-mentioned problems, it was found that the following resistive paste can be provided, and the inventors of the present application have completed the present invention. The resistive paste is a resistive paste obtained by mixing ruthenium dioxide powder and a glass frit organic carrier in a conductive material. Adjust the glass frit whose softening point is higher than the firing temperature of the paste to meet the surge resistance characteristics and the thick film resistance to obtain an appropriate resistance change amount when the pulse voltage is applied, so that the softening point is higher than the firing temperature of the paste The low ratio of the glass frit to the ruthenium compound powder with a specific surface area particle diameter of 30 nm or more and 100 nm or less has a resistance paste with surge and pulse resistance characteristics.
本發明之第1發明為一種厚膜電阻組成物，其為包含玻璃料與釕化合物粉末的電阻組成物，其特徵在於，該玻璃料包含軟化點為550℃以上且650℃以下的玻璃料LM、及顯示在較該玻璃料LM之軟化點高出200℃以上且350℃以下之範圍內的高溫軟化點的玻璃料HM，相對於玻璃料LM與玻璃料HM的合計量，含有15質量%以上且50質量%以下的玻璃料LM，釕化合物粉末之比表面積粒徑為30nm以上且100nm以下。 The first invention of the present invention is a thick film resistor composition comprising a glass frit and a ruthenium compound powder. The glass frit includes a glass frit LM having a softening point of 550°C or higher and 650°C or lower. , And the glass frit HM showing a high temperature softening point higher than the softening point of the glass frit LM by 200°C or more and 350°C or less, relative to the total amount of the glass frit LM and the glass frit HM, contains 15% by mass For the glass frit LM of 50% by mass or more, the specific surface area particle diameter of the ruthenium compound powder is 30 nm or more and 100 nm or less.
本發明之第2發明為一種厚膜電阻組成物，其特徵在於，含有15質量%以上且35質量%以下之第1發明中之釕化合物粉末。 The second invention of the present invention is a thick film resistor composition characterized by containing the ruthenium compound powder in the first invention of 15% by mass or more and 35% by mass or less.
本發明之第3發明為一種厚膜電阻組成物，其特徵在於，第1及第2發明中之釕化合物粉末為二氧化釕粉末。 The third invention of the present invention is a thick film resistor composition, characterized in that the ruthenium compound powder in the first and second inventions is a ruthenium dioxide powder.
本發明之第4發明為一種厚膜電阻組成物，其特徵在於，第1至第3發明中之玻璃料之50%體積累積粒度為20μm以下。 The fourth invention of the present invention is a thick film resistor composition characterized in that the 50% volume cumulative particle size of the glass frit in the first to third inventions is 20 μm or less.
本發明之第5發明為一種厚膜電阻糊，其特徵在於，包含第1至第4發明中之厚膜電阻組成物、與使樹脂溶解於有機溶劑而成的載體。 The fifth invention of the present invention is a thick-film resistor paste, characterized by comprising the thick-film resistor composition of the first to fourth inventions and a carrier in which the resin is dissolved in an organic solvent.
根據本發明，可獲得較習知厚膜電阻組成物大的電阻變化量，利用脈衝對電阻值進行調整時能夠容易地得到電阻變化幅度大的電阻，極有助於調整作業的改善，發揮工業上顯著的效果。 According to the present invention, it is possible to obtain a larger amount of resistance change than the conventional thick-film resistor composition. When the resistance value is adjusted by pulses, a resistance with a large resistance change range can be easily obtained, which greatly contributes to the improvement of the adjustment work and exerts industrial significance. Effect.
圖1為表示實施例6中之施加電力與電阻值變化率之關係的圖。 FIG. 1 is a graph showing the relationship between the applied power and the resistance change rate in Example 6. FIG.
本發明之厚膜電阻組成物係包含玻璃料及釕化合物粉末的電阻組成物，該玻璃料之構成係包含顯示550℃以上且650℃以下之軟化點的玻璃料LM、與顯示在較該玻璃料LM之軟化點高出200℃以上且350℃以下之範圍內的高溫軟化點的玻璃料HM，相對於玻璃料LM及玻璃料HM的合計量，含有15質量%以上且50質量%以下的玻璃料LM。進而，釕化合物粉末的特徵在於，其比表面積粒徑為30nm以上且100nm以下；另外，作為釕化合物粉末，較佳為「二氧化釕粉末」。 The thick film resistor composition of the present invention is a resistor composition including a glass frit and a ruthenium compound powder. The composition of the glass frit includes a glass frit LM exhibiting a softening point of 550° C. or higher and 650° C. The glass frit HM whose softening point of the LM is higher than the high temperature softening point within the range of 200°C or more and 350°C or less contains 15% by mass or more and 50% by mass or less of the glass frit LM and the total amount of the glass frit HM料LM. Furthermore, the ruthenium compound powder is characterized by a specific surface area particle size of 30 nm or more and 100 nm or less; and the ruthenium compound powder is preferably "ruthenium dioxide powder".
使用上述厚膜電阻組成物，將厚膜電阻組成物與後述有機載體混練，能夠得到厚膜電阻糊。 Using the above-mentioned thick-film resistor composition, the thick-film resistor composition is kneaded with an organic vehicle described later, and a thick-film resistor paste can be obtained.
將該所得厚膜電阻糊在氧化鋁基板等陶瓷基板的表面進行印刷等，形成含有厚膜電阻組成物的印刷膜並進行燒成，可得到厚膜電阻。 The obtained thick film resistor paste is printed on the surface of a ceramic substrate such as an alumina substrate, etc., and a printed film containing a thick film resistor composition is formed and fired to obtain a thick film resistor.
以下針對各構成要素進行說明。 Each component will be described below.
本發明之厚膜電阻組成物中所使用的玻璃料，係由軟化點為550℃以上且650℃以下之軟化點較低的玻璃料LM、與顯示在較該玻璃料LM之軟化點高出200℃以上且350℃以下之範圍內的高溫軟化點的玻璃料HM的兩種玻璃料所構成。 The glass frit used in the thick film resistor composition of the present invention is composed of a glass frit LM having a lower softening point of 550°C or higher and 650°C or lower, and showing a higher softening point than the glass frit LM The glass frit HM of the high-temperature softening point within the range of 200°C or more and 350°C or less is composed of two kinds of frits.
其中，玻璃料之軟化點係設為：在較藉由示差熱分析法(TG-DTA)在大氣中以每分鐘10℃將玻璃料升溫、加熱而得到之示差熱曲線的最低溫側的表現示差熱曲線減少的溫度更高溫側，其次之表現示差熱曲線減少的峰的溫度。尚且，本發明中使用之玻璃料的軟化點可藉由玻璃料之成分組成進行調整。 Among them, the softening point of the glass frit is set as the performance at the lowest temperature side of the differential thermal curve obtained by heating and heating the glass frit at 10°C per minute in the atmosphere by differential thermal analysis (TG-DTA) The temperature on which the differential thermal curve decreases is on the higher temperature side, followed by the temperature of the peak where the differential thermal curve decreases. Furthermore, the softening point of the glass frit used in the present invention can be adjusted by the composition of the glass frit.
厚膜電阻係藉由將厚膜電阻組成物燒成而得到。得到厚膜電阻時的燒成溫度如後述般，為800℃至900℃，軟化點較低的玻璃料LM係在燒成過程中熔融，玻璃料HM雖未如玻璃料LM般但亦軟化。而且，在將厚膜電阻組成物燒成的過程中，形成在玻璃料LM經熔融的基體中玻璃料HM點狀存在的厚膜電阻的玻璃基體(LH)。 The thick film resistor is obtained by firing the thick film resistor composition. The firing temperature at the time of obtaining the thick film resistor is 800°C to 900°C as described later, and the glass frit LM having a low softening point melts during the firing process, and the glass frit HM is not softened like the glass frit LM. Furthermore, in the process of firing the thick film resistor composition, a glass substrate (LH) of thick film resistors in which dots of the glass frit HM exist in the matrix where the glass frit LM is melted is formed.
為了形成在該基體中使具有較形成該基體之玻璃料LM之軟化點高的軟化點的玻璃料HM點狀存在的玻璃基體(LH)，玻璃料LM的軟化點必須為550℃以上且650℃以下。 In order to form a glass matrix (LH) in which the glass frit HM having a softening point higher than the softening point of the glass frit LM forming the matrix exists in the form of a dot (LH), the softening point of the glass frit LM must be 550°C or more and 650 Below ℃.
另外，形成此種玻璃基體(LH)，係對藉由脈衝修整進行的電阻值調整、與屬於對最終得到的厚膜電阻瞬間施加了高電力時之耐久性的耐電湧性造成影響。即，在軟化點較低的玻璃料LM的軟化點未滿550℃時，則得到的厚膜電阻的耐電湧性劣化。另一方面，若玻璃料LM的軟化點超過650℃，根據與軟化點高的玻璃料HM的調配比例，有藉由脈衝修整等之玻璃基體(LH)的軟化不足、藉由脈衝修整進行之電阻值調整的幅度變窄的情形。 In addition, the formation of such a glass substrate (LH) affects the resistance value adjustment by pulse trimming and the surge resistance that is the durability when high power is applied to the finally obtained thick-film resistor instantaneously. That is, when the softening point of the glass frit LM having a low softening point is less than 550° C., the surge resistance of the obtained thick film resistor is deteriorated. On the other hand, if the softening point of the glass frit LM exceeds 650°C, depending on the blending ratio with the glass frit HM having a high softening point, there is insufficient softening of the glass substrate (LH) by pulse trimming, etc., which is performed by pulse trimming The case where the adjustment range of the resistance value becomes narrow.
另外，玻璃料HM需要較玻璃料LM之軟化點高出200℃以上且350℃以下之範圍內的高溫軟化點。即，軟化點較高的玻璃料HM的軟化點係在玻璃料LM的軟化點加上了200℃至350 ℃的溫度的軟化點。在玻璃料HM的軟化點較玻璃料LM的軟化點僅高出未滿200℃的情況下，有對於厚膜電阻的玻璃基體(LH)的溫度變得柔軟故耐電湧性劣化的情形；在玻璃料HM的軟化點較玻璃料LM的軟化點高出超過350℃的情況下，有藉由脈衝修整進行之電阻值的調整幅度變小的情形。 In addition, the glass frit HM needs to have a softening point higher than the glass frit LM by a high-temperature softening point within a range of 200° C. to 350° C. That is, the softening point of the glass frit HM having a high softening point is the softening point of the glass frit LM plus the temperature of 200°C to 350°C. In the case where the softening point of the glass frit HM is only less than 200°C higher than the softening point of the glass frit LM, the temperature of the glass substrate (LH) of the thick film resistor becomes soft and the surge resistance may deteriorate; When the softening point of the glass frit HM is higher than the softening point of the glass frit LM by more than 350°C, the adjustment range of the resistance value by pulse trimming may become smaller.
本發明之厚膜電阻組成物中的玻璃料LM及玻璃料HM的兩軟化點，由於對厚膜電阻的玻璃基體(LH)的軟化造成影響，因此對藉由脈衝修整法進行的電阻值調整造成影響。因此，在厚膜電阻組成物中，藉由使玻璃料及釕化合物粉末的調配比例適當化，而調整所得之厚膜電阻的電阻值。 Since the two softening points of the glass frit LM and the glass frit HM in the thick film resistor composition of the present invention affect the softening of the glass substrate (LH) of the thick film resistor, the resistance value adjustment by the pulse trimming method is performed Cause an impact. Therefore, in the thick film resistor composition, the resistance value of the obtained thick film resistor is adjusted by optimizing the blending ratio of the glass frit and the ruthenium compound powder.
電阻值高的厚膜電阻組成物係釕化合物粉末的調配比例減少，電阻值低的厚膜電阻組成物係釕化合物粉末的調配比例增加。作為該調配比例的結果，在藉由脈衝修整法進行調整電阻值的方法中，發現如下傾向：相同脈衝電壓之施加前後的電阻值的變化量，係電阻值超過3000Ω般之高電阻者容易變大，而3000Ω以下之低電阻則變小。 The proportion of the ruthenium compound powder of the thick film resistor composition system having a high resistance value decreases, and the proportion of the ruthenium compound powder of the thick film resistor composition system having a low resistance value increases. As a result of the blending ratio, in the method of adjusting the resistance value by the pulse trimming method, the following tendency was found: the amount of change in the resistance value before and after the application of the same pulse voltage is likely to change if the resistance value exceeds 3000Ω. Large, and low resistance below 3000Ω becomes smaller.
在該脈衝修整法中，認為由於脈衝電壓的能量，構成厚膜電阻的玻璃基體再熔融或再軟化，導致電阻值的變化，並認為藉由脈衝電壓的施加而構成厚膜電阻的玻璃基體的熔融容易度係與電阻域所造成的電阻值變化率的大小有關。 In this pulse trimming method, it is considered that due to the energy of the pulse voltage, the glass substrate constituting the thick film resistor is remelted or resoftened, resulting in a change in resistance value, and that the application of the pulse voltage constitutes the glass substrate constituting the thick film resistor The ease of melting is related to the magnitude of the resistance value change rate caused by the resistance domain.
另外，由於高電阻域的厚膜電阻中所含的玻璃的量較低電阻域的調配比例多，因此構成厚膜電阻的玻璃基體的再熔融或再軟化容易進行，高電阻域的藉由脈衝修整法進行的電阻值變化變大。另一方面，低電阻域的厚膜電阻西，由於玻璃量少且導電物質 的調配比高，因此構成厚膜電阻的玻璃基體的再熔融或再軟化難以進行，故藉由脈衝修整法進行的電阻值變化變小。 In addition, since the amount of glass contained in the thick film resistor in the high resistance domain is lower than that in the resistance domain, the glass matrix constituting the thick film resistor can be easily remelted or resoftened. The change in resistance value by the trimming method becomes larger. On the other hand, the thick film resistors in the low resistance domain have a small amount of glass and a high ratio of conductive materials. Therefore, it is difficult to remelt or re-soften the glass substrate that constitutes the thick film resistors. The change in resistance value becomes smaller.
因此，本發明中為了作成使低電阻域的厚膜電阻可藉由脈衝修整法容易調整電阻值的厚膜電阻組成物，必須相對於軟化點較低的玻璃料LM、與軟化點較高的玻璃料HM的合計量，包含15質量%至50質量%的玻璃料LM。 Therefore, in the present invention, in order to make a thick-film resistor composition that can easily adjust the resistance value by a pulse trimming method for a thick-film resistor in a low-resistance domain, it is necessary to compare the glass frit LM with a low softening point and the one with a high softening point The total amount of the glass frit HM includes 15% by mass to 50% by mass of the glass frit LM.
在全部玻璃料中依超過50質量%使用玻璃料LM的情況下，對於耐電湧變弱，藉由脈衝修整調整電阻值後的穩定性等惡化。耐電湧性的劣化係構成厚膜電阻的玻璃基體(LH)的軟化的影響。以提高厚膜電阻之耐電湧性為目的，為了調整玻璃基體(LH)的軟化，在厚膜電阻組成物中需要有顯示較基體高之軟化點的玻璃料HM。 When the glass frit LM is used in an amount of more than 50% by mass in all glass frits, the resistance to surges becomes weak, and the stability after adjusting the resistance value by pulse trimming deteriorates. The deterioration of surge resistance is influenced by the softening of the glass substrate (LH) constituting the thick film resistor. For the purpose of improving the surge resistance of thick film resistors, in order to adjust the softening of the glass substrate (LH), a glass frit HM showing a softening point higher than that of the substrate is required in the thick film resistor composition.
即，含有50質量%以上的軟化點較高的玻璃料HM。另一方面，全部玻璃料中的玻璃料LM的含有率未滿15質量%時，則玻璃料HM過多，藉由脈衝修整進行的電阻值調整的幅度變小。 That is, it contains glass frit HM with a high softening point of 50 mass% or more. On the other hand, when the content of the glass frit LM in all the glass frits is less than 15% by mass, the glass frit HM is too much, and the width of resistance value adjustment by pulse trimming becomes small.
玻璃料的化學組成一般大多含有金屬氧化物，其中大多含有PbO、SiO2、B2O3、BaO、CaO、Al2O3等。其中，本發明之厚膜電阻組成物中能夠使用的玻璃料的化學組成，若為硼矽酸鉛系玻璃、硼矽酸鋇系玻璃、硼矽酸鈣系玻璃、硼矽酸鋅系玻璃等玻璃系、顯示軟化點、為可調整的組成即可。 The chemical composition of the glass frit generally contains metal oxides, and most of them contain PbO, SiO 2 , B 2 O 3 , BaO, CaO, Al 2 O 3 and so on. Among them, if the chemical composition of the glass frit that can be used in the thick film resistor composition of the present invention is lead borosilicate glass, barium borosilicate glass, calcium borosilicate glass, zinc borosilicate glass, etc. The glass system and the display softening point can be adjusted compositions.
為了得到軟化點較低的玻璃料LM，以氧化物換算計，若增加PbO、BaO、CaO、ZnO2、B2O3、Na2O等鹼金屬氧化物的調配比例即可；為了得到軟化點較高的玻璃料HM時，若增加SiO2的調配比例即可。進而，由於各玻璃料的構成成分的調配比例，玻璃料的燒成物的熱膨脹係數變化，因此可適當調整與使用的 基板間的最優化。 In order to obtain glass frit LM with a low softening point, in terms of oxides, it is sufficient to increase the proportion of alkali metal oxides such as PbO, BaO, CaO, ZnO 2 , B 2 O 3 , and Na 2 O; in order to obtain softening When the glass frit HM is higher, it is sufficient to increase the blending ratio of SiO 2 . Furthermore, since the blending ratio of the constituent components of each glass frit changes the thermal expansion coefficient of the burnt material of the glass frit, it is possible to appropriately adjust the optimization with the substrate used.
另外，玻璃料亦作為使厚膜電阻密黏於基板的黏著材料發揮功能。因此，在將厚膜電阻組成物進行燒成時，基板與玻璃料必須黏著。因此，玻璃料的組成必須為能夠與氧化鋁等陶瓷基板黏著的組成。若為硼矽酸鉛系玻璃、硼矽酸鋇系玻璃、硼矽酸鈣系玻璃、硼矽酸鋅系玻璃，則在將厚膜電阻組成物進行燒成的過程中能夠與氧化鋁基板黏著。特別是本發明的厚膜電阻組成物中，與基板的黏著性係受到軟化點較低的玻璃料LM熔融性的影響較大。 In addition, the glass frit also functions as an adhesive material that closely adheres the thick film resistor to the substrate. Therefore, when firing the thick film resistor composition, the substrate and the glass frit must be adhered. Therefore, the composition of the glass frit must be a composition capable of being adhered to a ceramic substrate such as alumina. If it is lead borosilicate glass, barium borosilicate glass, calcium borosilicate glass, zinc borosilicate glass, it can adhere to the alumina substrate during the firing of the thick film resistor composition . In particular, in the thick film resistor composition of the present invention, the adhesion to the substrate is greatly affected by the meltability of the glass frit LM having a low softening point.
不論軟化點較高的玻璃料HM或軟化點較低的玻璃料LM，在厚膜電阻組成物中所含的玻璃料的50%體積累積粒度(D50)較佳為0.5~20μm，更佳為0.5~15μm，再更佳為0.5~6μm，最好於判別粉體的凝聚狀態等之下進行選擇。尚且，50%體積累積粒度(D50)為體積累積粒度分佈的中位值，50%體積累積粒度可藉由雷射繞射‧散射式粒度分佈測定裝置的Microtrac(註冊商標)進行測定。 Regardless of the glass frit HM with a higher softening point or the glass frit LM with a lower softening point, the 50% volumetric cumulative particle size (D 50 ) of the glass frit contained in the thick film resistor composition is preferably 0.5-20 μm, more preferably It is 0.5~15μm, and more preferably 0.5~6μm. It is best to select under the condition of judging the aggregation state of the powder. Moreover, the 50% volume cumulative particle size (D 50 ) is the median value of the volume cumulative particle size distribution. The 50% volume cumulative particle size can be measured by Microtrac (registered trademark) of a laser diffraction/scattering particle size distribution measuring device.
若玻璃料的50%體積累積粒度超過20μm，則厚膜電阻的表面粗糙度變粗，在形成了厚膜電阻加熱器的情況，有不能充分地傳熱的情形。另一方面，如果50%體積累積粒度未滿0.5μm，則需要對玻璃料進行過度的粉碎處理，因此玻璃料的生產性降低，有雜質等混入亦增加之虞。 If the 50% volume cumulative particle size of the glass frit exceeds 20 μm, the surface roughness of the thick film resistor becomes coarse, and in the case where the thick film resistor heater is formed, heat transfer may not be sufficient. On the other hand, if the 50% volume cumulative particle size is less than 0.5 μm, the glass frit needs to be subjected to excessive pulverization treatment, so the productivity of the glass frit is lowered, and there is a possibility that the mixing of impurities and the like may increase.
其次，厚膜電阻組成物中的釕化合物粉末係作為導電性成分發揮功能。 Next, the ruthenium compound powder in the thick film resistor composition functions as a conductive component.
在該釕化合物粉末中，可使用二氧化釕粉末、釕酸鉛粉末、釕 酸鍶粉末般之釕複合氧化物粉末。 As the ruthenium compound powder, ruthenium composite oxide powder such as ruthenium dioxide powder, lead ruthenate powder, and strontium ruthenate powder can be used.
釕化合物粉末的各粒子的形狀並無特別限定，可為球形、橢圓形、板狀、針狀等。 The shape of each particle of the ruthenium compound powder is not particularly limited, and may be spherical, elliptical, plate-like, needle-like, or the like.
厚膜電阻組成物中較佳係含有15質量%以上且35質量%以下的釕化合物粉末，更佳20質量%以上且35質量%以下，再更佳為25質量%以上且35質量%以下。 The thick film resistor composition preferably contains 15% by mass or more and 35% by mass or less of ruthenium compound powder, more preferably 20% by mass or more and 35% by mass or less, and even more preferably 25% by mass or more and 35% by mass or less.
在厚膜電阻組成物中，係藉由玻璃料與釕化合物粉末的調配比例調整所得厚膜電阻的電阻值。在厚膜電阻組成物中所含的釕化合物粉末的含有率未滿15質量%時，則電阻值過高。另一方面，若厚膜電阻組成物中所含的釕化合物粉末的含有率超過35質量%，則厚膜電阻的燒結面未變得緻密，因此無法確保厚膜電阻的機械強度。 In the thick film resistor composition, the resistance value of the obtained thick film resistor is adjusted by the blending ratio of the glass frit and the ruthenium compound powder. When the content rate of the ruthenium compound powder contained in the thick film resistor composition is less than 15% by mass, the resistance value is too high. On the other hand, if the content of the ruthenium compound powder contained in the thick film resistor composition exceeds 35% by mass, the sintered surface of the thick film resistor does not become dense, so the mechanical strength of the thick film resistor cannot be ensured.
另外，由本發明之厚膜電阻組成物得到的厚膜電阻中，係將釕化合物粉末分散於上述玻璃基體(LH)中，依釕化合物粒子之型式存在而形成導電網路。 In addition, in the thick film resistor obtained from the thick film resistor composition of the present invention, a ruthenium compound powder is dispersed in the above-mentioned glass matrix (LH), and a conductive network is formed according to the type of ruthenium compound particles.
於使用脈衝修整法的電阻值調整時，認為藉由對於厚膜電阻施加脈衝電壓，由於其玻璃基體(LH)的再熔融、再軟化，釕化合物粒子存在的位置變化，釕化合物粒子的距離縮短等，進行導電網路的再建構。考慮此種脈衝修整性，選擇釕化合物粉末的比表面積粒徑。 When adjusting the resistance value using the pulse trimming method, it is believed that by applying a pulse voltage to the thick film resistor, the position of the ruthenium compound particles changes due to the remelting and resoftening of the glass matrix (LH), and the distance of the ruthenium compound particles is shortened Wait for the reconstruction of the conductive network. In consideration of such pulse dressability, the specific surface area particle size of the ruthenium compound powder is selected.
更具體地進行說明，釕化合物粉末的平均粒徑係由比表面積粒徑表示，為30nm以上且100nm以下。若釕化合物粉末的比表面積粒徑未滿30nm，有對厚膜電阻進行了脈衝修整時的電阻值變化率少的情況，電阻值的調整困難。其原因尚不明，但認為若釕化合物粉末的比表面積粒徑未滿30nm，則施加了脈衝電壓的厚膜電阻的玻璃基體的再熔融所造成的導電網路之再建構的規模較 小。 More specifically, the average particle size of the ruthenium compound powder is represented by the specific surface area particle size, and is 30 nm or more and 100 nm or less. If the specific surface area particle size of the ruthenium compound powder is less than 30 nm, there may be a small rate of change in the resistance value when the thick film resistor is subjected to pulse trimming, and adjustment of the resistance value is difficult. The reason for this is not clear, but if the specific surface area particle size of the ruthenium compound powder is less than 30 nm, the scale of the reconstruction of the conductive network caused by the remelting of the glass substrate of the thick film resistor to which the pulse voltage is applied is small.
另一方面，若釕化合物粉末的比表面積粒徑超過100nm，則有厚膜電阻的表面粗糙度變大的情形，而有不適於發熱電阻的情形。 On the other hand, if the specific surface area particle diameter of the ruthenium compound powder exceeds 100 nm, the surface roughness of the thick film resistor may become large, and it may not be suitable for the heating resistor.
比表面積粒徑可使用下述(1)式求得。另外，釕化合物粉末的比表面積可採用BET法測定。 The specific surface area particle size can be obtained using the following formula (1). In addition, the specific surface area of the ruthenium compound powder can be measured by the BET method.
[數1]D[nm]=6×103/(ρ‧S)‧‧‧(1) [Number 1] D[nm]=6×10 3 /( ρ ‧S)‧‧‧(1)
其中，D為釕化合物粉末的比表面積粒徑[nm]，ρ為釕化合物粉末的密度[g/cm3]，S為釕化合物粉末的比表面積[m2/g]。若於釕化合物粉末中使用二氧化釕粉末，則ρ可設為7.05[g/cm3]。 Where D is the specific surface area particle size [nm] of the ruthenium compound powder, ρ is the density [g/cm 3 ] of the ruthenium compound powder, and S is the specific surface area [m 2 /g] of the ruthenium compound powder. If ruthenium dioxide powder is used as the ruthenium compound powder, ρ can be set to 7.05 [g/cm 3 ].
於釕化合物較佳係使用二氧化釕。此係由於二氧化釕之電阻率較釕酸鉛等釕複合氧化物小，適合於實現低電阻域的厚膜電阻的電阻值50Ω~3000Ω的範圍。在藉由厚膜電阻作成發熱電阻的情況，考慮到脈衝修整性或所得厚膜電阻的消耗電力，較佳係使厚膜電阻的電阻值成為50Ω~1000Ω。 The ruthenium compound is preferably ruthenium dioxide. This is because the resistivity of ruthenium dioxide is smaller than that of ruthenium composite oxides such as lead ruthenate, and it is suitable for realizing the resistance value of the thick film resistors in the low resistance domain in the range of 50Ω to 3000Ω. In the case where the heating resistance is formed by the thick film resistor, the resistance value of the thick film resistor is preferably 50Ω to 1000Ω in consideration of the pulse trimming property or the power consumption of the obtained thick film resistor.
本發明之厚膜電阻組成物含有軟化點不同的2種玻璃料、即軟化點較低的玻璃料LM及軟化點較其高的玻璃料HM，並進一步含有釕化合物。另外，在厚膜電阻組成物中亦可添加具有調整屬於厚膜電阻之電特性之一的電阻溫度係數等效果的公知的TiO2粉末等。 The thick film resistor composition of the present invention contains two kinds of glass frit having different softening points, namely, glass frit LM having a lower softening point and glass frit HM having a higher softening point, and further contains a ruthenium compound. In addition, a well-known TiO 2 powder or the like having an effect of adjusting the temperature coefficient of resistance, which is one of the electrical characteristics of the thick film resistor, may be added to the thick film resistor composition.
本發明中使用的有機載體不需為特定載體，可為製造厚膜電阻糊時一般使用的載體。較佳係在乾燥及燒成時之脫黏著劑時揮發、分解而消失者。可使用下述的有機溶劑、例如乙基纖維素、硝基纖維素等纖維素系樹脂、丙烯酸系樹脂等樹脂。 The organic carrier used in the present invention does not need to be a specific carrier, but may be a carrier generally used when manufacturing a thick film resistor paste. It is preferably one that volatilizes, decomposes, and disappears when the debinding agent is dried and fired. The following organic solvents, for example, cellulose-based resins such as ethyl cellulose and nitrocellulose, and resins such as acrylic resins can be used.
可將此等樹脂溶解於萜品醇等萜烯醇類、薴烯等萜烯類、丁基卡必醇乙酸酯或丁基賽珞蘇乙酸酯等醚類等有機溶劑中者使用作為有機載體。為了厚膜電阻糊的粘度調整，可進一步添加萜品醇等有機溶劑。 These resins can be used in organic solvents such as terpene alcohols such as terpineol, terpenes such as tulene, ethers such as butyl carbitol acetate or butylcellulose acetate, etc. Organic carrier. To adjust the viscosity of the thick film resistor paste, an organic solvent such as terpineol may be further added.
另外，為了使厚膜電阻組成物分散於載體中，可添加具有羧基或胺基的高分子分散劑、硬脂酸等脂肪酸、卵磷脂等磷脂質類作為分散劑。 In addition, in order to disperse the thick film resistor composition in the carrier, a polymer dispersant having a carboxyl group or an amine group, fatty acids such as stearic acid, and phospholipids such as lecithin may be added as a dispersant.
較佳係使二氧化釕粉末、玻璃料、有機載體、有機溶劑均勻地分散。其方法並無限定，但較佳係公知之三輥研磨機的分散方法。 Preferably, the ruthenium dioxide powder, glass frit, organic vehicle, and organic solvent are uniformly dispersed. The method is not limited, but it is preferably a known three-roll mill dispersion method.
將所得之厚膜電阻糊，藉由網版印刷在氧化鋁等陶瓷基板上印刷厚膜電阻圖案，經過乾燥及燒成，可形成厚膜電阻。 The obtained thick film resistor paste is printed on a ceramic substrate such as alumina by screen printing, and then dried and fired to form a thick film resistor.
燒成條件可設為：在大氣中峰值溫度800℃至900℃下，該峰值溫度的保持時間為5分鐘至60分鐘，另外，將從室溫至峰值溫度的升溫時間設為5分鐘至60分鐘，在峰值溫度保持結束後，冷卻到室溫。在燒成過程的升溫時，進行將厚膜電阻糊的印刷膜中殘留的有機溶劑、樹脂成分除去的脫黏著劑處理。 The firing conditions can be set as follows: at a peak temperature of 800°C to 900°C in the atmosphere, the retention time of the peak temperature is 5 minutes to 60 minutes, and the temperature increase time from room temperature to the peak temperature is set to 5 minutes to 60 In minutes, after the peak temperature is maintained, cool to room temperature. At the temperature increase in the firing process, a de-tackifier treatment is performed to remove the organic solvent and resin components remaining in the printed film of the thick-film resistor paste.
在峰值溫度800℃至900℃下燒成的厚膜電阻，係調整為膜厚5μm~20μm，更佳膜厚為10μm~15μm。 The thick film resistor fired at a peak temperature of 800°C to 900°C is adjusted to a film thickness of 5 μm to 20 μm, and more preferably a film thickness of 10 μm to 15 μm.
進而，厚膜電阻係以可在600℃左右之燒成溫度進行燒成的玻璃糊被覆其表面，將該玻璃糊燒成而作成厚膜電阻的保護膜，藉此可製成具有保護膜的厚膜電阻器。藉由如此在厚膜電阻的表面配置由玻璃糊所形成的保護膜，可使厚膜電阻器的表面平滑。 Further, the thick film resistor is coated with a glass paste that can be fired at a firing temperature of about 600°C, and the glass paste is fired to form a protective film for the thick film resistor, whereby a protective film with a protective film can be made Thick film resistors. By disposing the protective film formed of glass paste on the surface of the thick film resistor in this way, the surface of the thick film resistor can be smoothed.
尚且，在厚膜電阻的形成之前，可採用公知的厚膜技術在陶瓷基板的表面形成成為厚膜電阻之端子的電極。 Furthermore, before the formation of the thick film resistor, a well-known thick film technique may be used to form an electrode that becomes a terminal of the thick film resistor on the surface of the ceramic substrate.
藉由脈衝修整法對燒成所得之厚膜電阻的電阻值進行調整。 The resistance value of the thick film resistor obtained by firing is adjusted by the pulse trimming method.
具體而言，將1000V~6000V的脈衝電壓施加於厚膜電阻，施加脈衝電壓直至成為既定的電阻值。施加電壓可根據厚膜電阻的電阻值而適當地選擇。逐次施加脈衝電壓1000V~6000V，相對於施加前的電阻值，在施加後的電阻值的變化率小於-40%的情況，有效率的電阻值調整困難。 Specifically, a pulse voltage of 1000 V to 6000 V is applied to the thick film resistor, and the pulse voltage is applied until it reaches a predetermined resistance value. The applied voltage can be appropriately selected according to the resistance value of the thick film resistor. When the pulse voltage is sequentially applied from 1000V to 6000V, relative to the resistance value before application, when the rate of change of the resistance value after application is less than -40%, it is difficult to adjust the resistance value efficiently.
以下根據實施例具體說明本發明，但本發明並不限定於此等實施例。 The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.
將本發明的實施例及比較例中使用的玻璃料的組成示於表1中。玻璃料(A)及(B)為軟化點較高的玻璃料HM，玻璃料(C)為軟化點較低的玻璃料LM。 Table 1 shows the composition of the glass frit used in Examples and Comparative Examples of the present invention. The glass frits (A) and (B) are glass frits HM with a high softening point, and the glass frit (C) are glass frits LM with a low softening point.
玻璃料(A)係軟化點為856℃、50%體積累積粒度(D50)為3.6μm，玻璃料(B)係將玻璃料(A)以球磨機粉碎、50%體積累積粒度 (D50)為1.4μm，玻璃料(C)係軟化點為640℃、50%體積累積粒度(D50)為1.5μm。各玻璃料的50%體積累積粒度(D50)的測定係使用MicrotracBEL公司製的Microtrac(註冊商標)進行。 The glass frit (A) has a softening point of 856°C and a 50% volume cumulative particle size (D 50 ) of 3.6 μm. The glass frit (B) is a glass frit (A) crushed by a ball mill and has a 50% volume cumulative particle size (D 50 ) It is 1.4 μm, and the glass frit (C) system has a softening point of 640° C. and a 50% volume cumulative particle size (D 50 ) of 1.5 μm. The 50% volume cumulative particle size (D 50 ) of each glass frit was measured using Microtrac (registered trademark) manufactured by MicrotracBEL.
於釕化合物粉末使用二氧化釕，使用藉BET法測定的比表面積粒徑為24nm(比表面積35m2/g)的二氧化釕粉末(A)、比表面積粒徑為40nm(比表面積21.5m2/g)的二氧化釕粉末(B)及比表面積粒徑為73nm(比表面積11.6m2/g)的二氧化釕粉末(C)。 Ruthenium dioxide was used for the ruthenium compound powder, and the ruthenium dioxide powder (A) with a specific surface area particle size measured by BET method of 24 nm (specific surface area 35 m 2 /g) and a specific surface area particle size of 40 nm (specific surface area 21.5 m 2 /g) ruthenium dioxide powder (B) and ruthenium dioxide powder (C) having a specific surface area particle size of 73 nm (specific surface area 11.6 m 2 /g).
相對於萜品醇的組成75質量%，添加乙基纖維素25質量%，於藉由氣動馬達攪拌下加熱至60℃、進行分散，製作有機載體。 Relative to the composition of terpineol at 75% by mass, ethyl cellulose was added at 25% by mass, and the mixture was heated to 60° C. with stirring by an air motor to disperse, and an organic vehicle was produced.
接著，於由表2及表3中所示比例的二氧化釕粉末及玻璃料所構成的厚膜電阻組成物100重量份中，加入表2及表3之重量份的有機載體與溶劑，進而視需要加入溶劑的萜品醇，使用三輥研磨機進一步混練，製作實施例1至6及比較例1至7的厚膜電阻糊。 Next, to 100 parts by weight of the thick film resistor composition composed of ruthenium dioxide powder and glass frit in the ratios shown in Table 2 and Table 3, the organic carrier and the solvent by weight parts of Table 2 and Table 3 were added, and The terpineol, which is added with a solvent as necessary, is further kneaded using a three-roll mill to prepare thick film resistor pastes of Examples 1 to 6 and Comparative Examples 1 to 7.
使用所製作的厚膜電阻糊，在藉厚膜法設置了銀電極的1吋氧化鋁基板印刷各實施例與各比較例的厚膜電阻糊，在大氣中依120℃乾燥後，依峰值溫度及其保持時間為810℃、9分鐘的條件，以帶式爐進行燒成，得到厚膜電阻。於帶式爐的升溫、峰值溫度保持、降溫所需的總時間合計設為30分鐘。厚膜電阻的尺寸係 長(電極間距離)0.3mm、寬0.3mm，膜厚大致調整為12μm。尚且，銀電極係將銀電極糊印刷於氧化鋁基板，於120℃乾燥5分鐘，在峰值溫度850℃下燒成9分鐘而設置。從帶式爐之入口至出口的時間設為30分鐘。 Using the prepared thick-film resistor paste, the thick-film resistor pastes of each example and each comparative example were printed on a 1-inch alumina substrate provided with a silver electrode by the thick-film method, dried at 120°C in the atmosphere, and then subjected to peak temperature With a holding time of 810°C and 9 minutes, firing was carried out in a belt furnace to obtain a thick film resistor. The total time required to raise the temperature, maintain the peak temperature, and lower the temperature of the belt furnace is 30 minutes. The thickness of the thick film resistor is 0.3 mm in length (distance between electrodes) and 0.3 mm in width, and the film thickness is adjusted to approximately 12 m. In addition, the silver electrode system was set by printing a silver electrode paste on an alumina substrate, drying at 120°C for 5 minutes, and firing at a peak temperature of 850°C for 9 minutes. The time from the entrance to the exit of the belt furnace was set at 30 minutes.
藉數位萬用表(KEITHLEY公司製、Model2001 Multimeter)測定所得厚膜電阻25個的電阻值。另外，電阻值變化率係對厚膜電阻依脈衝電壓1000V、1500V、2000V、2500V、3000V的順序各電壓施加1秒，由電壓施加前的電阻值與直至脈衝電壓3000V的電壓施加後的電阻值之差及電壓施加前的電阻值計算電阻值變化率。在實施例及比較例中表示電阻值變化率的最大值。 The resistance value of 25 thick-film resistors was measured with a digital multimeter (manufactured by Keithley, Model 2001 Multimeter). In addition, the resistance value change rate is applied to the thick film resistance in the order of pulse voltage 1000V, 1500V, 2000V, 2500V, 3000V for 1 second, from the resistance value before voltage application and the resistance value up to pulse voltage 3000V after voltage application The difference and the resistance value before voltage application calculate the resistance value change rate. In Examples and Comparative Examples, the maximum value of the resistance value change rate is shown.
進而，對實施例6的厚膜電阻5個，施加從1W至10W的電力，計算與初期電阻值的變化率，確認耐電湧特性。 Furthermore, power was applied to 5 thick film resistors of Example 6 from 1 W to 10 W, and the rate of change from the initial resistance value was calculated to confirm the surge resistance characteristics.
其結果係將實施例的結果示於表2中，將比較例的結果示於表3中。 As a result, the results of the examples are shown in Table 2, and the results of the comparative examples are shown in Table 3.
如實施例1~3般使用比表面積為11.6m2/g之二氧化釕粉末(C)的電阻糊，電阻值調整的幅度(電阻值變化率)的絕對值成為50%以上，獲得較大值。實施例4~6雖使用比表面積為21.5m2/g的二氧化釕粉末(B)，但此情況下電阻值調整的幅度(電阻值變化率)的絕對值亦均成為50%以上。 As in Examples 1 to 3, a resistance paste of ruthenium dioxide powder (C) with a specific surface area of 11.6 m 2 /g was used, and the absolute value of the resistance adjustment range (resistance value change rate) became 50% or more, which was large value. Although the ruthenium dioxide powder (B) having a specific surface area of 21.5 m 2 /g was used in Examples 4 to 6, in this case, the absolute value of the width of the resistance value adjustment (resistance value change rate) also became 50% or more.
比較例1表示習知組成中的電阻值變化率的結果，組成係將比表面積粒徑24nm(比表面積35m2/g)的二氧化釕粉末(A)與將玻璃料(A)以球磨機粉碎而成的玻璃料(B)及有機載體。 Comparative Example 1 shows the result of the change rate of the resistance value in the conventional composition. The composition system is to crush the ruthenium dioxide powder (A) with a specific surface area particle diameter of 24 nm (specific surface area 35 m 2 /g) and the glass frit (A) by a ball mill. The resulting glass frit (B) and organic vehicle.
由其脈衝電壓之施加前後的電阻值所求得的電阻值調整的幅度(電阻值變化率)的絕對值為34.2%，為較本發明之實施例小的結果。 The absolute value of the amplitude (resistance value change rate) of the resistance value adjustment obtained from the resistance values before and after the application of the pulse voltage is 34.2%, which is a result smaller than that of the embodiment of the present invention.
另外，在玻璃料中僅使用了未粉碎的粒徑大的玻璃料(A)的比較例2至6的電阻值變化率為些微(比較例2)、或者未變化(比較例3-5)，即使是降低的比較例6亦為-26.0%，與本發明之實施例相比，其絕對值小，而為電阻值變化率小的結果。 In addition, the change rate of the resistance value of Comparative Examples 2 to 6 in which only the unfractionated glass frit (A) having a large particle size is used for the glass frit is slight (Comparative Example 2) or unchanged (Comparative Examples 3-5) Even in the case of the lowered comparative example 6, it is -26.0%. Compared with the embodiment of the present invention, the absolute value is small, but the resistance value change rate is small.
進而，如比較例7所示般單獨使用了經粉碎的軟化點856℃的玻璃料(B)的情況下，並未獲得大的電阻值變化率。 Furthermore, when the ground glass frit (B) with a softening point of 856° C. was used alone as shown in Comparative Example 7, a large resistance value change rate was not obtained.
圖1中表示實施例6之情況的厚膜電阻的SST(級增應力試驗，Step Stress Test)時的施加電力與電阻值變化率的關係。 FIG. 1 shows the relationship between the applied power and the rate of change of the resistance value during the SST (Step Stress Test) of the thick film resistor in the case of Example 6.
相對於施加電力，於負區域中電阻值變化率並無變化。於負區域中電阻值變化率發生變化的情況，可預設為由於玻璃與導電填料等不均勻所造成的影響，但實施例6中於負區域中電阻值變化率不變化而為較習知物毫不遜色的結果。 The rate of change of resistance value in the negative region does not change relative to the application of power. In the case where the rate of change of the resistance value in the negative region changes, it can be preset to be caused by the unevenness of the glass and the conductive filler, etc., but in Example 6, the rate of change of the resistance value in the negative region does not change, which is more common The results are not inferior.
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| KR101958496B1 (en) * | 2011-06-21 | 2019-03-14 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Ruthenium Oxide Powder, Composition for Thick film Resistor Elements Using Same, and Thick film Resistor Element |
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| CN1111798A (en) * | 1993-06-07 | 1995-11-15 | 纳幕尔材邦公司 | Thick film resistor composition |
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