TWI798061B - Lead-free thick film resistor composition and lead-free thick film resistor - Google Patents
Lead-free thick film resistor composition and lead-free thick film resistor Download PDFInfo
- Publication number
- TWI798061B TWI798061B TW111114789A TW111114789A TWI798061B TW I798061 B TWI798061 B TW I798061B TW 111114789 A TW111114789 A TW 111114789A TW 111114789 A TW111114789 A TW 111114789A TW I798061 B TWI798061 B TW I798061B
- Authority
- TW
- Taiwan
- Prior art keywords
- lead
- thick film
- film resistor
- free thick
- weight
- Prior art date
Links
Landscapes
- Non-Adjustable Resistors (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Glass Compositions (AREA)
Abstract
本發明提供一種無鉛厚膜電阻組成物，其包含二氧化釕、一硼矽酸系玻璃、一添加成分、一有機載體以及一溶劑；其中，該添加成分包含一氧化銅或一氧化銅以及一選自由二氧化鈦、二氧化矽、五氧化二釩及其組合所組成的氧化物。以本發明之無鉛厚膜電阻組成物所製成之無鉛厚膜電阻係能夠在具有廣域電阻值的同時，仍具有電阻溫度係數介於±100 ppm/℃間的特性。The present invention provides a lead-free thick film resistor composition, which comprises ruthenium dioxide, a borosilicate glass, an additive component, an organic vehicle and a solvent; wherein, the additive component comprises copper oxide or copper oxide and a Oxides selected from titanium dioxide, silicon dioxide, vanadium pentoxide and combinations thereof. The lead-free thick-film resistor made of the lead-free thick-film resistor composition of the present invention can not only have a wide-range resistance value, but also have the characteristic of a temperature coefficient of resistance between ±100 ppm/°C.
Description
本發明係關於一種電阻組成物及電阻，尤指一種無鉛厚膜電阻組成物及無鉛厚膜電阻。The invention relates to a resistance composition and resistance, especially to a lead-free thick-film resistance composition and a lead-free thick-film resistance.
厚膜電阻係指厚度約為10微米(μm)至15 μm的電阻，其可藉由將漿料或糊料形態之厚膜電阻組成物印刷於具電極之絕緣陶瓷基板上，再經過鍛燒而製得，並且能廣泛應用於如晶片電阻器、混合積體電路或電阻網路等電子元件中。Thick film resistors refer to resistors with a thickness of about 10 microns (μm) to 15 μm, which can be printed by printing a thick film resistor composition in the form of a paste or paste on an insulating ceramic substrate with electrodes, and then calcined and can be widely used in electronic components such as chip resistors, hybrid integrated circuits or resistor networks.
一般而言，厚膜電阻組成物以導電粒子及玻璃作為主要成分，其中，導電粒子多選擇具金屬導電性的釕系氧化物，如金紅石型(rutile)結晶構造的二氧化釕(RuO 2)、焦綠石型(pyrochlore)的釕酸鉛(Pb 2Ru 2O 7)和釕酸鉍(BiRu 2O 7)或鈣鈦礦型(perovskite)的釕系鹼土金屬複合氧化物等；而玻璃則多選擇含有氧化鉛(PbO)的玻璃，從而獲得軟化溫度低、流動性好以及使導電粒子潤濕性佳等優點。當厚膜電阻組成物含有釕系氧化物與玻璃之組成時，除了在大氣環境下即可進行鍛燒製成厚膜電阻外，還可透過調整釕系氧化物與玻璃的組成比例以改變電阻值，並獲得廣域之電阻值範圍，同時也能夠使電阻溫度係數(temperature coefficient of resistance，TCR)接近於0，據此能夠應用於廣泛規格的電阻器中。 Generally speaking, the thick film resistor composition mainly uses conductive particles and glass as the main components. Among them, the conductive particles mostly choose ruthenium-based oxides with metal conductivity, such as ruthenium dioxide (RuO 2 ) with a rutile crystal structure. ), pyrochlore-type lead ruthenate (Pb 2 Ru 2 O 7 ) and bismuth ruthenate (BiRu 2 O 7 ) or perovskite-type (perovskite) ruthenium-based alkaline earth metal composite oxides, etc.; and As for the glass, the glass containing lead oxide (PbO) is mostly selected, so as to obtain the advantages of low softening temperature, good fluidity, and good wettability of conductive particles. When the thick film resistor composition contains ruthenium-based oxide and glass, in addition to being calcined in the atmosphere to form a thick-film resistor, the resistance can also be changed by adjusting the composition ratio of ruthenium-based oxide and glass. value, and a wide range of resistance values can be obtained, and at the same time, it can also make the temperature coefficient of resistance (temperature coefficient of resistance, TCR) close to 0, so that it can be applied to resistors with a wide range of specifications.
電阻溫度係數是電阻器的重要特性之一，其代表電阻值隨著溫度變化而改變的比例，由於電子元件運作中會產生熱能造成溫度變化，因此商用電阻器一般會規範電阻溫度係數需介於-100 ppm/℃至+100 ppm/℃之間，而當調整厚膜電阻組成物中釕系氧化物與玻璃的比例時，會同時改變電阻值以及電阻溫度係數。一般來說，釕系氧化物會使電阻值降低、使電阻溫度係數朝向正值方向改變；而玻璃則會使電阻值增加、使電阻溫度係數朝向負值方向改變，因此，在希望獲得電阻值降低之結果時，會使釕系氧化物比例增加、玻璃比例降低，而此時電阻溫度係數會往正值方向改變，反之則使釕系氧化物比例降低、玻璃比例增加，此時電阻溫度係數則會往負值方向改變，並且能獲得電阻值升高的結果。The temperature coefficient of resistance is one of the important characteristics of a resistor. It represents the ratio of the resistance value to change with temperature. Since electronic components will generate heat energy during operation to cause temperature changes, commercial resistors generally specify that the temperature coefficient of resistance needs to be between Between -100 ppm/°C and +100 ppm/°C, when adjusting the ratio of ruthenium oxide and glass in the thick film resistor composition, the resistance value and the temperature coefficient of resistance will be changed at the same time. Generally speaking, ruthenium-based oxides will reduce the resistance value and change the temperature coefficient of resistance toward a positive value; while glass will increase the resistance value and change the temperature coefficient of resistance toward a negative value. Therefore, when you want to obtain a resistance value As a result, the proportion of ruthenium-based oxides will increase and the proportion of glass will decrease. At this time, the temperature coefficient of resistance will change to a positive value. On the contrary, the proportion of ruthenium-based oxides will decrease and the proportion of glass will increase. At this time, the temperature coefficient of resistance It will change to a negative value, and the result of increasing the resistance value can be obtained.
不過，在片電阻值提高至約100 kΩ/□以上之高電阻值區域的情況下，會衍生出釕系氧化物比例偏低，造成導電網絡不易在玻璃中均勻形成，並且容易使電阻溫度係數過度往負值方向移動而低於-100 ppm/℃，無法符合商用規格的要求。對此，以往業界係採用電阻率較二氧化釕高的釕酸鉛或其他釕系複合氧化物作為導電粒子，以克服前述問題。然而，隨著近年來對於避免人體健康與環境危害的意識逐漸提高，各國紛紛要求電子製品中禁用有害物質，因此成分中包含釕酸鉛與含鉛玻璃的厚膜電阻逐漸消失於商用市場。However, when the sheet resistance value increases to about 100 kΩ/□ and above the high resistance value region, the proportion of ruthenium oxides is low, which makes it difficult for the conductive network to form uniformly in the glass, and it is easy to make the temperature coefficient of resistance Excessively moving in the negative direction and lower than -100 ppm/°C cannot meet the requirements of commercial specifications. In this regard, in the past, the industry used lead ruthenate or other ruthenium-based composite oxides with a higher resistivity than ruthenium dioxide as conductive particles to overcome the aforementioned problems. However, as the awareness of avoiding human health and environmental hazards has gradually increased in recent years, countries have requested that harmful substances be banned in electronic products. Therefore, thick film resistors containing lead ruthenate and lead glass have gradually disappeared in the commercial market.
至於前述不含鉛的釕系複合氧化物，其則具有在鍛燒過程中容易與玻璃或基板反應而分解還原為二氧化釕，造成電阻值下降的問題。針對此問題，US 7,476,342 B2公開一種電阻組成物，其藉由控制無鉛玻璃的組成成分以調整玻璃鹼度，進而抑制釕系複合氧化物的還原，並以析出玻璃結晶的方式安定導電網絡而獲得高於約100 kΩ/□以上之片電阻值，然而，所述玻璃結晶在鍛燒過程中不易控制其生長，而使得電阻值難以穩定控制，且其內容中並未探討所述玻璃結晶對於電阻溫度係數的影響。As for the aforementioned lead-free ruthenium-based composite oxide, it easily reacts with the glass or the substrate during the sintering process and is decomposed and reduced to ruthenium dioxide, resulting in a decrease in resistance value. To solve this problem, US 7,476,342 B2 discloses a resistance composition, which is obtained by controlling the composition of lead-free glass to adjust the glass alkalinity, thereby inhibiting the reduction of ruthenium-based composite oxides, and stabilizing the conductive network by precipitating glass crystals. The sheet resistance value is higher than about 100 kΩ/□. However, the growth of the glass crystals is difficult to control during the firing process, making it difficult to control the resistance value stably, and the content does not discuss the impact of the glass crystals on the resistance The effect of temperature coefficient.
據此，由於厚膜電阻朝向無鉛化發展，且釕系複合氧化物穩定性不佳，目前業界仍有待發展出一種無鉛厚膜電阻，具有在廣域片電阻值，甚至是高於約100 kΩ/□以上之高片電阻值的區域，仍然能夠具有電阻溫度係數介於±100 ppm/℃間的特性。Accordingly, due to the development of thick-film resistors towards lead-free and the poor stability of ruthenium-based composite oxides, the industry still needs to develop a lead-free thick-film resistor with a wide-area sheet resistance value, even higher than about 100 kΩ The region of high sheet resistance above /□ can still have the characteristic of the temperature coefficient of resistance between ±100 ppm/℃.
有鑑於上述現有技術所面臨的問題，本發明之一目的在於提供一種無鉛厚膜電阻組成物，其係以二氧化釕作為導電粒子，並且能夠用於製作具有約0.5 kΩ/□至約1100 kΩ/□之廣域片電阻值的無鉛厚膜電阻，且同時仍具有電阻溫度係數介於±100 ppm/℃間的特性。In view of the problems faced by the above-mentioned prior art, one object of the present invention is to provide a lead-free thick film resistor composition, which is based on ruthenium dioxide as conductive particles, and can be used to make It is a lead-free thick-film resistor with a wide-area sheet resistance value of /□, and still has the characteristics of a temperature coefficient of resistance between ±100 ppm/℃.
本發明之另一目的在於提供一種無鉛厚膜電阻組成物，其係以二氧化釕作為導電粒子，並且能夠用於製作具有約100 kΩ/□以上之高片電阻值的無鉛厚膜電阻，且同時仍具有電阻溫度係數介於±100 ppm/℃間的特性。Another object of the present invention is to provide a kind of lead-free thick-film resistor composition, and it is to use ruthenium dioxide as conductive particle, and can be used for making the lead-free thick-film resistor with high sheet resistance value above about 100 kΩ/□, and At the same time, it still has the characteristic that the temperature coefficient of resistance is between ±100 ppm/°C.
為了達成前述目的，本發明提供一種無鉛厚膜電阻組成物，其包含二氧化釕、一硼矽酸系玻璃、一添加成分、一有機載體以及一溶劑；其中，該添加成分包含一氧化銅(CuO)或一氧化銅以及一選自由二氧化鈦(TiO 2)、二氧化矽(SiO 2)、五氧化二釩(V 2O 5)及其組合所組成的氧化物。 In order to achieve the aforementioned object, the present invention provides a lead-free thick film resistor composition, which comprises ruthenium dioxide, a borosilicate glass, an additive component, an organic vehicle and a solvent; wherein, the additive component comprises copper oxide ( CuO) or copper monoxide and an oxide selected from titanium dioxide (TiO 2 ), silicon dioxide (SiO 2 ), vanadium pentoxide (V 2 O 5 ) and combinations thereof.
藉由選用特定種類的添加成分，能夠提供調整電阻值與穩定電阻溫度係數的作用，並且再與具有高穩定性之二氧化釕、硼矽酸系玻璃、有機載體以及溶劑一同製成無鉛厚膜電阻組成物，能夠使以該無鉛厚膜電阻組成物所製成之無鉛厚膜電阻在具有廣域片電阻值的情況下，同時仍具有電阻溫度係數介於±100 ppm/℃間的特性。By selecting specific types of additives, it can adjust the resistance value and stabilize the temperature coefficient of resistance, and then form a lead-free thick film together with highly stable ruthenium dioxide, borosilicate glass, organic vehicle and solvent The resistor composition enables the lead-free thick-film resistor made of the lead-free thick-film resistor composition to have a wide-area sheet resistance value while still having the characteristic of a temperature coefficient of resistance between ±100 ppm/°C.
較佳的，以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為0.1重量百分比(weight percent，wt%)至15 wt%。更佳的，以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為0.1 wt%至12 wt%。再更佳的，以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為0.2 wt%至11 wt%。Preferably, based on the total weight of the lead-free thick film resistor composition, the content of the added component is 0.1 weight percent (wt%) to 15 wt%. More preferably, based on the total weight of the lead-free thick film resistor composition, the content of the added component is 0.1 wt% to 12 wt%. Still more preferably, based on the total weight of the lead-free thick film resistor composition, the content of the added component is 0.2 wt% to 11 wt%.
於本發明的一些實施例中，該添加成分包含一氧化銅，且以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為0.2 wt%至0.8 wt%。較佳的，以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為0.25 wt%至0.7 wt%。更佳的，以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為0.25 wt%至0.6 wt%。In some embodiments of the present invention, the additive component includes copper oxide, and based on the total weight of the lead-free thick film resistor composition, the content of the additive component is 0.2 wt% to 0.8 wt%. Preferably, based on the total weight of the lead-free thick film resistor composition, the content of the added component is 0.25 wt% to 0.7 wt%. More preferably, based on the total weight of the lead-free thick film resistor composition, the content of the added component is 0.25 wt% to 0.6 wt%.
於本發明的一些實施例中，該添加成分包含一氧化銅以及二氧化矽，且以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為1 wt%至4 wt%；以該添加成分的總重量為基準，一氧化銅的含量為9 wt%至20 wt%，二氧化矽的含量為80 wt%至91 wt%。In some embodiments of the present invention, the added component includes copper monoxide and silicon dioxide, and based on the total weight of the lead-free thick film resistor composition, the content of the added component is 1 wt% to 4 wt%; Based on the total weight of the added components, the content of copper monoxide is 9 wt% to 20 wt%, and the content of silicon dioxide is 80 wt% to 91 wt%.
於本發明的一些實施例中，該添加成分包含一氧化銅、二氧化矽以及二氧化鈦，且以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為1 wt%至4 wt%；以該添加成分的總重量為基準，一氧化銅的含量為14 wt%至41 wt%，二氧化矽的含量為28 wt%至58 wt%，二氧化鈦的含量為5 wt%至58 wt%。In some embodiments of the present invention, the additive includes copper monoxide, silicon dioxide and titanium dioxide, and based on the total weight of the lead-free thick film resistor composition, the content of the additive is 1 wt% to 4 wt %; based on the total weight of the added ingredients, the content of copper monoxide is 14 wt% to 41 wt%, the content of silicon dioxide is 28 wt% to 58 wt%, and the content of titanium dioxide is 5 wt% to 58 wt% %.
於本發明的一些實施例中，該添加成分包含一氧化銅、二氧化矽以及五氧化二釩，且以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為1 wt%至9 wt%；以該添加成分的總重量為基準，一氧化銅的含量為15 wt%至58 wt%，二氧化矽的含量為28 wt%至83 wt%，五氧化二釩的含量為2 wt%至15 wt%。In some embodiments of the present invention, the additive includes copper monoxide, silicon dioxide, and vanadium pentoxide, and based on the total weight of the lead-free thick film resistor composition, the content of the additive is 1 wt%. to 9 wt%; based on the total weight of the added ingredients, the content of copper monoxide is 15 wt% to 58 wt%, the content of silicon dioxide is 28 wt% to 83 wt%, and the content of vanadium pentoxide is 2 wt% to 15 wt%.
於本發明的一些實施例中，該添加成分包含一氧化銅、二氧化鈦、二氧化矽以及五氧化二釩，且以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為8 wt%至11 wt%；以該添加成分的總重量為基準，一氧化銅的含量為18 wt%至20 wt%，二氧化鈦的含量為0.1 wt%至1.5 wt%，二氧化矽的含量為73 wt%至76 wt%，五氧化二釩的含量為5.5 wt%至6.5 wt%。In some embodiments of the present invention, the additives include copper monoxide, titanium dioxide, silicon dioxide and vanadium pentoxide, and based on the total weight of the lead-free thick film resistor composition, the content of the additives is 8 wt% to 11 wt%; based on the total weight of the added ingredients, the content of copper monoxide is 18 wt% to 20 wt%, the content of titanium dioxide is 0.1 wt% to 1.5 wt%, and the content of silicon dioxide is 73 wt%. wt% to 76 wt%, and the content of vanadium pentoxide is 5.5 wt% to 6.5 wt%.
於本發明的一些實施例中，該添加成分包含一氧化銅、二氧化矽以及一選自由二氧化鈦、五氧化二釩及其組合所組成的氧化物，且以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為1 wt%至15 wt%。In some embodiments of the present invention, the additive includes copper oxide, silicon dioxide, and an oxide selected from titanium dioxide, vanadium pentoxide, and combinations thereof, and the total amount of the lead-free thick film resistor composition Based on weight, the content of the added component is 1 wt% to 15 wt%.
於本發明的一些實施例中，該添加成分包含一氧化銅、二氧化矽與五氧化二釩之組合以及一氧化銅、二氧化矽、五氧化二釩與二氧化鈦之組合，且以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為1 wt%至15 wt%。較佳的，以該無鉛厚膜電阻組成物的總重量為基準，該添加成分的含量為1.5 wt%至12 wt%。In some embodiments of the present invention, the additive includes a combination of copper oxide, silicon dioxide, and vanadium pentoxide, and a combination of copper oxide, silicon dioxide, vanadium pentoxide, and titanium dioxide, and the lead-free thickness Based on the total weight of the membrane resistor composition, the content of the added component is 1 wt% to 15 wt%. Preferably, based on the total weight of the lead-free thick film resistor composition, the content of the added component is 1.5 wt% to 12 wt%.
較佳的，以該無鉛厚膜電阻組成物的總重量為基準，二氧化釕的含量為3 wt%至15 wt%。更佳的，以該無鉛厚膜電阻組成物的總重量為基準，二氧化釕的含量為5 wt%至15 wt%。再更佳的，以該無鉛厚膜電阻組成物的總重量為基準，二氧化釕的含量為5 wt%至12 wt%。Preferably, based on the total weight of the lead-free thick film resistor composition, the content of ruthenium dioxide is 3 wt% to 15 wt%. More preferably, based on the total weight of the lead-free thick film resistor composition, the content of ruthenium dioxide is 5 wt% to 15 wt%. Still more preferably, based on the total weight of the lead-free thick film resistor composition, the content of ruthenium dioxide is 5 wt% to 12 wt%.
較佳的，二氧化釕與該硼矽酸系玻璃的重量比為1：4至1：13。更佳的，二氧化釕與該硼矽酸系玻璃的重量比為1：4至1：12。再更佳的，二氧化釕與該硼矽酸系玻璃的重量比為1：4至1：11。Preferably, the weight ratio of ruthenium dioxide to the borosilicate glass is 1:4 to 1:13. More preferably, the weight ratio of ruthenium dioxide to the borosilicate glass is 1:4 to 1:12. Still more preferably, the weight ratio of ruthenium dioxide to the borosilicate glass is 1:4 to 1:11.
較佳的，二氧化釕的平均粒徑係大於或等於0.05 μm且小於或等於0.25 μm。Preferably, the average particle size of ruthenium dioxide is greater than or equal to 0.05 μm and less than or equal to 0.25 μm.
較佳的，該硼矽酸系玻璃包含二氧化矽、三氧化二硼(B 2O 3)、一氧化鎂(MgO)、一氧化鈣(CaO)、一氧化鋇(BaO)以及一氧化鋅(ZnO)，且以該硼矽酸系玻璃的總重量為基準，二氧化矽的含量為25 wt%至35 wt%、三氧化二硼的含量為20 wt%至30 wt%、一氧化鎂的含量為0.5 wt%至5 wt%、一氧化鈣的含量為3 wt%至5 wt%、一氧化鋇的含量為10 wt%至20 wt%以及一氧化鋅的含量為15 wt%至25 wt%。更佳的，以該硼矽酸系玻璃的總重量為基準，二氧化矽的含量為28 wt%至33 wt%、三氧化二硼的含量為21 wt%至28 wt%、一氧化鎂的含量為1 wt%至3 wt%、一氧化鈣的含量為3.5 wt%至4.5 wt%、一氧化鋇的含量為15 wt%至19 wt%以及一氧化鋅的含量為18 wt%至24 wt%。 Preferably, the borosilicate glass contains silicon dioxide, boron trioxide (B 2 O 3 ), magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO) and zinc oxide (ZnO), and based on the total weight of the borosilicate glass, the content of silicon dioxide is 25 wt% to 35 wt%, the content of diboron trioxide is 20 wt% to 30 wt%, magnesium oxide The content of 0.5 wt% to 5 wt%, the content of calcium monoxide is 3 wt% to 5 wt%, the content of barium monoxide is 10 wt% to 20 wt%, and the content of zinc monoxide is 15 wt% to 25 wt%. wt%. More preferably, based on the total weight of the borosilicate glass, the content of silicon dioxide is 28 wt% to 33 wt%, the content of diboron trioxide is 21 wt% to 28 wt%, and the content of magnesium monoxide 1 wt% to 3 wt%, calcium monoxide 3.5 wt% to 4.5 wt%, barium monoxide 15 wt% to 19 wt%, and zinc monoxide 18 wt% to 24 wt% %.
於本發明的一些實施例中，該硼矽酸系玻璃包含二氧化矽、三氧化二硼、一氧化鎂、一氧化鈣、一氧化鋇、一氧化鋅以及二氧化鈦，且以該硼矽酸系玻璃的總重量為基準，二氧化矽的含量為25 wt%至35 wt%、三氧化二硼的含量為20 wt%至30 wt%、一氧化鎂的含量為0.5 wt%至5 wt%、一氧化鈣的含量為3 wt%至5 wt%、一氧化鋇的含量為10 wt%至20 wt%、一氧化鋅的含量為15 wt%至25 wt%以及二氧化鈦的含量為0.2 wt%至2 wt%。In some embodiments of the present invention, the borosilicate glass includes silicon dioxide, boron trioxide, magnesium oxide, calcium oxide, barium oxide, zinc oxide, and titanium dioxide, and the borosilicate glass Based on the total weight of the glass, the content of silicon dioxide is 25 wt% to 35 wt%, the content of diboron trioxide is 20 wt% to 30 wt%, the content of magnesium monoxide is 0.5 wt% to 5 wt%, The content of calcium monoxide is 3 wt% to 5 wt%, the content of barium monoxide is 10 wt% to 20 wt%, the content of zinc monoxide is 15 wt% to 25 wt%, and the content of titanium dioxide is 0.2 wt% to 2 wt%.
於本發明的一些實施例中，該硼矽酸系玻璃包含二氧化矽、三氧化二硼、一氧化鎂、一氧化鈣、一氧化鋇、一氧化鋅、二氧化鈦、一氧化鈉(Na 2O)以及一氧化鉀(K 2O)，且以該硼矽酸系玻璃的總重量為基準，二氧化矽的含量為25 wt%至35 wt%、三氧化二硼的含量為20 wt%至30 wt%、一氧化鎂的含量為0.5 wt%至5 wt%、一氧化鈣的含量為3 wt%至5 wt%、一氧化鋇的含量為10 wt%至20 wt%、一氧化鋅的含量為15 wt%至25 wt%、二氧化鈦的含量為0.2 wt%至2 wt%以及一氧化鈉與一氧化鉀的含量總和為0.5 wt%至3 wt%。 In some embodiments of the present invention, the borosilicate glass comprises silicon dioxide, boron trioxide, magnesium monoxide, calcium monoxide, barium monoxide, zinc oxide, titanium dioxide, sodium monoxide (Na 2 O ) and potassium monoxide (K 2 O), and based on the total weight of the borosilicate glass, the content of silicon dioxide is 25 wt% to 35 wt%, and the content of diboron trioxide is 20 wt% to 30 wt%, the content of magnesium oxide is 0.5 wt% to 5 wt%, the content of calcium monoxide is 3 wt% to 5 wt%, the content of barium oxide is 10 wt% to 20 wt%, the content of zinc oxide The content is 15 wt% to 25 wt%, the content of titanium dioxide is 0.2 wt% to 2 wt%, and the total content of sodium monoxide and potassium monoxide is 0.5 wt% to 3 wt%.
於本發明的一些實施例中，以該無鉛厚膜電阻組成物的總重量為基準，該硼矽酸系玻璃的含量為40 wt%至70 wt%。較佳的，以該無鉛厚膜電阻組成物的總重量為基準，該硼矽酸系玻璃的含量為50 wt%至60 wt%。In some embodiments of the present invention, based on the total weight of the lead-free thick film resistor composition, the content of the borosilicate glass is 40 wt% to 70 wt%. Preferably, based on the total weight of the lead-free thick film resistor composition, the content of the borosilicate glass is 50 wt% to 60 wt%.
較佳的，該硼矽酸系玻璃的平均粒徑係大於或等於1 μm且小於或等於3 μm。Preferably, the average particle size of the borosilicate glass is greater than or equal to 1 μm and less than or equal to 3 μm.
較佳的，該硼矽酸系玻璃與該添加成分混合後所得之混合物的玻璃轉化溫度係大於或等於570℃且小於或等於620℃。更佳的，該硼矽酸系玻璃與該添加成分混合後所得之混合物的玻璃轉化溫度係大於或等於574℃且小於或等於615℃。Preferably, the glass transition temperature of the mixture obtained after mixing the borosilicate glass and the additive component is greater than or equal to 570°C and less than or equal to 620°C. More preferably, the glass transition temperature of the mixture obtained after mixing the borosilicate glass and the additive component is greater than or equal to 574°C and less than or equal to 615°C.
於本發明的一些實施例中，以該無鉛厚膜電阻組成物的總重量為基準，該有機載體的含量為15 wt%至40 wt%。較佳的，以該無鉛厚膜電阻組成物的總重量為基準，該有機載體的含量為20 wt%至30 wt%。In some embodiments of the present invention, based on the total weight of the lead-free thick film resistor composition, the content of the organic vehicle is 15 wt% to 40 wt%. Preferably, based on the total weight of the lead-free thick film resistor composition, the content of the organic vehicle is 20 wt% to 30 wt%.
於本發明的一些實施例中，該有機載體包含乙基纖維素、丙烯酸系樹脂或其組合。In some embodiments of the present invention, the organic vehicle includes ethyl cellulose, acrylic resin or a combination thereof.
於本發明的一些實施例中，該溶劑包含松油醇類、醚類、酯類或其組合。於本發明的一些實施例中，該溶劑係作為稀釋劑使用。In some embodiments of the present invention, the solvent includes terpineols, ethers, esters or combinations thereof. In some embodiments of the present invention, the solvent is used as a diluent.
另外，本發明另提供一種無鉛厚膜電阻，其包含一基板、一電阻層以及二電極(陽極和陰極)，該二電極係設置於該基板之相對兩側上，該電阻層係設置於該二電極以及該基板上，且該電阻層係由前述本發明之無鉛厚膜電阻組成物所製成。應理解的是，所述「該電阻層係設置於該二電極以及該基板上」係指該電阻層分別覆蓋該基板以及該二電極的至少一部分。更具體而言，所述「該電阻層係設置於該二電極以及該基板上」係指該電阻層分別覆蓋該基板以及該二電極的至少一部分，但不包含該電阻層完全覆蓋該基板以及該二電極的情況。In addition, the present invention also provides a lead-free thick film resistor, which includes a substrate, a resistor layer and two electrodes (anode and cathode), the two electrodes are arranged on opposite sides of the substrate, the resistor layer is arranged on the On the two electrodes and the substrate, and the resistance layer is made of the aforementioned lead-free thick film resistance composition of the present invention. It should be understood that "the resistive layer is disposed on the two electrodes and the substrate" means that the resistive layer covers at least a part of the substrate and the two electrodes respectively. More specifically, "the resistive layer is disposed on the two electrodes and the substrate" means that the resistive layer covers at least a part of the substrate and the two electrodes respectively, but does not include that the resistive layer completely covers the substrate and The condition of the two electrodes.
較佳的，該無鉛厚膜電阻的片電阻值係大於或等於0.5 kΩ/□且小於或等於1100 kΩ/□。更佳的，該無鉛厚膜電阻的片電阻值係大於或等於0.9 kΩ/□且小於或等於1090 kΩ/□。再更佳的，該無鉛厚膜電阻的片電阻值係大於或等於90 kΩ/□且小於或等於1090 kΩ/□。Preferably, the sheet resistance of the lead-free thick film resistor is greater than or equal to 0.5 kΩ/□ and less than or equal to 1100 kΩ/□. More preferably, the sheet resistance of the lead-free thick film resistor is greater than or equal to 0.9 kΩ/□ and less than or equal to 1090 kΩ/□. Still more preferably, the sheet resistance of the lead-free thick film resistor is greater than or equal to 90 kΩ/□ and less than or equal to 1090 kΩ/□.
較佳的，該無鉛厚膜電阻的電阻溫度係數係大於或等於-100 ppm/℃且小於或等於+100 ppm/℃。更佳的，該無鉛厚膜電阻的電阻溫度係數係大於或等於-98 ppm/℃且小於或等於+97 ppm/℃。Preferably, the temperature coefficient of resistance of the lead-free thick film resistor is greater than or equal to -100 ppm/°C and less than or equal to +100 ppm/°C. More preferably, the temperature coefficient of resistance of the lead-free thick film resistor is greater than or equal to -98 ppm/°C and less than or equal to +97 ppm/°C.
於本發明的一些實施例中，該基板可為絕緣陶瓷基板，例如氧化鋁陶瓷基板或氮化鋁陶瓷基板，但不限於此。In some embodiments of the present invention, the substrate may be an insulating ceramic substrate, such as an alumina ceramic substrate or an aluminum nitride ceramic substrate, but is not limited thereto.
於本發明的一些實施例中，該二電極可皆為銀鈀電極，但不限於此。In some embodiments of the present invention, the two electrodes can both be silver-palladium electrodes, but not limited thereto.
於本說明書中，由「小數值至大數值」表示的範圍，如果沒有特別指明，則表示其範圍係大於或等於該小數值且小於或等於該大數值。例如：含量為0.1 wt%至15 wt%，即表示含量的範圍係「大於或等於0.1 wt%且小於或等於15 wt%」。In this specification, the range represented by "small value to large value" means that the range is greater than or equal to the small value and less than or equal to the large value unless otherwise specified. For example: the content is 0.1 wt% to 15 wt%, which means the range of content is "greater than or equal to 0.1 wt% and less than or equal to 15 wt%".
以下列舉數種實施例之製作方法作為例示，說明本創作之實施方式；熟習此技藝者可經由本說明書之內容輕易地了解本創作所能達成之優點與功效，並且於不悖離本創作之精神下進行各種修飾與變更，以施行或應用本創作之內容。The production methods of several embodiments are listed below as examples to illustrate the implementation of this creation; those who are familiar with this technology can easily understand the advantages and effects that this creation can achieve through the contents of this manual, and without departing from the principles of this creation Various modifications and changes are made in order to implement or apply the content of this creation.
製備例：硼矽酸系玻璃Preparation example: borosilicate glass
本發明先準備三種不同組成之硼矽酸系玻璃，以用於製備本發明之無鉛厚膜電阻組成物。下表1中列出標示為編號A、B以及C之硼矽酸系玻璃的組成成分以及各成分的含量。
表1：三種硼矽酸系玻璃的組成成分與各成分的含量
實施例Example 11 至to 1414 ：無鉛厚膜電阻組成物: Lead-free thick film resistor composition
依照下表2所列出之無鉛厚膜電阻組成物的組成成分以及各成分的含量配比，選用適量之二氧化釕、上述編號A之硼矽酸系玻璃粉、添加成分、有機載體以及溶劑作為原料，其中，所述有機載體係選用乙基纖維素，而所述溶劑則選用松油醇以作為稀釋劑。According to the composition of the lead-free thick film resistor composition listed in Table 2 below and the content ratio of each component, select an appropriate amount of ruthenium dioxide, the borosilicate glass frit with the above number A, additional components, organic vehicle and solvent As the raw material, ethyl cellulose is selected as the organic carrier system, and terpineol is selected as the solvent as the diluent.
隨後，實施例1、3、4及12係將各原料均勻混合；而實施例2、5至11、13及14則係先將二氧化釕與添加成分中的二氧化矽預先均勻混合後，再與其餘原料均勻混合，進而製得實施例1至14之無鉛厚膜電阻組成物。Subsequently, embodiment 1, 3, 4 and 12 are that each raw material is mixed uniformly; And embodiment 2, 5 to 11, 13 and 14 then are first after ruthenium dioxide and silicon dioxide in the added component are mixed uniformly in advance, Then it is uniformly mixed with other raw materials to obtain the lead-free thick film resistor compositions of Examples 1 to 14.
實施例Example 1515 至to 3030 ：無鉛厚膜電阻組成物: Lead-free thick film resistor composition
依照下表2所列出之無鉛厚膜電阻組成物的組成成分以及各成分的含量配比，選用適量之二氧化釕、上述編號B之硼矽酸系玻璃粉、添加成分、有機載體以及溶劑作為原料，其中，所述有機載體係選用乙基纖維素，而所述溶劑則選用松油醇以作為稀釋劑。According to the composition of the lead-free thick film resistor composition listed in Table 2 below and the content ratio of each component, select an appropriate amount of ruthenium dioxide, the borosilicate glass powder of the above number B, additional components, organic vehicles and solvents As the raw material, ethyl cellulose is selected as the organic carrier system, and terpineol is selected as the solvent as the diluent.
隨後，實施例23以及24係將各原料均勻混合；而實施例15至22以及25至30則係先將二氧化釕與添加成分中的二氧化矽預先均勻混合後，再與其餘原料均勻混合，進而製得實施例15至30之無鉛厚膜電阻組成物。Subsequently, in Examples 23 and 24, the raw materials were uniformly mixed; while in Examples 15 to 22 and 25 to 30, the ruthenium dioxide and the silicon dioxide in the added ingredients were uniformly mixed in advance, and then mixed uniformly with the rest of the raw materials , and then the lead-free thick film resistor compositions of Examples 15 to 30 were obtained.
實施例Example 3131 至to 4141 ：無鉛厚膜電阻組成物: Lead-free thick film resistor composition
依照下表2所列出之無鉛厚膜電阻組成物的組成成分以及各成分的含量配比，選用適量之二氧化釕、上述編號C之硼矽酸系玻璃粉、添加成分、有機載體以及溶劑作為原料，其中，所述有機載體係選用乙基纖維素系，而所述溶劑則選用松油醇以作為稀釋劑。According to the composition of the lead-free thick film resistor composition listed in Table 2 below and the content ratio of each component, select an appropriate amount of ruthenium dioxide, the above-mentioned borosilicate glass powder with the number C, additional components, organic vehicles and solvents As the raw material, ethyl cellulose is used as the organic carrier system, and terpineol is used as the diluent as the solvent.
隨後，實施例32係將各原料均勻混合；而實施例31以及33至41則係先將二氧化釕與添加成分中的二氧化矽預先均勻混合後，再與其餘原料均勻混合，進而製得實施例31至41之無鉛厚膜電阻組成物。Subsequently, in Example 32, the raw materials were uniformly mixed; while in Examples 31 and 33 to 41, the ruthenium dioxide and the silicon dioxide in the added ingredients were uniformly mixed in advance, and then mixed uniformly with the rest of the raw materials to obtain The lead-free thick film resistor compositions of Examples 31 to 41.
比較例comparative example 11 至to 44 ：無鉛厚膜電阻組成物: Lead-free thick film resistor composition
比較例1至4的製備流程係與實施例1至14相似，其主要不同之處在於比較例1至4並未選用任何添加成分作為原料，即僅有將二氧化釕、上述編號A之硼矽酸系玻璃粉、有機載體以及溶劑作為原料，並將該等原料均勻混合後即製得比較例1至4之無鉛厚膜電阻組成物。The preparation process of Comparative Examples 1 to 4 is similar to that of Examples 1 to 14. The main difference is that Comparative Examples 1 to 4 do not use any additional ingredients as raw materials, that is, only ruthenium dioxide, the boron of the above-mentioned number A Silicic acid-based glass powder, an organic vehicle and a solvent are used as raw materials, and the lead-free thick film resistor compositions of Comparative Examples 1 to 4 are prepared after uniformly mixing these raw materials.
比較例comparative example 55 至to 77 ：無鉛厚膜電阻組成物: Lead-free thick film resistor composition
比較例5至7的製備流程係與實施例15至30相似，其主要不同之處在於比較例5至7並未選用任何添加成分作為原料，即僅有將二氧化釕、上述編號B之硼矽酸系玻璃粉、有機載體以及溶劑作為原料，並將該等原料均勻混合後即製得比較例5至7之無鉛厚膜電阻組成物。The preparation process of Comparative Examples 5 to 7 is similar to that of Examples 15 to 30. The main difference is that Comparative Examples 5 to 7 do not use any additional ingredients as raw materials, that is, only ruthenium dioxide, the boron of the above-mentioned number B Silicic acid-based glass powder, an organic vehicle and a solvent are used as raw materials, and the lead-free thick film resistor compositions of Comparative Examples 5 to 7 are prepared after uniformly mixing these raw materials.
比較例comparative example 88 至to 1010 ：無鉛厚膜電阻組成物: Lead-free thick film resistor composition
比較例8至10的製備流程係與實施例31至41相似，其主要不同之處在於比較例8至10並未選用任何添加成分作為原料，即僅有將二氧化釕、上述編號C之硼矽酸系玻璃粉、有機載體以及溶劑作為原料，並將該等原料均勻混合後即製得比較例8至10之無鉛厚膜電阻組成物。
表2：實施例1至41以及比較例1至10之無鉛厚膜電阻組成物的組成成分與各成分的含量
試驗例Test case 11 ：測定玻璃轉化溫度: Determination of glass transition temperature (Tg)(Tg)
本試驗例係選用實施例1至41之無鉛厚膜電阻組成物中的硼矽酸系玻璃粉以及添加成分之混合物作為測試樣品；另亦選用比較例1至10之無鉛厚膜電阻組成物中的硼矽酸系玻璃粉作為測試樣品，再根據ASTM E1545中的規範，利用差示掃描量熱法(differential scanning calorimetry，DSC)測定實施例1至41以及比較例1至10之測試樣品的玻璃轉化溫度，並將其結果列於下表3中。
表3：實施例1至41以及比較例1至10之測試樣品的玻璃轉化溫度
由上表3的結果可見，實施例1至41之測試樣品具有約574℃至615℃的玻璃轉化溫度，其與比較例1至10之測試樣品(約580℃至598℃)具有相近的玻璃轉化溫度。此外，在不同組成成分之硼矽酸系玻璃粉中添加特定成分、含量之添加成分後，可將玻璃轉化溫度控制在一定範圍內，以匹配後續在製備電阻層的鍛燒製程中之升溫曲線，協助電阻層緻密化。As can be seen from the results in Table 3 above, the test samples of Examples 1 to 41 have a glass transition temperature of about 574°C to 615°C, which is similar to that of the test samples of Comparative Examples 1 to 10 (about 580°C to 598°C). conversion temperature. In addition, the glass transition temperature can be controlled within a certain range after adding specific components and content of added components to borosilicate glass powders with different compositions, so as to match the subsequent temperature rise curve in the calcination process of preparing the resistance layer , to assist in the densification of the resistive layer.
實施例Example 1A1A 至to 41A41A ：無鉛厚膜電阻: Lead-free Thick Film Resistor
將銀鈀電極漿料以網版印刷的方式分別印刷於氧化鋁陶瓷基板之相對兩側的表面上，隨後以約100℃至150℃的溫度進行烘乾約10分鐘至15分鐘，接著，將實施例1至41之無鉛厚膜電阻組成物同樣以網版印刷的方式印刷於所述氧化鋁陶瓷基板以及銀鈀電極上，並覆蓋所述氧化鋁陶瓷基板以及銀鈀電極的部分表面，接著以約100℃至150℃的溫度進行烘乾約10分鐘至15分鐘後，再於約820℃至920℃的條件下進行鍛燒約10分鐘至15分鐘以形成電阻層，隨後待冷卻至室溫即製得實施例1A至41A之無鉛厚膜電阻。Print the silver-palladium electrode paste on the opposite sides of the alumina ceramic substrate by screen printing, and then dry it at a temperature of about 100°C to 150°C for about 10 minutes to 15 minutes, and then, The lead-free thick film resistor compositions of Examples 1 to 41 are also printed on the alumina ceramic substrate and the silver-palladium electrode by screen printing, and cover part of the surface of the alumina ceramic substrate and the silver-palladium electrode, and then After drying at a temperature of about 100°C to 150°C for about 10 minutes to 15 minutes, then calcining at a temperature of about 820°C to 920°C for about 10 minutes to 15 minutes to form a resistance layer, and then to be cooled to room temperature. The lead-free thick film resistors of Examples 1A to 41A were obtained immediately after warming.
比較例comparative example 1A1A 至to 10A10A ：無鉛厚膜電阻: Lead-free Thick Film Resistor
比較例1A至10A的製作流程係與實施例1A至41A相近，其主要不同之處在於比較例1A至10A係選用比較例1至10之無鉛厚膜電阻組成物製成所述電阻層，除此之外的流程皆與實施例1A至10A相同，並製得比較例1A至10A之無鉛厚膜電阻。The manufacturing process of Comparative Examples 1A to 10A is similar to that of Examples 1A to 41A, and the main difference is that Comparative Examples 1A to 10A use the lead-free thick film resistor composition of Comparative Examples 1 to 10 to make the resistance layer, except The other processes are the same as in Examples 1A to 10A, and the lead-free thick film resistors of Comparative Examples 1A to 10A are produced.
試驗例Test case 22 ：測定片電阻值: Measuring sheet resistance value
本試驗例係選用實施例1A至41A以及比較例1A至10A之無鉛厚膜電阻，並且依照IEC 60115-1 / JIS C 5201-1中第4.5條之規範進行片電阻值的測定，並將其結果列於下表4中。In this test example, the lead-free thick film resistors of Examples 1A to 41A and Comparative Examples 1A to 10A were selected, and the sheet resistance value was measured in accordance with the specification in Article 4.5 of IEC 60115-1 / JIS C 5201-1, and the The results are listed in Table 4 below.
試驗例Test case 33 ：測定電阻溫度係數: Determination of temperature coefficient of resistance
本試驗例係選用實施例1A至41A以及比較例1A至10A之無鉛厚膜電阻，並且依照IEC 60115-1中第4.8條之規範進行電阻溫度係數之測定；其中，其中，進行測試的溫度範圍係約25℃至約125℃，而電阻溫度係數則可由以下公式計算而得：電阻溫度係數 = (R
T-R
25)/R
25(T-25)/10
6，而R
T為於特定溫度進行量測之電阻值，R
25則為於約25℃進行量測之電阻值。實施例1A至41A以及比較例1A至10A之無鉛厚膜電阻的電阻溫度係數測定結果係列於下表4中。
表4：實施例1A至41A以及比較例1A至10A之無鉛厚膜電阻的片電阻值以及電阻溫度係數的測定結果
由上表4的結果可見，實施例1A至41A之無鉛厚膜電阻能夠具有約0.9 kΩ/□至約1090 kΩ/□之相當廣域的片電阻值，且同時仍然能夠維持電阻溫度係數介於±100 ppm/℃之間；反觀比較例1A至10A，僅有如比較例1A及5A係具有約2.1 kΩ/□及2.4 kΩ/□之較低片電阻值時，才能夠維持電阻溫度係數介於±100 ppm/℃之間，一但進一步提高片電阻值，如比較例2A至4A以及6A至10A皆具有高於約6.4 kΩ/□之片電阻值，則比較例2A至4A以及6A至10A所具有的電阻溫度係數皆明顯低於-100 ppm/℃。由此可證，藉由選用含有特定成種類之添加成分的實施例1至41之無鉛厚膜電阻組成物製成實施例1A至41A之無鉛厚膜電阻，進而能使其獲得在具有相當廣域之片電阻值的情況下，依然能維持其電阻溫度係數介於±100 ppm/℃之間的特性。From the results in Table 4 above, it can be seen that the lead-free thick film resistors of Examples 1A to 41A can have a fairly wide range of sheet resistance values from about 0.9 kΩ/□ to about 1090 kΩ/□, while still maintaining a temperature coefficient of resistance between ±100 ppm/°C; in contrast to Comparative Examples 1A to 10A, only when Comparative Examples 1A and 5A have lower sheet resistance values of about 2.1 kΩ/□ and 2.4 kΩ/□ can the temperature coefficient of resistance be maintained between Between ±100 ppm/°C, once the sheet resistance value is further increased, if Comparative Examples 2A to 4A and 6A to 10A all have a sheet resistance value higher than about 6.4 kΩ/□, then Comparative Examples 2A to 4A and 6A to 10A All have temperature coefficients of resistance significantly lower than -100 ppm/°C. From this, it can be proved that the lead-free thick film resistors of Examples 1A to 41A can be made by selecting the lead-free thick film resistor compositions of Examples 1 to 41 containing specific types of additives, and then it can be obtained in a wide range of applications. In the case of the sheet resistance value of the domain, it can still maintain the characteristics of its temperature coefficient of resistance between ±100 ppm/℃.
綜上所述，本發明之無鉛厚膜電阻組成物由於含有特定種類的添加成分，進而能夠製成具有廣域電阻值的無鉛厚膜電阻，並且同時仍具有電阻溫度係數介於±100 ppm/℃間的特性，使得本發明之無鉛厚膜電阻可應用於廣泛規格之電阻器中，並提升其在商業上的價值。To sum up, the lead-free thick film resistor composition of the present invention can be made into lead-free thick film resistors with a wide range of resistance values due to the specific additives contained in the composition of the present invention, and at the same time still have a temperature coefficient of resistance between ±100 ppm/ The characteristic between ℃ makes the lead-free thick-film resistor of the present invention applicable to resistors with a wide range of specifications, and increases its commercial value.
無。none.
無。none.
無。none.
無。none.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW111114789A TWI798061B (en) | 2022-04-19 | 2022-04-19 | Lead-free thick film resistor composition and lead-free thick film resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW111114789A TWI798061B (en) | 2022-04-19 | 2022-04-19 | Lead-free thick film resistor composition and lead-free thick film resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TWI798061B true TWI798061B (en) | 2023-04-01 |
| TW202343483A TW202343483A (en) | 2023-11-01 |
Family
ID=86945154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW111114789A TWI798061B (en) | 2022-04-19 | 2022-04-19 | Lead-free thick film resistor composition and lead-free thick film resistor |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI798061B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200419593A (en) * | 2002-11-21 | 2004-10-01 | Tdk Corp | Resistive paste, resistor body and electronic device |
| US20080157033A1 (en) * | 2005-03-09 | 2008-07-03 | Baker Michael F | Black conductive thick film compositions, black electrodes, and methods of forming thereof |
| TW201912586A (en) * | 2017-08-25 | 2019-04-01 | 日商住友金屬礦山股份有限公司 | Thick film resistor composition and thick film resistor paste containing the same |
-
2022
- 2022-04-19 TW TW111114789A patent/TWI798061B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200419593A (en) * | 2002-11-21 | 2004-10-01 | Tdk Corp | Resistive paste, resistor body and electronic device |
| US20080157033A1 (en) * | 2005-03-09 | 2008-07-03 | Baker Michael F | Black conductive thick film compositions, black electrodes, and methods of forming thereof |
| TW201912586A (en) * | 2017-08-25 | 2019-04-01 | 日商住友金屬礦山股份有限公司 | Thick film resistor composition and thick film resistor paste containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202343483A (en) | 2023-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI752170B (en) | Compositions for resistors, pastes for resistors containing the same, and thick film resistors using the same | |
| JPH0337281B2 (en) | ||
| TW201823380A (en) | Resistive paste and resistor produced by firing same | |
| JP2018092730A (en) | Composition for resistor and resistor paste containing the same furthermore thick film resistor therewith | |
| CN115461825A (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| TWI798061B (en) | Lead-free thick film resistor composition and lead-free thick film resistor | |
| JPS58165301A (en) | Glass frit composition for thick film resistor | |
| JP2005209744A (en) | Thick film resistor paste, thick film resistor, electronic component | |
| CN116994844A (en) | Lead-free thick film resistor composition and lead-free thick film resistor | |
| JP7095542B2 (en) | Compositions for thick film resistors, pastes for thick film resistors, and thick film resistors | |
| JP7295973B2 (en) | thick film resistor paste | |
| JP7135696B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| WO2021221175A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| JP7273266B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| JP7279551B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| WO2021221174A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| JP7116362B2 (en) | Resistor composition, resistor paste, and resistor | |
| JP7110780B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| TW202413280A (en) | Ruthenium oxide powder, composition for thick film resistor, paste for thick film resistor, thick film resistor | |
| JPH03183640A (en) | Resistor paste and ceramic substrate | |
| JP2023135971A (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| WO2021221172A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| JPH0458420B2 (en) | ||
| JPH03148101A (en) | Resistance paste | |
| JPWO2021221175A5 (en) |