TW202343483A

TW202343483A - Lead-free thick-film resistor composition and lead-free thick-film resistor having a TCR between ±100 ppm/DEG C while providing a wide range of resistance values

Info

Publication number: TW202343483A
Application number: TW111114789A
Authority: TW
Inventors: 曾俊儒; 朱立文
Original assignee: 華新科技股份有限公司
Priority date: 2022-04-19
Filing date: 2022-04-19
Publication date: 2023-11-01
Also published as: TWI798061B

Abstract

The present invention provides a lead-free thick-film resistor composition, which includes ruthenium dioxide, borosilicate-based glass, an additive component, an organic carrier and a solvent, wherein the additive component includes copper monoxide or includes copper monoxide and an oxide selected from the group consisting of titanium dioxide, silicon dioxide, vanadium pentoxide, and a combination thereof. The lead-free thick-film resistor made of the lead-free thick-film resistor composition of the present invention has a temperature coefficient of resistance (TCR) between ±100 ppm/DEG C while providing a wide range of resistance values.

Description

Lead-free thick film resistor composition and lead-free thick film resistor

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 resistor composition and a resistor, in particular to a lead-free thick film resistor composition and a lead-free thick film resistor.

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. They can be printed by printing thick film resistor compositions in the form of paste or paste on an insulating ceramic substrate with electrodes, and then calcining It is produced 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, thick film resistor compositions use conductive particles and glass as the main components. Among them, the conductive particles are mostly ruthenium-based oxides with metallic conductivity, such as rutile crystal structure ruthenium dioxide (RuO ₂ ), pyrochlore type lead ruthenate (Pb ₂ Ru ₂ O ₇ ) and bismuth ruthenate (BiRu ₂ O ₇ ) or perovskite type (perovskite) ruthenium alkaline earth metal composite oxide, etc.; and Glass containing lead oxide (PbO) is often chosen, which has the advantages of low softening temperature, good fluidity and good wettability of conductive particles. When the thick film resistor composition contains a composition of ruthenium-based oxide and glass, in addition to being calcined in an atmospheric environment 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 obtain a wide range of resistance values, while also making the temperature coefficient of resistance (TCR) close to 0, which can be used in resistors of 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 proportion of resistance value that changes with temperature. Since the operation of electronic components will generate heat energy and cause temperature changes, commercial resistors generally specify that the temperature coefficient of resistance must be between Between -100 ppm/℃ and +100 ppm/℃, when adjusting the ratio of ruthenium-based oxide and glass in the thick film resistor composition, the resistance value and temperature coefficient of resistance will change 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 When the result is reduced, the proportion of ruthenium-based oxide will increase and the proportion of glass will decrease. At this time, the temperature coefficient of resistance will change in the positive direction. On the contrary, the proportion of ruthenium-based oxide will decrease and the proportion of glass will increase. At this time, the temperature coefficient of resistance will change. It will change in the direction of negative value, and the result of the resistance value increasing 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 increases to a high resistance area of about 100 kΩ/□ or above, the proportion of ruthenium-based oxides will be low, making it difficult for the conductive network to form uniformly in the glass, and it is easy to increase the temperature coefficient of resistance. If it moves too far into the negative direction and is lower than -100 ppm/℃, it 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, in recent years, as awareness of avoiding hazards to human health and the environment has gradually increased, countries have required the ban on hazardous substances in electronic products. Therefore, thick film resistors containing lead ruthenate and lead-containing glass have gradually disappeared from 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 has the problem of easily reacting with glass or substrate during the calcination process and decomposing and reducing to ruthenium dioxide, resulting in a decrease in resistance value. In response to this problem, US 7,476,342 B2 discloses a resistor composition, which is obtained by controlling the composition of lead-free glass to adjust the glass alkalinity, thereby inhibiting the reduction of the ruthenium-based composite oxide, 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 crystal is difficult to control during the firing process, making it difficult to stably control the resistance value, and the effect of the glass crystal on the resistance is not discussed in the content. 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. Areas with high sheet resistance values above /□ can still have characteristics with a 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 above-mentioned problems faced by the prior art, one object of the present invention is to provide a lead-free thick film resistor composition, which uses ruthenium dioxide as conductive particles and can be used to produce a resistor with a resistance of about 0.5 kΩ/□ to about 1100 kΩ. It is a lead-free thick film resistor with a wide area chip resistance value of /□, while still having 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 lead-free thick film resistor composition, which uses ruthenium dioxide as conductive particles and can be used to produce lead-free thick film resistors with a high sheet resistance value of about 100 kΩ/□ or more, and At the same time, it still has the characteristics of resistance temperature coefficient between ±100 ppm/℃.

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 above object, the present invention provides a lead-free thick film resistor composition, which includes ruthenium dioxide, a borosilicate glass, an additive component, an organic carrier and a solvent; wherein the additive component includes copper monoxide ( CuO) or copper monoxide and an oxide selected from the group consisting of 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 use it with highly stable ruthenium dioxide, borosilicate glass, organic carriers and solvents to form a lead-free thick film. 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 a resistance temperature coefficient of ±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%. Even 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 additional components include copper monoxide and silicon dioxide, and based on the total weight of the lead-free thick film resistor composition, the content of the additional components is 1 wt% to 4 wt%; Based on the total weight of the added ingredients, 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 additional components include 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 additional components 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 additional ingredients include 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 additional ingredients is 1 wt%. to 9 wt%; based on the total weight of the added ingredients, the copper monoxide content is 15 wt% to 58 wt%, the silicon dioxide content is 28 wt% to 83 wt%, and the vanadium pentoxide content 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 additional components 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 additional components is 8 wt% to 11 wt%; based on the total weight of the added ingredients, the copper monoxide content is 18 wt% to 20 wt%, the titanium dioxide content is 0.1 wt% to 1.5 wt%, and the silicon dioxide content is 73 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 component includes copper monoxide, silicon dioxide, and an oxide selected from the group consisting of titanium dioxide, vanadium pentoxide, and combinations thereof, and the total amount of the lead-free thick film resistor composition is The content of this added ingredient is 1 wt% to 15 wt% based on weight.

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 component includes a combination of copper monoxide, silicon dioxide and vanadium pentoxide and a combination of copper monoxide, silicon dioxide, vanadium pentoxide and titanium dioxide, and the lead-free thick Based on the total weight of the film 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%. Even 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 and the borosilicate glass is 1:4 to 1:13. More preferably, the weight ratio of ruthenium dioxide and the borosilicate glass is 1:4 to 1:12. Even more preferably, the weight ratio of ruthenium dioxide and 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 monoxide (MgO), calcium monoxide (CaO), barium monoxide (BaO) and zinc monoxide (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%, and the content of magnesium monoxide is The content of calcium 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%, and the content of zinc monoxide is 15 wt% to 25 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 is 28 wt% to 33 wt%. 1 wt% to 3 wt%, calcium monoxide from 3.5 wt% to 4.5 wt%, barium monoxide from 15 wt% to 19 wt% and zinc monoxide from 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 monoxide, calcium monoxide, barium monoxide, zinc monoxide and titanium dioxide, and the borosilicate glass is Based on the total weight of the glass, the content of silicon dioxide is 25 wt% to 35 wt%, the content of boron trioxide is 20 wt% to 30 wt%, and the content of magnesium monoxide is 0.5 wt% to 5 wt%. The calcium monoxide content is from 3 wt% to 5 wt%, the barium monoxide content is from 10 wt% to 20 wt%, the zinc monoxide content is from 15 wt% to 25 wt%, and the titanium dioxide content is from 0.2 wt% to 2wt%.

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 includes silicon dioxide, boron trioxide, magnesium monoxide, calcium monoxide, barium monoxide, zinc monoxide, 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 boron trioxide is 20 wt% to 30 wt%, magnesium monoxide content from 0.5 wt% to 5 wt%, calcium monoxide content from 3 wt% to 5 wt%, barium monoxide content from 10 wt% to 20 wt%, zinc monoxide content The content is 15 wt% to 25 wt%, the titanium dioxide content is 0.2 wt% to 2 wt%, and the sum 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 added 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 carrier 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 carrier 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 carrier 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 further provides a lead-free thick film resistor, which includes a substrate, a resistor layer and two electrodes (anode and cathode). The two electrodes are disposed on opposite sides of the substrate, and the resistor layer is disposed on the On the two electrodes and the substrate, the resistance layer is made of the aforementioned lead-free thick film resistor 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 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 part of the substrate and the two electrodes respectively, but does not include that the resistive layer completely covers the substrate and The two-electrode situation.

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 value 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 value of the lead-free thick film resistor is greater than or equal to 0.9 kΩ/□ and less than or equal to 1090 kΩ/□. Even better, the sheet resistance value 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/℃ and less than or equal to +100 ppm/℃. More preferably, the temperature coefficient of resistance of the lead-free thick film resistor is greater than or equal to -98 ppm/℃ and less than or equal to +97 ppm/℃.

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 may both be silver-palladium electrodes, but are 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 expressed by "a small value to a large value", unless otherwise specified, means that the range is greater than or equal to the small value and less than or equal to the large value. For example: the content is 0.1 wt% to 15 wt%, which means that the content range 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 invention; those familiar with this art can easily understand the advantages and effects that this invention can achieve through the content of this description, and do not deviate from the principles of this invention. Various modifications and changes may be 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編號 SiO ₂(wt%) B ₂O ₃(wt%) MgO (wt%) CaO (wt%) BaO (wt%) Na ₂O (wt%) K ₂O (wt%) ZnO (wt%) TiO ₂(wt%) A 33.0 21.0 2.5 4.5 19.0 -- -- 18.0 2.0 B 28.0 28.0 1.0 4.0 15.0 -- -- 24.0 -- C 31.0 23.0 3.0 3.5 16.0 2.0 0.5 20.0 1.0 In the present invention, three types of borosilicate glasses with different compositions are first prepared for preparing the lead-free thick film resistor composition of the present invention. Table 1 below lists the compositions of the borosilicate glasses marked with numbers A, B, and C and the contents of each component. Table 1: Composition and content of each component of three borosilicate glasses No. SiO ₂ (wt%) B ₂ O ₃ (wt%) MgO (wt%) CaO(wt%) BaO(wt%) Na ₂ O (wt%) K ₂ O (wt%) ZnO(wt%) TiO ₂ (wt%) A 33.0 21.0 2.5 4.5 19.0 -- -- 18.0 2.0 B 28.0 28.0 1.0 4.0 15.0 -- -- 24.0 -- C 31.0 23.0 3.0 3.5 16.0 2.0 0.5 20.0 1.0

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 and the content ratio of each component listed in Table 2 below, select an appropriate amount of ruthenium dioxide, the above-mentioned borosilicate glass powder numbered A, additional ingredients, organic carriers 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, in Examples 1, 3, 4 and 12, each raw material was uniformly mixed; while in Examples 2, 5 to 11, 13 and 14, ruthenium dioxide and silica in the added ingredients were uniformly mixed in advance, Then, the mixture is uniformly mixed with the remaining raw materials to prepare 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 and the content ratio of each component listed in Table 2 below, select an appropriate amount of ruthenium dioxide, the above-mentioned borosilicate glass powder numbered B, additional ingredients, organic carriers 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, each raw material is uniformly mixed; while in Examples 15 to 22 and 25 to 30, ruthenium dioxide and silica in the added ingredients are uniformly mixed in advance, and then uniformly mixed with the remaining raw materials. , and then the lead-free thick film resistor compositions of Examples 15 to 30 were prepared.

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 and the content ratio of each component listed in Table 2 below, select an appropriate amount of ruthenium dioxide, the above-mentioned borosilicate glass powder numbered C, additional ingredients, organic carriers and solvents. As the raw material, the organic carrier system is selected from the ethyl cellulose system, and the solvent is selected from terpineol as the diluent.

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, each raw material is uniformly mixed; while in Examples 31 and 33 to 41, ruthenium dioxide and silica in the added ingredients are uniformly mixed in advance, and then uniformly mixed with the remaining raw materials to prepare 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 processes of Comparative Examples 1 to 4 are similar to 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 and the boron numbered A mentioned above are used. Silicic acid glass powder, organic carrier and solvent are used as raw materials, and these raw materials are uniformly mixed to prepare the lead-free thick film resistor compositions of Comparative Examples 1 to 4.

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 processes of Comparative Examples 5 to 7 are similar to 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 and the boron numbered B above are used. Silicic acid-based glass powder, organic carrier and solvent are used as raw materials, and these raw materials are uniformly mixed to prepare the lead-free thick film resistor compositions of Comparative Examples 5 to 7.

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組別 RuO ₂(wt%) 硼矽酸系玻璃粉添加成分 (wt%) 有機載體 (wt%) 溶劑 (wt%) 編號含量 (wt%) CuO TiO ₂ SiO ₂ V ₂O ₅ 實施例1 11.13 A 55.64 0.28 -- -- -- 23.42 9.53 實施例2 10.54 52.71 1.05 -- 4.22 0.26 22.19 9.03 實施例3 8.58 57.23 0.29 -- -- -- 24.09 9.81 實施例4 8.56 57.07 0.57 -- -- -- 24.02 9.78 實施例5 8.49 56.58 0.57 0.28 0.57 -- 23.82 9.69 實施例6 8.44 56.26 0.73 0.11 1.13 -- 23.69 9.64 實施例7 8.34 55.58 0.83 -- 2.22 0.11 23.4 9.52 實施例8 8.22 54.81 0.93 -- 3.29 0.27 23.07 9.41 實施例9 8.12 54.13 1.08 -- 4.33 0.27 22.79 9.28 實施例10 8.00 53.32 1.33 -- 5.33 0.43 22.45 9.14 實施例11 7.97 53.13 1.59 -- 5.31 0.53 22.36 9.11 實施例12 5.87 58.74 0.59 -- -- -- 24.73 10.07 實施例13 5.48 54.78 1.37 -- 5.48 0.44 23.06 9.39 實施例14 5.46 54.57 1.64 -- 5.46 0.55 22.97 9.35 實施例15 10.74 B 53.70 0.54 1.07 2.15 -- 22.6 9.2 實施例16 11.04 55.18 0.28 0.28 0.55 -- 23.23 9.44 實施例17 8.28 55.18 0.55 1.1 2.21 -- 23.23 9.45 實施例18 8.51 56.74 0.28 0.28 0.57 -- 23.89 9.73 實施例19 8.36 55.76 0.56 -- 2.23 0.06 23.47 9.56 實施例20 8.16 54.37 0.82 -- 4.35 0.11 22.89 9.30 實施例21 8.44 56.26 1.13 -- 0.56 0.28 23.69 9.64 實施例22 7.89 52.57 1.58 -- 6.31 0.53 22.13 8.99 實施例23 5.89 58.92 0.29 -- -- -- 24.8 10.1 實施例24 5.87 58.74 0.59 -- -- -- 24.73 10.07 實施例25 5.67 56.74 0.57 1.13 2.27 -- 23.89 9.73 實施例26 5.84 58.40 0.29 0.29 0.58 -- 24.58 10.02 實施例27 5.74 57.36 0.57 -- 2.29 0.06 24.15 9.83 實施例28 5.59 55.89 0.84 -- 4.47 0.11 23.53 9.57 實施例29 5.79 57.89 1.16 -- 0.58 0.29 24.37 9.92 實施例30 5.40 53.99 1.62 -- 6.48 0.54 22.73 9.24 實施例31 10.94 C 54.72 0.27 1.09 0.55 -- 23.04 9.39 實施例32 8.58 57.23 0.29 -- -- -- 24.09 9.81 實施例33 8.44 56.26 0.28 1.13 0.56 -- 23.69 9.64 實施例34 8.49 56.58 0.28 -- 1.13 -- 23.82 9.7 實施例35 8.45 56.33 0.17 -- 1.69 -- 23.71 9.65 實施例36 8.28 55.18 0.55 -- 3.31 -- 23.23 9.45 實施例37 8.07 53.81 1.08 -- 4.84 0.32 22.65 9.23 實施例38 7.87 52.46 1.68 0.1 6.29 0.52 22.08 9.00 實施例39 7.73 51.51 1.85 0.05 7.73 0.62 21.68 8.83 實施例40 5.39 53.87 1.72 0.11 6.46 0.54 22.68 9.23 實施例41 5.29 52.87 1.90 0.05 7.93 0.63 22.26 9.07 比較例1 11.16 A 55.79 -- -- -- -- 23.49 9.56 比較例2 8.61 57.39 -- -- -- -- 24.16 9.84 比較例3 5.91 59.09 -- -- -- -- 24.87 10.13 比較例4 4.78 59.80 -- -- -- -- 25.17 10.25 比較例5 8.61 B 57.39 -- -- -- -- 24.16 9.84 比較例6 5.91 59.09 -- -- -- -- 24.87 10.13 比較例7 4.78 59.80 -- -- -- -- 25.17 10.25 比較例8 8.61 C 57.39 -- -- -- -- 24.16 9.84 比較例9 5.91 59.09 -- -- -- -- 24.87 10.13 比較例10 4.78 59.80 -- -- -- -- 25.17 10.25 The preparation processes of Comparative Examples 8 to 10 are similar to Examples 31 to 41. The main difference is that Comparative Examples 8 to 10 do not use any additional ingredients as raw materials, that is, only ruthenium dioxide and the boron numbered C above are used. Silicic acid-based glass powder, organic carrier and solvent are used as raw materials, and these raw materials are uniformly mixed to prepare the lead-free thick film resistor compositions of Comparative Examples 8 to 10. Table 2: Composition and content of each component of the lead-free thick film resistor compositions of Examples 1 to 41 and Comparative Examples 1 to 10 Group RuO ₂ (wt%) Borosilicate glass powder Added ingredients(wt%) Organic carrier (wt%) Solvent(wt%) No. Content(wt%) CuO TiO ₂ SiO ₂ V ₂ O ₅ Example 1 11.13 A 55.64 0.28 -- -- -- 23.42 9.53 Example 2 10.54 52.71 1.05 -- 4.22 0.26 22.19 9.03 Example 3 8.58 57.23 0.29 -- -- -- 24.09 9.81 Example 4 8.56 57.07 0.57 -- -- -- 24.02 9.78 Example 5 8.49 56.58 0.57 0.28 0.57 -- 23.82 9.69 Example 6 8.44 56.26 0.73 0.11 1.13 -- 23.69 9.64 Example 7 8.34 55.58 0.83 -- 2.22 0.11 23.4 9.52 Example 8 8.22 54.81 0.93 -- 3.29 0.27 23.07 9.41 Example 9 8.12 54.13 1.08 -- 4.33 0.27 22.79 9.28 Example 10 8.00 53.32 1.33 -- 5.33 0.43 22.45 9.14 Example 11 7.97 53.13 1.59 -- 5.31 0.53 22.36 9.11 Example 12 5.87 58.74 0.59 -- -- -- 24.73 10.07 Example 13 5.48 54.78 1.37 -- 5.48 0.44 23.06 9.39 Example 14 5.46 54.57 1.64 -- 5.46 0.55 22.97 9.35 Example 15 10.74 B 53.70 0.54 1.07 2.15 -- 22.6 9.2 Example 16 11.04 55.18 0.28 0.28 0.55 -- 23.23 9.44 Example 17 8.28 55.18 0.55 1.1 2.21 -- 23.23 9.45 Example 18 8.51 56.74 0.28 0.28 0.57 -- 23.89 9.73 Example 19 8.36 55.76 0.56 -- 2.23 0.06 23.47 9.56 Example 20 8.16 54.37 0.82 -- 4.35 0.11 22.89 9.30 Example 21 8.44 56.26 1.13 -- 0.56 0.28 23.69 9.64 Example 22 7.89 52.57 1.58 -- 6.31 0.53 22.13 8.99 Example 23 5.89 58.92 0.29 -- -- -- 24.8 10.1 Example 24 5.87 58.74 0.59 -- -- -- 24.73 10.07 Example 25 5.67 56.74 0.57 1.13 2.27 -- 23.89 9.73 Example 26 5.84 58.40 0.29 0.29 0.58 -- 24.58 10.02 Example 27 5.74 57.36 0.57 -- 2.29 0.06 24.15 9.83 Example 28 5.59 55.89 0.84 -- 4.47 0.11 23.53 9.57 Example 29 5.79 57.89 1.16 -- 0.58 0.29 24.37 9.92 Example 30 5.40 53.99 1.62 -- 6.48 0.54 22.73 9.24 Example 31 10.94 C 54.72 0.27 1.09 0.55 -- 23.04 9.39 Example 32 8.58 57.23 0.29 -- -- -- 24.09 9.81 Example 33 8.44 56.26 0.28 1.13 0.56 -- 23.69 9.64 Example 34 8.49 56.58 0.28 -- 1.13 -- 23.82 9.7 Example 35 8.45 56.33 0.17 -- 1.69 -- 23.71 9.65 Example 36 8.28 55.18 0.55 -- 3.31 -- 23.23 9.45 Example 37 8.07 53.81 1.08 -- 4.84 0.32 22.65 9.23 Example 38 7.87 52.46 1.68 0.1 6.29 0.52 22.08 9.00 Example 39 7.73 51.51 1.85 0.05 7.73 0.62 21.68 8.83 Example 40 5.39 53.87 1.72 0.11 6.46 0.54 22.68 9.23 Example 41 5.29 52.87 1.90 0.05 7.93 0.63 22.26 9.07 Comparative example 1 11.16 A 55.79 -- -- -- -- 23.49 9.56 Comparative example 2 8.61 57.39 -- -- -- -- 24.16 9.84 Comparative example 3 5.91 59.09 -- -- -- -- 24.87 10.13 Comparative example 4 4.78 59.80 -- -- -- -- 25.17 10.25 Comparative example 5 8.61 B 57.39 -- -- -- -- 24.16 9.84 Comparative example 6 5.91 59.09 -- -- -- -- 24.87 10.13 Comparative example 7 4.78 59.80 -- -- -- -- 25.17 10.25 Comparative example 8 8.61 C 57.39 -- -- -- -- 24.16 9.84 Comparative example 9 5.91 59.09 -- -- -- -- 24.87 10.13 Comparative example 10 4.78 59.80 -- -- -- -- 25.17 10.25

試驗例Test example 11 ：測定玻璃轉化溫度:Measurement 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組別 Tg (℃) 組別 Tg (℃) 組別 Tg (℃) 組別 Tg (℃) 實施例1 590 實施例2 614 實施例3 590 實施例4 584 實施例5 595 實施例6 600 實施例7 603 實施例8 610 實施例9 614 實施例10 612 實施例11 606 實施例12 584 實施例13 612 實施例14 606 實施例15 601 實施例16 589 實施例17 601 實施例18 589 實施例19 596 實施例20 604 實施例21 605 實施例22 601 實施例23 597 實施例24 582 實施例25 601 實施例26 589 實施例27 596 實施例28 604 實施例29 605 實施例30 601 實施例31 591 實施例32 574 實施例33 591 實施例34 596 實施例35 607 實施例36 613 實施例37 615 實施例38 610 實施例39 608 實施例40 610 實施例41 608 比較例1 598 比較例2 598 比較例3 598 比較例4 598 比較例5 595 比較例6 595 比較例7 595 比較例8 580 比較例9 580 比較例10 580 -- -- In this test example, a mixture of borosilicate glass powder and additive ingredients in the lead-free thick film resistor compositions of Examples 1 to 41 was selected as the test sample; in addition, a mixture of the lead-free thick film resistor compositions of Comparative Examples 1 to 10 was used as the test sample. The borosilicate glass powder was used as a test sample, and then according to the specifications in ASTM E1545, differential scanning calorimetry (DSC) was used to measure the glass of the test samples of Examples 1 to 41 and Comparative Examples 1 to 10. conversion temperatures and the results are listed in Table 3 below. Table 3: Glass transition temperatures of test samples of Examples 1 to 41 and Comparative Examples 1 to 10 Group Tg(℃) Group Tg(℃) Group Tg(℃) Group Tg(℃) Example 1 590 Example 2 614 Example 3 590 Example 4 584 Example 5 595 Example 6 600 Example 7 603 Example 8 610 Example 9 614 Example 10 612 Example 11 606 Example 12 584 Example 13 612 Example 14 606 Example 15 601 Example 16 589 Example 17 601 Example 18 589 Example 19 596 Example 20 604 Example 21 605 Example 22 601 Example 23 597 Example 24 582 Example 25 601 Example 26 589 Example 27 596 Example 28 604 Example 29 605 Example 30 601 Example 31 591 Example 32 574 Example 33 591 Example 34 596 Example 35 607 Example 36 613 Example 37 615 Example 38 610 Example 39 608 Example 40 610 Example 41 608 Comparative example 1 598 Comparative example 2 598 Comparative example 3 598 Comparative example 4 598 Comparative example 5 595 Comparative example 6 595 Comparative example 7 595 Comparative example 8 580 Comparative example 9 580 Comparative example 10 580 -- --

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。It can be seen from the results in Table 3 above that the test samples of Examples 1 to 41 have glass transition temperatures of approximately 574°C to 615°C, which are similar to the test samples of Comparative Examples 1 to 10 (approximately 580°C to 598°C). conversion temperature. In addition, by adding specific components and contents to borosilicate glass powders of different compositions, the glass transition temperature can be controlled within a certain range to match the subsequent temperature rise curve in the sintering process for preparing the resistance layer. , assisting in the densification of the resistance 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。The silver palladium electrode paste is printed on the surfaces of the opposite sides of the alumina ceramic substrate by screen printing, and then dried 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 were also printed on the alumina ceramic substrate and silver palladium electrode by screen printing, and covered part of the surface of the alumina ceramic substrate and silver palladium electrode, and then After drying at a temperature of about 100°C to 150°C for about 10 minutes to 15 minutes, it is then calcined at a temperature of about 820°C to 920°C for about 10 minutes to 15 minutes to form a resistance layer, and then cooled to room temperature. The lead-free thick film resistors of Examples 1A to 41A were thus obtained.

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 Embodiments 1A to 41A. The main difference is that Comparative Examples 1A to 10A use the lead-free thick film resistor compositions of Comparative Examples 1 to 10 to make the resistor layer. The other processes are the same as those of Examples 1A to 10A, and the lead-free thick film resistors of Comparative Examples 1A to 10A are produced.

試驗例Test example 22 ：測定片電阻值:Measurement of chip 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 used, and the sheet resistance value was measured in accordance with the specifications of 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 example 33 ：測定電阻溫度係數:Measurement 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組別片電阻值(kΩ/□) 電阻溫度係數(ppm/℃) 實施例1A 1.0 3 實施例2A 5.8 21 實施例3A 5.2 -95 實施例4A 3.6 33 實施例5A 7.6 -73 實施例6A 9.8 -65 實施例7A 16.6 -93 實施例8A 25.0 -81 實施例9A 37.9 -47 實施例10A 33.8 23 實施例11A 27.8 41 實施例12A 18.8 -88 實施例13A 197.3 -32 實施例14A 107.7 -16 實施例15A 1.3 73 實施例16A 0.9 97 實施例17A 7.1 -4 實施例18A 5.3 3 實施例19A 6.4 93 實施例20A 21.4 35 實施例21A 30.8 51 實施例22A 42.1 68 實施例23A 12.2 -19 實施例24A 11.4 33 實施例25A 50.1 -89 實施例26A 28.4 -95 實施例27A 45.8 -82 實施例28A 99.8 -73 實施例29A 235.8 -98 實施例30A 312.8 -86 實施例31A 1.1 88 實施例32A 2.9 73 實施例33A 5.2 21 實施例34A 8.4 14 實施例35A 46.3 -87 實施例36A 183.8 -38 實施例37A 217.0 2 實施例38A 153.8 72 實施例39A 173.0 88 實施例40A 978.4 -89 實施例41A 1090.0 -92 比較例1A 2.4 -27 比較例2A 11.3 -272 比較例3A 53.9 -376 比較例4A 112.0 -436 比較例5A 2.1 -50 比較例6A 12.0 -159 比較例7A 44.6 -247 比較例8A 6.4 -149 比較例9A 37.6 -271 比較例10A 48.8 -261 This test example uses the lead-free thick film resistors of Examples 1A to 41A and Comparative Examples 1A to 10A, and the resistance temperature coefficient is measured in accordance with the specifications of Article 4.8 of IEC 60115-1; among them, the temperature range of the test is about 25℃ to about 125℃, and the temperature coefficient of resistance can be calculated by the following formula: Temperature coefficient of resistance = ( _RT -R ₂₅ )/R ₂₅ (T-25)/10 ⁶ , and R _T is a specific The resistance value is measured at temperature, and R ₂₅ is the resistance value measured at approximately 25°C. The measurement results of the temperature coefficient of resistance of the lead-free thick film resistors of Examples 1A to 41A and Comparative Examples 1A to 10A are shown in Table 4 below. Table 4: Measurement results of sheet resistance values and resistance temperature coefficients of lead-free thick film resistors of Examples 1A to 41A and Comparative Examples 1A to 10A Group Chip resistance value (kΩ/□) Temperature coefficient of resistance (ppm/℃) Example 1A 1.0 3 Example 2A 5.8 twenty one Example 3A 5.2 -95 Example 4A 3.6 33 Example 5A 7.6 -73 Example 6A 9.8 -65 Example 7A 16.6 -93 Example 8A 25.0 -81 Example 9A 37.9 -47 Example 10A 33.8 twenty three Example 11A 27.8 41 Example 12A 18.8 -88 Example 13A 197.3 -32 Example 14A 107.7 -16 Example 15A 1.3 73 Example 16A 0.9 97 Example 17A 7.1 -4 Example 18A 5.3 3 Example 19A 6.4 93 Example 20A 21.4 35 Example 21A 30.8 51 Example 22A 42.1 68 Example 23A 12.2 -19 Example 24A 11.4 33 Example 25A 50.1 -89 Example 26A 28.4 -95 Example 27A 45.8 -82 Example 28A 99.8 -73 Example 29A 235.8 -98 Example 30A 312.8 -86 Example 31A 1.1 88 Example 32A 2.9 73 Example 33A 5.2 twenty one Example 34A 8.4 14 Example 35A 46.3 -87 Example 36A 183.8 -38 Example 37A 217.0 2 Example 38A 153.8 72 Example 39A 173.0 88 Example 40A 978.4 -89 Example 41A 1090.0 -92 Comparative example 1A 2.4 -27 Comparative example 2A 11.3 -272 Comparative example 3A 53.9 -376 Comparative Example 4A 112.0 -436 Comparative example 5A 2.1 -50 Comparative Example 6A 12.0 -159 Comparative Example 7A 44.6 -247 Comparative example 8A 6.4 -149 Comparative Example 9A 37.6 -271 Comparative example 10A 48.8 -261

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。It can be seen from the results in Table 4 above that the lead-free thick film resistors of Examples 1A to 41A can have a relatively wide range of sheet resistance values from about 0.9 kΩ/□ to about 1090 kΩ/□, and at the same time, they can still maintain a resistance temperature coefficient between ±100 ppm/℃; in contrast, comparative examples 1A to 10A, only when comparative examples 1A and 5A have lower sheet resistance values of approximately 2.1 kΩ/□ and 2.4 kΩ/□ can the resistance temperature coefficient be maintained between ±100 ppm/℃, once the sheet resistance value is further increased, for example, Comparative Examples 2A to 4A and 6A to 10A all have sheet resistance values higher than about 6.4 kΩ/□, then Comparative Examples 2A to 4A and 6A to 10A All have resistance temperature coefficients significantly lower than -100 ppm/℃. It can be proved from this that by selecting the lead-free thick film resistor compositions of Examples 1 to 41 containing specific types of additive components to make the lead-free thick film resistors of Examples 1A to 41A, the lead-free thick film resistors of Examples 1A to 41A can be obtained in a wide range of applications. Even if the chip resistance value is within the same range, it can still maintain 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。In summary, since the lead-free thick film resistor composition of the present invention contains specific types of additives, it can be made into a lead-free thick film resistor with a wide range of resistance values, and at the same time still has a resistance temperature coefficient of ±100 ppm/ The characteristics between ℃ allow the lead-free thick film resistor of the present invention to be used in resistors of a wide range of specifications and enhance its commercial value.

無。without.

Claims

A lead-free thick film resistor composition, which includes ruthenium dioxide, a borosilicate glass, an additive component, an organic carrier and a solvent; wherein the additive component includes copper monoxide or copper monoxide and a titanium dioxide selected from the group consisting of oxides of the group consisting of , silicon dioxide, vanadium pentoxide and their combinations.

The lead-free thick film resistor composition as claimed in claim 1, wherein the content of the additive component is 0.1 to 15 weight percent based on the total weight of the lead-free thick film resistor composition.

The lead-free thick film resistor composition according to claim 1, wherein the content of ruthenium dioxide is 3 to 15 weight percent based on the total weight of the lead-free thick film resistor composition.

The lead-free thick film resistor composition according to claim 1, wherein the weight ratio of ruthenium dioxide and the borosilicate glass is 1:4 to 1:13.

The lead-free thick film resistor composition according to claim 1, wherein the average particle size of the ruthenium dioxide is greater than or equal to 0.05 microns and less than or equal to 0.25 microns.

The lead-free thick film resistor composition according to claim 1, wherein the borosilicate glass contains silicon dioxide, diboron trioxide, magnesium monoxide, calcium monoxide, barium monoxide and zinc monoxide, and Based on the total weight of the borosilicate glass, the content of silicon dioxide is 25 to 35 weight percent, the content of diboron trioxide is 20 to 30 weight percent, and the content of magnesium monoxide is 0.5 weight percent. to 5 weight percent, calcium monoxide from 3 to 5 weight percent, barium monoxide from 10 to 20 weight percent, and zinc monoxide from 15 to 25 weight percent.

The lead-free thick film resistor composition according to claim 6, wherein the borosilicate glass further contains titanium dioxide, and based on the total weight of the borosilicate glass, the content of titanium dioxide is 0.2 weight percent to 2 weight percent. percentage.

The lead-free thick film resistor composition according to claim 7, wherein the borosilicate glass further contains sodium monoxide and potassium monoxide, and based on the total weight of the borosilicate glass, sodium monoxide and The total content of potassium monoxide is 0.5% by weight to 3% by weight.

The lead-free thick film resistor composition according to claim 1, wherein the average particle size of the borosilicate glass is greater than or equal to 1 micron and less than or equal to 3 microns.

The lead-free thick film resistor composition according to any one of claims 1 to 9, wherein 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 570°C. equal to 620℃.

A lead-free thick film resistor, which includes a substrate, a resistance layer and two electrodes, the two electrodes are arranged on opposite sides of the substrate, the resistance layer is arranged on the two electrodes and the substrate, and the resistance layer It is made of the lead-free thick film resistor composition as described in any one of claims 1 to 10.

Such as the lead-free thick film resistor of claim 11, wherein the sheet resistance value of the lead-free thick film resistor is greater than or equal to 0.5 kΩ/□ and less than or equal to 1100 kΩ/□.

The lead-free thick film resistor as described in claim 12 or 13, wherein the temperature coefficient of resistance of the lead-free thick film resistor is greater than or equal to -100 ppm/℃ and less than or equal to +100 ppm/℃.