JP2018067640A - Composition for positive temperature coefficient resistor, paste for positive temperature coefficient resistor, positive temperature coefficient resistor, and method for manufacturing positive temperature coefficient resistor - Google Patents
Composition for positive temperature coefficient resistor, paste for positive temperature coefficient resistor, positive temperature coefficient resistor, and method for manufacturing positive temperature coefficient resistor Download PDFInfo
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
- H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/006—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
- H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
Abstract
Description
本発明は、正温度係数抵抗体の製造において用いられる組成物および抵抗ペーストに関する。さらには、この抵抗ペーストを用いて形成した正温度係数抵抗体に関する。 The present invention relates to compositions and resistance pastes used in the manufacture of positive temperature coefficient resistors. Furthermore, it is related with the positive temperature coefficient resistor formed using this resistance paste.
正温度係数抵抗体は、温度の上昇と共にその比抵抗が増加する抵抗体である。特にある温度で比抵抗が急激に増加するものは「ＰＴＣサーミスタ」と呼ばれ、温度制御素子、過電流制御素子、低温度発熱体等として広く応用されている。
この「ＰＴＣサーミスタ」は、ＢａＴｉＯ３系セラミックスを代表とする無機系の材料を利用するものと、熱可塑性のポリマーにカーボンブラック等の導電性充填剤を分散させた有機系材料を利用するものに大別される。
The positive temperature coefficient resistor is a resistor whose specific resistance increases as the temperature increases. In particular, those whose specific resistance increases rapidly at a certain temperature are called “PTC thermistors” and are widely applied as temperature control elements, overcurrent control elements, low-temperature heating elements, and the like.
This “PTC thermistor” uses inorganic materials such as BaTiO 3 ceramics and organic materials in which a conductive filler such as carbon black is dispersed in a thermoplastic polymer. Broadly divided.
ＢａＴｉＯ３系セラミックスは、Ｂａ、Ｔｉ等の原料を均一に混合した後、仮焼して複合酸化物の結晶化を進めておく必要があり、この結晶化させた複合酸化物を加圧形成した成形体を焼成する事によって製造される。
このため素子の形状に制限があり、小型化が難しい。また、スイッチング温度と呼ばれる、ＢａＴｉＯ３系セラミックスの比抵抗が急激に変化する温度は、一般にキュリー点の１２０℃程度の温度である。
In BaTiO 3 ceramics, it is necessary to uniformly mix raw materials such as Ba and Ti, and then calcined to advance crystallization of the composite oxide. The crystallized composite oxide was formed under pressure. Manufactured by firing the compact.
For this reason, the shape of the element is limited, and it is difficult to reduce the size. Moreover, the temperature at which the specific resistance of BaTiO 3 ceramics changes rapidly, which is called the switching temperature, is generally about 120 ° C. of the Curie point.
特許文献１には、ＢａＴｉＯ３系セラミックのＢａの一部をアルカリ金属元素に置換したり、Ｔｉの一部をＮｂ等の５族元素に置換したサーミスタ磁器組成物が開示されているが、２５０℃より高温のキュリー点の開示はなく、これをより高温にするのは非常に困難である。更に、調整可能なセラミックスの比抵抗の範囲が小さい。 Patent Document 1 discloses a thermistor porcelain composition in which a part of Ba in a BaTiO 3 ceramic is substituted with an alkali metal element, or a part of Ti is substituted with a group 5 element such as Nb. There is no disclosure of the Curie point above 0 ° C., and it is very difficult to make it higher. Furthermore, the range of the specific resistance of the adjustable ceramic is small.
一方、有機系材料を用いた「ＰＴＣサーミスタ」は素子形状の制限が少なく、導電性充填剤の種類や含有率によって比抵抗を変える事が出来、調整可能な比抵抗の範囲が広い利点がある。しかし、熱可塑性のポリマーが軟化する温度から、得られるスイッチング温度には制限があり、高温で抵抗値が急激に変化する素子を作る事ができない。また、マトリックスであるポリマーは、高温における長期使用や繰り返し高温となる環境では分解が進んでしまい信頼性に乏しい欠点がある。 On the other hand, “PTC thermistors” using organic materials are less limited in element shape, can change specific resistance depending on the type and content of conductive filler, and have the advantage of a wide range of adjustable specific resistance. . However, the switching temperature obtained from the temperature at which the thermoplastic polymer softens is limited, and an element in which the resistance value changes rapidly at high temperatures cannot be produced. Moreover, the polymer which is a matrix has a defect that the decomposition proceeds under long-term use at a high temperature or in an environment where the temperature is repeatedly high, resulting in poor reliability.
この他、Ａｇ等の導電性粒子をガラス中に分散させた「ＰＴＣサーミスタ」も特許文献２に提案されているが、低い比抵抗に限られることと、スイッチング温度が高過ぎて４００℃以下にはならなく、スイッチング温度より低い温度において、高い正の温度係数となるなどの欠点がある。
In addition, a “PTC thermistor” in which conductive particles such as Ag are dispersed in glass is also proposed in
そこで、２５０℃以上、４００℃以下の温度範囲において、スイッチング動作を可能とする抵抗体の開発が望まれている。 Therefore, it is desired to develop a resistor that can perform a switching operation in a temperature range of 250 ° C. or more and 400 ° C. or less.
このような状況の中、本発明は、素子形状の制限が少なく、調整可能な比抵抗の範囲が広く、２５０℃〜４００℃の範囲でスイッチングする、高温における信頼性の高い正温度係数抵抗体用の組成物、その組成物による抵抗体ペースト、その抵抗体ペーストから形成される抵抗体、及びその製造方法を提供するものである。 Under such circumstances, the present invention is a positive temperature coefficient resistor with high reliability at high temperatures, which has a limited element shape, has a wide range of adjustable specific resistance, and switches in the range of 250 ° C. to 400 ° C. Composition, a resistor paste made of the composition, a resistor formed from the resistor paste, and a manufacturing method thereof.
本発明は、導電性粒子としてルテニウム系酸化物粒子とガラス転移点が２５０℃〜４００℃のガラス粉末を混合した正温度係数抵抗体用組成物および抵抗体ペーストを課題解決の手段とする。 The present invention uses a composition for a positive temperature coefficient resistor and a resistor paste, in which ruthenium-based oxide particles and glass powder having a glass transition point of 250 ° C. to 400 ° C. are mixed as conductive particles.
本発明の第１の発明は、金属酸化物系導電性粒子と４００℃以下のガラス転移点を有するガラス粉末とを含有することを特徴とする正温度係数抵抗体用組成物である。 1st invention of this invention is a composition for positive temperature coefficient resistors containing a metal oxide type electroconductive particle and the glass powder which has a glass transition point of 400 degrees C or less.
本発明の第２の発明は、第１の発明における金属酸化物系導電性粒子が、ルテニウム系酸化物粒子であることを特徴とする正温度係数抵抗体用組成物である。 A second invention of the present invention is a composition for a positive temperature coefficient resistor, wherein the metal oxide conductive particles in the first invention are ruthenium oxide particles.
本発明の第３の発明は、第２の発明におけるルテニウム系酸化物粒子が、酸化ルテニウム粒子であることを特徴とする正温度係数抵抗体用組成物である。 A third invention of the present invention is a composition for a positive temperature coefficient resistor, wherein the ruthenium-based oxide particles in the second invention are ruthenium oxide particles.
本発明の第４の発明は、有機ビヒクルと、前記第１から第３の発明のいずれかに記載の正温度係数抵抗体用組成物を含有することを特徴とする正温度係数抵抗体用ペーストである。 4th aspect of this invention contains the composition for positive temperature coefficient resistors in any one of said 1st to 3rd invention, and the organic vehicle, The paste for positive temperature coefficient resistors characterized by the above-mentioned It is.
本発明の第５の発明は、４００℃以下のガラス転移点を有するガラス中に金属酸化物系導電性粒子が含まれていることを特徴とする正温度係数抵抗体である。 According to a fifth aspect of the present invention, there is provided a positive temperature coefficient resistor characterized in that metal oxide based conductive particles are contained in a glass having a glass transition point of 400 ° C. or lower.
本発明の第６の発明は、第５の発明における金属酸化物系導電性粒子が、ルテニウム系酸化物粒子であることを特徴とする正温度係数抵抗体である。 A sixth invention of the present invention is a positive temperature coefficient resistor, wherein the metal oxide conductive particles in the fifth invention are ruthenium oxide particles.
本発明の第７の発明は、第６の発明におけるルテニウム系酸化物粒子が、酸化ルテニウム粒子であることを特徴とする正温度係数抵抗体である。 A seventh invention of the present invention is a positive temperature coefficient resistor, wherein the ruthenium-based oxide particles in the sixth invention are ruthenium oxide particles.
本発明の第８の発明は、第４の発明に記載の正温度係数抵抗体用ペーストを、絶縁基板上に塗布、焼成することによって、有機溶剤と有機樹脂を消失させ、ガラス粉末を軟化させて前記正温度係数抵抗体用ペーストに含まれる金属酸化物系導電性粒子を、前記正温度係数抵抗体用ペーストに含有されるガラス粉末により形成されるガラスマトリックス内に取り込み、乾燥して固化させることによって製造されることを特徴とする正温度係数抵抗体の製造方法である。 According to an eighth aspect of the present invention, the paste for positive temperature coefficient resistor according to the fourth aspect is applied onto an insulating substrate and baked, thereby eliminating the organic solvent and the organic resin and softening the glass powder. The metal oxide conductive particles contained in the positive temperature coefficient resistor paste are taken into the glass matrix formed by the glass powder contained in the positive temperature coefficient resistor paste and dried to solidify. It is the manufacturing method of the positive temperature coefficient resistor characterized by the above-mentioned.
本発明によれば、素子形状の制限が少なく、調整可能な比抵抗の範囲が広く、２５０℃〜４００℃の範囲でスイッチングする、高温における信頼性の高い正温度係数抵抗体用の組成物、その組成物による抵抗体ペースト、その抵抗体ペーストから形成される抵抗体を容易に得られる。 According to the present invention, a composition for a positive temperature coefficient resistor with high reliability at high temperatures, which has a limited element shape, has a wide range of adjustable specific resistance, and switches in a range of 250 ° C. to 400 ° C., A resistor paste made of the composition and a resistor formed from the resistor paste can be easily obtained.
本発明は、ルテニウム酸化物粒子等の金属酸化物系導電性粒子とガラス粉末を含有する正温度係数抵抗体用組成物において、ガラス転移点が２５０℃以上、４００℃以下のガラス粉末を使用することによって得られた抵抗体が、２５０℃以上、４００℃以下の温度範囲内の設定温度を境に急激に抵抗値が変化する現象を見出し、さらに鋭意開発した結果、このようなガラス転移点を持つガラス粉末と金属酸化物系導電性粒子との組合せにより、温度上昇に対する比抵抗の上昇割合が変化する温度であるスイッチング温度が２５０℃から４００℃の範囲で制御可能な正温度係数抵抗体の完成に至ったものである。 The present invention uses a glass powder having a glass transition point of 250 ° C. or higher and 400 ° C. or lower in a composition for positive temperature coefficient resistor containing metal oxide conductive particles such as ruthenium oxide particles and glass powder. As a result of finding a phenomenon in which the resistance value suddenly changes at a set temperature within a temperature range of 250 ° C. or more and 400 ° C. or less, and further earnestly developing, A positive temperature coefficient resistor that can be controlled in a switching temperature range of 250 ° C. to 400 ° C., which is a temperature at which the rate of increase in the specific resistance with respect to the temperature rise varies by the combination of the glass powder and the metal oxide conductive particles. It has been completed.
一般に、ガラスマトリックス中に、導電性粒子が分散している厚膜抵抗体では、ガラスマトリックスの体積膨張によって導電性粒子間の接触が弱くなり比抵抗の増加を招くものである。
ところで、ガラスは、そのガラス転移点を境に体積膨張率が大きく変化し、ガラス転移点の高温側では、低温側よりも体積膨張率が高い性質を持っている。
本発明に係る正温度係数抵抗体でも、ガラス転移点の高温側で体積膨張率が高くなるので、ガラス転移点を境に比抵抗の増加率も変化する。すなわちガラス転移点以上の温度では、ガラス転移点以下の温度よりも抵抗値の増加率が急激に大きくなると期待された。
In general, in a thick film resistor in which conductive particles are dispersed in a glass matrix, contact between the conductive particles is weakened due to volume expansion of the glass matrix, leading to an increase in specific resistance.
By the way, glass has a property that the volume expansion coefficient changes greatly at the boundary of the glass transition point, and the volume expansion coefficient is higher on the high temperature side of the glass transition point than on the low temperature side.
Even in the positive temperature coefficient resistor according to the present invention, the volume expansion coefficient is increased on the high temperature side of the glass transition point, so that the increase rate of the specific resistance also changes at the glass transition point. That is, at a temperature above the glass transition point, it was expected that the rate of increase in resistance value would be sharply greater than at temperatures below the glass transition point.
しかしながら、一般的な厚膜抵抗体は８５０℃前後で焼成されるが、ガラス転移点が低いガラスを用いるとガラスが過度に軟化し、厚膜抵抗体の形状が維持できないなど不具合が生じるため、５００℃以上のガラス転移点を示すガラスを用いることが一般的である。 However, although a general thick film resistor is fired at around 850 ° C., if a glass having a low glass transition point is used, the glass is excessively softened, and problems such as failure to maintain the shape of the thick film resistor occur. It is common to use a glass exhibiting a glass transition point of 500 ° C. or higher.
ところで、ガラス転移点が５００℃以上のガラス粉末と金属酸化物系導電性粒子を用いると、スイッチング温度が５００℃以上の正温度係数抵抗体が可能と考えられるが、スイッチング温度が５００℃を超える正温度係数抵抗体が得られたとすると、この正温度係数抵抗体は、５００℃以上の温度で動作することとなる。そのために、正温度係数抵抗体だけではなく、厚膜抵抗体に組み込まれる端子電極などの周辺部品も５００℃以上の温度に曝されることになり、端子電極の劣化などの問題が生じる。
また、スイッチング温度を５００℃より低く抑えたい場合には、これらの組合せは利用できなかった。
By the way, when glass powder having a glass transition point of 500 ° C. or higher and metal oxide conductive particles are used, it is considered that a positive temperature coefficient resistor having a switching temperature of 500 ° C. or higher is possible, but the switching temperature exceeds 500 ° C. If a positive temperature coefficient resistor is obtained, the positive temperature coefficient resistor will operate at a temperature of 500 ° C. or higher. For this reason, not only the positive temperature coefficient resistor but also peripheral components such as a terminal electrode incorporated in the thick film resistor are exposed to a temperature of 500 ° C. or more, which causes problems such as deterioration of the terminal electrode.
Further, when it is desired to keep the switching temperature below 500 ° C., these combinations cannot be used.
このような問題からすれば、厚膜抵抗体で正温度係数抵抗体を形成する場合、そのスイッチング温度が４００℃以下の抵抗体を望まれた場合には対応できず、その対応品の提供が希求されている。 In view of such a problem, when a positive temperature coefficient resistor is formed with a thick film resistor, it cannot cope with a resistor whose switching temperature is 400 ° C. or lower, and provision of a corresponding product is not possible. It is sought after.
そこで、本発明で用いるガラス粉末は、ガラス転移点が４００℃以下、好ましくは２５０℃以上、４００℃以下の範囲にガラス転移点を持つ成分組成のガラス粉末を用いる。
上記のようなガラス転移点を有するガラス粉末の組成は限定されないが、例としてはホウ酸鉛系のガラスや、リン酸スズ系のガラス、バナジウム酸テルルガラスなどがある。
Therefore, the glass powder used in the present invention is a glass powder having a component composition having a glass transition point in the range of 400 ° C. or lower, preferably 250 ° C. or higher and 400 ° C. or lower.
The composition of the glass powder having the glass transition point as described above is not limited, but examples include lead borate glass, tin phosphate glass, and tellurium vanadate glass.
本発明におけるガラス粉末のガラス転移点の下限は限定しないが、現時点では酸化物ガラスでは実質上２４０℃を下回るものは見出されていないので、望ましい範囲として２５０℃以上、４００℃以下とする。なお、本発明で用いるガラス粉末のガラス転移点や軟化点は、ガラス粉末の組成により調整できる。具体的には、ガラスを構成するケイ素、ホウ素、アルミニウム、亜鉛、鉛、ビスマスなどの各元素の配合割合を調整すればよい。
ここで、ガラス転移点は、ガラス粉末を再溶融などして得られるロッド状の試料を熱機械分析法（ＴＭＡ）にて大気中で測定し、熱膨張曲線の屈曲点を示す温度として測定される。
Although the lower limit of the glass transition point of the glass powder in the present invention is not limited, no oxide glass having a temperature substantially lower than 240 ° C. has been found at present, so that the desirable range is 250 ° C. or more and 400 ° C. or less. In addition, the glass transition point and softening point of the glass powder used by this invention can be adjusted with the composition of glass powder. Specifically, the blending ratio of each element such as silicon, boron, aluminum, zinc, lead, and bismuth constituting the glass may be adjusted.
Here, the glass transition point is measured as a temperature indicating the inflection point of the thermal expansion curve when a rod-shaped sample obtained by remelting the glass powder is measured in the atmosphere by thermomechanical analysis (TMA). The
また、本発明で用いるガラス粉末の軟化点は、ガラス転移点より５０℃以上高い温度であることが望ましい。
ガラス粉末の軟化点は、ガラスの軟化が起こる最も低い温度であり、軟化点を大きく超える温度では正温度係数抵抗体の形状を維持できない。本発明に係る正温度係数抵抗体は、ガラス転移点を超える温度でも正温度係数抵抗体を維持する必要がある。そのため、本発明で用いるガラス粉末の軟化点はガラス転移点より５０℃以上高い温度で、後述する焼成温度の上限値未満の温度が望ましい。
In addition, the softening point of the glass powder used in the present invention is desirably a temperature higher by 50 ° C. or more than the glass transition point.
The softening point of the glass powder is the lowest temperature at which the softening of the glass occurs, and the shape of the positive temperature coefficient resistor cannot be maintained at a temperature that greatly exceeds the softening point. The positive temperature coefficient resistor according to the present invention needs to maintain the positive temperature coefficient resistor even at a temperature exceeding the glass transition point. Therefore, the softening point of the glass powder used in the present invention is preferably 50 ° C. or more higher than the glass transition point, and is preferably less than the upper limit of the firing temperature described later.
ここで軟化点は、ガラス粉末を示差熱分析法（ＴＧ−ＤＴＡ）にて大気中で測定し、最も低温側の示差熱曲線の減少が発現する温度よりも高温側の次の示差熱曲線が減少するピークの温度である。
なお、本発明で用いるガラス粉末のガラス転移点や軟化点は、ガラス粉末の成分組成により調整するものである。
Here, the softening point is determined by measuring the glass powder in the atmosphere by differential thermal analysis (TG-DTA), and the following differential thermal curve on the higher temperature side than the temperature at which the decrease in the differential thermal curve on the lowest temperature side appears. The temperature of the decreasing peak.
In addition, the glass transition point and softening point of the glass powder used by this invention are adjusted with the component composition of glass powder.
ガラス粉末の粒径は特に制限しないが、抵抗値のバラツキや安定性を考慮するとレーザ回折散乱型の粒度分布計の体積分布径のメジアン値（Ｄ５０）が１０μｍ以下のものが望ましく、さらに望ましくは３μｍ以下である。 The particle size of the glass powder is not particularly limited. However, in consideration of resistance variation and stability, the median value (D 50 ) of the volume distribution diameter of the laser diffraction scattering type particle size distribution meter is preferably 10 μm or less, and more preferably. Is 3 μm or less.
本発明における導電性粒子には、金属酸化物系導電性粒子を用いる。
その金属酸化物系導電性粒子としてはルテニウム系酸化物粒子、酸化イリジウム粒子、酸化スズ粒子やアンチモン添加酸化スズ粒子等の酸化スズ系粒子、スズ添加酸化インジウム粒子が挙げられる。
これらの金属酸化物系導電性粒子の製造方法は、例えば、水溶液中で金属元素の水酸化物の沈殿を得て、添加元素の化合物と、大気雰囲気や不活性雰囲気などを適宜選択し加熱焙焼することで得ることができる。
As the conductive particles in the present invention, metal oxide conductive particles are used.
Examples of the metal oxide conductive particles include ruthenium oxide particles, iridium oxide particles, tin oxide particles such as tin oxide particles and antimony-added tin oxide particles, and tin-added indium oxide particles.
These metal oxide-based conductive particles can be produced by, for example, obtaining a precipitate of a metal element hydroxide in an aqueous solution, selecting an additive element compound, an air atmosphere, an inert atmosphere, etc. It can be obtained by baking.
上記金属酸化物系導電性粒子のうち、導電率の高さから、ルテニウム系酸化物粒子が好ましく、そのルテニウム系酸化物粒子としては、二酸化ルテニウム（以下酸化ルテニウムという）の他ルテニウム酸鉛、ルテニウム酸ビスマス等のパイロクロア型結晶構造を有するものや、ルテニウム酸ストロンチウム、ルテニウム酸カルシウム等のペロブスカイト型の結晶構造を有する酸化物粒子が好適である。
さらに、ルテニウム酸化物は、ガラスとの配合比を変えることによって広い抵抗値領域をカバーすることができ、しかも特定の金属酸化物等を少量添加することによって抵抗温度係数を調整することができる。
Of the above metal oxide based conductive particles, ruthenium based oxide particles are preferred because of their high conductivity. Examples of the ruthenium based oxide particles include ruthenium dioxide (hereinafter referred to as ruthenium oxide), lead ruthenate, ruthenium. Oxide particles having a pyrochlore type crystal structure such as bismuth acid and perovskite type crystal structures such as strontium ruthenate and calcium ruthenate are suitable.
Furthermore, ruthenium oxide can cover a wide resistance range by changing the compounding ratio with glass, and the resistance temperature coefficient can be adjusted by adding a small amount of a specific metal oxide or the like.
ガラス粉末とルテニウム系酸化物粒子の混合割合は、ガラス粉末と導電性粒子の合計に対し導電性粒子が１０質量％〜５０質量％である。導電性粒子が１０質量％より小さいと抵抗値が高くなりすぎ、５０質量％より多いと膜が脆くなりすぎる。
このようなガラス粉末とルテニウム系酸化物粒子の配合割合ならば、本発明に係る正温度係数抵抗体用組成物から得られる正温度係数抵抗体の表面は、平滑になり膜構造が保たれ、温度変化などで正温度係数抵抗体が破損することはない。
The mixing ratio of the glass powder and the ruthenium-based oxide particles is 10% by mass to 50% by mass of the conductive particles with respect to the total of the glass powder and the conductive particles. When the conductive particles are less than 10% by mass, the resistance value becomes too high, and when it is more than 50% by mass, the film becomes too brittle.
If the mixing ratio of such glass powder and ruthenium-based oxide particles, the surface of the positive temperature coefficient resistor obtained from the composition for positive temperature coefficient resistor according to the present invention is smooth and the film structure is maintained, The positive temperature coefficient resistor is not damaged by temperature changes.
また、ガラスとの配合比によってなだらかに抵抗値を調整する観点から、導電性粒子の粒径は限定されないが、０．１μｍ以下が望ましい。導電性粒子の粒径の測定方法は、ＢＥＴ法で比表面積を測定し、粒状に換算して粒径を求めてもよい。 Further, from the viewpoint of adjusting the resistance value gently depending on the mixing ratio with glass, the particle diameter of the conductive particles is not limited, but is preferably 0.1 μm or less. As a method for measuring the particle diameter of the conductive particles, the specific surface area may be measured by the BET method, and the particle diameter may be obtained by converting into a granular form.
ところで、ガラス粉末と導電性粒子を含む抵抗体組成物の導電性粒子には、金属酸化物系粒子の他に、銀−パラジウム合金粒子等の金属粒子を用いることも知られているが、導電性粒子を金属粒子のみで構成する場合、金属粒子が酸化したり焼結することがあり所望の抵抗値が得られない、あるいは温度変化などで正温度係数抵抗体が破損する恐れがあるために、本発明に係る正温度係数抵抗体用組成物に用いることは望ましくない。 By the way, it is also known to use metal particles such as silver-palladium alloy particles in addition to metal oxide particles as the conductive particles of the resistor composition including glass powder and conductive particles. If the conductive particles are composed only of metal particles, the metal particles may oxidize or sinter, resulting in failure to obtain the desired resistance value, or the positive temperature coefficient resistor may be damaged due to temperature changes. It is not desirable to use the positive temperature coefficient resistor composition according to the present invention.
そこで、本発明の正温度係数抵抗体用組成物には、抵抗値や抵抗温度係数の改善、調整を目的として添加剤を加えても良く、ＭｎＯ２、Ｎｂ２Ｏ５、Ｔａ２Ｏ５、ＴｉＯ２、ＣｕＯ、ＺｒＯ２、Ａｌ２Ｏ３、ＳｉＯ２、Ｍｇ２ＳｉＯ４、ＺｒＳｉＯ４があげられる。
これらの添加剤を加えることで、より優れた特性を有する正温度係数抵抗体を作製する事ができる。その添加する量は目的によって調整されるが、ルテニウム酸化物導電粒子とガラス粉末の合計１００重量部に対して通常２０重量部以下である。
なお、添加剤は、個数平均径のメジアン値（Ｄ５０）で３μｍ以下の粉末状でも良いし、正温度係数抵抗体用ペーストを焼成する過程で有機金属化合物が分解して、これら添加剤の化合物を生じてもよい。
Therefore, an additive may be added to the composition for a positive temperature coefficient resistor of the present invention for the purpose of improving and adjusting the resistance value and the resistance temperature coefficient, such as MnO 2 , Nb 2 O 5 , Ta 2 O 5 , Examples thereof include TiO 2 , CuO, ZrO 2 , Al 2 O 3 , SiO 2 , Mg 2 SiO 4 , and ZrSiO 4 .
By adding these additives, a positive temperature coefficient resistor having more excellent characteristics can be produced. The amount to be added is adjusted depending on the purpose, but is usually 20 parts by weight or less with respect to 100 parts by weight of the total of the ruthenium oxide conductive particles and the glass powder.
The additive may be in the form of a powder having a median value of number average diameter (D 50 ) of 3 μm or less, or the organometallic compound decomposes in the process of firing the paste for positive temperature coefficient resistor, Compounds may be produced.
ルテニウム酸化物導電粒子とガラス粉末は、必要に応じて添加剤と共に印刷用のペーストとするために有機ビヒクル中に混合、分散される。
使用する有機ビヒクルには特に制限はなく、ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート等の溶剤にエチルセルロース、アクリル酸エステル、メタアクリル酸エステル、ロジン、マレイン酸エステル等の樹脂を溶解した有機ビヒクルが用いられる。また、必要に応じて、分散剤や可塑剤などを加える事ができる。
分散方法も特に制限されないが、微細な粒子を分散させる３本ロールミルやビーズミル、遊星ミル等を用いるのが一般的である。有機ビヒクルの配合比率は印刷や塗布方法によって適宣調整されるが、ルテニウム酸化物導電粒子、ガラス粉末、添加剤の合計１００重量部に対して２０〜２００重量部程度である。
The ruthenium oxide conductive particles and the glass powder are mixed and dispersed in an organic vehicle to form a paste for printing together with additives as necessary.
The organic vehicle to be used is not particularly limited, and an organic vehicle in which a resin such as ethyl cellulose, acrylic acid ester, methacrylic acid ester, rosin, maleic acid ester or the like is dissolved in a solvent such as terpineol, butyl carbitol, or butyl carbitol acetate. Used. Moreover, a dispersing agent, a plasticizer, etc. can be added as needed.
Although the dispersion method is not particularly limited, it is common to use a three-roll mill, a bead mill, a planetary mill or the like that disperses fine particles. The blending ratio of the organic vehicle is appropriately adjusted by printing or coating method, and is about 20 to 200 parts by weight with respect to 100 parts by weight of the total ruthenium oxide conductive particles, glass powder, and additives.
［抵抗体の製造方法］
本発明に係る正温度係数抵抗体の製造方法の一例は、正温度係数抵抗体用ペーストをセラミック等の絶縁基板上に公知のスクリーン印刷法等で塗布する印刷工程、正温度係数抵抗体用ペーストに含まれる溶剤を加熱除去し乾燥膜を得る乾燥工程、得られた乾燥膜を焼成する焼成工程の各工程を順に経て製造される。
[Manufacturing method of resistor]
An example of a method for producing a positive temperature coefficient resistor according to the present invention is a printing process in which a paste for a positive temperature coefficient resistor is applied to an insulating substrate such as a ceramic by a known screen printing method, a paste for a positive temperature coefficient resistor The solvent contained in is heated and removed to obtain a dry film, and the baking process for baking the obtained dry film is sequentially performed.
焼成工程では、樹脂を加熱して除去する脱バインダーを経て、使用したガラス粉末の軟化点より高い温度で焼成し、ガラス粉末が軟化して粒子同士が融着・溶融してガラス膜状のガラスマトリックスを形成するとともに、基材に固着される。
また導電性粒子は、ガラス粉末の周囲に存在し、乾燥膜を焼成する際に、ガラス粉末の融着により形成されたガラスマトリックス内に固着される。
結果的に、正温度係数抵抗体は、ガラス粉末が融着して形成されたガラスマトリックス中に導電性粒子が導入された焼成体として得られる。
In the firing process, the resin is removed by heating to remove the binder, and then fired at a temperature higher than the softening point of the used glass powder. The glass powder is softened and the particles are fused and melted to form a glass film glass. A matrix is formed and secured to the substrate.
The conductive particles exist around the glass powder, and are fixed in a glass matrix formed by fusing the glass powder when the dried film is fired.
As a result, the positive temperature coefficient resistor is obtained as a fired body in which conductive particles are introduced into a glass matrix formed by fusing glass powder.
その焼成工程における焼成温度は、使用するガラス粉末のガラス転移点、及び軟化点を考慮して決定するもので、焼成温度が高すぎる場合では、所定形状に焼成体を形成できず、低すぎる場合にも焼成が不十分となり所定形状の焼成体が得られず、また導電性粒子の焼成体内への導入が不十分となる。
その温度範囲として、軟化点＋５０℃〜１５０℃が好ましく、軟化点＋６０℃〜１３０℃がより好ましい。
The firing temperature in the firing step is determined in consideration of the glass transition point and softening point of the glass powder to be used. When the firing temperature is too high, the fired body cannot be formed into a predetermined shape and is too low. However, firing is insufficient and a fired body having a predetermined shape cannot be obtained, and introduction of conductive particles into the fired body is insufficient.
The temperature range is preferably a softening point + 50 ° C to 150 ° C, more preferably a softening point + 60 ° C to 130 ° C.
なお、乾燥工程の乾燥温度や乾燥時間はペースト中の溶剤が揮発させるのに十分な条件を適時選択する事ができる。
絶縁基板には、アルミナなどのセラミック基板が用いられる。また、得られた正温度係数抵抗体に端子電極を設けて電気回路と接続させる。なお、前記端子電極は、あらかじめ絶縁基板に、公知の厚膜銀ペースト等を用いて形成してもよい。
これまで、本発明を説明してきたが、本発明に係る正温度係数抵抗体用組成物を焼成することで得られる抵抗体が、本発明に係る正温度係数抵抗体であり、本発明に係る正温度計数抵抗体組成物を有機ビヒクルに分散することで正温度係数抵抗体用ペーストを得ることができる。
In addition, conditions sufficient for the solvent in a paste to volatilize can be selected timely about the drying temperature and drying time of a drying process.
A ceramic substrate such as alumina is used for the insulating substrate. Further, a terminal electrode is provided on the obtained positive temperature coefficient resistor and connected to an electric circuit. The terminal electrode may be formed on an insulating substrate in advance using a known thick film silver paste or the like.
So far, the present invention has been described. However, the resistor obtained by firing the composition for positive temperature coefficient resistor according to the present invention is the positive temperature coefficient resistor according to the present invention. A positive temperature coefficient resistor paste can be obtained by dispersing the positive temperature counting resistor composition in an organic vehicle.
本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
本発明の実施例と比較例に使用したガラス粉末の成分組成、個数平均径のメジアン値（Ｄ５０）、ガラス転移点を表１に示す。
導電性粒子には、ＢＥＴ法による比表面積測定から求めた比表面積が２０ｍ／ｇ、粒径４０ｎｍの酸化ルテニウム粒子を用い、ガラス粉末には、レーザ回折散乱型の粒度分布計の個数平均径のメジアン値（Ｄ５０）が１．５μｍの表１に示す各ガラス粉末を用いた。
上記導電性粒子とガラス粉末を表２に示す混合比とし、その合計１００重量部に対して、４３重量部の有機ビヒクル中に、添加、混合後、３本ロールミルで分散させて供試材の抵抗ペーストを作製した。
The present invention will be specifically described, but the present invention is not limited to these examples.
Table 1 shows the component composition, the median value (D 50 ) of the number average diameter, and the glass transition point of the glass powder used in Examples and Comparative Examples of the present invention.
For the conductive particles, ruthenium oxide particles having a specific surface area of 20 m / g and a particle diameter of 40 nm determined from the specific surface area measurement by the BET method are used. For the glass powder, the number average diameter of a laser diffraction scattering type particle size distribution meter is used. Each glass powder shown in Table 1 having a median value (D 50 ) of 1.5 μm was used.
The conductive particles and glass powder were mixed at the mixing ratio shown in Table 2, and added to and mixed with 43 parts by weight of an organic vehicle with respect to a total of 100 parts by weight. Resistive paste was prepared.
次に、予めアルミナ基板に焼成して形成したＡｇの電極上に、作製した抵抗ペーストを印刷し、１５０℃×５分の条件で乾燥後、表２に示す各ガラス粉末の軟化度合に合わせた温度まで昇温した後１０分間保持する条件で焼成し室温まで下げて抵抗体を形成した。
供試材の抵抗体サイズは、抵抗体幅を１．０ｍｍ、抵抗体長さ（電極間）を１．０ｍｍとなるようにした。
Next, the produced resistance paste was printed on an Ag electrode formed by firing on an alumina substrate in advance, dried at 150 ° C. for 5 minutes, and adjusted to the softening degree of each glass powder shown in Table 2. After heating up to the temperature, firing was performed for 10 minutes and the temperature was lowered to room temperature to form a resistor.
The resistor size of the test material was such that the resistor width was 1.0 mm and the resistor length (between electrodes) was 1.0 mm.
作製した抵抗体が示す「抵抗値の温度依存性」を、温度制御のできるオーブンを用い、そのオーブン内に４端子法の電位抵抗測定試料とした上記供試材を載置し、オーブン温度を変えながら、４端子法により電気抵抗をデジタルマルチメータで測定した。
その測定結果を、図１から図５（実施例１から実施例５）、図６（比較例１）、図７（比較例２）に示す。
Using the oven that can control the temperature dependence of the resistance value shown by the prepared resistor, place the above test material as a potential resistance measurement sample of the 4-terminal method in the oven, and set the oven temperature to While changing, the electrical resistance was measured with a digital multimeter by the 4-terminal method.
The measurement results are shown in FIGS. 1 to 5 (Example 1 to Example 5), FIG. 6 (Comparative Example 1), and FIG. 7 (Comparative Example 2).
実施例１、２は、ガラス転移点２４０℃のガラス粉末と酸化ルテニウム粒子からなる抵抗体である。図１、図２に示される抵抗値の温度特性から、およそ２５０℃で温度に対する抵抗値変化（抵抗温度係数）が変わっている事がわかる。この抵抗温度係数の変曲点は原料であるガラスのガラス転移点とほぼ一致する。
実施例３、４は、ガラス転移点２７０℃のガラス粉末と酸化ルテニウム粒子からなる抵抗体である。図３、４から抵抗温度係数の変曲点がおよそ２８０℃で現われ、ガラスの転移点とほぼ一致する。
実施例５は、ガラス転移点が４００℃のガラス粉末と酸化ルテニウム粒子からなる抵抗体である。図５から抵抗温度係数の変曲点がおよそ４００℃で現われ、ガラスの転移点とほぼ一致する。
Examples 1 and 2 are resistors made of glass powder having a glass transition point of 240 ° C. and ruthenium oxide particles. It can be seen from the temperature characteristics of the resistance values shown in FIGS. 1 and 2 that the change in resistance value (resistance temperature coefficient) with respect to temperature changes at about 250 ° C. The inflection point of the temperature coefficient of resistance almost coincides with the glass transition point of the glass material.
Examples 3 and 4 are resistors made of glass powder having a glass transition point of 270 ° C. and ruthenium oxide particles. 3 and 4, the inflection point of the resistance temperature coefficient appears at about 280 ° C., which almost coincides with the glass transition point.
Example 5 is a resistor composed of glass powder having a glass transition point of 400 ° C. and ruthenium oxide particles. From FIG. 5, the inflection point of the temperature coefficient of resistance appears at about 400 ° C., which is almost coincident with the glass transition point.
以上の実施例に対して、図６、７に示す比較例１、２ではガラス転移点が５１０℃と５５０℃のガラスと酸化ルテニウムからなる抵抗体の抵抗温度特性を示した。いずれも２５℃〜５００℃の温度範囲では、抵抗温度特性の変曲点は現われなかった。 In contrast to the above examples, Comparative Examples 1 and 2 shown in FIGS. In any case, the inflection point of the resistance temperature characteristic did not appear in the temperature range of 25 ° C to 500 ° C.
実施例、比較例から判るように、本発明によれば、従来困難であった２５０℃から４００℃の温度範囲で抵抗温度係数が変化する正温係数抵抗体を製造することができ、抵抗温度係数の変曲点は原料ガラスのガラス転移点を調整することによって選択することが可能となる。 As can be seen from the examples and comparative examples, according to the present invention, it is possible to manufacture a positive temperature coefficient resistor whose resistance temperature coefficient changes in a temperature range of 250 ° C. to 400 ° C., which has been difficult in the past, The inflection point of the coefficient can be selected by adjusting the glass transition point of the raw glass.
Claims (8)
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| JP2016205560A JP6848327B2 (en) | 2016-10-19 | 2016-10-19 | A method for producing a composition for a positive temperature coefficient resistor, a paste for a positive temperature coefficient resistor, a positive temperature coefficient resistor, and a positive temperature coefficient resistor. |
| TW106132982A TWI654624B (en) | 2016-10-19 | 2017-09-26 | Composition for positive temperature coefficient resistor, paste for positive temperature coefficient resistor, positive temperature coefficient resistor and manufacturing method of positive temperature coefficient resistor |
| KR1020170133807A KR20180043173A (en) | 2016-10-19 | 2017-10-16 | Composition for positive temperature coefficient resistor, paste for positive temperature coefficient resistor, positive temperature coefficient resistor and method for producing positive temperature coefficient resistor |
| CN202011420907.5A CN112670045A (en) | 2016-10-19 | 2017-10-19 | Composition for positive temperature coefficient resistor, paste, resistor, and method for producing resistor |
| CN201710973679.6A CN107967973A (en) | 2016-10-19 | 2017-10-19 | Positive temperature coefficient resistor body composition, paste, the manufacture method of resistive element and resistive element |
| KR1020190070811A KR102341611B1 (en) | 2016-10-19 | 2019-06-14 | Composition for positive temperature coefficient resistor, paste for positive temperature coefficient resistor, positive temperature coefficient resistor and method for producing positive temperature coefficient resistor |
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| JP2020151983A (en) * | 2019-03-20 | 2020-09-24 | ローム株式会社 | Thermal print head |
| US11610853B2 (en) | 2019-03-25 | 2023-03-21 | Delta Electronics (Shanghai) Co., Ltd | Semiconductor chip |
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| KR101138238B1 (en) * | 2010-12-24 | 2012-04-24 | (주) 케이엠씨 테크놀러지 | Manufacturing method of paste composition for resistor using coating metal oxide, thick film resistor and manufacturing method of the resistor |
| KR101138246B1 (en) * | 2010-12-24 | 2012-04-24 | (주) 케이엠씨 테크놀러지 | Manufacturing method of paste composition having low temperature coefficient resistance for resistor, thick film resistor and manufacturing method of the resistor |
| KR101958496B1 (en) * | 2011-06-21 | 2019-03-14 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Ruthenium Oxide Powder, Composition for Thick film Resistor Elements Using Same, and Thick film Resistor Element |
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