JP2023077053A - Composition for thick film resistor, paste for the thick film resistor, and the thick film resistor - Google Patents
Composition for thick film resistor, paste for the thick film resistor, and the thick film resistor Download PDFInfo
- Publication number
- JP2023077053A JP2023077053A JP2021190171A JP2021190171A JP2023077053A JP 2023077053 A JP2023077053 A JP 2023077053A JP 2021190171 A JP2021190171 A JP 2021190171A JP 2021190171 A JP2021190171 A JP 2021190171A JP 2023077053 A JP2023077053 A JP 2023077053A
- Authority
- JP
- Japan
- Prior art keywords
- thick film
- film resistor
- powder
- composition
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 104
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 73
- 239000011521 glass Substances 0.000 claims abstract description 66
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 14
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 39
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical group O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 20
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000010304 firing Methods 0.000 description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 229910052707 ruthenium Inorganic materials 0.000 description 9
- 230000005611 electricity Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- -1 etc. Chemical compound 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical class [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Non-Adjustable Resistors (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、厚膜抵抗体用組成物、厚膜抵抗体用ペースト、及び厚膜抵抗体に関する。 The present invention relates to a composition for thick film resistors, a paste for thick film resistors, and a thick film resistor.
一般にチップ抵抗器、ハイブリットＩＣ、または、抵抗ネットワーク等の厚膜抵抗体は、セラミック基板に厚膜抵抗体用ペーストを印刷して焼成することによって形成されている。厚膜抵抗体用ペーストに用いる厚膜抵抗体用組成物としては、導電粒子である酸化ルテニウムを代表とするルテニウム系導電粒子と、ガラス粉末と、を主な成分としたものが広く用いられている。 Thick-film resistors such as chip resistors, hybrid ICs, and resistor networks are generally formed by printing and firing a thick-film resistor paste on a ceramic substrate. As a composition for a thick film resistor used in a paste for a thick film resistor, a composition mainly containing ruthenium-based conductive particles, typically ruthenium oxide, which is a conductive particle, and glass powder is widely used. there is
ルテニウム系導電粒子と、ガラス粉末とを含む組成物が厚膜抵抗体の原料として広く用いられる理由としては、空気中での焼成ができ、広い領域の抵抗値の厚膜抵抗体が形成可能であること等が挙げられる。 The reason why a composition containing ruthenium-based conductive particles and glass powder is widely used as a raw material for thick film resistors is that it can be fired in air to form a thick film resistor with a wide range of resistance values. There are certain things.
ルテニウム系導電粒子とガラス粉末とを含む厚膜抵抗体用組成物を用いて厚膜抵抗体を作製した場合、その配合比によって抵抗値が変わる。ルテニウム系導電粒子の配合比を多くすると抵抗値が下がり、ルテニウム系導電粒子の配合比を少なくすると抵抗値が上がる。このことを利用して、厚膜抵抗体では、ルテニウム系導電粒子とガラス粉末の配合比を調整して所望する抵抗値を出現させている。 When a thick-film resistor composition containing ruthenium-based conductive particles and glass powder is used to fabricate a thick-film resistor, the resistance value changes depending on the compounding ratio. When the compounding ratio of the ruthenium-based conductive particles is increased, the resistance value decreases, and when the compounding ratio of the ruthenium-based conductive particles is decreased, the resistance value increases. Utilizing this fact, in the thick film resistor, a desired resistance value is produced by adjusting the compounding ratio of the ruthenium-based conductive particles and the glass powder.
厚膜抵抗体の原料組成物に特に使用されているルテニウム系導電粒子としては、ルチル型の結晶構造を有する酸化ルテニウム（ＲｕＯ２）や、パイロクロア型の結晶構造を有するルテニウム酸鉛（Ｐｂ２Ｒｕ２Ｏ６．５）などのルテニウム酸化物のパイロクロル化合物が挙げられる。これらはいずれも金属的な導電性を示す酸化物で、抵抗値のばらつきの少ない厚膜抵抗体を製造できる。また、短時間過負荷や静電気破壊による抵抗値変化も小さく耐電性にも優れていることから、厚膜抵抗体の導電粒子として優れている。特許文献１には、ルテニウム酸化物の導電性パイロクロルと銀とパラジウムを導電体成分とし、鉛ガラスをガラス結着剤として用いた厚膜抵抗体用組成物が開示されている。 Ruthenium-based conductive particles that are particularly used in the raw material composition of thick film resistors include ruthenium oxide (RuO 2 ) having a rutile-type crystal structure and lead ruthenate (Pb 2 Ru) having a pyrochlore-type crystal structure. 2 O 6.5 ) and other pyrochlore compounds of ruthenium oxides. All of these are oxides that exhibit metallic conductivity, and can produce thick film resistors with little variation in resistance value. In addition, since the change in resistance value due to short-time overload or electrostatic breakdown is small and the resistance to electricity is also excellent, it is excellent as a conductive particle for a thick film resistor. Patent Literature 1 discloses a composition for a thick-film resistor using conductive pyrochlore of ruthenium oxide, silver, and palladium as conductor components, and lead glass as a glass binder.
しかし、近年、環境保護の観点から、電子部品の鉛フリー化が進んでおり、厚膜抵抗体においても鉛フリー化が望まれている。しかし、厚膜抵抗体用ペーストを鉛フリー化するとルテニウム酸鉛などを使用した場合と比べ、抵抗値のばらつきや電流ノイズは大きくなり、耐電性や静電気に対する耐サージ特性（ＥＳＤ）も劣るといった問題があった。 However, in recent years, from the viewpoint of environmental protection, lead-free electronic components have been promoted, and lead-free thick film resistors are desired. However, when lead-free thick-film resistor paste is used, compared to the case of using lead ruthenate, etc., the variation in resistance value and current noise increase, and the electrical resistance and surge resistance (ESD) against static electricity are also inferior. was there.
そこで、特許文献２には、鉛成分を含まないルテニウム系導電性成分と、ガラスの塩基度（Ｐｏ値）が０．４～０．９である鉛成分を含まないガラスで構成される抵抗体組成物が開示されている。特許文献２の抵抗体組成物では、厚膜抵抗体中に結晶物が存在することで、ＴＣＲや電流ノイズが改善されるとある。特許文献２には、ルテニウム系導電性成分が少なく、ガラスが多い配合の抵抗体組成物のみが開示されている。 Therefore, in Patent Document 2, a resistor composed of a ruthenium-based conductive component that does not contain a lead component and glass that does not contain a lead component and has a glass basicity (Po value) of 0.4 to 0.9 A composition is disclosed. In the resistor composition of Patent Document 2, TCR and current noise are improved by the presence of crystals in the thick film resistor. Patent Document 2 discloses only a resistor composition containing less ruthenium-based conductive component and containing more glass.
このような事情に鑑み、本発明の目的は、鉛フリーの厚膜抵抗体でガラス成分が少ない組成でも、耐サージ特性（ＥＳＤ）に優れた厚膜抵抗体用組成物を提供することにある。 In view of such circumstances, it is an object of the present invention to provide a composition for a lead-free thick film resistor, which is excellent in anti-surge characteristics (ESD) even with a composition containing a small amount of glass components. .
上記課題を解決するため本発明は、鉛成分を含まない導電物粉末とガラス粉末と酸化マンガン粉末を含む厚膜抵抗体用組成物であって、該組成物が焼成されて得られる厚膜抵抗体をＸ線回折するとマンガン化合物が検出されない厚膜抵抗体用組成物である。 In order to solve the above problems, the present invention provides a composition for a thick film resistor containing lead-free conductor powder, glass powder, and manganese oxide powder, wherein the thick film resistor is obtained by sintering the composition. It is a composition for thick film resistors in which no manganese compound is detected by X-ray diffraction of the body.
本発明によれば、耐サージ特性（ＥＳＤ）の優れた厚膜抵抗体が製造できる。 According to the present invention, a thick film resistor having excellent anti-surge characteristics (ESD) can be manufactured.
以下、本実施形態の厚膜抵抗体用組成物、厚膜抵抗体用ペースト、及び厚膜抵抗体の一実施形態について説明する。 An embodiment of the composition for a thick film resistor, the paste for a thick film resistor, and the thick film resistor of the present embodiment will be described below.
［厚膜抵抗体用組成物］
本実施形態の厚膜抵抗体用組成物は、導電物粉末とガラス粉末と酸化マンガン粉末を含む。厚膜抵抗体用組成物は、厚膜抵抗体用ペーストに加工され、さらには、焼成されて厚膜抵抗体に加工される。
[Composition for thick film resistor]
The thick film resistor composition of the present embodiment contains conductive powder, glass powder and manganese oxide powder. The thick-film resistor composition is processed into a thick-film resistor paste, and further fired to be processed into a thick-film resistor.
１．導電物粉末
導電物粉末は、鉛成分を含まない酸化ルテニウム粉末（ＲｕＯ２粉末）である。なお、鉛成分を含まない酸化ルテニウム粉末とは、鉛を意図して添加していないことを意味する。ただし、製造工程等で不純物成分、不可避成分として混入することを排除するものではない。
1. Conductive powder Conductive powder is lead-free ruthenium oxide powder ( RuO2 powder). The ruthenium oxide powder containing no lead component means that lead is not intentionally added. However, it does not exclude the contamination as an impurity component or an unavoidable component in the manufacturing process or the like.
酸化ルテニウム粉末の調製方法や、物性は特に限定されるものではないが、例えば、水酸化ルテニウム粉末を８００℃以上９００℃以下の焼成温度で、空気中で焼成することで得られる。 The preparation method and physical properties of the ruthenium oxide powder are not particularly limited.
酸化ルテニウム粉末の平均粒径は１５ｎｍ～６０ｎｍであることが望ましい。酸化ルテニウム粉末の平均粒径が６０ｎｍを超えると、耐サージ特性（ＥＳＤ）が悪化することがある。一方、酸化ルテニウム粉末の粒径が１５ｎｍ未満では、ＴＣＲがマイナス側にシフトしてしまうこともある。 The ruthenium oxide powder preferably has an average particle size of 15 nm to 60 nm. If the average particle size of the ruthenium oxide powder exceeds 60 nm, the surge resistance (ESD) may deteriorate. On the other hand, if the particle size of the ruthenium oxide powder is less than 15 nm, the TCR may shift to the negative side.
上記平均粒径は、酸化ルテニウム粉末の比表面積をＢＥＴ法によって測定し、その比表面積と酸化ルテニウム粉末の密度から求めることができる。具体的には、係る平均粒径（ｎｍ）は、粉末の比表面積をＳ（ｍ２／ｇ）、密度をρ（ｇ／ｃｍ３）と表したときの６×１０３／（ρ・Ｓ）の計算値とすることができる。 The average particle size can be determined from the specific surface area of the ruthenium oxide powder measured by the BET method and the density of the ruthenium oxide powder. Specifically, the average particle size (nm) is 6 ×10 3 / (ρ S ) can be calculated.
さらに、所望の抵抗値領域に応じて、銀粉末、パラジウム粉末といった貴金属を含む粉末をさらに添加、含有することもできる。 Furthermore, depending on the desired resistance value range, powders containing noble metals such as silver powders and palladium powders can be further added and contained.
２．ガラス粉末
本実施形態で用いるガラス粉末は鉛成分を含まないガラス粉末である。なお、鉛成分を含まないガラス粉末とは、鉛を意図して添加していないことを意味する。ただし、製造工程等で不純物成分、不可避成分として混入することを排除するものではない。
2. Glass Powder The glass powder used in this embodiment is a glass powder containing no lead component. The glass powder containing no lead component means that lead is not intentionally added. However, it does not exclude the contamination as an impurity component or an unavoidable component in the manufacturing process or the like.
本実施形態で用いるガラス粉末は、ＳｉＯ２とＢ２Ｏ３とＲＯ（ＲはＣａ、Ｓｒ、Ｂａから選択される１種類以上のアルカリ土類元素を示す）を含むガラス粉末である。ガラス粉末は、厚膜抵抗体用組成物を焼成する際の熱で溶融し、導電物粉末の結着剤として作用するとともに、厚膜抵抗体を構成するガラスマトリックスとなる。 The glass powder used in this embodiment is a glass powder containing SiO 2 , B 2 O 3 and RO (R represents one or more alkaline earth elements selected from Ca, Sr and Ba). The glass powder is melted by the heat generated when the composition for thick film resistors is fired, acts as a binder for the conductive powder, and becomes a glass matrix that constitutes the thick film resistor.
そして、ガラス粉末は、ガラスの骨格となるＳｉＯ２以外の金属酸化物を配合することによって焼成時の流動性を調整することが可能となる。ＳｉＯ２以外の金属酸化物としては、Ｂ２Ｏ３及びＲＯ（ＲはＣａ、Ｓｒ、Ｂａから選択された１種類以上のアルカリ土類元素を示す）を用いることができる。なお、ＲＯについて、Ｒが２種類以上の場合とは、ＣａＯ、ＳｒＯ、及びＢａＯから選択された２種類以上を含むことを意味する。 The glass powder can be adjusted in fluidity during firing by blending a metal oxide other than SiO 2 that serves as the skeleton of the glass. B 2 O 3 and RO (R represents one or more alkaline earth elements selected from Ca, Sr and Ba) can be used as metal oxides other than SiO 2 . Regarding RO, the case where R is two or more means that two or more types selected from CaO, SrO, and BaO are included.
ガラス粉末の組成のＳｉＯ２、Ｂ２Ｏ３、ＲＯの含有量の合計を１００質量部とした場合、ＳｉＯ２を１０質量部以上５０質量部以下、Ｂ２Ｏ３を８質量部以上３０質量部以下、ＲＯを４０質量部以上６５質量部以下の割合で含むことが好ましい。 When the total content of SiO 2 , B 2 O 3 , and RO in the composition of the glass powder is 100 parts by mass, SiO 2 is 10 parts by mass or more and 50 parts by mass or less, and B 2 O 3 is 8 parts by mass or more and 30 parts by mass. parts or less, and preferably contains RO in a proportion of 40 parts by mass or more and 65 parts by mass or less.
ガラス粉末のガラス組成におけるＳｉＯ２、Ｂ２Ｏ３、ＲＯの合計を１００質量部とした場合に、ＳｉＯ２の含有割合を５０質量部以下とすることで流動性を十分に高めることができる。一方、ＳｉＯ２の含有割合が１０質量部より小さいとガラスになり難くなる場合がある。 When the total of SiO 2 , B 2 O 3 , and RO in the glass composition of the glass powder is 100 parts by mass, the fluidity can be sufficiently enhanced by setting the content of SiO 2 to 50 parts by mass or less. On the other hand, if the content of SiO 2 is less than 10 parts by mass, it may become difficult to form glass.
また、Ｂ２Ｏ３を８質量部以上とすることで、流動性を十分に高めることができ、３０質量部以下とすることで耐候性を高めることができる。 Moreover, by making B 2 O 3 8 parts by mass or more, fluidity can be sufficiently improved, and by making it 30 parts by mass or less, weather resistance can be improved.
ＲＯの含有割合を４０質量部以上とすることで、焼成時のガラスの流動性を得ることができる。またＲＯの含有割合を６５質量部以下とすることで、結晶化を抑制し、ガラスを形成し易くすることができる。 By setting the content ratio of RO to 40 parts by mass or more, the fluidity of the glass during firing can be obtained. Also, by setting the RO content to 65 parts by mass or less, crystallization can be suppressed and glass can be easily formed.
本実施形態の厚膜抵抗体用組成物に含まれるガラスの組成は、既述のＳｉＯ２とＢ２Ｏ３とＲＯに加えて、ガラスの耐候性や焼成時の流動性を調整する目的で他の成分を含有することもできる。任意の添加成分の例としては、Ａｌ２Ｏ３、ＺｒＯ２、ＴｉＯ２、ＳｎＯ２、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等が挙げられ、これらの化合物から選択された１種類以上をガラスに添加することもできる。 The composition of the glass contained in the composition for a thick film resistor of the present embodiment is, in addition to the above-mentioned SiO 2 , B 2 O 3 and RO, for the purpose of adjusting the weather resistance of the glass and fluidity during firing. Other ingredients may also be included. Examples of optional additive components include Al 2 O 3 , ZrO 2 , TiO 2 , SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O and the like, and one selected from these compounds The above can also be added to the glass.
Ａｌ２Ｏ３はガラスの分相を抑制しやすく、ＺｒＯ２、ＴｉＯ２はガラスの耐候性を向上させる働きがある。また、ＳｎＯ２、ＺｎＯ、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等は溶融時のガラスの流動性を高める働きがある。 Al 2 O 3 tends to suppress phase separation of the glass, and ZrO 2 and TiO 2 work to improve the weather resistance of the glass. Also, SnO 2 , ZnO, Li 2 O, Na 2 O, K 2 O, etc. have the function of increasing the fluidity of the glass during melting.
ガラスの焼成時の流動性に影響する尺度として軟化点がある。一般に、厚膜抵抗体を製造する際の、厚膜抵抗体用組成物を焼成する温度は８００℃以上９００℃以下である。 The softening point is a measure that affects the fluidity of glass during firing. In general, the temperature for baking the composition for thick film resistors is 800° C. or higher and 900° C. or lower when manufacturing thick film resistors.
このように、厚膜抵抗体を製造する際の厚膜抵抗体用組成物の焼成温度が８００℃以上９００℃以下の場合、本実施形態に係る厚膜抵抗体用組成物に用いるガラスの軟化点は、６００℃以上８００℃以下が好ましく、６００℃以上７５０℃以下がより好ましい。 As described above, when the baking temperature of the composition for a thick film resistor is 800° C. or more and 900° C. or less when manufacturing a thick film resistor, the glass used for the composition for a thick film resistor according to the present embodiment softens. The point is preferably 600° C. or higher and 800° C. or lower, more preferably 600° C. or higher and 750° C. or lower.
ここで、軟化点は、ガラスを示差熱分析法（ＴＧ－ＤＴＡ）にて大気中で、１０℃／ｍｉｎで昇温、加熱し、得られた示差熱曲線の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。 Here, the softening point is the differential thermal curve on the lowest temperature side of the differential thermal curve obtained by heating and heating the glass at 10 ° C./min in the atmosphere by differential thermal analysis (TG-DTA). It is the peak temperature at which the next differential thermal curve decreases, which is higher than the temperature at which the decrease occurs.
ガラスは、一般的に、所定の成分またはそれらの前駆体を目的とする配合にあわせて混合し、得られた混合物を溶融し急冷することによって製造できる。溶融温度は特に限定されるものではないが例えば１４００℃前後とすることができる。また、急冷の方法についても特に限定されないが、溶融物を冷水中に入れるか冷ベルト上に流すことにより行うことができる。 Glasses can generally be produced by mixing the given components or their precursors into a desired formulation, melting and quenching the resulting mixture. Although the melting temperature is not particularly limited, it can be around 1400°C, for example. Also, the method of quenching is not particularly limited, but it can be carried out by placing the melt in cold water or flowing it on a cooling belt.
ガラスの粉砕にはボールミル、遊星ミル、ビーズミルなど用いることができるが、粒度をシャープにするには湿式粉砕が望ましい。 A ball mill, a planetary mill, a bead mill, or the like can be used for pulverizing the glass, but wet pulverization is desirable for sharpening the particle size.
使用するガラス粉末の粒度は、レーザー回折を利用した粒度分布計により測定したガラスの５０％体積累計粒度は５μｍ以下が好ましく、３μｍ以下であることがさらに好ましい。ガラスの粒度が大きすぎると厚膜抵抗体の抵抗値ばらつきの増大や耐サージ特性（ＥＳＤ）の悪化、ＴＣＲのマイナス側へのシフトの原因となる。一方、ガラスの粒度を過度に小さくすると、生産性が低くなり、不純物等の混入も増える恐れがあることから、ガラスの５０％体積累計粒度は０．1μｍ以上が好ましい。 Regarding the particle size of the glass powder used, the 50% volume cumulative particle size of the glass measured by a particle size distribution meter using laser diffraction is preferably 5 μm or less, more preferably 3 μm or less. If the grain size of the glass is too large, it causes an increase in the variation in the resistance value of the thick film resistor, a deterioration in the surge resistance (ESD), and a shift of the TCR to the minus side. On the other hand, if the particle size of the glass is excessively small, the productivity may be lowered and the contamination of impurities may increase.
３．酸化マンガン粉末
本実施形態で用いる酸化マンガン粉末は、ＭｎＯ２粉末やＭｎ３Ｏ４粉末を用いることができる。このうち、Ｍｎ３Ｏ４粉末が、より好ましい。本実施形態の厚膜抵抗体用組成物を焼成して厚膜抵抗体に加工される過程で、Ｍｎ３Ｏ４粉末は、ガラスマトリックスに取り込まれやすい。
3. Manganese Oxide Powder MnO 2 powder or Mn 3 O 4 powder can be used as the manganese oxide powder used in this embodiment. Among these, Mn 3 O 4 powder is more preferable. The Mn 3 O 4 powder is likely to be incorporated into the glass matrix during the process of firing the thick film resistor composition of the present embodiment to process it into a thick film resistor.
発明者が、酸化マンガンの含まれている厚膜抵抗体のＸ線回折を行ったところ、耐サージ特性（ＥＳＤ）が劣る厚膜抵抗体には、酸化マンガンや、酸化マンガン由来の化合物の結晶物が残存していることと、耐サージ特性（ＥＳＤ）が優れる厚膜抵抗体からはＸ線回折では酸化マンガンや、酸化マンガン由来の化合物は検出されないことが確認された。耐サージ特性に優れる厚膜抵抗体は、酸化マンガンがガラスに取り込まれていて、Ｘ線回折で判別できる大きさの酸化マンガンや酸化マンガン由来の化合物が存在しないことを意味する。ここで、酸化マンガン由来の化合物とは、ガラスと反応で生じるＺｎＭｎ２Ｏ４などがある。 When the inventor conducted X-ray diffraction of a thick film resistor containing manganese oxide, it was found that thick film resistors with inferior surge resistance (ESD) include crystals of manganese oxide and compounds derived from manganese oxide. Manganese oxide and compounds derived from manganese oxide were not detected by X-ray diffraction from the thick film resistor with excellent anti-surge characteristics (ESD). A thick-film resistor with excellent surge resistance means that manganese oxide is incorporated in the glass, and there is no manganese oxide or a compound derived from manganese oxide of a size that can be determined by X-ray diffraction. Here, the compound derived from manganese oxide includes ZnMn 2 O 4 and the like generated by reaction with glass.
Ｘ線回折で判別できる大きさの酸化マンガンや酸化マンガン由来の化合物が厚膜抵抗体中に存在すると、厚膜抵抗体中の導電物粉末で形成される導電経路に偏りが生じ、その結果、厚膜抵抗体に印加された静電気の負荷により局所的な厚膜抵抗体の導電経路の破壊が生じ、その結果として抵抗値変化率が大きくなる。一方、Ｘ線回折で判別できる大きさの酸化マンガンや酸化マンガン由来の化合物が厚膜抵抗体中に存在しないと、導電経路の偏りが生じないので、静電気が印加されても、導電経路の局所的な破壊が生じにくい。 If manganese oxide or a manganese oxide-derived compound of a size that can be determined by X-ray diffraction exists in the thick film resistor, the conductive path formed by the conductive powder in the thick film resistor is biased, resulting in the following: The static electricity load applied to the thick film resistor causes local destruction of the conductive path of the thick film resistor, resulting in a large rate of change in resistance value. On the other hand, unless manganese oxide or a manganese oxide-derived compound of a size that can be determined by X-ray diffraction exists in the thick-film resistor, the conductive path will not be biased. destruction is unlikely to occur.
酸化マンガン粉末は、抵抗温度係数を調整したり、耐サージ特性を改善する目的として使用される。特に２００Ω以下の低抵抗領域の厚膜抵抗体においては、導電物粉末の酸化ルテニウム粉末の含有量が増やし、更に低い抵抗域を実現する場合は、導電物粉末にＡｇ粉末とＰｄ粉末が使用される。酸化ルテニウム量の増量やＡｇ粉末とＰｄ粉末を含有する厚膜抵抗体は、抵抗値が下がる一方で、ＴＣＲがプラス側に大きくシフトする。このようなＴＣＲのプラス側へのシフトを解消するため、酸化マンガン粉末を厚膜抵抗体用組成物に添加する。 Manganese oxide powder is used for the purpose of adjusting the temperature coefficient of resistance and improving surge resistance. Especially in thick film resistors in the low resistance range of 200 Ω or less, when the content of ruthenium oxide powder in the conductive powder is increased to achieve a lower resistance range, Ag powder and Pd powder are used as the conductive powder. be. A thick film resistor containing an increased amount of ruthenium oxide or containing Ag powder and Pd powder has a lower resistance value, but a large shift in TCR to the positive side. Manganese oxide powder is added to the composition for thick film resistors in order to eliminate such a shift of the TCR to the positive side.
酸化マンガン粉末の平均粒径は０．２μｍ～１．０μｍが望ましい。平均粒径が０．２μｍ未満の物でも使用できるが、０．２μｍ以上の物の方が容易に手に入りやすく、コスト面を考慮すると０．２μｍ以上が望ましい。一方、平均粒径が１．０μｍを超えると、各粉末と均等な分散ができない。そして、分散が不十分な酸化マンガン粉末が厚膜抵抗体用ペーストに含まれると、焼成後に得られる厚膜抵抗体にＸ線回折でマンガン化合物が析出することがある。 The manganese oxide powder preferably has an average particle size of 0.2 μm to 1.0 μm. Although particles with an average particle size of less than 0.2 μm can be used, particles with an average particle size of 0.2 μm or more are more readily available, and 0.2 μm or more is desirable in consideration of cost. On the other hand, if the average particle size exceeds 1.0 μm, uniform dispersion with each powder cannot be achieved. If the thick-film resistor paste contains insufficiently dispersed manganese oxide powder, the manganese compound may be precipitated by X-ray diffraction in the thick-film resistor obtained after firing.
酸化マンガン粉末の平均粒径は、走査型電子顕微鏡（ＳＥＭ）像を画像解析して評価することができる。 The average particle size of the manganese oxide powder can be evaluated by analyzing a scanning electron microscope (SEM) image.
また、酸化マンガン粉末の凝集を取り除く目的として、ボールミル、ポットミル、ライカイ機などの粉砕装置を用いると良い。特に粉砕条件は定めないが１０時間以上行えば十分である。 Further, for the purpose of removing agglomeration of the manganese oxide powder, it is preferable to use a pulverizing device such as a ball mill, a pot mill, or a Raikai machine. Although the pulverization conditions are not particularly specified, it is sufficient to carry out the pulverization for 10 hours or more.
酸化マンガン粉末の添加量は、導電物粉末とガラス粉末の合計を１００質量部としたときに０．０５質量部以上１０質量部以下が望ましく、更には０．０８質量部以上８質量部以下が望ましい。酸化マンガン粉末の添加量が０．０５量部未満であると添加の効果が殆ど見込めないかでる。一方、１０質量部を超えると、偏析が顕著となりガラスに溶け込きらず、酸化マンガンや、酸化マンガン由来の化合物が析出するなどして、特性に悪影響を与えるからである。また、ガラスとの反応などから、由来の結晶物が析出するからである。 The amount of manganese oxide powder added is preferably 0.05 parts by mass or more and 10 parts by mass or less, and more preferably 0.08 parts by mass or more and 8 parts by mass or less when the total of the conductive material powder and the glass powder is 100 parts by mass. desirable. If the amount of manganese oxide powder to be added is less than 0.05 part by weight, the effect of the addition can hardly be expected. On the other hand, if it exceeds 10 parts by mass, the segregation becomes pronounced and the manganese oxide and the manganese oxide-derived compound are precipitated, which adversely affects the properties. In addition, it is because the derived crystals are precipitated from the reaction with the glass.
また、予め有機ビヒクルと酸化マンガン粉末を混錬しておき、ペースト状にしてから厚膜抵抗体用ペーストと混合することも有効である。 It is also effective to knead an organic vehicle and manganese oxide powder in advance to form a paste, and then mix the paste with the thick film resistor paste.
４．厚膜抵抗体用組成物の配合
本実施形態の厚膜抵抗体用組成物は、導電物粉末、ガラス粉末、酸化マンガン粉末を含む。導電物粉末の酸化ルテニウム粉末とガラス粉末の割合は、両者の合計を１００質量部としたときに、酸化ルテニウムが２５質量部から７０質量部が望ましく、更には３０質量部から６０質量部であることが望ましい。本実施形態では、厚膜抵抗体用組成物のガラス粉末の含有率が、導電物粉末とガラス粉末の合計を１００質量部としたときに、ガラス粉末の含有率が３０質量部から７５質量部しか含まれていないので、添加する酸化マンガン粉末の添加量や粒径を適切に管理しないと、焼成して得られる厚膜抵抗体に、Ｘ線回折で判別できる大きさの酸化マンガンや酸化マンガン由来の化合物が析出するのである。
4. Formulation of Composition for Thick Film Resistor The composition for thick film resistor of the present embodiment contains conductive material powder, glass powder, and manganese oxide powder. The ratio of the ruthenium oxide powder and the glass powder in the conductive powder is preferably 25 to 70 parts by mass, more preferably 30 to 60 parts by mass, when the total of both is 100 parts by mass. is desirable. In the present embodiment, the glass powder content of the thick film resistor composition is 30 to 75 parts by mass when the total of the conductive material powder and the glass powder is 100 parts by mass. Therefore, unless the amount and particle size of the manganese oxide powder to be added are properly controlled, manganese oxide or manganese oxide having a size that can be determined by X-ray diffraction will be present in the thick film resistor obtained by firing. The originating compound is precipitated.
本実施形態の厚膜抵抗体用組成物は、抵抗体の抵抗値や抵抗温度係数や負荷特性、トリミング性の改善、調整を目的として一般に使用される添加剤を含有することもできる。添加剤としては、Ａｌ２Ｏ３、ＳｉＯ２、ＴｉＯ２、Ｎｂ２Ｏ５、ＣｕＯといった酸化物粉末を挙げることができる。これらの酸化物粉末の平均粒径は特に限定されないが、添加剤の平均粒径は０．５μｍ以下であることが好ましく、０．１μｍ以下であることがより好ましい。 The thick-film resistor composition of the present embodiment can also contain additives generally used for the purpose of improving and adjusting the resistance value, temperature coefficient of resistance, load characteristics, and trimming properties of the resistor. Examples of additives include oxide powders such as Al 2 O 3 , SiO 2 , TiO 2 , Nb 2 O 5 and CuO. The average particle size of these oxide powders is not particularly limited, but the average particle size of the additive is preferably 0.5 μm or less, more preferably 0.1 μm or less.
［厚膜抵抗体用ペースト］
本実施形態の厚膜抵抗体用ペーストの一構成例について説明する。
本実施形態の厚膜抵抗体用ペーストは、既述の厚膜抵抗体用組成物と、有機ビヒクルとを有することができる。そして、本実施形態の厚膜抵抗体用組成物は、既述の厚膜抵抗体用組成物を有機ビヒクル中に分散した構成を有することができる。
[Paste for thick film resistors]
A configuration example of the thick film resistor paste of the present embodiment will be described.
The thick film resistor paste of the present embodiment can have the thick film resistor composition described above and an organic vehicle. The composition for thick film resistors of the present embodiment can have a structure in which the composition for thick film resistors described above is dispersed in an organic vehicle.
有機ビヒクルは特に制限はなく、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から選択された１種類以上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から選択された１種類以上の樹脂を溶解した溶液を用いることができる。 The organic vehicle is not particularly limited, and one or more solvents selected from terpineol, butyl carbitol, butyl carbitol acetate, etc., ethyl cellulose, acrylic acid ester, methacrylic acid ester, rosin, maleic acid ester, etc. A solution of one or more resins can be used.
また、厚膜抵抗体用ペーストには、必要に応じて分散剤や可塑剤など加えることもできる。既述の厚膜抵抗体用組成物や、添加剤等を有機ビヒクルに分散させる際の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、遊星ミル等から選択された１種類以上の方法を用いることができる。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、厚膜抵抗体用組成物を１００質量部した場合に、有機ビヒクルを２０質量部以上８０質量部以下となるように混練、調製することができる。 Moreover, a dispersant, a plasticizer, etc. can also be added to the paste for thick film resistors as needed. The dispersion method for dispersing the composition for thick film resistors and the additives in the organic vehicle is not particularly limited, but it is selected from three roll mills, bead mills, planetary mills, etc. that disperse fine particles. One or more methods can be used. The mixing ratio of the organic vehicle is appropriately adjusted according to the printing or coating method. can be prepared.
［厚膜抵抗体］
本実施形態の厚膜抵抗体は、既述の厚膜抵抗体用組成物を含有することができる。
本実施形態の厚膜抵抗体の製造方法は特に限定されないが、例えば既述の厚膜抵抗体用組成物を、セラミック基板上に配置し、焼成して形成することができる。また、既述の厚膜抵抗体用ペーストを、アルミナ等のセラミック基板に塗布した後、８０℃以上２００℃以下の温度の下での乾燥により厚膜抵抗体用ペーストに含まれる溶剤を除去し、ピーク温度８００℃以上９００℃以下、保持時間１分以上３０分以下の大気雰囲気下で焼成して形成することもできる。
[Thick film resistor]
The thick film resistor of this embodiment can contain the composition for thick film resistors described above.
The method for manufacturing the thick film resistor of the present embodiment is not particularly limited, but for example, the thick film resistor composition described above can be arranged on a ceramic substrate and fired. Further, after applying the thick film resistor paste described above to a ceramic substrate such as alumina, the solvent contained in the thick film resistor paste is removed by drying at a temperature of 80° C. or more and 200° C. or less. , a peak temperature of 800° C. or higher and 900° C. or lower, and a holding time of 1 minute or longer and 30 minutes or shorter in an air atmosphere.
厚膜抵抗体の構造は、ガラス粉末から形成されるガラスマトリックスと、導電物粉末から形成される導電経路から形成される構造である。厚膜抵抗体が形成される過程を考察すると、焼成の熱により、ガラス粉末の各粒子が軟化し、融着し、ガラスマトリックスを形成し、ガラスマトリックスの隙間で導電物粉末の各粒子が、融着し、導電経路を形成する。すなわち、前記ガラスマトリックスの周囲に導電物粉末が存在する分散状態を維持して厚膜抵抗体の中に導電経路が形成される。 The structure of the thick film resistor is a structure formed from a glass matrix formed from glass powder and conductive paths formed from conductive powder. Considering the process of forming a thick film resistor, each particle of the glass powder is softened by the heat of firing and fused to form a glass matrix. It fuses and forms a conductive path. That is, a conductive path is formed in the thick film resistor by maintaining a dispersed state in which the conductive powder exists around the glass matrix.
セラミック基板には、一対の電極を公知の厚膜銀ペーストや厚膜銀・パラジウムペースト等の厚膜技術で形成しておき、該一対の電極の間に本実施形態の厚膜抵抗体を形成すれば、該電極を端子とする抵抗器を形成することもできる。 A pair of electrodes are formed on the ceramic substrate by a known thick-film technology such as thick-film silver paste or thick-film silver/palladium paste, and the thick-film resistor of this embodiment is formed between the pair of electrodes. Then, a resistor having the electrodes as terminals can be formed.
以下に具体的な実施例、比較例を挙げて説明するが、本発明はこれらの実施例に限定されるものではない。 Although specific examples and comparative examples will be given below, the present invention is not limited to these examples.
［実施例１］
平均粒径４０ｎｍの導電物粉末の酸化ルテニウム粉末４５質量部と、平均粒径が１．５μｍのガラス粉末５５質量部とし、導電物粉末とガラス粉末の合計１００質量部に対し平均粒径が０．５μｍのＭｎ３Ｏ４粉末４質量部を秤量し、そこに有機ビヒクル４０質量部を加え３本ロールで混錬し、実施例１に係る厚膜抵抗体用ペーストを得た。なお、有機ビヒクルは、エチルセルロース１０質量％とテルピノール９０質量％を混合して得た。
[Example 1]
45 parts by mass of ruthenium oxide powder, which is a conductive powder with an average particle size of 40 nm, and 55 parts by mass of glass powder with an average particle size of 1.5 μm. 4 parts by mass of Mn 3 O 4 powder of 0.5 μm was weighed, 40 parts by mass of an organic vehicle was added thereto, and the mixture was kneaded with a triple roll to obtain a thick film resistor paste according to Example 1. The organic vehicle was obtained by mixing 10% by mass of ethyl cellulose and 90% by mass of terpinol.
ガラス粉末の組成は、ＳｉＯ２ ３０質量％、Ｂ２Ｏ３ １７質量％ Ａｌ２Ｏ３ ３ 質量％ ＣａＯ ２２質量％ ＢａＯ １２質量％ ＺｎＯ １６質量％であった。 The composition of the glass powder was SiO 2 30 mass %, B 2 O 3 17 mass % Al 2 O 3 3 mass % CaO 22 mass % BaO 12 mass % ZnO 16 mass %.
酸化ルテニウム粉末の平均粒径は、ＢＥＴ法から測定される比表面積から算出した。ガラス粉末の粒度Ｄ５０は、レーザー回折を利用した粒度分布計により測定したガラス粉末の５０％体積累計粒度である。Ｍｎ３Ｏ４粉末の平均粒径はＳＥＭ像から算出した。 The average particle size of the ruthenium oxide powder was calculated from the specific surface area measured by the BET method. The particle size D50 of the glass powder is the 50% volume cumulative particle size of the glass powder measured by a particle size distribution meter using laser diffraction. The average particle size of the Mn 3 O 4 powder was calculated from the SEM image.
実施例１に係る厚膜抵抗体用ペーストを、Ａｇ／Ｐｄペーストによって電極を形成された１インチ四方のアルミナ基板に印刷して、１ｍｍ角の抵抗ペースト形状体を得た後に、１２０℃２０分乾燥、ピーク温度が８５０℃９分間保持するベルト型焼成炉にて焼成して厚膜抵抗体を得た。また、厚膜抵抗体にＭｎ３Ｏ４粉末に起因する析出物を確認するため、１インチ四方のアルミナ基板に２０ｍｍ四方の正方形で焼成後の膜厚が７μｍとなるように印刷し、得られた１ｍｍ角の厚膜抵抗体と同様に乾燥、焼成を行った。 The thick-film resistor paste according to Example 1 was printed on a 1-inch square alumina substrate on which electrodes were formed with Ag/Pd paste to obtain a 1-mm-square resistor paste shape, followed by heating at 120° C. for 20 minutes. It was dried and fired in a belt-type firing furnace with a peak temperature of 850° C. for 9 minutes to obtain a thick film resistor. In addition, in order to confirm deposits caused by Mn 3 O 4 powder on the thick film resistor, a square of 20 mm square was printed on an alumina substrate of 1 inch square so that the film thickness after firing was 7 μm. It was dried and fired in the same manner as the 1 mm square thick film resistor.
得られた厚膜抵抗体について、デジタルマルチメーター（ＫＥＩＴＨＬＥＹ社製、２００１番）により抵抗値を測定し、得られた抵抗値を、厚膜抵抗体の厚さが７μｍの場合に換算して、その抵抗体厚膜の抵抗値とした。 The resistance value of the obtained thick film resistor was measured with a digital multimeter (manufactured by KEITHLEY, No. 2001), and the obtained resistance value was converted to the thickness of the thick film resistor of 7 μm. The resistance value of the resistor thick film was used.
膜厚は、各実施例、比較例において同様にして作製した５個の厚膜抵抗体について、触針の厚さ粗さ計（東京精密社製 型番：サーフコム４８０Ｂ）により膜厚を測定し、測定した値を平均することで算出した。 The film thickness was measured with a stylus thickness and roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., model number: Surfcom 480B) for five thick-film resistors produced in the same manner in each example and comparative example. It was calculated by averaging the measured values.
得られた厚膜抵抗体の抵抗値の１．５倍となるように、シングルカットのレーザートリミングを行った後、２００ｐＦのコンデンサに１ｋＶ、２ｋＶで充電した静電気を５回放電し、静電気放電（ＥＳＤ）を行った後、抵抗値を測定し、初期抵抗値と放電後の抵抗変化率を求めた。 After single-cut laser trimming was performed so that the resistance value of the obtained thick film resistor was 1.5 times, static electricity charged at 1 kV and 2 kV in a 200 pF capacitor was discharged five times. After performing ESD), the resistance value was measured to obtain the initial resistance value and the rate of change in resistance after discharge.
また得られた厚膜抵抗体のＸ線回折を行い物質の同定を行ったところ、酸化ルテニウムおよびアルミナ基板に帰属されるピークは確認されたものの、添加したＭｎ３Ｏ４粉末およびマンガン化合物は検出されなかった。結果を表２に示す。 When the obtained thick film resistor was subjected to X-ray diffraction to identify the substance, peaks attributed to ruthenium oxide and alumina substrate were confirmed, but the added Mn 3 O 4 powder and manganese compound were detected. it wasn't. Table 2 shows the results.
［実施例２］
表１の配合割合といた以外は実施例１と同様に実施例２に係る厚膜抵抗体用ペーストを作製し評価した。結果を表２に示す。
[Example 2]
A paste for a thick film resistor according to Example 2 was prepared and evaluated in the same manner as in Example 1 except that the blending ratios in Table 1 were used. Table 2 shows the results.
［実施例３］
表１の配合割合といた以外は実施例１と同様に実施例３に係る厚膜抵抗体用ペーストを作製し評価した。結果を表２に示す。
[Example 3]
A paste for a thick film resistor according to Example 3 was prepared and evaluated in the same manner as in Example 1 except that the blending ratios in Table 1 were used. Table 2 shows the results.
［比較例１］
表１の配合割合といた以外は実施例１と同様に比較例１に係る厚膜抵抗体用ペーストを作製し評価した。結果を表２に示す。
[Comparative Example 1]
A paste for a thick film resistor according to Comparative Example 1 was prepared and evaluated in the same manner as in Example 1 except that the blending ratios in Table 1 were used. Table 2 shows the results.
［比較例２］
表１の配合割合といた以外は実施例１と同様に比較例２に係る厚膜抵抗体用ペーストを作製し評価した。結果を表２に示す。
[Comparative Example 2]
A paste for a thick film resistor according to Comparative Example 2 was prepared and evaluated in the same manner as in Example 1 except that the blending ratios in Table 1 were used. Table 2 shows the results.
表１に示されるように実施例１、２および３に係る厚膜抵抗体ではＸ線回折の結果、Ｍｎ３Ｏ４粉末に起因する結晶は確認されず、耐サージ特性（ＥＳＤ）として２ｋＶの静電気が印加されても、抵抗値変化率は１．７％に抑えられている。なお、印加する静電気が１ｋＶの場合の抵抗値変化率は－１から＋１％であれば実用に問題なく、印加する静電気が２ｋＶの場合の抵抗値変化率は、－２％から＋２％であれば実用上問題ない。 As shown in Table 1, X-ray diffraction of the thick film resistors of Examples 1, 2 and 3 revealed no crystals caused by the Mn 3 O 4 powder, and the surge resistance (ESD) was 2 kV. Even if static electricity is applied, the resistance value change rate is suppressed to 1.7%. If the applied static electricity is 1 kV, the resistance value change rate is -1 to +1% for practical use, and if the applied static electricity is 2 kV, the resistance value change rate is -2% to +2%. There is no problem in practical use.
一方、比較例１および２は、Ｘ線回折の結果、Ｍｎ３Ｏ４粉末に起因する結晶が確認され、耐サージ特性は２ｋＶの静電気が印加されると、抵抗値変化率は－２％から＋２％の範囲を超え、比較例１では２．８％、比較例２では３％となっており、劣ることが分かる。 On the other hand, in Comparative Examples 1 and 2, as a result of X-ray diffraction, crystals caused by Mn 3 O 4 powder were confirmed, and the resistance value change rate was from -2% to -2% when static electricity of 2 kV was applied. The range of +2% is exceeded, and it is 2.8% in Comparative Example 1 and 3% in Comparative Example 2, indicating that they are inferior.
Claims (8)
焼成されて得られる厚膜抵抗体をＸ線回折するとマンガン化合物が検出されない厚膜抵抗体用組成物。 Contains lead-free conductive powder, glass powder and manganese oxide powder,
A composition for a thick film resistor in which no manganese compound is detected by X-ray diffraction of the fired thick film resistor.
Ｘ線回折するとマンガン化合物が検出されない厚膜抵抗体。 Contains lead-free conductive powder, glass and manganese compounds,
A thick film resistor in which no manganese compounds are detected by X-ray diffraction.
8. The glass contains no lead component and contains SiO 2 , B 2 O 3 and RO (R represents one or more alkaline earth elements selected from Ca, Sr and Ba). A thick film resistor as described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021190171A JP2023077053A (en) | 2021-11-24 | 2021-11-24 | Composition for thick film resistor, paste for the thick film resistor, and the thick film resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021190171A JP2023077053A (en) | 2021-11-24 | 2021-11-24 | Composition for thick film resistor, paste for the thick film resistor, and the thick film resistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2023077053A true JP2023077053A (en) | 2023-06-05 |
Family
ID=86610400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021190171A Pending JP2023077053A (en) | 2021-11-24 | 2021-11-24 | Composition for thick film resistor, paste for the thick film resistor, and the thick film resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2023077053A (en) |
-
2021
- 2021-11-24 JP JP2021190171A patent/JP2023077053A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6708093B2 (en) | Resistor paste and resistor produced by firing the paste | |
| CN110291599B (en) | Composition for resistor, paste for resistor, and thick film resistor | |
| JP2018092730A (en) | Composition for resistor and resistor paste containing the same furthermore thick film resistor therewith | |
| JP2019040782A (en) | Thick film resistor composition and thick film resistor paste containing the same | |
| WO2021221173A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| WO2021221172A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| JP2021125303A (en) | Composition for thick film resistor, paste for thick film resistor and thick film resistor | |
| JP2009007199A (en) | Thick film resistor composition, resistor paste, and thick film resistor | |
| JP2023077053A (en) | Composition for thick film resistor, paste for the thick film resistor, and the thick film resistor | |
| JP2023064822A (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| TWI803673B (en) | Composition for thick film resistors, paste for thick film resistors, and thick film resistors | |
| JP7139691B2 (en) | Composition for thick film resistor, thick film resistor paste and thick film resistor | |
| JP2009026903A (en) | Thick film resistor composition, resistance paste, and thick film resistor | |
| JP7390103B2 (en) | Resistor compositions, resistance pastes, thick film resistors | |
| JP7279551B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| JP2020061467A (en) | Composition for thick film resistor, paste for thick film resistor and thick film resistor | |
| JP2005129806A (en) | Resistor paste and thick film resistor | |
| WO2021221175A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| JP7297409B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| JP7273266B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| JP7183507B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| JP2018092986A (en) | Resistor composition, and resistor paste including the composition, and thick film resistor using the same | |
| KR20230004486A (en) | Thick Film Resistor Pastes, Thick Film Resistors, and Electronic Components | |
| JP2008218379A (en) | Thick film resistor composition, resistance paste, and thick film resistor | |
| JP2023144072A (en) | Thick film resistor composition, thick film resistor paste, and thick film resistor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20240725 |