JPH09162454A - Electrode material of piezoelectric ceramic - Google Patents
Electrode material of piezoelectric ceramicInfo
- Publication number
- JPH09162454A JPH09162454A JP33996795A JP33996795A JPH09162454A JP H09162454 A JPH09162454 A JP H09162454A JP 33996795 A JP33996795 A JP 33996795A JP 33996795 A JP33996795 A JP 33996795A JP H09162454 A JPH09162454 A JP H09162454A
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric ceramic
- acrylic adhesive
- powder
- electrode
- electrode material
- 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.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 36
- 239000007772 electrode material Substances 0.000 title claims abstract description 22
- 239000003522 acrylic cement Substances 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000002003 electrode paste Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229960004643 cupric oxide Drugs 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- -1 acryl Chemical group 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- UUDQUXWIZNNGNO-UHFFFAOYSA-N copper;ethanol Chemical compound [Cu].CCO.CCO UUDQUXWIZNNGNO-UHFFFAOYSA-N 0.000 description 1
- QFYBRRIPNPVECS-UHFFFAOYSA-N copper;methanol Chemical compound [Cu].OC.OC QFYBRRIPNPVECS-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Piezo-Electric Transducers For Audible Bands (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、圧電セラミックの
電極材料に関し、特に圧電セラミックを金属振動板にア
クリル系接着剤を用いて接着する際に、その接着が良好
に成される圧電セラミックの電極材料に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic electrode material, and more particularly, to a piezoelectric ceramic electrode which is adhered well when the piezoelectric ceramic is adhered to a metal diaphragm using an acrylic adhesive. It is about materials.
【０００２】[0002]
【従来の技術】圧電ブザー或いは圧電スピーカとして使
用されている圧電振動板は、両面に電極が形成された圧
電セラミックを、黄銅或いはステンレス等の金属振動板
に接着剤を用いて接着し、製造されている。2. Description of the Related Art A piezoelectric vibrating plate used as a piezoelectric buzzer or a piezoelectric speaker is manufactured by bonding a piezoelectric ceramic having electrodes on both sides to a metallic vibrating plate of brass or stainless steel with an adhesive. ing.
【０００３】ここで従来、上記圧電セラミックの両面に
形成される電極の材料としては、Ａｇペースト〔Ａｇ粉
末と少量のガラス粉末（フリット）とを、有機ビヒクル
中に分散させ、ペースト状としたもの〕が一般的に用い
られ、該Ａｇペーストをセラミック上に塗布し、焼結さ
せて電極を形成することが成されている。Heretofore, as a material for electrodes formed on both surfaces of the above-mentioned piezoelectric ceramic, Ag paste [Ag powder and a small amount of glass powder (frit) are dispersed in an organic vehicle to form a paste] ] Is generally used, and the Ag paste is applied onto a ceramic and sintered to form an electrode.
【０００４】また、上記圧電セラミックと金属振動板と
の接着には、アクリル系接着剤、例えば嫌気性硬化型ア
クリル接着剤を用いて成されている。An acrylic adhesive such as an anaerobic curable acrylic adhesive is used to bond the piezoelectric ceramic and the metal diaphragm.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記し
た電極材料を用いて電極を形成した圧電セラミックにあ
っては、アクリル系接着剤を用いて金属振動板に接着す
る際、その接着性が悪いと言う課題を有していたため
に、接着時において１００℃前後に加熱することが成さ
れ、その加熱による熱歪等が原因となって、得られた圧
電振動板の共振周波数が、理論共振周波数から大きくズ
レると言う課題が生じていた。However, in the piezoelectric ceramic in which the electrodes are formed by using the above-mentioned electrode material, when the adhesive is badly adhered to the metal diaphragm by using the acrylic adhesive. Because of the above-mentioned problem, heating is performed at about 100 ° C. at the time of adhesion, and the resonance frequency of the obtained piezoelectric diaphragm is changed from the theoretical resonance frequency due to thermal strain due to the heating. There was a problem of a large deviation.
【０００６】本発明は、上述した従来の電極材料を用い
て電極を形成した圧電セラミックの接着性の悪さに鑑み
成されたものであって、その目的は、アクリル系接着剤
を用いて金属振動板に良好に接着できる圧電セラミック
の電極材料を提供することにある。The present invention has been made in view of the poor adhesion of a piezoelectric ceramic having an electrode formed by using the above-mentioned conventional electrode material, and its object is to vibrate metal by using an acrylic adhesive. An object is to provide a piezoelectric ceramic electrode material that can be well adhered to a plate.
【０００７】[0007]
【課題を解決するための手段】本発明は、上記した目的
を達成するため、金属振動板にアクリル系接着剤を用い
て接着する圧電セラミックの電極材料において、Ａｇを
主体とし、少量のＣｕを含有する圧電セラミックの電極
材料とした。In order to achieve the above object, the present invention is a piezoelectric ceramic electrode material which is adhered to a metal diaphragm by using an acrylic adhesive. The electrode material of the contained piezoelectric ceramic was used.
【０００８】上記した本発明にかかる圧電セラミックの
電極材料によれば、該電極材料により形成した圧電セラ
ミックの電極には、Ｃｕイオンが存在することとなり、
該Ｃｕイオンが、アクリル系接着剤を用いて圧電セラミ
ックを金属振動板に接着する際にプライマー（接着性を
向上させるための下地処理材）としての役割を果たし、
アクリル系接着剤の反応を促進させる。これにより、接
着時においてさほど加熱しなくとも両者の接着がアクリ
ル系接着剤により良好に成され、加熱による熱歪等が原
因の共振周波数のズレを低減できる。According to the above-mentioned piezoelectric ceramic electrode material of the present invention, Cu ions are present in the piezoelectric ceramic electrode formed of the electrode material.
The Cu ions play a role as a primer (a base material for improving the adhesiveness) when the piezoelectric ceramic is adhered to the metal vibration plate using the acrylic adhesive,
Accelerates the reaction of acrylic adhesives. As a result, the two can be well bonded by the acrylic adhesive even if they are not heated so much at the time of bonding, and the deviation of the resonance frequency due to the thermal strain due to heating can be reduced.
【０００９】ここで、上記電極材料中のＣｕの含有量
は、Ａｇに対し、ＣｕＯ換算で０．１〜１０．０ｗｔ％
であることが好ましい。これは、０．１ｗｔ％に満たな
い含有量では、接着性改善の効果が少なく、また、１
０．０ｗｔ％を越える含有量では、該電極材料により形
成した電極へのハンダ濡れ性が悪くなり、リード線等の
ハンダによる電極への接続が困難となるためである。Here, the content of Cu in the electrode material is 0.1 to 10.0 wt% in terms of CuO with respect to Ag.
It is preferred that This is because when the content is less than 0.1 wt%, the effect of improving the adhesiveness is small, and
This is because if the content exceeds 0.0 wt%, the solder wettability to the electrode formed of the electrode material deteriorates, and it becomes difficult to connect the lead wire or the like to the electrode.
【００１０】なお、上記Ｃｕは、Ａｇと合金状態或いは
複合状態で存在しても良く、また、例えば従来より電極
材料として存在するＡｇペースト〔Ａｇ粉末と少量のガ
ラス粉末（フリット）とを、有機ビヒクル中に分散さ
せ、ペースト状としたもの〕に、酸化銅、或いは焼結時
の加熱により銅酸化物になる金属銅粉、或いは銅アセチ
ルアセトナート、ジエトキシ銅、ジメトキシ銅等の有機
銅、更には他のＣｕを含む化合物を添加する等の方法で
含有させても良い。The Cu may be present in an alloyed state or in a composite state with Ag. Further, for example, an Ag paste [Ag powder and a small amount of glass powder (frit)], which has been conventionally used as an electrode material, is mixed with an organic material. Dispersed in a vehicle to form a paste], copper oxide, or metal copper powder that becomes copper oxide by heating during sintering, or organic copper such as copper acetylacetonate, diethoxy copper, and dimethoxy copper, May be contained by a method such as adding another compound containing Cu.
【００１１】[0011]
【発明の実施の形態】以下、上記した本発明にかかる圧
電セラミックの電極材料を使用して作製した圧電振動板
の実施の形態につき説明し、本発明にかかる圧電セラミ
ックの電極材料を使用した場合の効果を記載する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of a piezoelectric vibrating plate produced by using the above-mentioned piezoelectric ceramic electrode material according to the present invention will be described, and in the case where the piezoelectric ceramic electrode material according to the present invention is used. Describe the effect of.
【００１２】−電極ペーストの作製− Ａｇ粉末〔昭栄化学工業株式会社製：Ag-102（比表面積
1.2m2/g）〕と、前記Ａｇ粉末に対して 0.5wt％の量の
フリット（ホウケイ酸ガラス）と、前記Ａｇ粉末に対
し、表１に示した種々の量の CuO粉末〔関東化学株式会
社製 酸化第二銅（平均粒径 0.8μｍ）〕とを、各々有
機ビヒクル（エチルセルロースをオクチルアルコールに
溶かした23％溶液のもの）中に分散させ、三本ロール
（アシザワ株式会社製：３インチロール）にて練り混
ぜ、Ｃｕの含有量の異なる（Ｃｕを含有しないものも含
む：試験例１）９種類の電極ペーストを作製した。-Preparation of electrode paste- Ag powder [Ag-102 (manufactured by Shoei Chemical Industry Co., Ltd., specific surface area
1.2 m 2 / g)], frit (borosilicate glass) in an amount of 0.5 wt% with respect to the Ag powder, and various amounts of CuO powder shown in Table 1 with respect to the Ag powder [Kanto Chemical Co., Inc. Company-made cupric oxide (average particle size 0.8 μm)] and three-roll rolls (Ashizawa Co., Ltd .: 3 inches) are dispersed in an organic vehicle (23% solution of ethyl cellulose dissolved in octyl alcohol). 9) electrode pastes having different Cu contents (including those not containing Cu: Test Example 1) were prepared by kneading with a roll.
【００１３】−圧電セラミックの作製− ＰＺＴ系セラミックス〔株式会社メガセラ製：Ｄ材（比
表面積５m2/g）〕で製造した直径15mm、厚さ0.05mmの圧
電セラミックス焼結体の表裏面に、上記Ｃｕの含有量の
異なる９種類の電極ペーストを各々スクリーン印刷し、
常法によって焼き付けて膜厚３μｍの電極を形成した
後、該電極を利用して圧電セラミックス焼結体を分極
し、電極材料の異なる９種類の圧電セラミックを作製し
た。-Production of Piezoelectric Ceramics- PZT-based ceramics [manufactured by Mega Cera Co., Ltd .: D material (specific surface area 5 m 2 / g)] on the front and back surfaces of a piezoelectric ceramics sintered body having a diameter of 15 mm and a thickness of 0.05 mm. 9 kinds of electrode pastes having different Cu contents are screen-printed,
After baking by an ordinary method to form an electrode having a film thickness of 3 μm, the piezoelectric ceramic sintered body was polarized by using the electrode to fabricate nine types of piezoelectric ceramics having different electrode materials.
【００１４】−圧電振動板の作製− 42Ni-Feアロイ〔東洋精箔株式会社製〕で製造した直径2
0mm、厚さ0.05mmの金属振動板に、上記電極材料の異な
る９種類の圧電セラミックを、各々アクリル系接着剤
〔スリーボンド株式会社製 3000シリーズ（紫外線硬化
型接着剤）〕を用いて、70℃−20秒で接着し、圧電ブザ
ー或いは圧電スピーカ等として使用される９種類の圧電
振動板の作製した。-Preparation of piezoelectric diaphragm-Diameter 2 manufactured from 42Ni-Fe alloy [manufactured by Toyo Seifoil Co., Ltd.]
Nine kinds of piezoelectric ceramics with different electrode materials are applied to a 0 mm thick 0.05 mm thick metal vibrating plate using acrylic adhesives [3000 series (UV curable adhesives) manufactured by ThreeBond Co., Ltd.] at 70 ° C. Nine kinds of piezoelectric vibrating plates, which are used as a piezoelectric buzzer, a piezoelectric speaker, etc., were adhered in -20 seconds.
【００１５】−評価試験− ハンダ濡れ試験 表裏面に電極が形成された９種類の上記圧電セラミック
に、各々フラックスを塗布、乾燥後、 230℃の共晶ハン
ダに２秒間浸漬し、ハンダの濡れ面積を各々測定した
（判定基準：80％以上の濡れ面積が確認できれば良
好）。-Evaluation Test-Solder Wetting Test Flux is applied to each of the above 9 types of piezoelectric ceramics having electrodes formed on the front and back surfaces, dried, and then dipped in eutectic solder at 230 ° C for 2 seconds to obtain a wetted area of the solder. Was measured (judgment criterion: 80% or more wet area can be confirmed).
【００１６】接着性試験 圧電セラミックを金属振動板にアクリル系接着剤にて接
着して作製した９種類の上記圧電振動板を、手によって
その中央付近において折り曲げ、接着されている圧電セ
ラミックを割り、その際の圧電セラミックの金属振動板
からの剥がれを各々測定した（判定基準：１mm□以上の
剥がれが存在する場合＝× １mm□に満たない剥がれの
場合＝○）。Adhesion Test The above 9 kinds of piezoelectric vibrating plates prepared by adhering a piezoelectric ceramic to a metal vibrating plate with an acrylic adhesive were bent by hand near the center thereof, and the adhering piezoelectric ceramic was broken. At that time, peeling of the piezoelectric ceramic from the metal vibration plate was measured (determination criterion: if peeling of 1 mm □ or more is present = × if peeling is less than 1 mm □ = ○).
【００１７】共振周波数試験 圧電セラミックを金属振動板にアクリル系接着剤にて接
着して作製した９種類の上記圧電振動板を、ノード支持
の状態でインピーダンス フェズゲイン アナライザー
（横河・ヒューレット・パッカード株式会社製：４１９
４Ａ）によって各々共振周波数を測定した（表１には、
下記した式１によって計算した理論共振周波数に対す
る、測定した上記各々共振周波数のズレを記載した）。Resonance Frequency Test Nine types of the above piezoelectric vibrating plates prepared by adhering a piezoelectric ceramic to a metal vibrating plate with an acrylic adhesive were used in an impedance phase gain analyzer (Yokogawa / Hewlett-Packard Co. Made: 419
4A) was used to measure the resonance frequency (Table 1,
The deviation of each measured resonance frequency from the theoretical resonance frequency calculated by the following Equation 1 is described).
【式１】 (Equation 1)
【００１８】−評価試験結果− 上記した各評価試験の結果を、表１に併記する。-Evaluation Test Results-Table 1 shows the results of the above-described evaluation tests.
【表１】 [Table 1]
【００１９】表１より、Ｃｕを含有していない従来より
使用されているＡｇペースト（試験例１）によって形成
した電極では、70℃−20秒の加熱接着ではその接着性が
悪く、また共振周波数のズレも大きいことが判る。ま
た、表１より、Ｃｕが含まれていたとしてもその含有量
が、Ａｇに対し、ＣｕＯ換算で 0.1wt％に満たない量
（試験例２）では、接着性改善の効果が少なく、また1
0.0wt％を越える含有量（試験例９）では、該電極材料
により形成した電極へのハンダ濡れ性が悪くなり、リー
ド線等のハンダによる電極への接続が困難となることが
判る。これに対し、Ｃｕの含有量が、Ａｇに対し、Ｃｕ
Ｏ換算で 0.1〜10.0wt％である場合（試験例３〜８）に
は、ハンダ濡れ性及び接着性が共に良好で、共振周波数
のズレも僅かであることが判る。From Table 1, it can be seen that the electrode formed by the Ag paste (Test Example 1) which does not contain Cu and which has been used conventionally has poor adhesiveness when heat-bonded at 70 ° C. for 20 seconds, and has a resonance frequency. It can be seen that the deviation is large. Further, from Table 1, even if Cu is contained, if the content is less than 0.1 wt% in terms of CuO with respect to Ag (Test Example 2), the effect of improving the adhesiveness is small, and 1
It can be seen that when the content exceeds 0.0 wt% (Test Example 9), the wettability of solder to the electrode formed of the electrode material becomes poor, and it becomes difficult to connect the lead wire or the like to the electrode. On the other hand, the content of Cu is less than that of Ag.
When it is 0.1 to 10.0 wt% in terms of O (Test Examples 3 to 8), it is understood that both the solder wettability and the adhesiveness are good and the deviation of the resonance frequency is slight.
【００２０】[0020]
【発明の効果】以上、説明した本発明にかかる圧電セラ
ミックの電極材料によれば、該電極材料により形成した
圧電セラミックの電極には、Ｃｕイオンが存在すること
となり、該Ｃｕイオンが、アクリル系接着剤を用いて圧
電セラミックを金属振動板に接着する際にプライマー
（接着性を向上させるための下地処理材）としての役割
を果たし、アクリル系接着剤の反応を促進させる。これ
により、接着時においてさほど加熱しなくとも両者の接
着がアクリル系接着剤により良好に成され、加熱による
熱歪等が原因の共振周波数のズレを低減できる効果があ
る。According to the above-described piezoelectric ceramic electrode material of the present invention, Cu ions are present in the piezoelectric ceramic electrode formed of the electrode material, and the Cu ions are acryl-based. When the piezoelectric ceramic is bonded to the metal diaphragm by using the adhesive, it plays a role as a primer (a base treatment material for improving the adhesiveness) and accelerates the reaction of the acrylic adhesive. As a result, the two can be bonded well by the acrylic adhesive even if they are not heated so much at the time of bonding, and there is an effect that the deviation of the resonance frequency due to the thermal strain due to heating can be reduced.
Claims (2)
接着する圧電セラミックの電極材料において、Ａｇを主
体とし、少量のＣｕを含有することを特徴とする圧電セ
ラミックの電極材料。1. A piezoelectric ceramic electrode material adhered to a metal diaphragm using an acrylic adhesive, which is mainly composed of Ag and contains a small amount of Cu.
Ｏ換算で０．１〜１０．０ｗｔ％であることを特徴とす
る、請求項１記載の圧電セラミックの電極材料。2. The content of Cu is such that Cu is added to Ag.
The electrode material of the piezoelectric ceramic according to claim 1, which is 0.1 to 10.0 wt% in terms of O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33996795A JP3671081B2 (en) | 1995-12-04 | 1995-12-04 | Piezoelectric ceramic electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33996795A JP3671081B2 (en) | 1995-12-04 | 1995-12-04 | Piezoelectric ceramic electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09162454A true JPH09162454A (en) | 1997-06-20 |
| JP3671081B2 JP3671081B2 (en) | 2005-07-13 |
Family
ID=18332470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33996795A Expired - Lifetime JP3671081B2 (en) | 1995-12-04 | 1995-12-04 | Piezoelectric ceramic electrode material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3671081B2 (en) |
-
1995
- 1995-12-04 JP JP33996795A patent/JP3671081B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3671081B2 (en) | 2005-07-13 |
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