JP3008940B1 - Separation / recovery method of electronic device using lead-containing piezoelectric material - Google Patents
Separation / recovery method of electronic device using lead-containing piezoelectric materialInfo
- Publication number
- JP3008940B1 JP3008940B1 JP27086498A JP27086498A JP3008940B1 JP 3008940 B1 JP3008940 B1 JP 3008940B1 JP 27086498 A JP27086498 A JP 27086498A JP 27086498 A JP27086498 A JP 27086498A JP 3008940 B1 JP3008940 B1 JP 3008940B1
- Authority
- JP
- Japan
- Prior art keywords
- electronic device
- piezoelectric material
- lead
- piezoelectric
- separating
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000000926 separation method Methods 0.000 title claims description 8
- 238000011084 recovery Methods 0.000 title claims description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004808 supercritical fluid chromatography Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)
Abstract
【要約】
【課題】 電子デバイスの分離回収を容易に行う
【解決手段】 鉛を含む圧電材料を用いた電子デバイス
の分離・回収方法として、第一に有機溶剤に投入し、乾
燥後高温雰囲気に暴露し、最後に酸に投入する連続した
プロセスを用いている。Abstract: A method for easily separating and collecting an electronic device. [MEANS FOR SOLVING PROBLEMS] As a method for separating and collecting an electronic device using a piezoelectric material containing lead, first, an electronic device is put into an organic solvent, dried, and then dried to a high temperature atmosphere A continuous process of exposing and finally charging the acid is used.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、鉛を含む圧電材料
を用いた電子デバイスの分離・回収方法に関する。The present invention relates to a method for separating and collecting electronic devices using a piezoelectric material containing lead.
【０００２】[0002]
【従来の技術】従来から、圧電材料を用いた電子デバイ
スは、携帯電話やコンピュータの電子デバイスとして多
く用いられている。具体的には圧電振動子及び発音体及
び音声検出器及びセラミックフィルタ及びアクチュエー
タ及び圧電トランスなどである。これらの電子デバイス
に用いられている圧電材料のほとんどが鉛を含む圧電材
料でありペロブスカイト構造を有することを特徴として
いる。2. Description of the Related Art Conventionally, electronic devices using piezoelectric materials have been widely used as electronic devices for mobile phones and computers. Specifically, it includes a piezoelectric vibrator, a sounding body, a sound detector, a ceramic filter, an actuator, and a piezoelectric transformer. Most of the piezoelectric materials used in these electronic devices are lead-containing piezoelectric materials and have a perovskite structure.
【０００３】その歴史は古く特にジルコン酸鉛（ＰｂＺ
ｒＯ3）とチタン酸鉛（ＰｂＴｉＯ3）の混合系であるＰ
ＺＴは非常に高い圧電特性を示すことは衆知の事実とな
っている。ＰＺＴは現在に至るまで、第３の組成物とし
て複合ペロブスカイト型酸化物をさらに混合したり、新
たに添加物を加えるなどして、それぞれのデバイス用途
に対応した形で研究開発が行われ、よりいっそうの特性
の向上が図られてきた。[0003] Its history is old and especially lead zirconate (PbZ)
rO 3 ) and lead titanate (PbTiO 3 )
It is a well-known fact that ZT exhibits very high piezoelectric properties. Until now, PZT has been researched and developed in a form corresponding to each device application by further mixing a composite perovskite-type oxide as a third composition or adding a new additive. Further improvements in characteristics have been achieved.
【０００４】その結果、鉛を含む圧電材料は他の圧電材
料と比較した時に、明白な特性の優位性を現在も維持し
続けており、上記の電子デバイスに欠かすことのできな
い最適な材料として利用されているのが現状である。[0004] As a result, the lead-containing piezoelectric material still maintains a distinctive superiority of properties when compared with other piezoelectric materials, and is used as an optimal material indispensable for the above electronic devices. That is the current situation.
【０００５】一方、近年世界的に環境問題がとりあげら
れ、ダイオキシンに代表される環境ホルモンに対する規
制、発生源となるハロゲン（主に塩素）を含む物質の規
制が厳しくなっている。またオゾン層を破壊するフロン
に対しても代替えフロンの開発が急速に進むなど２１世
紀に向けて環境に配慮した研究開発・商品開発が要望さ
れているのが現状である。On the other hand, in recent years, environmental issues have been taken up worldwide, and regulations on environmental hormones represented by dioxins and regulations on substances containing halogen (mainly chlorine) as a source have been strict. At the present, there is a demand for environmentally friendly R & D and product development toward the 21st century, as the development of alternative CFCs has rapidly progressed for CFCs that destroy the ozone layer.
【０００６】上記のように通常使用されている電子デバ
イスには鉛化合物が含まれている。[0006] As described above, a commonly used electronic device contains a lead compound.
【０００７】[0007]
【発明が解決しようとする課題】本発明は近年の環境問
題へ対応を目的とし、鉛を含む圧電材料を用いた電子デ
バイスへの要望に対して、電子デバイスの分離回収を容
易に行うことを可能とし高圧電特性・高信頼性を有する
材料を従来どおりに使用可能すると同時に、電極材料・
外装樹脂などについても容易な分離・回収方法を提供す
ることである。SUMMARY OF THE INVENTION An object of the present invention is to cope with recent environmental problems and to easily separate and recover an electronic device in response to a demand for an electronic device using a piezoelectric material containing lead. As a result, materials with high piezoelectric characteristics and high reliability can be used as before, and at the same time, electrode materials and
An object of the present invention is to provide an easy separation / collection method for exterior resin and the like.
【０００８】[0008]
【課題を解決するための手段】この課題を解決するため
に本発明は、鉛を含む圧電材料を用いた電子デバイスに
おいて、第一に有機溶剤に投入し乾燥後高温雰囲気に暴
露し、最後に酸に投入するプロセスを用いることを特徴
とし、高圧電特性・高信頼性を有する材料を従来どおり
に使用可能すると同時に、電子デバイスを構成する電極
材料・外装樹脂などについても分離回収を容易に可能と
し、産業廃棄物の削減にも貢献するものである。SUMMARY OF THE INVENTION In order to solve this problem, the present invention relates to an electronic device using a piezoelectric material containing lead, which is first charged in an organic solvent, dried, exposed to a high-temperature atmosphere, and finally exposed. It is characterized by the use of the process of pouring into acid, allowing materials with high piezoelectric characteristics and high reliability to be used as before, while also allowing easy separation and recovery of electrode materials and exterior resins that make up electronic devices. And contribute to the reduction of industrial waste.
【０００９】[0009]
【発明の実施の形態】請求項１記載の鉛を含む圧電材料
を用いた電子デバイスの分離・回収方法は、第一に有機
溶剤に投入し、乾燥後高温雰囲気に暴露し、最後に酸に
投入する連続したプロセスを用いて電子デバイスを分離
し回収を行うことを特徴とする。The method for separating and recovering an electronic device using a piezoelectric material containing lead according to the first aspect of the present invention is as follows. First, the device is charged into an organic solvent, dried, exposed to a high-temperature atmosphere, and finally exposed to an acid. The electronic device is separated and collected by using a continuous process of charging.
【００１０】請求項２記載の分離・回収方法は、請求項
１記載の鉛を含む圧電材料を用いた電子デバイスの分離
回収方法において、有機溶剤が第2種有機溶剤の少なく
とも１種類を含むことを特徴とする。According to a second aspect of the present invention, there is provided a method of separating and recovering an electronic device using a lead-containing piezoelectric material according to the first aspect, wherein the organic solvent includes at least one of a second type organic solvent. It is characterized by.
【００１１】請求項３記載の分離・回収方法は、請求項
１または２記載の鉛を含む圧電材料を用いた電子デバイ
スの分離・回収方法において、有機溶剤投入時に、超音
波を使用することを特徴とする。According to a third aspect of the present invention, there is provided a method for separating and recovering an electronic device using a piezoelectric material containing lead according to the first or second aspect, wherein ultrasonic waves are used when an organic solvent is charged. Features.
【００１２】請求項４記載の電子デバイスの分離・回収
方法は、請求項１または２または３記載の鉛を含む圧電
材料を用いた電子デバイスの分離・回収方法において、
高温雰囲気の温度が３００度以上８００度以下であるこ
とを特徴とする。According to a fourth aspect of the present invention, there is provided a method for separating and recovering an electronic device using a lead-containing piezoelectric material according to the first or second or third aspect.
The temperature of the high-temperature atmosphere is 300 degrees or more and 800 degrees or less.
【００１３】請求項５記載の電子デバイスの分離・回収
方法は、請求項１または２または３または４記載の鉛を
含む圧電材料を用いた電子デバイスの分離・回収方法に
おいて、酸が硫酸、硝酸、塩酸のうち少なくとも１つを
含む酸であることを特徴とする。According to a fifth aspect of the present invention, there is provided a method for separating and recovering an electronic device using a piezoelectric material containing lead, wherein the acid is sulfuric acid or nitric acid. And at least one of hydrochloric acid.
【００１４】請求項６記載の電子デバイスの分離・回収
方法は、請求項１または２または３または４または５記
載の鉛を含む圧電材料を用いた電子デバイスの分離・回
収方法において、鉛を含む圧電材料を用いた電子デバイ
スが圧電振動子及び発音体及び音声検出器及びセラミッ
クフィルタ及びアクチュエータ及び圧電トランスである
ことを特徴とする。According to a sixth aspect of the present invention, there is provided a method for separating and collecting an electronic device using a lead-containing piezoelectric material according to the first or second or third or fourth or fifth aspect. An electronic device using a piezoelectric material is a piezoelectric vibrator, a sounding body, a sound detector, a ceramic filter, an actuator, and a piezoelectric transformer.
【００１５】請求項７記載の電子デバイスの分離・回収
方法は、鉛を含む圧電材料を用いた電子デバイスの分離
・回収方法において、水を用いた超臨界流体を用いて高
分子材料を分解するプロセスを含むことを特徴とする。According to a seventh aspect of the present invention, in the method for separating and collecting an electronic device using a piezoelectric material containing lead, the polymer material is decomposed using a supercritical fluid using water. It is characterized by including a process.
【００１６】図１にこの発明の実施例におけるフローチ
ャートを示す。鉛を含む圧電材料を用いた電子デバイス
の分離・回収方法として、第一に有機溶剤に投入し、乾
燥後高温雰囲気に暴露し、最後に酸に投入する連続した
プロセスを用いている。FIG. 1 shows a flowchart in an embodiment of the present invention. As a method for separating and collecting an electronic device using a piezoelectric material containing lead, a continuous process of first charging an organic solvent, drying, exposing to a high-temperature atmosphere, and finally charging an acid is used.
【００１７】図２は本発明の圧電材料の一つである強誘
電性ペロブスカイト型酸化物の相図である。ここで強誘
電性ペロブスカイト型酸化物（１）は、チタン酸鉛（化
学式ＰｂＴｉＯ3を以降ＰＴと略す）とジルコン酸鉛
（化学式ＰｂＺｒＯ3を以降ＰＺと略す）とマグネシウ
ムニオブ酸鉛（化学式Ｐｂ（Ｍｇ1/3Ｎｂ2/3）Ｏ3を以
降ＰＭＮと略す）の組成物を強誘電性ペロブスカイト型
複合酸化物として、所望の圧電材料を得る。FIG. 2 is a phase diagram of a ferroelectric perovskite oxide which is one of the piezoelectric materials of the present invention. Here, the ferroelectric perovskite oxide (1) is composed of lead titanate (chemical formula PbTiO 3 , hereinafter abbreviated as PT), lead zirconate (chemical formula PbZrO 3 , abbreviated as PZ) and lead magnesium niobate (chemical formula Pb ( A desired piezoelectric material is obtained by using a composition of Mg 1/3 Nb 2/3 ) O 3 (hereinafter abbreviated as PMN) as a ferroelectric perovskite-type composite oxide.
【００１８】いわゆるＰＺＴ系はｘＰＴ−（１−ｘ）Ｐ
Ｚの組成式で表され、ｘが０．４２から０．４８の範囲
に正方晶系と菱面体晶系の相境界が存在する。図２に示
した圧電材料は、これにＰＭＮを添加した三成分系の材
料で、ｘＰＴ―ｙＰＺ―（１―ｘ―ｙ）ＰＭＮの組成式
で表され詳細に研究されており（例えば、OUCHIらによ
るJ. American Ceramic Society Vol.４８ No.１
２の６３０ページ〜６３５ページ）、１−ｘ−ｙをｚで
表すと図２の相図に示すように（ｘ，ｙ，ｚ）＝（0.43
75，0.125，0.4375）で示される３重点付近で大きな圧
電特性をもつ圧電材料である。The so-called PZT system is xPT- (1-x) P
A tetragonal and rhombohedral phase boundary exists when x is in the range of 0.42 to 0.48 as represented by the composition formula of Z. The piezoelectric material shown in FIG. 2 is a ternary material obtained by adding PMN to the piezoelectric material. The piezoelectric material is represented by a composition formula of xPT-yPZ- (1-xy) PMN and has been studied in detail (for example, OUCHI). J. American Ceramic Society Vol.48 No.1
2, pages 630 to 635), and 1-xy is represented by z, as shown in the phase diagram of FIG. 2, (x, y, z) = (0.43
75, 0.125, and 0.4375) are piezoelectric materials having large piezoelectric properties near the triple point.
【００１９】上記以外にもＰＺＴ系材料の特性の改善・
改良を図るため、さまざまな三成分系の材料が一般的に
知られている。また、同じ目的で各種の添加剤や、鉛を
他の元素（Ｂａ，Ｓｒなど）で一部置換するなどして、
現在さまざまな電子デバイスに応用されている。In addition to the above, the characteristics of PZT-based materials can be improved.
For improvement, various ternary materials are generally known. For the same purpose, various additives and lead are partially replaced with other elements (Ba, Sr, etc.)
Currently applied to various electronic devices.
【００２０】これらを用いた電子デバイスは、長期間の
研究開発により特性の向上や工程の工夫が図られ、電極
構成、リード線の取り付け、外装などがより複雑な構造
になってきている。そのため、これら電子デバイスの分
離・回収が困難となっており産業廃棄物として現在処理
されている。The electronic devices using these devices have been improved in characteristics and processes by means of long-term research and development, and have become more complicated in electrode configuration, lead wire attachment, exterior, and the like. Therefore, it is difficult to separate and collect these electronic devices, and these electronic devices are currently treated as industrial waste.
【００２１】これらの電子デバイスの分離回収方法とし
て、本発明は第一に有機溶剤に投入しこれにより、外装
樹脂などの有機化合物を溶解する。有機溶剤は多種多彩
に存在しているが、代表的に使用される有機溶剤は、労
働安全衛生法施行令に定められており、これらは有機溶
剤中毒予防規則において、第1種第2種第3種に分類され
ている。この中で、第1種有機溶剤はクロムや臭素を含
む。また第3種有機溶剤は、石油類であり可燃性、揮発
性が高く工業用に大量に使用するものとしては適さない
と考えられる。As a method for separating and recovering these electronic devices, the present invention firstly introduces the compound into an organic solvent, thereby dissolving an organic compound such as an exterior resin. Although there are a wide variety of organic solvents, organic solvents that are typically used are specified in the Ordinance for Enforcement of the Industrial Safety and Health Law, and these are classified into Class 1 It is classified into three types. Among them, the first type organic solvent contains chromium and bromine. The third type organic solvent is petroleum, and has high flammability and volatility, and is considered to be unsuitable for industrial use in large quantities.
【００２２】そこで本発明で使用する有機溶剤は、環境
負荷が比較的少なく可燃性・揮発性も比較的小さい第２
種有機溶剤を使用する。また、選択にあたっては、所望
の有機化合物を短時間で容易に溶解するものを事前に確
認し選択しておくことが望ましい。さらに、有機溶剤に
投入時には超音波を使用することによりより短時間での
溶解が可能となる。Therefore, the organic solvent used in the present invention has a relatively low environmental load and a relatively low flammability and volatility.
Use seed organic solvent. In addition, it is desirable to select and select in advance those that readily dissolve the desired organic compound in a short time. Furthermore, the dissolution in a shorter time can be achieved by using ultrasonic waves when injected into the organic solvent.
【００２３】本発明は第二のプロセスとして、有機溶剤
で外装樹脂を溶解後、乾燥し高温雰囲気に暴露する。こ
れは、残った有機化合物を酸化分解すると同時に、銀焼
付け電極中のガラスフリットや半田など、接着を目的と
して使用されている無機化合物を溶融することで、無機
化合物の除去と接着物（リード線など）をデバイスから
はずすことを目的としている。In the present invention, as a second process, after dissolving the exterior resin with an organic solvent, the resin is dried and exposed to a high-temperature atmosphere. This involves oxidatively decomposing the remaining organic compounds and simultaneously melting the inorganic compounds used for bonding, such as glass frit and solder in the silver-baked electrode, to remove the inorganic compounds and to remove the adhesive (lead wire). Etc.) from the device.
【００２４】デバイス中に含まれる高温で溶融しかつ主
に接着を目的とした無機化合物は半田、あるいはガラス
フリットに代表されるように３００〜８００度に融点を
持つものが多い。８００℃以上では多くの金属が酸化反
応を起こすため３００〜８００℃に融点をもつものが使
用されていると考えられる。本発明第二プロセスの高温
雰囲気の暴露は、この理由から３００〜８００℃の温度
範囲に設定することで十分な効果を得ることができる。Many of the inorganic compounds contained in the device, which are melted at a high temperature and mainly used for bonding, have a melting point of 300 to 800 degrees as represented by solder or glass frit. If the temperature is 800 ° C. or more, many metals cause an oxidation reaction, and it is considered that a material having a melting point of 300 to 800 ° C. is used. Exposure to a high-temperature atmosphere in the second process of the present invention can provide a sufficient effect by setting the temperature in the range of 300 to 800 ° C. for this reason.
【００２５】本発明の分離回収方法は、最後に酸に投入
する。第二のプロセスを終了した状態で、電子デバイス
は鉛を含む圧電材料と電極（主に銀）のみとなってい
る。これを硝酸に投入すると銀は硝酸銀となって酸中に
溶解する。他の材料の電極も同様に酸を最適に選択する
ことで、溶解が可能である。これらに使用される酸は、
電極を溶解することを目的としており、強酸（硫酸、塩
酸、硝酸）を少なくとも1種類含むことが必要となる。
また、圧電材料は酸には全く溶解しないので、惨に投入
することで圧電材料と電極が容易に分離・回収が可能で
ある。In the separation and recovery method of the present invention, the acid is finally charged. After the completion of the second process, the electronic device includes only a piezoelectric material containing lead and electrodes (mainly silver). When this is put into nitric acid, silver becomes silver nitrate and dissolves in the acid. Similarly, electrodes of other materials can be dissolved by optimally selecting an acid. The acids used for these are
The purpose is to dissolve the electrode, and it is necessary to include at least one kind of strong acid (sulfuric acid, hydrochloric acid, nitric acid).
Further, since the piezoelectric material does not dissolve in the acid at all, it is possible to easily separate and recover the piezoelectric material and the electrode by disposing the piezoelectric material.
【００２６】これらの連続したプロセスを用いること
で、有機化合物は有機溶剤に溶解した形で分離回収さ
れ、リード線や半田は高温雰囲気において分離回収し、
金属の電極は酸に溶解した状態で分離回収される。最終
的に、鉛を含む圧電材料のみが残るので鉛を含む材料単
独での分離回収が可能となる。この結果、現状の産業廃
棄物の削減と同時に、有機物、金属電極、圧電材料など
を単独で回収できるため各々の材料の再利用が容易に可
能となる。By using these continuous processes, organic compounds are separated and recovered in a form dissolved in an organic solvent, and lead wires and solder are separated and recovered in a high-temperature atmosphere.
The metal electrode is separated and recovered while being dissolved in an acid. Finally, since only the piezoelectric material containing lead remains, it is possible to separate and collect the material containing lead alone. As a result, at the same time as the current industrial waste is reduced, organic materials, metal electrodes, piezoelectric materials, and the like can be independently recovered, so that each material can be easily reused.
【００２７】超臨界流体は、物質を臨界温度以上に保
ち、臨界圧力付近に加圧した状態をいう。この時、圧力
すなわち物質の密度を調整することで超臨界流体内の試
料の溶解度を調整することが可能である。この性質は超
臨界流体クロマトグラフィに応用されているが、我々は
この有機材料の分解効果を本プロセスでの応用を試み
た。超臨界流体は、有機溶剤だけでなく二酸化炭素やペ
ンタンなどの炭化水素なども利用することが可能であ
る。我々はさまざま超臨界流体のうち、環境への影響の
ない水を超臨界流体に最も注目しており、これを用いる
ことにより有機溶剤を全く使用することなく電子デバイ
スの分離回収が可能となる。A supercritical fluid is a state in which a substance is maintained at a temperature equal to or higher than a critical temperature and is pressurized near a critical pressure. At this time, it is possible to adjust the solubility of the sample in the supercritical fluid by adjusting the pressure, that is, the density of the substance. This property has been applied to supercritical fluid chromatography, but we tried to apply the decomposition effect of this organic material to this process. As the supercritical fluid, not only organic solvents but also hydrocarbons such as carbon dioxide and pentane can be used. Among various supercritical fluids, water that has no influence on the environment is paid the most attention to the supercritical fluid, and the use of the supercritical fluid enables separation and recovery of electronic devices without using any organic solvent.
【００２８】以下、本発明の実施例について説明する。
なお、この発明の効果は実施例に記載の電子デバイスの
分離回収方法に限定されるものではない。Hereinafter, embodiments of the present invention will be described.
The effects of the present invention are not limited to the method for separating and recovering electronic devices described in the embodiments.
【００２９】（実施例１）図３に本発明の実施例におけ
る発音体の一例を示した。(Embodiment 1) FIG. 3 shows an example of a sounding body according to an embodiment of the present invention.
【００３０】発音体は、有機化合物（通常高分子化合
物）や金属のケース中に圧電振動子を配置した構造をも
つ。圧電振動子は、圧電材料の両面に電極を設け金属板
に貼り付けただけの簡単な構造となっている。The sounding body has a structure in which a piezoelectric vibrator is arranged in a case made of an organic compound (usually a high molecular compound) or a metal. The piezoelectric vibrator has a simple structure in which electrodes are provided on both surfaces of a piezoelectric material and attached to a metal plate.
【００３１】これら発音体のうち金属ケースの発音体を
本発明の分離回収方法プロセスを用いて、分離回収を行
った。Of these sounding bodies, the sounding bodies in the metal case were separated and recovered by using the separation and recovery method process of the present invention.
【００３２】まず第一のプロセスとして、有機溶剤にテ
トラヒドロフランを用い、超音波中に５分間発音体を投
入した。この時、リード線の被覆と、圧電振動子と金属
板の接着剤および圧電振動子をケースに接着している接
着剤が溶剤によって溶解した。First, as a first process, a sounding body was charged into ultrasonic waves for 5 minutes using tetrahydrofuran as an organic solvent. At this time, the coating of the lead wire, the adhesive between the piezoelectric vibrator and the metal plate, and the adhesive bonding the piezoelectric vibrator to the case were dissolved by the solvent.
【００３３】つぎに発音体をとりだし８０℃で３０分乾
燥を行ったあと、４５０℃の高温雰囲気に投入した。こ
のとき、リード線と圧電振動子間の半田が溶解するの
で、リード線を容易にとりはずすことができた。Next, the sounding body was taken out, dried at 80 ° C. for 30 minutes, and then placed in a 450 ° C. high temperature atmosphere. At this time, since the solder between the lead wire and the piezoelectric vibrator was melted, the lead wire could be easily removed.
【００３４】最後に本発音体を高温中から取り出し、冷
却後、銀電極の溶解を目的としてして硝酸に投入した。
３０分投入したところ、銀だけが硝酸銀となって溶解し
たので、圧電材料のみを単独で回収した。Finally, the sounding body was taken out of the high temperature, cooled, and then put into nitric acid for dissolving the silver electrode.
After charging for 30 minutes, only silver was dissolved as silver nitrate, so only the piezoelectric material was recovered alone.
【００３５】（実施例２）図４に本発明の実施例におけ
るバイモルフ型アクチュエータの一例について示した。
基本構成は圧電素子を積層した形であって、圧電振動子
を一点以上で支えて音声振動を検出できる構造にしてい
る。(Embodiment 2) FIG. 4 shows an example of a bimorph actuator according to an embodiment of the present invention.
The basic configuration is a form in which piezoelectric elements are laminated, and has a structure in which a voice vibrator can be detected by supporting a piezoelectric vibrator at one or more points.
【００３６】バイモルフ型アクチュエータに対して、本
発明のプロセスを用いて、鉛を含む圧電材料のみを単独
で回収を行った。それそれの過程で（表１）に示す有機
溶剤、高温雰囲気、酸を用いたところ、容易に圧電材料
の回収が可能であった。Using the process of the present invention, only the piezoelectric material containing lead was independently recovered from the bimorph type actuator. When the organic solvent, high-temperature atmosphere, and acid shown in Table 1 were used in each process, the piezoelectric material could be easily recovered.
【００３７】[0037]
【表１】 [Table 1]
【００３８】（実施例３）図５に弾性板と圧電素子との
積層型アクチュエータの一例について示した。図５と同
様に一部を支えて音声振動を検出することが可能な構造
にしている。(Embodiment 3) FIG. 5 shows an example of a laminated actuator including an elastic plate and a piezoelectric element. As in FIG. 5, the structure is such that the voice vibration can be detected by supporting a part.
【００３９】弾性板と圧電素子との積層型アクチュエー
タに対して、本発明のプロセスを用いて、鉛を含む圧電
材料のみを単独で回収を行った。それそれの過程で（表
１）に示す有機溶剤、高温雰囲気、酸を用いたところ、
容易に圧電材料の回収が可能であった。 （実施例４）図６に本発明の実施例における超音波探触
子のアレイ構造の一例について示した。Using the process of the present invention, only the piezoelectric material containing lead was independently recovered from the laminated actuator including the elastic plate and the piezoelectric element. When using the organic solvent, high temperature atmosphere and acid shown in (Table 1) in each process,
It was possible to easily recover the piezoelectric material. (Embodiment 4) FIG. 6 shows an example of an array structure of an ultrasonic probe according to an embodiment of the present invention.
【００４０】超音波探触子のアレイに対して、本発明の
プロセスを用いて、鉛を含む圧電材料のみを単独で回収
を行った。それそれの過程で（表１）に示す有機溶剤、
高温雰囲気、酸を用いたところ、容易に圧電材料の回収
が可能となった。 （実施例５）図７に圧電トランスの一例について示し
た。Using the process of the present invention, only the piezoelectric material containing lead was solely recovered from the array of ultrasonic probes. In each process, the organic solvents shown in (Table 1)
The use of a high-temperature atmosphere and an acid made it possible to easily recover the piezoelectric material. Embodiment 5 FIG. 7 shows an example of a piezoelectric transformer.
【００４１】圧電トランスに対して、本発明のプロセス
を用いて、鉛を含む圧電材料のみを単独で回収を行っ
た。それそれの過程で（表１）に示す有機溶剤、高温雰
囲気、酸を用いたところ、容易に圧電材料の回収が可能
となった。Using the process of the present invention, only the piezoelectric material containing lead was independently recovered from the piezoelectric transformer. When the organic solvent, high temperature atmosphere, and acid shown in Table 1 were used in each process, the piezoelectric material could be easily recovered.
【００４２】（実施例６）次に水を使用した超臨界流体
を用いて、実施例1と同様の発音体の分離回収を行っ
た。(Example 6) Next, a sound-generating body was separated and recovered in the same manner as in Example 1 by using a supercritical fluid using water.
【００４３】最初に、水に発音体を投入し、これを５０
０気圧以上に加圧し超臨界流体とした。この状態で３０
分間保持したところ、リード線の被覆と、圧電振動子と
金属板の接着剤および圧電振動子をケースに接着してい
る接着剤が超臨界流体によって溶解した。First, a sounding body is put into water, and this is put into 50
It was pressurized to 0 atm or more to obtain a supercritical fluid. 30 in this state
After holding for 1 minute, the coating of the lead wire, the adhesive between the piezoelectric vibrator and the metal plate, and the adhesive bonding the piezoelectric vibrator to the case were dissolved by the supercritical fluid.
【００４４】これを減圧後、実施例1と同様に８０℃で
３０分の乾燥を行い、４５０℃の高温雰囲気投入により
リード線と圧電振動子間の半田が溶解した。この時、リ
ード線を容易にとりはずすことができた。After the pressure was reduced, drying was performed at 80 ° C. for 30 minutes in the same manner as in Example 1, and the solder between the lead wire and the piezoelectric vibrator was melted by introducing a high-temperature atmosphere at 450 ° C. At this time, the lead wire could be easily removed.
【００４５】最後に本発音体を高温中から取り出し、冷
却後、硝酸に投入した。３０分投入したところ、銀だけ
が硝酸銀となって溶解したので、圧電材料のみを単独で
回収した。Finally, the sounding body was taken out of a high temperature, cooled, and then put into nitric acid. After charging for 30 minutes, only silver was dissolved as silver nitrate, so only the piezoelectric material was recovered alone.
【００４６】このように超臨界流体を用いることによ
り、有機溶剤を全く使用せずに電子デバイスの分離回収
を容易に行うことが可能となった。The use of the supercritical fluid makes it possible to easily separate and collect electronic devices without using any organic solvent.
【００４７】[0047]
【発明の効果】この発明は、鉛を含む圧電材料を用いた
電子デバイスにおいて、第一に有機溶剤に投入し、乾燥
後高温雰囲気に暴露し、最後に酸に投入するプロセスを
用いて電子デバイスを分離し回収を行うことを特徴とす
る分離・回収方法であって、これらの連続したプロセス
を用いることで、デバイス中の有機化合物は有機溶剤に
溶解・分離され、リード線や半田は高温雰囲気において
デバイスより分離回収し、金属の電極は酸に溶解した状
態で分離回収される。According to the present invention, there is provided an electronic device using a piezoelectric material containing lead, wherein the electronic device is first charged into an organic solvent, dried, exposed to a high-temperature atmosphere, and finally charged into an acid. Is a separation and recovery method characterized by separating and recovering the organic compound in the device by using these continuous processes, the organic compound in the device is dissolved and separated in an organic solvent, and the lead wires and solder are placed in a high-temperature atmosphere. In the above, the metal electrode is separated and collected in a state of being dissolved in an acid.
【００４８】最終的に、鉛を含む圧電材料のみが残るの
で鉛を含む材料単独での分離回収が可能である。本発明
によれば、現状の産業廃棄物の削減と同時に、有機物、
金属電極などの材料の再利用が容易に可能となる。Finally, since only the piezoelectric material containing lead remains, it is possible to separate and recover the material containing lead alone. According to the present invention, at the same time as reducing the current industrial waste, organic matter,
Materials such as metal electrodes can be easily reused.
【００４９】本発明の効果は実施例に記述したした溶
剤、高温雰囲気、酸に限定されることはない。また、電
子デバイスも、圧電振動子、発音体、超音波検出器用、
アクチュエータに限定されないことはいうまでもないな
い。例えば、音声検出器や加速度検出器用、セラミック
フィルタの圧電素子に用いることができる。The effects of the present invention are not limited to the solvents, high-temperature atmospheres, and acids described in the examples. In addition, electronic devices are also used for piezoelectric vibrators, sound generators, ultrasonic detectors,
Needless to say, the invention is not limited to the actuator. For example, it can be used for a voice detector, an acceleration detector, and a piezoelectric element of a ceramic filter.
【図１】鉛を分離回収する方法を示した図FIG. 1 shows a method for separating and recovering lead.
【図２】Ｔ−ＰＺ−ＰＭＮの相図FIG. 2 is a phase diagram of T-PZ-PMN.
【図３】発音体・レシーバの概略図FIG. 3 is a schematic diagram of a sounding body and a receiver.
【図４】バイモルフ型アクチュエータあるいは加速度セ
ンサ概略図FIG. 4 is a schematic diagram of a bimorph type actuator or an acceleration sensor.
【図５】積層型アクチュエータあるいは加速度センサ概
略図FIG. 5 is a schematic diagram of a laminated actuator or an acceleration sensor.
【図６】超音波探触子アレイ構造の概略図FIG. 6 is a schematic diagram of an ultrasonic probe array structure.
【図７】圧電トランスの概略図FIG. 7 is a schematic diagram of a piezoelectric transformer.
１ 強誘電体ペロブスカイト型酸化物 ２ 金属電極 ３ 振動板 ４ 発音孔 ５ メッシュ状背面孔 ６ 共鳴筐体 ７ 支持部 ８ 弾性体 DESCRIPTION OF SYMBOLS 1 Ferroelectric perovskite type oxide 2 Metal electrode 3 Vibration plate 4 Sounding hole 5 Mesh back hole 6 Resonance case 7 Supporting part 8 Elastic body
Claims (7)
において、第一に有機溶剤に投入し、乾燥後高温雰囲気
に暴露し、最後に酸に投入するプロセスを用いて電子デ
バイスを分離し回収を行うことを特徴とする分離・回収
方法。In an electronic device using a piezoelectric material containing lead, the electronic device is separated and recovered by using a process in which the device is first charged into an organic solvent, dried, exposed to a high-temperature atmosphere, and finally charged into an acid. A separation and recovery method.
１種類を含むことを特徴とする請求項１記載の鉛を含む
圧電材料を用いた電子デバイスの分離・回収方法。2. The method for separating and recovering an electronic device using a lead-containing piezoelectric material according to claim 1, wherein the organic solvent contains at least one of the second organic solvents.
とを特徴とする請求項１または２記載の鉛を含む圧電材
料を用いた電子デバイスの分離・回収方法。3. The method for separating and collecting an electronic device using a lead-containing piezoelectric material according to claim 1, wherein ultrasonic waves are used when the organic solvent is charged.
度以下であることを特徴とする請求項１または２または
３記載の鉛を含む圧電材料を用いた電子デバイスの分離
・回収方法。4. The temperature of a high-temperature atmosphere is 300 degrees or more and 800.
The method for separating and recovering an electronic device using a lead-containing piezoelectric material according to claim 1, wherein the temperature is equal to or lower than the temperature.
１つを含む酸であることを特徴とする請求項１または２
または３または４記載の鉛を含む圧電材料を用いた電子
デバイスの分離・回収方法。5. The method according to claim 1, wherein the acid is an acid containing at least one of sulfuric acid, nitric acid and hydrochloric acid.
Or a method for separating and collecting an electronic device using the piezoelectric material containing lead described in 3 or 4.
が圧電振動子及び発音体及び音声検出器及びセラミック
フィルタ及びアクチュエータ及び圧電トランスであるこ
とを特徴とする請求項１または２または３または４また
は５記載の鉛を含む圧電材料を用いた電子デバイスの分
離・回収方法。6. An electronic device using a piezoelectric material containing lead is a piezoelectric vibrator, a sounding body, a sound detector, a ceramic filter, an actuator, and a piezoelectric transformer. Or a method for separating and recovering an electronic device using the piezoelectric material containing lead according to 5.
の分離・回収方法において、水を用いた超臨界流体を用
いて高分子材料を分解するプロセスを含むことを特徴と
する分離・回収方法。7. A method for separating and recovering an electronic device using a piezoelectric material containing lead, comprising a process of decomposing a polymer material using a supercritical fluid using water. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27086498A JP3008940B1 (en) | 1998-09-25 | 1998-09-25 | Separation / recovery method of electronic device using lead-containing piezoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27086498A JP3008940B1 (en) | 1998-09-25 | 1998-09-25 | Separation / recovery method of electronic device using lead-containing piezoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP3008940B1 true JP3008940B1 (en) | 2000-02-14 |
| JP2000101161A JP2000101161A (en) | 2000-04-07 |
Family
ID=17492046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27086498A Expired - Fee Related JP3008940B1 (en) | 1998-09-25 | 1998-09-25 | Separation / recovery method of electronic device using lead-containing piezoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3008940B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4562297B2 (en) * | 2001-02-06 | 2010-10-13 | 株式会社アサカ理研 | Method for recovering inorganic component materials from electronic components using supercritical water |
| KR101085346B1 (en) * | 2003-04-14 | 2011-11-23 | 세키스이가가쿠 고교가부시키가이샤 | Separation method of adherend, method for recovering electronic part from electronic part laminate, and separation method of laminate glass |
| JP2006023098A (en) * | 2004-07-06 | 2006-01-26 | Matsushita Electric Ind Co Ltd | Ultrasonic oscillator, and ultrasonic flow measuring instrument using the same |
| JP6198274B2 (en) * | 2014-07-01 | 2017-09-20 | 公益財団法人鉄道総合技術研究所 | Piezoelectric material collection method and reuse method |
-
1998
- 1998-09-25 JP JP27086498A patent/JP3008940B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000101161A (en) | 2000-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rödel et al. | Transferring lead-free piezoelectric ceramics into application | |
| Uchino | Advanced piezoelectric materials: Science and technology | |
| Holmes-Siedle et al. | PVdF: An electronically-active polymer for industry | |
| Xu et al. | Dielectric hysteresis from transverse electric fields in lead zirconate titanate thin films | |
| JP3008940B1 (en) | Separation / recovery method of electronic device using lead-containing piezoelectric material | |
| Dong et al. | Ultrasonic transducer with BiScO3-PbTiO3-based ceramics of operating temperature over 400° C | |
| Salowitz et al. | Screen printed piezoceramic actuators/sensors microfabricated on organic films and stretchable networks | |
| Denishev | Some metal oxides and their applications for creation of Microsystems (MEMS) and Energy Harvesting Devices (EHD) | |
| WO1996007774A1 (en) | Preparation of lead-zirconium-titanium film and powder by electrodeposition | |
| Govindarajan et al. | Piezoelectric strain sensor through reverse replication based on two-photon polymerization | |
| Kim et al. | Piezoelectrics | |
| EP2392696B1 (en) | Method for firmly fixing particles, and method for producing structure having firmly fixed particles | |
| Kang et al. | A thickness-mode piezoelectric micromachined ultrasound transducer annular array using a PMN–PZT single crystal | |
| Feng et al. | BiScO3-BiFeO3-PbTiO3-BaTiO3 high-temperature piezoelectric ceramic and its application on high-temperature acoustic emission sensor | |
| Ganie et al. | Piezoelectric ceramics: Advanced applications in electrochemical and electronic fields | |
| JPH05160458A (en) | Laminated piezoelectric element and piezoelectric element | |
| Zhang | Piezoelectric paint sensor for nondestructive structural condition monitoring | |
| Shah et al. | Evaluation of Ru–Ti Electrode-Based TSM Langasite Resonators for High-Temperature Applications | |
| JP2008014690A (en) | Piezoelectric/electrostrictive film type sensor | |
| ryung Kwon et al. | A new type of microphone using flexoelectric barium strontium titnate | |
| Jeong et al. | Effect of geometry on properties of multilayer structure actuator | |
| Tandon et al. | Particle size dependence of piezoelectric and acoustical response of a composite hydrophone | |
| Kambale et al. | Reliability of ferroelectric multilayer PZT thick films fabricated by aerosol deposition | |
| Tatardar et al. | New materials for the electromechanical and acoustoelectric transducers | |
| Yang et al. | Lead free 0.9 Na1/2Bi1/2TiO3–0.1 BaZr0. 2Ti0. 8O3 thin film with large piezoelectric electrostrain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |