JP2002177922A - Method for recovering valuable material from discarded printed board - Google Patents
Method for recovering valuable material from discarded printed boardInfo
- Publication number
- JP2002177922A JP2002177922A JP2000376420A JP2000376420A JP2002177922A JP 2002177922 A JP2002177922 A JP 2002177922A JP 2000376420 A JP2000376420 A JP 2000376420A JP 2000376420 A JP2000376420 A JP 2000376420A JP 2002177922 A JP2002177922 A JP 2002177922A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- resin
- dissolving
- recovering valuable
- base metal
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Landscapes
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、廃棄されたパッケ
ージ基板等のプリント基板（以下、廃基板ともいう）か
ら効果的に有価物を分離して回収する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for effectively separating and recovering valuable resources from a printed board such as a discarded package board (hereinafter also referred to as a waste board).
【０００２】[0002]
【従来の技術】従来、廃棄されたパッケージ基板等のプ
リント基板は、破砕して基板に亀裂等を生じさせ、基板
の担体に形成された卑金属回路の断面部分等を露出させ
た後に、卑金属や貴金属を回収していた。2. Description of the Related Art Conventionally, a printed circuit board such as a discarded package board is crushed to cause a crack or the like in the board, exposing a cross section of a base metal circuit formed on a carrier of the board, and then removing the base metal or the like. Precious metals were being recovered.
【０００３】このような金属の回収方法として、特開昭
５１−６１２４号公報には、硫酸と過酸化水素の混合酸
を用いて金属を溶解した後、これらの金属を分離・回収
する方法が開示されている。回路を構成する金属を溶解
させる際、金属の回収率を向上させるために、特開平１
１−３６０２０号公報では、硝酸、塩酸、硫酸といった
強酸等を使用しており、また、最近では、シアン化合物
を用いている。As a method for recovering such metals, Japanese Patent Laid-Open Publication No. Sho 51-6124 discloses a method in which metals are dissolved using a mixed acid of sulfuric acid and hydrogen peroxide, and then these metals are separated and recovered. It has been disclosed. In order to improve the metal recovery rate when dissolving the metal constituting the circuit, Japanese Patent Application Laid-Open
In JP-A-36020, a strong acid such as nitric acid, hydrochloric acid, and sulfuric acid is used, and recently, a cyanide compound is used.
【０００４】また、特開平２−８８７２５号公報や、特
開平１０−２９６２２５号公報等においては、プリント
基板を８００℃以上に加熱した後、破砕して篩い分けす
る方法が開示されており、特開２０００−１０４１２６
号公報では、プリント基板を破砕した後、溶融精錬炉で
１３００〜１６００℃に加熱し、溶融分離する方法等が
提案されている。Japanese Patent Application Laid-Open Nos. 2-87725 and 10-296225 disclose a method of heating a printed circuit board to 800 ° C. or higher, followed by crushing and sieving. Opening 2000-104126
In Japanese Patent Application Laid-Open Publication No. H11-264, a method is proposed in which a printed board is crushed and then heated to 1300 to 1600 ° C. in a melting and refining furnace to melt and separate.
【０００５】しかしながら、近年、プリント基板は微細
化が進みパッケージ化が急速に進行しているため、粉砕
・溶解処理法を用いて廃基板を処理しようとすると、従
来程度の粉砕処理だけで回路の金属面の大部分を露出さ
せることが困難で、より細かく破砕しなければならなく
なってきている。そのため、粉砕作業コストは増大し、
破砕作業環境の悪化や粉砕工程の複雑化を招いている。However, in recent years, printed circuit boards have been miniaturized and packaging has been progressing rapidly. Therefore, if a waste substrate is to be treated using a crushing / dissolving treatment method, a circuit is formed only by a conventional crushing treatment. It is difficult to expose most of the metal surface, and it has become necessary to crush it more finely. As a result, the grinding operation cost increases,
This leads to deterioration of the crushing work environment and complication of the crushing process.
【０００６】また、回路を構成している卑金属の露出が
不完全になりやすく、従来と同じような金属の回収効率
を得ることが困難になってきている。また、微細化され
た廃基板は、回路を構成する金属の溶解工程における溶
解液の分離・洗浄作業において、破砕が進めば進むほど
に洗浄は不完全になり易く、その洗浄コストは増大化し
ている。さらに、微細に破砕された合成樹脂とガラス繊
維とからなる非溶解混合物は、微細に粉砕された混合状
態ゆえに再利用が進まず、主として埋立て処理されてい
る。In addition, the exposure of the base metal constituting the circuit is likely to be incomplete, making it difficult to obtain the same metal recovery efficiency as in the prior art. In addition, the finer waste substrate is more likely to be incompletely cleaned as the crushing progresses in the separation and cleaning work of the solution in the process of melting the metal constituting the circuit, and the cleaning cost increases. I have. Furthermore, a non-dissolved mixture composed of a finely crushed synthetic resin and glass fiber is not recycled because of the finely crushed mixed state, and is mainly buried.
【０００７】一方、加熱・篩分離法では、廃基板の担体
成分であるガラス繊維が冷却時に熱ショックを受ける８
００℃以上という高い加熱温度を必要とする割には比重
差を利用する風選工程で完全に金属成分の分離ができ
ず、分離物質毎に溶解しても各金属成分の混じった溶液
になって、精製工程の複雑さが解消されておらず、溶融
法は、合金から個別の金属を回収するという発想で、容
易に高効率に分離回収する方法とは言い難い。[0007] On the other hand, in the heating / sieving separation method, a glass fiber as a carrier component of a waste substrate receives a heat shock during cooling.
Despite the necessity of a high heating temperature of at least 00 ° C, metal components cannot be completely separated in the air-selection process using the specific gravity difference, and even if each separated substance is dissolved, it becomes a mixed solution of each metal component. However, the complexity of the refining process has not been eliminated, and the melting method cannot be said to be an easy and highly efficient method of separating and recovering from the idea of recovering individual metals from the alloy.
【０００８】[0008]
【発明が解決しようとする課題】上述のように、廃基板
の破砕・溶解処理法において、金属の回収率を上げよう
とすれば廃基板を微細に破砕せねばならず、このように
微細に破砕すると再利用が困難になる。一方、廃基板を
疎な破砕ですませると金属の回収率が低下してしまう。
また、強引に回収率を上げようと貴金属と卑金属との両
方を同時に溶解する王水等を使用すると、貴金属と卑金
属との混在液が得られるため、分離工程が複雑になると
いうジレンマが生じていた。As described above, in the method of crushing and dissolving a waste substrate, in order to increase the metal recovery rate, the waste substrate must be finely crushed. Crushing makes reuse difficult. On the other hand, if the waste substrate is sparsely crushed, the metal recovery rate decreases.
In addition, if aqua regia or the like that simultaneously dissolves both the noble metal and the base metal is used in order to forcibly increase the recovery rate, a mixed solution of the noble metal and the base metal is obtained, which causes a dilemma that the separation process becomes complicated. Was.
【０００９】[0009]
【課題を解決するための手段】本発明は、上記課題を解
決するためになされたものであり、廃基板から有価物を
回収する方法において、廃基板を微細に破砕することな
く、回路を形成する金属を高効率に、しかも貴金属と卑
金属とが分かれた状態で回収することができる方法を提
供するものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and a method for recovering valuable resources from a waste substrate is provided. It is an object of the present invention to provide a method capable of recovering a high-efficiency metal in a state in which a noble metal and a base metal are separated.
【００１０】すなわち、本発明は、廃棄されたプリント
基板からの有価物の回収法であって、上記プリント基板
を構成する樹脂部と回路部とのうち、上記樹脂部の樹脂
成分を溶解分離した後、上記回路部を構成している金属
を溶解して回収することを特徴とする廃棄されたプリン
ト基板からの有価物の回収法である。That is, the present invention relates to a method for recovering valuable resources from discarded printed circuit boards, wherein a resin component of the resin section is dissolved and separated from a resin section and a circuit section constituting the printed circuit board. A method of recovering valuable resources from discarded printed circuit boards, characterized by dissolving and recovering the metal constituting the circuit section.
【００１１】上記有価物の回収法において、上記樹脂成
分を溶解分離する方法は、特に限定されるものではない
が、例えば、加熱・加圧水酸化処理する方法を用いるこ
とで、上記樹脂成分を溶解分離し、上記樹脂部で覆われ
ていた回路部の金属面を露出させた後、上記回路部を構
成する金属を溶解して回収することが望ましい。さら
に、金属を溶解回収する際、回路部を構成する金属であ
る卑金属と貴金属とを、個別に順次溶解して回収するこ
とが望ましい。In the method of recovering valuable resources, the method of dissolving and separating the resin component is not particularly limited. For example, the method of dissolving and separating the resin component by using a method of heating and pressurizing hydroxylation is used. Then, after exposing the metal surface of the circuit portion covered with the resin portion, it is desirable to dissolve and collect the metal constituting the circuit portion. Furthermore, when dissolving and recovering the metal, it is desirable that the base metal and the noble metal, which are the metals constituting the circuit section, are individually melted and recovered sequentially.
【００１２】このように、廃基板を反応器内で加熱・加
圧しながら水溶液と接触させ、樹脂部を構成する合成樹
脂成分を固体から液体に変化させ、ガラス繊維と分離
し、これにより生じた空間から回路を構成する金属成分
を溶解させる方法を採用することにより、効率よくこれ
らの金属を回収することができる。As described above, the waste substrate is brought into contact with the aqueous solution while being heated and pressurized in the reactor to change the synthetic resin component constituting the resin portion from a solid to a liquid, and to separate from the glass fiber. By employing a method of dissolving metal components constituting a circuit from space, these metals can be efficiently recovered.
【００１３】すなわち、上記方法により、樹脂部が占め
ていたスペースは空間となり、基板内で回路を形成して
いた銅等の卑金属は、樹脂に被覆された状態から空間に
露出された状態となるため、溶解液と直接かつ同時に無
数の場所で接触させることができ、貴金属を溶解せず、
卑金属のみを溶解する塩酸等の一般的な酸の使用が可能
となる。その結果、卑金属の溶解・分離後に王水やシア
ン化塩等を用いて貴金属を溶解することができ、従来の
ように卑金属と貴金属との混合液から貴金属を分離する
必要がなくなる。したがって、卑金属と貴金属とが最初
から分離した溶液を得ることができ、精製工程を簡単に
することができる。That is, according to the above method, the space occupied by the resin portion becomes a space, and the base metal such as copper which has formed a circuit in the substrate changes from a state covered with the resin to a state exposed to the space. Therefore, it can be brought into contact with the solution directly and simultaneously in countless places, without dissolving the noble metal,
It is possible to use a general acid such as hydrochloric acid that dissolves only the base metal. As a result, the noble metal can be dissolved using aqua regia or cyanide salt after dissolving / separating the base metal, and it is not necessary to separate the noble metal from the mixed solution of the base metal and the noble metal as in the related art. Therefore, a solution in which the base metal and the noble metal are separated from the beginning can be obtained, and the purification step can be simplified.
【００１４】また、溶解液は露出した金属と数多くの場
所で容易に素早く、かつ、同時に接触することができる
ために、従来のように金属を溶解した溶解液がさらにそ
の奥の金属を溶解するために溶解液の濃度を高濃度にす
る必要が無くなると同時に溶解に要する時間を従来より
大幅に短縮することができ、また、溶解液量は必要最小
限に少なくすることができる。以下、本発明を実施の形
態により、具体的に説明する。Further, since the dissolving solution can easily and quickly come into contact with the exposed metal in many places at the same time, the dissolving solution dissolving the metal further dissolves the metal behind it as in the prior art. Therefore, it is not necessary to increase the concentration of the dissolving solution, and at the same time, the time required for dissolving can be significantly reduced, and the amount of the dissolving solution can be minimized. Hereinafter, the present invention will be described specifically with reference to embodiments.
【００１５】[0015]
【発明の実施の形態】本発明は、プリント基板を構成す
る樹脂部と回路部とのうち、上記樹脂部の樹脂成分を溶
解分離した後、上記回路部を構成している金属を溶解し
て回収することを特徴とする廃棄されたプリント基板か
らの有価物の回収法である。BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, of a resin part and a circuit part constituting a printed circuit board, a resin component of the resin part is dissolved and separated, and then a metal constituting the circuit part is dissolved. This is a method of recovering valuable resources from discarded printed circuit boards, which is characterized by collecting.
【００１６】以下、本発明を図面に基づいて説明する。
図１は本発明の廃棄されたプリント基板からの有価物の
回収法における各工程を示すチャート図であり、図２
は、樹脂溶解洗浄工程における物質の流れを示すフロー
図であり、図３は、卑金属溶解洗浄工程及び貴金属溶解
洗浄工程における物質の流れを示すフロー図である。Hereinafter, the present invention will be described with reference to the drawings.
FIG. 1 is a chart showing each step in the method for recovering valuable resources from discarded printed circuit boards according to the present invention.
FIG. 3 is a flow chart showing a flow of a substance in a resin dissolution cleaning step, and FIG. 3 is a flow chart showing a flow of a substance in a base metal dissolution cleaning step and a noble metal dissolution cleaning step.
【００１７】図１に示すように、本発明の上記有価物の
回収法は、樹脂溶解洗浄工程、卑金属溶解洗浄工程、及
び、貴金属溶解洗浄工程から成り立っている。As shown in FIG. 1, the method for recovering valuable resources according to the present invention comprises a resin dissolving and washing step, a base metal dissolving and washing step, and a noble metal dissolving and washing step.
【００１８】本発明では、まず、樹脂溶解洗浄工程を行
う。本発明で対象となる廃基板としては、例えば、半導
体チップを搭載した単層又は複数層の導体回路を有する
パッケージ基板等が挙げられる。In the present invention, first, a resin dissolution washing step is performed. Examples of the waste substrate that is a target of the present invention include a package substrate having a single-layer or multiple-layer conductor circuit on which a semiconductor chip is mounted.
【００１９】これらの廃基板は、上述したように、通
常、樹脂部と回路部とからなり、樹脂部は、合成樹脂の
ほかに補強材としてガラス繊維等が含まれている。樹脂
部を構成する樹脂成分としては、例えば、エポキシ樹
脂、フェノール樹脂、ポリイミド樹脂、ポリアミド樹
脂、マレイミド樹脂等が挙げられる。また、回路部は、
Ｃｕ、Ａｌ、Ｎｉ、Ｃｒ等の卑金属とＡｕ、Ａｇ、Ｐｄ
等の貴金属よりなり、Ａｕ等の貴金属は、回路が露出す
る部分を酸化から保護するための保護層として形成され
ている。As described above, these waste substrates usually include a resin portion and a circuit portion, and the resin portion contains glass fiber or the like as a reinforcing material in addition to the synthetic resin. Examples of the resin component constituting the resin portion include an epoxy resin, a phenol resin, a polyimide resin, a polyamide resin, a maleimide resin, and the like. The circuit part is
Base metals such as Cu, Al, Ni, Cr and Au, Ag, Pd
The noble metal such as Au is formed as a protective layer for protecting a portion where a circuit is exposed from oxidation.
【００２０】上記樹脂溶解洗浄工程においては、図２に
示すように、全ての弁を閉じた状態で反応器１の中に廃
基板を入れ、弁５ａ、５ｄ及び５ｅを開いて薬液注入ポ
ンプ２ａを作動させ、樹脂溶解液槽３から樹脂溶解液を
予熱用熱交換器４を経由して反応器１中に注入した後、
弁５ａ、５ｄ及び５ｅを閉じて反応器１を密閉状態と
し、反応器１に設けられた加熱器手段で、反応器１を加
熱・加圧して、廃基板の樹脂部を構成する樹脂成分を固
体状態から液体状態にする。In the resin dissolution washing step, as shown in FIG. 2, a waste substrate is put into the reactor 1 with all valves closed, and the valves 5a, 5d and 5e are opened to open the chemical liquid injection pump 2a. Is operated to inject the resin solution from the resin solution tank 3 into the reactor 1 via the preheating heat exchanger 4,
The reactors 5 are closed by closing the valves 5a, 5d and 5e, and the reactor 1 is heated and pressurized by a heater means provided in the reactor 1 so that the resin component constituting the resin portion of the waste substrate is removed. Change from a solid state to a liquid state.
【００２１】そして、弁５ｂを開いて反応器１中の液体
成分と固体成分とをフィルター９で濾過分離した後、弁
５ｃを開いて洗浄液注入ポンプ２ｂによって洗浄液槽６
から注入される洗浄液及び／又は弁５ｆを開いて注入さ
れるスチームで、反応器１及びフィルター９上の固体成
分を洗浄する。なお、上記液体成分は、上記加熱・加圧
工程で溶解した樹脂成分と該樹脂成分の溶解に用いた樹
脂溶解液との混合液体であり、この液体成分は、比重の
差によって水と樹脂分解生成物とに分離することができ
る。また、上記固体成分は、ガラス繊維と回路部を構成
する金属（卑金属及び貴金属）とを含有する溶解残渣で
ある。After the valve 5b is opened and the liquid component and the solid component in the reactor 1 are separated by filtration through the filter 9, the valve 5c is opened and the cleaning liquid tank 6 is opened by the cleaning liquid injection pump 2b.
The solid components on the reactor 1 and the filter 9 are washed with the washing liquid injected from the reactor and / or the steam injected by opening the valve 5f. The liquid component is a mixed liquid of the resin component dissolved in the heating and pressurizing step and the resin solution used for dissolving the resin component, and the liquid component is decomposed with water due to a difference in specific gravity. It can be separated into products. In addition, the solid component is a dissolved residue containing glass fibers and metals (base metals and noble metals) constituting the circuit section.
【００２２】反応器１は、廃基板をその内部に搬入する
ためのハッチが設けられており、予熱用熱交換器４、フ
ィルター９及びトラップ８に、それぞれ弁及び配管を介
して接続している。このような反応器１としては、例え
ば、高温、高圧及び気密特性に優れるオートクレーブ等
を挙げることができる。The reactor 1 is provided with a hatch for carrying the waste substrate into the reactor 1, and is connected to the preheating heat exchanger 4, the filter 9 and the trap 8 via valves and pipes, respectively. . An example of such a reactor 1 is an autoclave having excellent high-temperature, high-pressure and airtight properties.
【００２３】上記樹脂溶解液は、廃基板１重量部に対し
て、アルカリ剤を含んだ水溶液５０〜１００重量部であ
ることが望ましい。上記アルカリ剤としては、例えば、
水酸化ナトリウム、水酸化カリウム等が挙げられ、その
ｐＨは、８．５〜９．０程度に調整されることが望まし
い。The above-mentioned resin solution is desirably 50 to 100 parts by weight of an aqueous solution containing an alkali agent with respect to 1 part by weight of a waste substrate. As the alkaline agent, for example,
Examples thereof include sodium hydroxide and potassium hydroxide, and the pH thereof is desirably adjusted to about 8.5 to 9.0.
【００２４】反応器１の加熱温度は、２６０〜５００℃
が望ましく、３２０〜４６０℃がより望ましい。加熱温
度が２６０℃未満であると、樹脂成分を充分に溶解する
ことができない場合があり、一方、加熱温度が５００℃
を超えると、樹脂成分を完全に溶解することはできる
が、反応器１の破損を防止するためには極めて大規模な
装置とする必要があり、コスト面で問題が生じる。発生
するガスは、弁５ｄからトラップ８を経由して外部に排
出することができる。なお、加熱温度（反応温度）を２
９５℃以上に上昇させると、樹脂成分の溶解速度が向上
する。下記の表１には、反応温度と積層基板（Ｎ・ＰＧ
Ａ廃基板）の重量減少との関係を示している。The heating temperature of the reactor 1 is 260-500 ° C.
And 320 to 460 ° C. is more preferable. If the heating temperature is lower than 260 ° C, the resin component may not be sufficiently dissolved, while the heating temperature may be 500 ° C.
If it exceeds, the resin component can be completely dissolved, but in order to prevent the damage of the reactor 1, it is necessary to use an extremely large-scale apparatus, which causes a problem in cost. The generated gas can be discharged from the valve 5d to the outside via the trap 8. The heating temperature (reaction temperature) is 2
When the temperature is raised to 95 ° C. or higher, the dissolution rate of the resin component is improved. Table 1 below shows the reaction temperature and the laminated substrate (N · PG
A waste substrate).
【００２５】[0025]
【表１】 [Table 1]
【００２６】反応器１の加圧は、１２〜２５ＭＰａであ
ることが望ましく、１４．６〜２３ＭＰａであることが
より望ましい。加圧が１２ＭＰａ未満であると、樹脂成
分を充分に溶解することができない場合があり、一方、
加圧が２５ＭＰａを超えると、反応器１が破損する可能
性がある。The pressure in the reactor 1 is preferably from 12 to 25 MPa, more preferably from 14.6 to 23 MPa. When the pressure is less than 12 MPa, the resin component may not be sufficiently dissolved, while
If the pressure exceeds 25 MPa, the reactor 1 may be damaged.
【００２７】反応器１の加熱・加圧時間は、１０〜１２
０分であることが望ましく、２０〜４０分であることが
より望ましい。加熱・加圧時間が１０分未満であると、
樹脂成分を充分に溶解することができない場合があり、
一方、１２０分を超えると、樹脂成分の溶解の進行は殆
ど見られなくなるため、これ以上続けると作業効率の低
下を招く。The heating and pressurizing time of the reactor 1 is 10-12.
The time is preferably 0 minutes, and more preferably 20 to 40 minutes. If the heating and pressurizing time is less than 10 minutes,
It may not be possible to dissolve the resin component sufficiently,
On the other hand, if it exceeds 120 minutes, the progress of dissolution of the resin component is hardly observed, and if it continues more than this, the work efficiency will be reduced.
【００２８】このような条件で、反応器１中に搬入した
廃基板を樹脂溶解液とともに加熱・加圧することによ
り、廃基板中の樹脂部を構成する樹脂成分が低分子状態
の液体状態にまで分解し、上記樹脂部を構成していた樹
脂成分とガラス繊維とを分離することができる。Under these conditions, the waste substrate carried into the reactor 1 is heated and pressurized together with the resin solution so that the resin component constituting the resin portion in the waste substrate is brought into a low molecular liquid state. It can be decomposed to separate the resin component and the glass fiber constituting the resin portion.
【００２９】次いで、卑金属溶解洗浄工程を行う。この
卑金属溶解洗浄工程では、図３に示すように、全ての弁
を閉じた状態で、反応器から取り出した廃基板の溶解残
渣を溶解槽１０に投入した後、弁１５ａを開き、薬液注
入ポンプ１２ａを用い、卑金属の溶解液を貯蔵した卑金
属溶解液槽１３から一般的な酸を溶解槽１０に注入し、
回路部を構成する卑金属を溶解させる。この後、弁１５
ｂを開き、フィルター１９で濾過し、卑金属溶解残渣と
卑金属含有液とを分離し、卑金属含有液を卑金属液槽１
７ａに貯留する。なお、上記卑金属が溶解する際にガス
が発生するが、この発生したガスは、ガス洗浄槽１４を
通って洗浄された後、外部に排出されるようになってい
る。Next, a base metal dissolving and washing step is performed. In the base metal dissolving and cleaning step, as shown in FIG. 3, after dissolving the residue of the waste substrate taken out of the reactor into the dissolving tank 10 with all the valves closed, the valve 15a is opened, and the chemical liquid injection pump is opened. Using 12a, a general acid is injected into the dissolution tank 10 from the base metal solution tank 13 storing the base metal solution,
Dissolve the base metal that constitutes the circuit section. After this, valve 15
b, is filtered with a filter 19 to separate the base metal-dissolved residue and the base metal-containing liquid, and the base metal-containing liquid is transferred to the base metal liquid tank 1
Store in 7a. A gas is generated when the base metal dissolves, and the generated gas is discharged through the gas cleaning tank 14 and then discharged to the outside.
【００３０】次に、弁１５ａ、１５ｂを閉じてから、弁
１５ｃ、１５ｄを開け、洗浄液注入ポンプ１２ｃによっ
て洗浄液層１６から注入される洗浄液、及び／又は、弁
１５ｈを開いて注入されるスチームで溶解槽１０の卑金
属溶解残渣を洗浄し、洗浄排水を洗浄液排水槽１７ｂに
貯留する。この卑金属溶解洗浄工程が終了した後、再
度、全ての弁を閉じる。Next, after closing the valves 15a and 15b, the valves 15c and 15d are opened, and the cleaning liquid injected from the cleaning liquid layer 16 by the cleaning liquid injection pump 12c and / or the steam injected by opening the valve 15h. The base metal dissolution residue in the dissolution tank 10 is washed, and the washing wastewater is stored in the washing liquid drainage tank 17b. After the base metal dissolving and washing step is completed, all valves are closed again.
【００３１】卑金属を溶解する一般的な酸としては、例
えば、塩酸、硝酸、硫酸、リン酸等が挙げられる。例え
ば、一般的な酸として塩酸を使用する場合、その濃度
は、３〜６Ｎが望ましい。従って、このような酸を卑金
属溶解液槽１３に貯蔵しておき、溶解槽１０に注入する
が、その際に、溶解時間を短縮するために加温する手法
を排除するものではない。Examples of general acids that dissolve base metals include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. For example, when hydrochloric acid is used as a general acid, its concentration is preferably 3 to 6N. Therefore, such an acid is stored in the base metal dissolving solution tank 13 and injected into the dissolving tank 10, but at this time, a method of heating to shorten the dissolving time is not excluded.
【００３２】次いで、貴金属溶解洗浄工程を行う。この
貴金属溶解洗浄工程では、図３に示すように、弁１５ｅ
を開き、薬液注入ポンプ１２ｂを用い、貴金属の溶解液
を貯蔵した貴金属溶解液槽１４から貴金属溶解液を溶解
槽１０に注入し、卑金属溶解残渣中の貴金属を溶解させ
た後、弁１５ｆを開き、フィルタ１９で濾過し、貴金属
溶解残渣と貴金属含有液とを分離し、貴金属含有液を貴
金属液槽１８ａに貯留する。なお、上記貴金属が溶解す
る際にガスが発生するが、この発生したガスは、ガス洗
浄槽１４を通って洗浄された後、外部に排出されるよう
になっている。Next, a noble metal dissolution washing step is performed. In the precious metal dissolving and cleaning step, as shown in FIG.
Is opened, the noble metal solution is injected into the melting tank 10 from the noble metal solution tank 14 storing the noble metal solution using the chemical solution injection pump 12b, and the noble metal in the base metal melting residue is dissolved, and then the valve 15f is opened. Then, the mixture is filtered with a filter 19 to separate the noble metal dissolved residue from the noble metal-containing liquid, and the noble metal-containing liquid is stored in the noble metal liquid tank 18a. A gas is generated when the noble metal is dissolved, and the generated gas is discharged through the gas cleaning tank 14 and then discharged to the outside.
【００３３】次に、弁１５ｅ、１５ｆを閉じてから、弁
１５ｃ、１５ｇを開け、洗浄液注入ポンプ１２ｃによっ
て洗浄液槽１６から注入される洗浄液、及び／又は、弁
１５ｈを開いて注入されるスチームで溶解槽１０の貴金
属溶解残渣を洗浄し、洗浄排水を洗浄液排水槽１８ｂに
貯留する。フィルタ１９上に残留した上記貴金属溶解残
渣は、例えば、ガラス繊維強化プラスチックの成分であ
ったガラス繊維である。Next, after closing the valves 15e and 15f, the valves 15c and 15g are opened, and the cleaning liquid injected from the cleaning liquid tank 16 by the cleaning liquid injection pump 12c and / or the steam injected by opening the valve 15h. The noble metal dissolution residue in the dissolution tank 10 is washed, and the washing wastewater is stored in the washing liquid drain tank 18b. The noble metal dissolution residue remaining on the filter 19 is, for example, glass fiber which is a component of glass fiber reinforced plastic.
【００３４】回路部を構成する貴金属を溶解する溶液と
しては、例えば、王水、シアン化塩溶液等が挙げられ
る。例えば、貴金属を溶解する溶液として、シアン化塩
溶液を使用する場合、その濃度は、０．０１〜１ｍｏｌ
／Ｌが望ましい。従って、このような溶液を貴金属溶解
液槽１４に貯蔵し、溶解槽１０に注入するが、その際
に、溶解時間を短縮するために加温する手法を講じるの
を排除するものではない。Examples of the solution for dissolving the noble metal constituting the circuit section include aqua regia and cyanide salt solution. For example, when a cyanide salt solution is used as a solution for dissolving a noble metal, its concentration is 0.01 to 1 mol.
/ L is desirable. Therefore, such a solution is stored in the noble metal solution tank 14 and injected into the solution tank 10, but at this time, it is not excluded that a method of heating to shorten the melting time is taken.
【００３５】[0035]
【実施例】以下、実施例により本発明を説明するが、本
発明は、これらの実施例に限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００３６】実施例１ 本実施例では、プラスチックパッケージ（ＢＧＡ）基板
の廃基板を対象として、有価物の回収を行った。図４
は、プラスチックパッケージ基板を模式的に示す断面図
であり、ガラス繊維を含有するベース基板２３の上に銅
等の卑金属からなる回路部２２が形成されており、回路
が露出する両端部には、金等の貴金属からなる被覆層２
１が形成されている。Example 1 In this example, valuable resources were collected from waste plastic package (BGA) substrates. FIG.
FIG. 2 is a cross-sectional view schematically showing a plastic package substrate. A circuit portion 22 made of a base metal such as copper is formed on a base substrate 23 containing glass fiber. Coating layer 2 made of noble metal such as gold
1 is formed.
【００３７】本実施例では、このような構成のプラスチ
ックパッケージ基板の廃基板（２．１９７６１ｇ／枚）
を反応器に入れた後、該反応器にｐＨ８．５に調整した
水酸化ナトリウム水溶液を１００ｇ注入し、３２０℃、
１５ＭＰａまで加熱・加圧して１０分間保持した後に減
圧、洗浄した。そして、溶解残渣中の卑金属（Ｃｕ）
を、４Ｎの塩酸を用いて溶解させた後、水洗し、次い
で、王水で貴金属（Ａｕ）を溶解させた後、水洗した。
その結果、表２に示すように、従来法で行った下記の比
較例１に対して、銅を２７１倍の４３４．１６ｍｇ回収
することができ、金は最初から露出しているために差が
生じなくて０．０３ｍｇと同じ量を回収することができ
た。In this embodiment, a waste plastic package substrate (2,9761 g / sheet) having such a configuration is used.
Was introduced into the reactor, 100 g of an aqueous sodium hydroxide solution adjusted to pH 8.5 was injected into the reactor,
After heating and pressurizing to 15 MPa and holding for 10 minutes, reduced pressure and washing were performed. And the base metal (Cu) in the melting residue
Was dissolved with 4N hydrochloric acid and then washed with water, and then a noble metal (Au) was dissolved with aqua regia and then washed with water.
As a result, as shown in Table 2, 434.16 mg of copper was recovered 271 times that of Comparative Example 1 described below, which was performed by the conventional method, and there was a difference since gold was exposed from the beginning. The same amount as 0.03 mg could be recovered without generation.
【００３８】比較例１ 実施例１と同じ構成のプラスチックパッケージ基板の廃
基板を二つ割にした後、王水処理し、卑金属（Ｃｕ）及
び貴金属（Ａｕ）を同時に回収した。その結果を表２に
示す。COMPARATIVE EXAMPLE 1 A waste plastic package substrate having the same structure as in Example 1 was divided into two, and then subjected to aqua regia treatment to simultaneously recover a base metal (Cu) and a noble metal (Au). Table 2 shows the results.
【００３９】[0039]
【表２】 [Table 2]
【００４０】実施例２ 実施例１とは異なるプラスチックパッケージ基板の廃基
板（１．８０９５７ｇ／枚）を実施例１と同じ条件で処
理した結果、表３に示すように、比較例２に比べ、銅を
９７２倍の３５０．０４ｍｇ、金を３．５倍の０．０９
５ｍｇ回収することができた。Example 2 A waste plastic package substrate (1.80957 g / sheet) different from that of Example 1 was treated under the same conditions as in Example 1, and as shown in Table 3, compared with Comparative Example 2, 972 times 350.04 mg of copper and 3.5 times 0.09 of gold
5 mg could be recovered.
【００４１】比較例２ 実施例２と同じ構成のプラスチックパッケージ基板の廃
基板を二つ割にした後、王水処理し、卑金属（Ｃｕ）及
び貴金属（Ａｕ）を同時に回収した。その結果を表３に
示す。COMPARATIVE EXAMPLE 2 A waste plastic package substrate having the same structure as in Example 2 was divided into two, and then subjected to aqua regia treatment to simultaneously recover the base metal (Cu) and the noble metal (Au). Table 3 shows the results.
【００４２】[0042]
【表３】 [Table 3]
【００４３】実施例３ 本実施例では、積層基板の廃基板を対象として、有価物
の回収を行った。図５は、積層基板を模式的に示す断面
図であり、ガラス繊維を含有するベース基板２３の上に
銅等の卑金属からなる回路２２が層間樹脂絶縁層２４を
挟んで複数層積層形成されており、回路が露出する端部
には、金等の貴金属からなる被覆層２１が形成されてい
る。Example 3 In this example, valuable resources were collected from waste substrates of the laminated substrate. FIG. 5 is a cross-sectional view schematically showing a laminated substrate, in which a circuit 22 made of a base metal such as copper is formed on a base substrate 23 containing glass fiber by laminating a plurality of layers with an interlayer resin insulating layer 24 interposed therebetween. In addition, a coating layer 21 made of a noble metal such as gold is formed at an end where the circuit is exposed.
【００４４】図５に示す積層基板の廃基板（９．２２９
１１ｇ／枚）を反応器に入れた後、該反応器にｐＨ８．
５に調整した水酸化ナトリウム水溶液を６７５ｇ注入
し、３５０℃、２０ＭＰａまで加熱・加圧して２０分間
保持した後に減圧、洗浄した。そして、溶解残渣中の卑
金属（Ｃｕ）を、４Ｎの塩酸を用いて溶解させた後、水
洗し、次いで、王水で貴金属（Ａｕ）を溶解させた後、
水洗した。その結果、表４に示すように、従来法で行っ
た下記の比較例３に対して、銅を１２倍の６５３ｍｇ、
金が１．５倍の２．９６９ｍｇが回収することができ
た。The waste substrate (9.229) of the laminated substrate shown in FIG.
11 g / sheet) was placed in the reactor, and then the pH of the reactor was adjusted to 8.0.
675 g of an aqueous sodium hydroxide solution adjusted to 5 was injected, heated and pressurized to 350 ° C. and 20 MPa, held for 20 minutes, and then washed under reduced pressure. After dissolving the base metal (Cu) in the dissolved residue using 4N hydrochloric acid, washing with water, and then dissolving the noble metal (Au) with aqua regia,
Washed with water. As a result, as shown in Table 4, compared to Comparative Example 3 below, which was performed by the conventional method, copper was 12 times 653 mg,
2.969 mg of 1.5 times gold could be recovered.
【００４５】比較例３ 実施例３と同じ構成の積層基板の廃基板を二つ割にした
後、王水処理し、卑金属（Ｃｕ）及び貴金属（Ａｕ）を
同時に回収した。その結果を表４に示す。Comparative Example 3 A waste substrate of a laminated substrate having the same configuration as that of Example 3 was divided into two, and then subjected to aqua regia treatment to simultaneously recover a base metal (Cu) and a noble metal (Au). Table 4 shows the results.
【００４６】[0046]
【表４】 [Table 4]
【００４７】[0047]
【発明の効果】以上の説明から明らかなように、本発明
の廃棄されたプリント基板からの有価物の回収法を用い
ると、樹脂成分が占めていた区域が空間になって樹脂成
分に覆われていた回路金属部分が露出し、回路部を構成
する卑金属は容易に一般的な酸に溶解できるようにな
り、次の工程で貴金属との分離溶解が可能となる。この
ために卑金属の回収率が大幅に向上し、貴金属との分離
工程が不要となって、産業への寄与は大きい。As is clear from the above description, when the method of recovering valuable resources from discarded printed circuit boards of the present invention is used, the area occupied by the resin component becomes a space and is covered by the resin component. The exposed circuit metal portion is exposed, and the base metal forming the circuit portion can be easily dissolved in a general acid, and can be separated and dissolved from the noble metal in the next step. For this reason, the recovery rate of the base metal is greatly improved, and a step of separating the base metal from the precious metal is not required, and the contribution to the industry is great.
【図１】本発明の廃棄されたプリント基板からの有価物
の回収法における各工程を示すチャート図である。FIG. 1 is a chart showing each step in a method for recovering valuable resources from discarded printed circuit boards according to the present invention.
【図２】本発明の樹脂溶解洗浄工程の一実施例を示すシ
ステムフロー図である。FIG. 2 is a system flow chart showing one embodiment of a resin dissolution washing step of the present invention.
【図３】本発明の卑金属及び貴金属溶解洗浄工程の一実
施例を示すシステムフロー図である。FIG. 3 is a system flow chart showing one embodiment of a base metal and noble metal dissolving and cleaning step of the present invention.
【図４】プラスチックパッケージ基板を模式的に示す断
面図である。FIG. 4 is a cross-sectional view schematically showing a plastic package substrate.
【図５】積層基板を模式的に示す断面図である。FIG. 5 is a sectional view schematically showing a laminated substrate.
１ 反応器 ２ａ 薬液注入ポンプ ２ｂ 洗浄液注入ポンプ ３ 樹脂溶解液槽 ４ 予熱用熱交換器 ５ａ〜ｄ 弁 ６ 洗浄液槽 ７ 加熱器 ８ トラップ ９ フィルタ １０ 溶解槽 １１ ガス洗浄器 １２ａ、ｂ 薬液注入ポンプ １２ｃ 洗浄液注入ポンプ １３ 卑金属溶解液槽 １４ 貴金属溶解液槽 １５ａ〜ｇ 弁 １６ 洗浄液槽 １７ａ 卑金属液槽 １７ｂ 洗浄液排水槽 １８ａ 貴金属液槽 １８ｂ 洗浄液排水槽 １９ フィルタ ２１ 被覆層 ２２ 回路部 ２３ ベース基板 ２４ 樹脂部 DESCRIPTION OF SYMBOLS 1 Reactor 2a Chemical liquid injection pump 2b Cleaning liquid injection pump 3 Resin solution tank 4 Preheat heat exchanger 5a-d Valve 6 Cleaning liquid tank 7 Heater 8 Trap 9 Filter 10 Dissolution tank 11 Gas washer 12a, b Chemical liquid injection pump 12c Cleaning liquid injection pump 13 Base metal solution tank 14 Precious metal solution tank 15a to g Valve 16 Cleaning liquid tank 17a Base metal liquid tank 17b Cleaning liquid drain tank 18a Precious metal liquid tank 18b Cleaning liquid drain tank 19 Filter 21 Coating layer 22 Circuit section 23 Base substrate 24 Resin section
フロントページの続き Ｆターム(参考） 4D004 AA24 AB03 AB10 BA05 CA12 CA13 CA29 CA34 CA35 CA36 CA39 CA40 CA41 CA47 CB04 CB31 CC01 CC03 CC04 CC11 CC12 DA06 DA07 4F301 AA22 AA24 AA27 AA30 AB02 AD01 AD02 AD04 CA09 CA23 CA24 CA26 CA42 CA53 CA64 CA65 CA68 CA72 CA73 4K001 AA04 AA09 BA22 CA49 DB02 DB08 Continued on the front page F term (reference) 4D004 AA24 AB03 AB10 BA05 CA12 CA13 CA29 CA34 CA35 CA36 CA39 CA40 CA41 CA47 CB04 CB31 CC01 CC03 CC04 CC11 CC12 DA06 DA07 4F301 AA22 AA24 AA27 AA30 AB02 AD01 AD02 AD04 CA09 CA23 CA24 CA26 CA53 CA68 CA72 CA73 4K001 AA04 AA09 BA22 CA49 DB02 DB08
Claims (4)
回収法であって、前記プリント基板を構成する樹脂部と
回路部とのうち、前記樹脂部の樹脂成分を溶解分離した
後、前記回路部を構成している金属を溶解して回収する
ことを特徴とする廃棄されたプリント基板からの有価物
の回収法。1. A method of recovering valuable resources from a discarded printed circuit board, comprising: dissolving and separating a resin component of the resin section from a resin section and a circuit section constituting the printed circuit board; A method for recovering valuable resources from discarded printed circuit boards, comprising dissolving and recovering the metal constituting the part.
熱・加圧水酸化処理する方法を用いる請求項１記載の廃
棄されたプリント基板からの有価物の回収法。2. The method for recovering valuable resources from discarded printed circuit boards according to claim 1, wherein a method of heating and pressurizing hydroxylation is used as a method of dissolving and separating the resin component.
ていた回路部の金属面を露出させた後、前記回路部を構
成する金属を溶解して回収する請求項１または２記載の
廃棄されたプリント基板からの有価物の回収法。3. The method according to claim 1, wherein the resin component is dissolved and separated, and after exposing the metal surface of the circuit portion covered with the resin portion, the metal constituting the circuit portion is dissolved and recovered. A method of recovering valuable resources from discarded printed circuit boards.
金属とを、個別に順次溶解して回収する請求項１〜３の
いずれかに記載の廃棄されたプリント基板からの有価物
の回収法。4. The method for recovering valuable resources from a discarded printed circuit board according to claim 1, wherein the base metal and the noble metal, which are metals constituting the circuit portion, are individually melted and recovered. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000376420A JP2002177922A (en) | 2000-12-11 | 2000-12-11 | Method for recovering valuable material from discarded printed board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000376420A JP2002177922A (en) | 2000-12-11 | 2000-12-11 | Method for recovering valuable material from discarded printed board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002177922A true JP2002177922A (en) | 2002-06-25 |
Family
ID=18845280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000376420A Pending JP2002177922A (en) | 2000-12-11 | 2000-12-11 | Method for recovering valuable material from discarded printed board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002177922A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003051545A1 (en) * | 2001-12-18 | 2003-06-26 | Denso Corporation | Printed circuit board recycle method and apparatus thereof |
| WO2004092292A1 (en) * | 2003-04-14 | 2004-10-28 | Sekisui Chemical Co., Ltd. | Method for releasing adhered article |
| JP2009221273A (en) * | 2008-03-14 | 2009-10-01 | National Institute Of Advanced Industrial & Technology | Method for solubilization treatment of thermosetting resin, and solvent to be used in the treatment |
| JP2009242877A (en) * | 2008-03-31 | 2009-10-22 | Dowa Eco-System Co Ltd | Method for leaching of metal from liquid crystal panel |
| CN103071662A (en) * | 2012-12-14 | 2013-05-01 | 清华大学 | Environmentally friendly method for rapidly disassembling waste circuit board through applying [BMIm]BF4 |
| JP2015003287A (en) * | 2013-06-19 | 2015-01-08 | 国立大学法人 千葉大学 | Method for separating core and resin of element |
| CN104928480A (en) * | 2015-07-17 | 2015-09-23 | 兰州理工大学 | Functionalized ionic liquid pyrolysis water leaching method for recovering metal from circuit board |
-
2000
- 2000-12-11 JP JP2000376420A patent/JP2002177922A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7107661B2 (en) | 2001-12-18 | 2006-09-19 | Denso Corporation | Method of recycling printed circuit board |
| WO2003051545A1 (en) * | 2001-12-18 | 2003-06-26 | Denso Corporation | Printed circuit board recycle method and apparatus thereof |
| US7296340B2 (en) | 2001-12-18 | 2007-11-20 | Denso Corporation | Apparatus of recycling printed circuit board |
| US7909959B2 (en) | 2003-04-14 | 2011-03-22 | Sekisui Chemical Co., Ltd. | Method for releasing adhered article |
| JPWO2004092292A1 (en) * | 2003-04-14 | 2006-07-06 | 積水化学工業株式会社 | Method of peeling adherend |
| CN100368497C (en) * | 2003-04-14 | 2008-02-13 | 积水化学工业株式会社 | Method for releasing adhered article,and method for recovering electronic part from a laminate and laminated glass releasing method |
| JP4599294B2 (en) * | 2003-04-14 | 2010-12-15 | 積水化学工業株式会社 | Laminated glass peeling method |
| WO2004092292A1 (en) * | 2003-04-14 | 2004-10-28 | Sekisui Chemical Co., Ltd. | Method for releasing adhered article |
| JP2009221273A (en) * | 2008-03-14 | 2009-10-01 | National Institute Of Advanced Industrial & Technology | Method for solubilization treatment of thermosetting resin, and solvent to be used in the treatment |
| JP2009242877A (en) * | 2008-03-31 | 2009-10-22 | Dowa Eco-System Co Ltd | Method for leaching of metal from liquid crystal panel |
| CN103071662A (en) * | 2012-12-14 | 2013-05-01 | 清华大学 | Environmentally friendly method for rapidly disassembling waste circuit board through applying [BMIm]BF4 |
| JP2015003287A (en) * | 2013-06-19 | 2015-01-08 | 国立大学法人 千葉大学 | Method for separating core and resin of element |
| CN104928480A (en) * | 2015-07-17 | 2015-09-23 | 兰州理工大学 | Functionalized ionic liquid pyrolysis water leaching method for recovering metal from circuit board |
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