JPH05305203A - Method for removing organic solvent embedded in structure of solid substance - Google Patents
Method for removing organic solvent embedded in structure of solid substanceInfo
- Publication number
- JPH05305203A JPH05305203A JP4110986A JP11098692A JPH05305203A JP H05305203 A JPH05305203 A JP H05305203A JP 4110986 A JP4110986 A JP 4110986A JP 11098692 A JP11098692 A JP 11098692A JP H05305203 A JPH05305203 A JP H05305203A
- Authority
- JP
- Japan
- Prior art keywords
- solid substance
- carbon dioxide
- solvent
- organic solvent
- solid
- 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
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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機溶剤をその内部組
織中に埋没している固体物質から有機溶剤を除去する方
法に関する。FIELD OF THE INVENTION The present invention relates to a method for removing organic solvents from solid substances which are embedded in their internal tissues.
【０００２】[0002]
【従来の技術】従来、固体物質を精製する際には、固体
物質を有機溶剤に溶解し、温度を変えて析出させたり、
又は他の溶媒を混合させて析出させる等の条件を変えて
行っており、このような方法によって析出されたものに
対し通常の濾過及び乾燥を行っても、固体物質内部に包
含されてしまった有機溶剤はかなりの量が固体物質中に
残存している。固体物質をよりいっそう精製するために
は、不純物として固体中に存在する有機溶剤を固体物質
中から除去せねばならない。特に医薬品においては、不
純物である残留有機溶剤をできるだけ低濃度となるよう
に除去することが望まれている。2. Description of the Related Art Conventionally, when purifying a solid substance, the solid substance is dissolved in an organic solvent and deposited at different temperatures.
Or, it is carried out under different conditions such as mixing with another solvent for precipitation, and even if the product precipitated by such a method is subjected to ordinary filtration and drying, it is included in the solid substance. A significant amount of organic solvent remains in the solid material. In order to further purify the solid substance, the organic solvent present in the solid as an impurity must be removed from the solid substance. Particularly in pharmaceuticals, it is desired to remove residual organic solvent, which is an impurity, so that the concentration is as low as possible.
【０００３】ところで、有機溶剤を含有する固体物質か
ら有機溶剤を除去するには、従来、加熱乾燥法、真空乾
燥法、気流乾燥法等が用いられてきたが、何れの方法で
も、固体物質と親和性の良い溶媒が用いられており、有
機溶剤の除去は困難であった。特に、医薬品のような高
純度な物質のように、結晶化している固体物質は、結晶
中に有機溶剤が閉じ込められ、その内部に包含された有
機溶剤の除去は困難であり、不完全であった。特に、加
熱乾燥法では、熱に弱い固体物質に対しては成分の分解
が起こるという問題があった。By the way, in order to remove an organic solvent from a solid substance containing an organic solvent, conventionally, a heating drying method, a vacuum drying method, a gas stream drying method and the like have been used. Since a solvent having a good affinity was used, it was difficult to remove the organic solvent. In particular, in the case of a solid substance that is crystallized, such as a high-purity substance such as a drug, the organic solvent is trapped in the crystal, and the removal of the organic solvent contained therein is difficult and incomplete. It was In particular, the heating and drying method has a problem that decomposition of components occurs with respect to a solid substance that is weak against heat.
【０００４】近年、液体二酸化炭素や超臨界二酸化炭素
を用いて、固体物質中の有機溶剤を除去する方法が提案
されており、かなり低濃度まで有機溶剤を除去すること
ができることが知られている。また、超臨界二酸化炭素
を用いた抽出方法は、不揮発性物質や熱に弱い物質に適
用できる方法として知られている。Recently, a method of removing an organic solvent in a solid substance using liquid carbon dioxide or supercritical carbon dioxide has been proposed, and it is known that the organic solvent can be removed to a considerably low concentration. .. The extraction method using supercritical carbon dioxide is known as a method applicable to non-volatile substances and heat-sensitive substances.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前記液
体二酸化炭素や超臨界二酸化炭素を用いて有機溶剤を除
去する方法は、有機溶剤が固体物質の組織中に埋没され
ているもの、即ち、固体物質が結晶体で、有機溶剤がそ
の結晶内部に包含されているようなものに対してはその
有機溶剤の除去は困難であり、超臨界流体を用いた除去
方法でも有機溶剤が残留していた。However, the method of removing the organic solvent by using the liquid carbon dioxide or supercritical carbon dioxide is one in which the organic solvent is buried in the tissue of the solid substance, that is, the solid substance. Is a crystalline substance, and it is difficult to remove the organic solvent even if the organic solvent is contained inside the crystal, and the organic solvent remained even by the removal method using a supercritical fluid.
【０００６】そこで本発明は、超臨界流体を用いた、固
体物質の組織中に埋没されている有機溶剤を除去する方
法において、従来の方法よりもさらに除去効果の高い、
固体物質の組織中に埋没されている有機溶剤を除去する
方法を提供することを目的とする。Therefore, the present invention is a method for removing an organic solvent buried in the structure of a solid substance using a supercritical fluid, which has a higher removal effect than conventional methods.
It is an object of the present invention to provide a method for removing an organic solvent buried in the tissue of a solid substance.
【０００７】[0007]
【課題を解決するための手段】前記した問題点を解決す
るために、本発明は、固体物質の組織中に埋没されてい
る有機溶剤を除去するに当り、固体試料を溶解すること
のできる助溶剤と二酸化炭素とを混合して混合流体と
し、その混合流体を超臨界流体にし、その超臨界流体を
固体物質と接触させることにより、固体物質の組織の一
部を破壊し、内部に閉じ込められていた溶剤を排出する
ことを特徴とする固体物質の組織中に埋没されている有
機溶剤を除去する方法とするものである。In order to solve the above-mentioned problems, the present invention is capable of dissolving a solid sample in removing an organic solvent buried in the tissue of a solid substance. By mixing a solvent and carbon dioxide into a mixed fluid, turning the mixed fluid into a supercritical fluid, and contacting the supercritical fluid with a solid substance, a part of the tissue of the solid substance is destroyed and trapped inside. The conventional solvent is discharged, and the organic solvent buried in the tissue of the solid substance is removed.
【０００８】本発明で、「固体物質の組織中に埋没され
ている」とは、例えば、結晶状態のように強固な固体組
織の中に閉じ込められているような状態をいう。本発明
の固体物質の組織中に埋没されている有機溶剤を除去す
る方法に使用される装置は、図１のブロック図に示され
る。１は二酸化炭素を貯蔵し、供給する二酸化炭素供給
部、２は助溶剤を貯蔵し、供給する助溶剤供給部、３は
二酸化炭素供給部１から供給された二酸化炭素と助溶剤
供給部２から供給された助溶剤とを混合する混合部、４
は有機溶剤が抽出されるべき固体物質が配置され、固体
物質の組織中に埋没されている有機溶剤を抽出する溶剤
抽出部、５は抽出された有機溶剤及び助溶剤を回収する
溶剤回収部である。In the present invention, "being buried in the structure of a solid substance" means, for example, a state of being confined in a solid solid structure such as a crystalline state. The apparatus used in the method of removing the organic solvent embedded in the tissue of the solid material of the present invention is shown in the block diagram of FIG. 1 is a carbon dioxide supply unit for storing and supplying carbon dioxide, 2 is a co-solvent supplying unit for storing and supplying co-solvent, and 3 is carbon dioxide supplied from the carbon dioxide supplying unit 1 and from the co-solvent supplying unit 2. Mixing section for mixing with the supplied co-solvent, 4
Is a solvent extraction unit for extracting the organic solvent embedded in the tissue of the solid substance, in which the solid substance from which the organic solvent is to be extracted is arranged, and 5 is a solvent recovery unit for collecting the extracted organic solvent and cosolvent. is there.
【０００９】本発明の固体物質の組織中に埋没されてい
る有機溶剤を除去する方法を図１に基づいて次に説明す
る。有機溶剤をその組織中に埋没している固体物質は溶
剤抽出部４の容器に予め入れられる。二酸化炭素供給部
１では、二酸化炭素を臨界圧力以上、即ち、７２．８ａ
ｔｍ以上に保たれ、混合部３へ供給される。一方、固体
物質を溶解する能力を持った有機溶剤の中から選ばれた
助溶剤は、助溶剤供給部２で前記二酸化炭素供給部１に
おける二酸化炭素の圧力と同じ圧力に保たれ、混合部３
へ供給され、前記二酸化炭素供給部１から供給された二
酸化炭素と混合される。さらにこの混合部３では、温度
が二酸化炭素の臨界点以上、即ち、３１．１℃以上に上
げられ、二酸化炭素と助溶剤の混合物は超臨界状態とな
り、次いでこの超臨界状態の混合物は溶剤抽出部４に導
入される。A method of removing the organic solvent buried in the structure of the solid substance of the present invention will be described below with reference to FIG. The solid substance in which the organic solvent is embedded in the tissue is put in the container of the solvent extraction part 4 in advance. In the carbon dioxide supply unit 1, carbon dioxide is equal to or higher than the critical pressure, that is, 72.8a.
It is maintained at tm or more and supplied to the mixing section 3. On the other hand, the cosolvent selected from the organic solvents having the ability to dissolve the solid substance is kept in the cosolvent supply unit 2 at the same pressure as the carbon dioxide pressure in the carbon dioxide supply unit 1, and the mixing unit 3
And is mixed with the carbon dioxide supplied from the carbon dioxide supply unit 1. Further, in this mixing section 3, the temperature is raised to the critical point of carbon dioxide or higher, that is, 31.1 ° C. or higher, the mixture of carbon dioxide and the co-solvent becomes a supercritical state, and then the mixture in the supercritical state is subjected to solvent extraction. Introduced in Part 4.
【００１０】この溶剤抽出部４では、固体物質の組織の
一部がミクロ的に溶解し、その中に包含されている有機
溶剤は超臨界状態の混合流体により溶解され抽出除去さ
れる。有機溶剤を溶解した超臨界流体は溶剤回収部５
で、減圧されることにより有機溶剤及び助溶剤と、二酸
化炭素に分離される。有機溶剤と助溶剤はさらに通常の
蒸留により分離してもよい。一方、二酸化炭素は二酸化
炭素供給部１にそのままリサイクルしてもよいが、二酸
化炭素には、分離しきれない微量の有機溶剤が溶解され
ている場合があるので、固体試料中に許容される残留有
機溶剤の濃度以上になる場合には、有機溶剤を吸着除去
する手段を付加してリサイクルするか、又はリサイクル
せずに二酸化炭素をパージする。更に、必要に応じてフ
レッシュな超臨界二酸化炭素のみで抽出を行う。In the solvent extraction unit 4, a part of the structure of the solid substance is microscopically dissolved, and the organic solvent contained therein is dissolved and extracted by the mixed fluid in the supercritical state. The supercritical fluid in which the organic solvent is dissolved is the solvent recovery unit 5
Then, the organic solvent and the auxiliary solvent are separated into carbon dioxide by reducing the pressure. The organic solvent and cosolvent may be further separated by conventional distillation. On the other hand, carbon dioxide may be recycled to the carbon dioxide supply unit 1 as it is, but since a small amount of organic solvent that cannot be separated may be dissolved in carbon dioxide, the residual residue in the solid sample is acceptable. If the concentration exceeds the concentration of the organic solvent, a means for adsorbing and removing the organic solvent is added for recycling, or carbon dioxide is purged without recycling. Furthermore, if necessary, extraction is performed only with fresh supercritical carbon dioxide.
【００１１】本発明の対象とする、固体物質の組織中に
埋没されている有機溶剤は、超臨界二酸化炭素に溶解す
ることが可能な有機溶剤である。また、助溶剤は固体物
質を溶解するものの中から選ばれる。助溶剤の二酸化炭
素に対する混合割合が大きすぎると固体物質を余分に溶
解してしまい、目的物質である固体物質の歩留まりが悪
くなるため、有機溶剤をその組織の内部に埋没している
固体物質に対しミクロな穴をあける程度の量が好まし
い。そのミクロな穴とは、超臨界流体と埋没されていた
有機溶剤の接触を可能にする程度の必要にして最小限の
大きさの穴とすることが望ましい。The organic solvent embedded in the tissue of the solid substance, which is the object of the present invention, is an organic solvent capable of dissolving in supercritical carbon dioxide. The cosolvent is selected from those which dissolve the solid substance. If the mixing ratio of the cosolvent to carbon dioxide is too large, the solid substance will be dissolved excessively, and the yield of the solid substance that is the target substance will deteriorate, so the organic solvent will be added to the solid substance buried inside the tissue. On the other hand, the amount is preferably such that micro holes can be formed. It is desirable that the micro holes have necessary and minimum sizes that allow contact between the supercritical fluid and the buried organic solvent.
【００１２】また助溶剤の二酸化炭素に対する混合割合
が大きいと、混合流体を超臨界状態にするために過度の
温度圧力を必要とするためエネルギーを多く必要とし、
また熱に敏感な固体物質は変質してしまうため好ましく
ない。そのため助溶剤の二酸化炭素に対する混合割合は
１０％以下とすることが望ましい。Further, if the mixing ratio of the cosolvent to carbon dioxide is large, excessive temperature and pressure are required to bring the mixed fluid into a supercritical state, which requires a large amount of energy,
Further, a heat-sensitive solid substance is unfavorably altered in quality. Therefore, the mixing ratio of the cosolvent to carbon dioxide is preferably 10% or less.
【００１３】[0013]
【作用】本発明は、上記のような構成であって、二酸化
炭素に助溶剤を混合した流体を超臨界状態にし、有機溶
剤を包含した固体物質に接触することにより、固体物質
の組織、例えば，結晶組織にミクロな穴をあけて超臨界
流体と有機溶剤の接触を可能にするように、必要にして
最小限に固体物質の一部を溶解して包含されている有機
溶剤を除去しようとするものである。The present invention, which has the above-mentioned structure, brings a fluid of carbon dioxide mixed with a cosolvent into a supercritical state and brings it into contact with a solid substance containing an organic solvent so that the texture of the solid substance, for example, ， Try to remove the contained organic solvent by dissolving a part of the solid substance to the minimum necessary so as to allow the contact between the supercritical fluid and the organic solvent by making micro holes in the crystal structure. To do.
【００１４】これに対して、従来、二酸化炭素を超臨界
流体として用いた一般的な抽出技術において、二酸化炭
素の性状を変える目的で、超臨界流体に助溶剤を添加し
て物質の抽出を行うことがあった。この従来技術によれ
ば、超臨界状態の二酸化炭素は非極性溶媒としての性質
を有し、抽出したい物質が極性溶媒に親和性であるもの
に対しては、二酸化炭素の超臨界流体だけでは十分に抽
出することができず、この二酸化炭素の超臨界流体に極
性溶媒を助溶剤として混ぜることにより、二酸化炭素の
超臨界流体に極性を付与させて抽出すべき物質との親和
性を持たせて抽出を行い、抽出効率を上げるものであ
る。On the other hand, in a conventional general extraction technique using carbon dioxide as a supercritical fluid, a substance is extracted by adding a cosolvent to the supercritical fluid for the purpose of changing the properties of carbon dioxide. There was something. According to this conventional technique, carbon dioxide in a supercritical state has a property as a non-polar solvent, and for a substance to be extracted having an affinity for a polar solvent, a supercritical fluid of carbon dioxide is sufficient. However, by mixing a polar solvent as a co-solvent with this carbon dioxide supercritical fluid, the carbon dioxide supercritical fluid is made polar and has an affinity with the substance to be extracted. Extraction is performed to improve extraction efficiency.
【００１５】したがって、従来、一般的な抽出に使用さ
れていた助溶剤は、抽出物と親和性のある助溶剤が用い
られているのに対して、本発明の固体物質の組織中に埋
没されている有機溶剤の除去のための助溶剤は、固体物
質中の組織をミクロに破壊するための、固体物質に対し
溶解作用のある物質が用いられる点において、両者の目
的、作用及び使用方法が異なる。Therefore, the cosolvent which has been conventionally used for general extraction is a cosolvent having an affinity for the extract, while it is buried in the tissue of the solid substance of the present invention. The co-solvent for removing the organic solvent, which is used, is to use a substance having a dissolving action on the solid substance for microscopically destroying the structure in the solid substance, and the purpose, action and method of use of both are different.
【００１６】[0016]
【実施例１】メチルイソブチルケトン（以下，ＭＩＢＫ
という）により晶析され、真空乾燥されて脱溶媒された
抗生物質中のＭＩＢＫ濃度は０．３％であり、真空乾燥
だけではこれ以上下げることはできない。本実施例で
は、固体試料として、メタノール、エタノールに可溶、
水に微溶である性質を有するＭＩＢＫを０．３％その結
晶組織中に埋没している抗生物質を用いた。Example 1 Methyl isobutyl ketone (hereinafter, MIBK
The concentration of MIBK in the antibiotic that was crystallized by (1), vacuum-dried, and desolvated was 0.3%, and cannot be further reduced only by vacuum-drying. In this example, as a solid sample, soluble in methanol and ethanol,
An antibiotic with 0.3% of MIBK having the property of being slightly soluble in water embedded in its crystal structure was used.
【００１７】この抗生物質に対して、超臨界二酸化炭素
に助溶剤としてメタノールを５％混合した温度３５℃、
圧力２００ａｔｍの超臨界状態の混合物を用いて抽出を
行った。その結果、固体物質中のＭＩＢＫ濃度は０．０
９％に減少していた。なお、ＭＩＢＫ濃度の測定方法は
ガスクロマトグラフィーによって行った。To this antibiotic, supercritical carbon dioxide was mixed with 5% methanol as a co-solvent at a temperature of 35 ° C.
Extraction was performed using a supercritical mixture at a pressure of 200 atm. As a result, the MIBK concentration in the solid substance is 0.0
It had decreased to 9%. The MIBK concentration was measured by gas chromatography.
【００１８】[0018]
【実施例２】実施例１において、超臨界状態の混合物の
温度を６０℃とした以外は、実施例１と全く同じ条件で
抽出を行った。その結果、固体物質中のＭＩＢＫ濃度は
０．００５％未満に減少していた。Example 2 Extraction was carried out under the same conditions as in Example 1 except that the temperature of the mixture in the supercritical state was 60 ° C. As a result, the MIBK concentration in the solid substance was reduced to less than 0.005%.
【００１９】[0019]
【実施例３】実施例２において、助溶剤として５％エタ
ノールを使用した以外は、実施例２と全く同じ条件で抽
出を行った。その結果、固体物質中のＭＩＢＫ濃度は
０．０７％に減少していた。 〔比較例１〕ＭＩＢＫを０．３％埋没している固体試料
を真空加熱乾燥したところ、ＭＩＢＫの濃度は０．３％
となり、これ以下には下がらなかった。Example 3 Extraction was carried out under the same conditions as in Example 2, except that 5% ethanol was used as a cosolvent. As a result, the MIBK concentration in the solid substance was reduced to 0.07%. [Comparative Example 1] A solid sample having 0.3% of MIBK buried therein was vacuum-heat-dried, and the concentration of MIBK was 0.3%.
And did not fall below this.
【００２０】〔比較例２〕ＭＩＢＫを０．３％埋没して
いる固体試料に対し、温度３５℃、圧力２００ａｔｍの
超臨界状態の二酸化炭素を用いて抽出を行った。その結
果、固体物質中のＭＩＢＫ濃度は０．２７％に減少して
いた。以上の、実施例１〜３、及び比較例１，２を次の
表１にまとめた。Comparative Example 2 A solid sample having 0.3% of MIBK buried therein was subjected to extraction using carbon dioxide in a supercritical state at a temperature of 35 ° C. and a pressure of 200 atm. As a result, the MIBK concentration in the solid substance was reduced to 0.27%. The above Examples 1 to 3 and Comparative Examples 1 and 2 are summarized in Table 1 below.
【００２１】[0021]
【表１】 [Table 1]
【００２２】表１によれば、真空加熱乾燥又は超臨界二
酸化炭素のみの抽出方法では固体物質の組織中に埋没さ
れている有機溶剤は殆ど除去できないが、固体物質の組
織を溶解することのできる助溶剤を併用することによ
り、固体物質中の有機溶剤の残留濃度を著しく低減でき
ることが分かる。According to Table 1, the organic solvent buried in the tissue of the solid substance can hardly be removed by the vacuum heating drying method or the extraction method using only supercritical carbon dioxide, but the tissue of the solid substance can be dissolved. It can be seen that the residual concentration of the organic solvent in the solid substance can be significantly reduced by using the co-solvent together.
【００２３】[0023]
【発明の効果】本発明は、固体試料を溶解することので
きる助溶剤と二酸化炭素とを混合して混合流体とし、超
臨界状態にした混合流体を用いて固体物質の組織中に埋
没されている有機溶剤を除去するので、固体物質中の有
機溶剤の残留濃度を著しく低減できる。INDUSTRIAL APPLICABILITY According to the present invention, a co-solvent capable of dissolving a solid sample and carbon dioxide are mixed to form a mixed fluid, which is embedded in the tissue of a solid substance using the mixed fluid in a supercritical state. Since the existing organic solvent is removed, the residual concentration of the organic solvent in the solid substance can be significantly reduced.
【図１】本発明を実施するための超臨界流体を用いた固
体物質中の有機溶剤を除去する装置のブロック図を示
す。FIG. 1 shows a block diagram of an apparatus for removing an organic solvent in a solid substance using a supercritical fluid for carrying out the present invention.
１ 二酸化炭素供給部 ２ 助溶剤供給部 ３ 混合部 ４ 溶剤抽出部 ５ 溶剤回収部 1 Carbon dioxide supply part 2 Auxiliary solvent supply part 3 Mixing part 4 Solvent extraction part 5 Solvent recovery part
Claims (1)
溶剤を除去するに当り、固体試料を溶解することのでき
る助溶剤と二酸化炭素とを混合して混合流体とし、その
混合流体を超臨界流体にし、その超臨界流体を固体物質
と接触させることにより、固体物質の組織の一部を破壊
し、内部に閉じ込められていた有機溶剤を排出すること
を特徴とする固体物質の組織中に埋没されている有機溶
剤を除去する方法。1. When removing an organic solvent embedded in the tissue of a solid substance, a cosolvent capable of dissolving a solid sample and carbon dioxide are mixed to form a mixed fluid, and the mixed fluid is By making a supercritical fluid and contacting the supercritical fluid with a solid substance, a part of the tissue of the solid substance is destroyed and the organic solvent trapped inside is discharged into the tissue of the solid substance. Method to remove buried organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4110986A JP3012085B2 (en) | 1992-04-30 | 1992-04-30 | Method for removing organic solvent embedded in tissue of solid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4110986A JP3012085B2 (en) | 1992-04-30 | 1992-04-30 | Method for removing organic solvent embedded in tissue of solid material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05305203A true JPH05305203A (en) | 1993-11-19 |
| JP3012085B2 JP3012085B2 (en) | 2000-02-21 |
Family
ID=14549512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4110986A Expired - Fee Related JP3012085B2 (en) | 1992-04-30 | 1992-04-30 | Method for removing organic solvent embedded in tissue of solid material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3012085B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08191063A (en) * | 1994-06-07 | 1996-07-23 | Lg Semicon Co Ltd | Removal method of etching residue |
| US11083979B2 (en) | 2017-09-12 | 2021-08-10 | Lg Chem, Ltd. | Solvent separation method and solvent separation apparatus |
-
1992
- 1992-04-30 JP JP4110986A patent/JP3012085B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08191063A (en) * | 1994-06-07 | 1996-07-23 | Lg Semicon Co Ltd | Removal method of etching residue |
| US11083979B2 (en) | 2017-09-12 | 2021-08-10 | Lg Chem, Ltd. | Solvent separation method and solvent separation apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3012085B2 (en) | 2000-02-21 |
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