TW200900540A - Method for reuse of phosphoric acid-containing metal etchant or phosphoric acid - Google Patents

Abstract

The invention provides a process for regenerating efficiently a phosphoric acid containing etchant for metals which further contains volatile impurities such as volatile and hydrophilic etching inhibitor substances and other impurities such as metal ions into an etchant free from these impurities. The process comprises the step (1) of ridding a phosphoric acid containing etchant for metals which further contains at least one acid other than phosphoric acid and volatile and hydrophilic impurities of the volatile components by heating, vacuumization, blasting, or a combination of two or three of them and the step (2) of extracting metal ions from the residue obtained in the step (1) which contains phosphoric acid as the main component by the use of an extract ant containing both a phosphoric monoester and a phosphoric diester.

Description

200900540 IX. Description of the Invention: [Technical Field] The present invention relates to a metal-containing engraving solution containing phosphoric acid derived from photoresist, etc., which is volatile and hydrophilic, such as miscellaneous or metal ions. Or a method of regenerating a metal etchant or phosphoric acid containing a domain acid containing no impurities such as a metal ion. [Prior Art] In the nightingale semiconductor manufacturing industry, the insect engraving liquid is used for the pattern formation of a metal film such as aluminum, molybdenum, titanium, yttria, tantalum nitride or nickel which has been subjected to photoresist treatment. The development of these industries uses a large amount of etching liquid. Such an etching solution is generally a mixture of acetic acid, nitric acid, phosphoric acid or phosphoric acid. When the etching liquid is used for the etching treatment, the etching rate of the used etching liquid becomes slower than that of the new etching liquid. Further, if the metal impurity/initial in the etching liquid is used, the metal impurities in the rhyme liquid will remain in the silver engraving, which is a cause of leakage current, and has a problem of affecting the element. If the impurities can be removed from the above-mentioned etching liquid, the etching liquid can be recovered and reused, and it is meaningful from the viewpoints of resources and environment. Conventionally, in order to remove metal impurities from a solvent, distillation is often used. However, in this method, if the solvent is evaporated, the metal remains in the form of a residue in the bottom of the pot. Since the phosphoric acid which is the main component of the etching solution is not volatile, the metal is concentrated in the phosphoric acid and is difficult to be applied for removal. Metal impurities in the etchant. (1) In this case, in Patent Document 1, the metal is not removed, but the squaric acid is extracted to 'separate and recover the phosphoric acid. However, there is a 5 200900540 residual ion in the acid. Problems with ions, titanium, titanium nitride, oxidized oxide, tantalum nitride, nickel, and the like. Further, it is known that extraction and separation of aluminum ions are carried out by using acidic phosphoric acid vinegar (for example, refer to Patent Document 2 and Non-Patent Document υ. However, it is effective only in a state where the acidity of the used etching liquid is low, and the acid concentration is high. In the state of the invention, it is not possible to sufficiently extract and separate the ions. In Non-Patent Document 2, it is described that Versatic acid 1〇 (fat f-type acid) is used to extract the ions. However, in order to make the partition coefficient of the ionic ions 1 or more, It is necessary to add a base to adjust the pH to 2 2 to 2 5, and since the phosphoric acid becomes a bowl acid salt, it is not suitable for recycling and reuse as an etching liquid. In Patent Documents 3 and 4, an extractant for extracting molybdenum ions can be effectively extracted, There are di-2-ethylhexylphosphoric acid (D2EHPA) or 2-ethylhexyldecanoic acid mono-2-ethylhexyl ester [made by Daiba Chemical Industry Co., Ltd.: trade name pc_88A], with double_2,4 , 4-trimethylpentylphosphonic acid as a component of acidic phosphide [Kyanex 272, manufactured by KIDAI INDUSTRIAL CO., LTD.], etc. Although it is possible to use (acid phosphide from sulfuric acid effluent from waste desulfurization catalyst, Extraction of molybdenum ions by solvent extraction, however, There is a problem that aluminum ions cannot be extracted from an aqueous phase having a high acid concentration. Patent Document 5 describes that a waste liquid containing aluminum ions is desulfurized by electrodialysis, and then aluminum ions are extracted using an acidic phosphate. In the method of Patent Document 6, 'the method of extracting acid by using an aqueous solution containing a tribasic acid-filled vinegar', an aqueous solution containing an impurity, and an impurity is extracted. Further, in Patent Document 7, a distillation is described. After distilling off an acid other than phosphoric acid and water from a mixed acid solution containing a metal, the phosphoric acid is melt-crystallized, and the metal 200900540 is used as an aqueous solution and the acid is solid as a solvent. However, 'from the used (four) liquid When extracting metal ions and the like, the concentration of metal ions in the right stroke liquid increases, and the extraction rate is used to remove the metal ions in the stroke liquid. However, since the molybdenum ions are at very low = inverse Stroke can be extracted to an acidic extractant such as quinic acid, so it is also subjected to reverse extraction by mineral acid, but it needs to be subjected to reverse extraction by a test such as dihydrate. For acid extraction, =:! To be subjected to reverse extraction, emulsification, etc., such as inorganic test or ammonia test, there is a problem in stratification, and even if the stratification: the product change is very large... After the treatment of mineral acid, the second test: "Although the stratification can be improved" will lead to an increase in the number of steps, which has problems in industrial applications. [Patent Document 1] Japanese Special Opening 2〇〇4_16〇292 [Patent Document 2] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. (1987) 351-365 [Non-Patent Document 2] Sasaki, Sakamoto Metal Society, 1〇8〇~1〇87 pages, 1988 200900540 [Summary of the Invention] As described above, 'using the phosphoric acid-containing etching solution The etching performance is restored to the same as the new etching solution, and the metal impurity concentration is reduced to new Engraved with the degree of recycling the liquid to the etching solution, this and other conventional techniques difficult lines. Therefore, in the past, the used etching solution containing phosphoric acid was generally subjected to neutralization treatment and discarded. Further, there is a case where the phosphoric acid is separated and recovered, and the fertilizer is chemically grown. However, the method of recovering the phosphoric acid-containing etching solution and recovering it by using the etching liquid is not present. Further, in the past, attention has been paid to the removal of metal impurities, but whether or not the metal impurities are removed from the used etching liquid can restore the performance as an etching liquid. Therefore, the object of the present invention is to provide a method for recovering the use of the used acid or the acid containing the acid acid to the same as that of the new etching liquid, and reducing the metal impurity concentration, recycling and recycling. The liquid method, Utti (the species can be 挥发性 有 有 有 有 有 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光 光In order to solve the above problems, the present inventors have found out the volatility from the photoresist and are hydrophilic substances in order to solve the above problems. The biological site will hinder the etching, and it is found that by using the method of removing the obstruction material, the method of removing the cloud and removing the metal ions, and the method for effectively removing the impurity, the impurity is removed. The method for regenerating a stroke liquid or the like can solve the above-mentioned problems', thereby completing the present invention. That is, the present invention is a method for regenerating a metal-containing etching solution containing a phosphoric acid-containing metal etchant 200900540 containing a heterologous + eight umbrellas, characterized in that it comprises :From a scaly acid-containing metal (IV) liquid having a volatile and affinity impurity, or a phosphoric acid containing a volatile and pro- 7: impurity and a metal ion, #heating, decompressing or supplying gas or any two Or a combination of three kinds to remove the volatile component (1); = a residue containing phosphoric acid as a main component obtained from the above-mentioned step (1), using a Wei monoester having the oxime represented by the following formula (1) and The extract liquid composed of the dish acid-S曰 represented by the general formula [2] is subjected to the step (2) of extracting the metal ions contained as impurities into the extract.

Ri〇 \ H07 '\ 0H R20 \ / R3. 〆 , 0H

[1] [2] In the formula, R1 is a saturated fat of a side chain with a carbon number of eight knives and a side chain, and a lipid (tetra) group having a carbon or carbon double bond having a linear or side chain, 曰"基,芳a base or an aralkyl group. The scale 2 and the r3 are each independently a carbon number 3 to an aliphatic group having a linear or (d) saturated simple group, having a linear or side side and having a carbon-carbon double bond. , an alicyclic group, an aryl group or an aryl group. 200900540 Other aspects of the invention are a method for regenerating a phosphoric acid-containing metal surname or phosphoric acid containing impurities, which comprises: a metal residue containing a dish of acid, or a phosphoric acid containing a volatile and hydrophilic impurity and a metal ion, by heating, decompressing or supplying gas or a combination of any two or three of these. The step (1) of removing volatile components; and the residue containing phosphoric acid as a main component obtained from the above step (1) 'using a phosphate monoester represented by the above formula [1], the above formula [ 2] a non-phosphoric acid diester and a condensed phosphate ester represented by the following formula [3] and/or a condensed phosphate ester represented by the following formula [4] The constituent extract is further subjected to the step (2) of extracting the metal ion containing the impurity into the extract. (R4)p(H)q(P„03n+1) [3] (R5)r(H) )s(Pm03m) [4] In the above formula, R1 is the carbon number... "I 八·wj tends to be full

U and an aliphatic group, an aliphatic group, an alicyclic group, an aryl group or an aralkyl group having a carbon-carbon double bond having a linear or side chain. R2 and R3 are each independently a saturated aliphatic group having a linear or side chain having a carbon number of 3 to 25, an aliphatic group having a carbon-carbon double bond having a linear or side chain, an alicyclic group, , Fangmei or aryl-based H R5 are each independently a carbon number of 7 to 17 having a straight = or side chain age (four) secret, having a linear or (d) aliphatic group containing a carbon-bond, an alicyclic group, Aryl or aralkyl. η and the claw are each an integer of 2 or more, and p and q satisfy an integer of p + q = n + 2, and ^ and s satisfy an integer. In the case of a plurality of feet 4 and R5, ... 舆 can be the same, 10 200900540 can also be different. Another aspect of the present invention is a metal sulphur-containing metal sulphuric acid containing metal ions or a metal ion-containing phosphoric acid purification method characterized by 'from a metal ion-containing phosphoric acid-containing metal etching solution or phosphoric acid' The metal ion is extracted into the extract by using an extract liquid containing the monobasic acid ester represented by the above formula [1] and the acid amide represented by the above formula [2]. Another aspect of the present invention is a method for purifying a metal-containing liquid crystal containing a metal ion containing phosphoric acid or a phosphoric acid containing a metal ion, which is characterized by 'from a metal etchant containing phosphoric acid or a phosphoric acid containing phosphoric acid, using the above-mentioned a phosphoric acid monoester represented by the formula [1], a disc acid diester represented by the above formula [2], and a condensed phosphate ester represented by the above formula [3] and/or a condensation represented by the above formula [4] The disc acid ester extracts the aforementioned metal ions into the extract. Other aspects of the present invention are those containing a phosphoric acid-containing metal etching solution containing a volatile and hydrophilic substance which is an impurity which hinders etching, by decompression or gas supply, or the like. Or a combination of three, a method of obtaining phosphoric acid by removing volatile components. Another aspect of the present invention is a method for regenerating an organic extracting night containing a metal ion, which comprises: (A) a fluorine-containing aqueous solution and an organic extract containing the genus ion by extracting metal ions from the extract; / or an aqueous solution of oxalic acid, or (B) an aqueous solution of an alkanolamine having a carbon number of 3 or more and/or an aqueous solution of an alkylamine having a carbon number of 3 or more, and extracting the metal ions. Another aspect of the present invention is an acid-containing metal etching solution regenerated by the above method. 11 200900540 According to the present invention, the following effects can be exhibited. (1) Since an acidic extractant is used as an extract, it is possible to efficiently and efficiently obtain an aqueous solution having a composition change and a high purity. (2) The metal ions can be extracted from the extract to separate and recover from the extract containing the metal and the reverse extraction step. (3) Since no special device is required, the phosphoric acid can be purified at a low cost.

(4) Since it is not necessary to specifically replace the extract, it can be continuously operated. () Ρ 彳 冋 冋 辰 / Chen Chen strong acid solution, can also be extracted without the need to adjust the pH of the metal ions (especially aluminum ions, (4) due to the removal of the substance to remove _, so the regeneration button The etchant returns to the same level of etching performance as the new etchant. [Embodiment] Step (1) In the step (1), a metal etchant containing an acid containing a volatile and hydrophilic impurity, or containing a volatilization Acidic and hydrophilic impurities and metal ions of phosphoric acid 'by heating, decompression or gas supply or a combination of these two or three: to remove volatile substances. Examples of the metal ion include, for example, ruthenium, ruthenium, titanium, titanium nitride, oxidation t: nitridation, silver, zinc oxide, and the like. The phosphoric acid-containing alloy can be made of liquid crystal. The metal pattern of the substrate of the industry is formed by an etching solution containing a dish of acid, 丄, and a main component, etc. The etching solution containing phosphoric acid may contain at least one other acid other than an acid, and the other acid may be used. Lift 12 200900540 = as (4) m and so on Acidic acid, etc. Specific. 2: For example, the etching liquid of the metal such as aluminum or molybdenum, the phosphoric acid 10 to 85 〇, the § citric acid 1 to 2 〇% and the nitrate, 1 to (4), and the rest is water. The type of the volatile and hydrophilic substance is not particularly limited, and may be, for example, a monodimer in a resin of a ruthenium component (such as a ruthenium resin, etc.). Among the volatile and hydrophilic impurities,

:: As described later, it contains a resisting substance. The above-mentioned volatility and hydrophilic hindrance substances are often used in the use of (4). Although it may not be easy to specify the origin or substance, even in the 18th generation, it cannot be decomposed, but may be combined with other acids other than phosphoric acid. Water material. The inventors of the present invention have a hydrophilicity and a volatile impurity which are at least resistive (four) engraved from i. Therefore, in the present invention, the volatile component is such that at least one other acid, water, or the like of the etching material f, acid, or the like can be prevented from being heated and decompressed by the volatile and hydrophilic impurities of the resist. The substance that is supplied by the gas to the museum. In the present invention, the above volatile components are heated (for example, by), reduced (such as 10 torr), or supplied with gas or any two or three of them are extracted from a metal containing phosphoric acid. Removed in etchant or phosphoric acid. For example, distillation at normal pressure, distillation using reduced pressure, use of a base for gas supply: 3 bursts, distillation by heating and decompression, volatilization by heating or heating and volatilization or evaporation of gas supply, etc. To remove the volatile component of the metal etchant or phosphoric acid, so as to remove other acid (tetra) acid other than phosphoric acid, «, etc., water and resisting pure engraved material. 13 200900540 When it is not decomposed by heating, it is concentrated with metal acids such as sulphuric acid, acetic acid, and water-derived metal ions to form a steel residue which is a residue of impurities. It becomes a phosphoric acid-based cause: 'another aspect of the present invention' is also a method of obtaining phosphoric acid from a phosphoric acid-containing metal etching solution by the above steps. Since the acid usually contains impurities, it is obtained in the form of crude phosphoric acid, which is obtained by the above-mentioned method. It is also necessary to remove impurities such as metal ions and purify them. Step (2) further, from the residue containing phosphoric acid as a main component obtained by the above step (1), using a bowl containing the above-mentioned grandfather n) correction - > upper _ η (four) single S and the above formula [2] The acid diester is extracted and extracted into the extract. The metal ion in which the metal ion is 3 is an impurity which is contained in the rhyme step, and the type thereof is not particularly limited, and examples thereof include a cation and an indium ion. Is a single acid vinegar having a linear or side chain saturated aliphatic group having a carbon number of 7 to 17 (heptyl, octyl, decyl, decyl, 2-ethylhexyl, isoindole) Base, etc., having a linear or side chain, a group containing a carbon-carbon double bond ((a) group), an alicyclic group (cycloheptyl group), an aryl group (tolyl group) or an aromatic earth group, benzene Phosphate monoester of ethyl or the like. Specific examples include acid-breaking early (2·ethylhexyl), (10) monoterpene, and monoisophosphoric acid. This temple compound can be used in one type or in two or more types. When the carbon number is less than 7, the organic layer is layered, and the extraction ratio is also lowered. If the carbon number is more than 17, the emulsification occurs, so that the carbon number is limited to the above range. Among these, it is preferred to use bismuth sulphate, p-beta 14 200900540 hexyl hexyl ester, monodecyl phosphate, and monoisodecyl phosphate. The above phosphodiester has a linear or pendant saturated aliphatic group having a carbon number of 3 to 25 (propyl, isobutyl, heptyl, octyl, decyl, undecyl, 2-ethyl) Hexyl, isodecyl, etc., having a linear or side chain: an aliphatic group (allyl, butenyl, heptenyl, etc.) having a carbon-carbon double bond, an alicyclic group (cyclopropyl group) , a cyclohexyl group, a cyclooctyl group, etc.), an aryl group (phenyl, fluorenylphenyl or the like) or an aralkyl (benzyl, phenethyl, etc.) phosphodiester. Specifically, for example, phosphoric acid ( 2·ethylhexyl ester), dinonyl phosphate, diisononyl phosphate, etc. These compounds may be used alone or in combination of two or more. When the carbon number is less than 3, the organic layer is layered and the extraction rate is lowered. When the carbon number is more than 25, emulsification occurs, so that the carbon number is limited to the above range. Among them, di(2-ethylhexyl phosphate) phosphate, dinonyl phosphate, and diisononyl phosphate are preferred. The blend ratio of the phosphoric acid monoester represented by the above formula [1] to the diacetic acid diacetate represented by the above formula [2] is preferably from 1 to 7: 9 to 3 in terms of the molar ratio of the monoester:diester. , to 4~6:6~4 for more 〇The above extracts are considered from the removal and stratification of aluminum ions, particularly preferably a mixture of mono(2-ethylhexyl phosphate) and di(2-ethylhexyl phosphate) (mixed molar ratio) 4~9:6~1). The total concentration of the phosphoric acid monoester and the phosphodiester in the extract is preferably 0.1 mol / 1 or more. If the concentration is not reached, the extraction rate of the metal ion will change. The upper limit is not particularly limited, and is generally not more than 2.5 mol/l, more preferably less than 2 mol/l. Further, in the step (2), the extract may also be used to contain the above formula [1]. The acid-filled monoester shown, the phytic acid dimer represented by the above formula [2], and the condensed phosphate ester represented by the above formula [3] and/or the condensed phosphoric acid 15 represented by the above formula [4] 200900540 An ester-derived extract. The combination is, for example, a phosphate monoester represented by the above formula [1], a phosphodiester represented by the above formula [2], and a condensation represented by the above formula [3]. a combination of a phosphate ester and a condensed phosphate ester represented by the above formula [4]; a scaly monoester represented by the above formula [1], an acid-filled diester represented by the above formula [2], and the above formula [ 3] shown a combination of a condensed phosphate ester; a combination of a phosphoric acid monoester represented by the above formula [1], a phosphodiester represented by the above formula [2], and a condensed disc acid ester represented by the above formula [4]. The condensed phosphate ester represented by the above formula [3] and/or the condensed phosphate ester represented by the above formula [4] are also referred to as "the above-mentioned condensed disc acid I". The condensed phosphate ester has a carbon number. 7 to 17 of a saturated aliphatic group having a linear or side chain (heptyl, octyl, decyl, dodecyl, 2-ethylhexyl, decyl, isodecyl), having a linear or Condensation of an aliphatic group (heptenyl), an alicyclic group (cycloheptyl), an aryl (tolyl) or an aryl group (nodal group, phenethyl group, etc.) containing a carbon-carbon double bond in a side chain Fill the acid with S. The condensed sulphuric acid is a mono-, di-, *- or tetra-ester ester of linear phosphoric acid (pyrophosphate, tripolyphosphoric acid, tetrapolyphosphoric acid), and a cyclic phosphoric acid (such as a metaphosphoric acid such as hexametaphosphoric acid). Mono-, di-, tri- or tetra-ester esters, mono-, di-, tri- or tetra-ester esters of linear phosphate and cyclic phosphoric acid linkages. These compounds may be used alone or in combination of two or more. Among these, it is preferably selected from pyrophosphoric acid (mono-, di-, tri- or tetra-) 2-ethylhexyl ester, triphosphate (single-, di-, tri-, tetra- or penta-) 2 _Ethylhexyl ester, pyrophosphoric acid (mono-, di-, tri- or tetra-) decyl ester, triphosphate (mono-, di-, tri-, tetra- or penta-) oxime ester, coke filling acid (single Preferably, at least one of the group consisting of _, di-, tri- or tetra-)isodecyl ester and triphosphate (mono-, di-, tri-, tetra- or penta-)isodecyl ester is preferred. In this case, it is preferable to use a pyrophosphate which is low in viscosity in the condensate 16 200900540 acid ester. The compounding ratio of the phosphoric acid monoester represented by the above formula [1], the disc acid of the above formula [2], and the condensed phosphate ester is preferably lm 〇 1 /1 or more in terms of the total mol concentration. If this concentration is not reached, the extraction rate of metal ions will become low, so it is not good. The upper limit is not particularly limited, and the total m〇1 concentration is 2 5 guana 1/2 or less, preferably 2 mol / 1 or less. The above extract is determined from the viewpoint of the removal property and delamination of aluminum ions. The combination of the above phosphates is particularly preferably mono(2-ethylhexyl phosphate) and di(2-ethylhexyl phosphate). A combination of ester), pyrophosphate (mono-, di-...tri- or tetra-)-2-ethylhexyl ester. The total concentration of the acid-filled monoester represented by the above formula [丨], the phosphoric acid diester represented by the above formula [2], and the condensed phosphate ester in the extract is preferably 0.1 mol/l or more. If this concentration is not reached, the extraction rate of metal ions will become low, so it is not good. The upper limit is not particularly limited, and is generally 2.5 mο 1 / 1 or less, preferably 2 mol / 1 or less. In order to adjust the extraction rate of the metal ions, the above extract may be further added with an acid phosphate or a phosphonic acid, and the kind thereof is not particularly limited. For example, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester or phosphine may be used. Acid di-2,4,4-tridecylpentyl ester and the like. It is considered from the viewpoint of the removal property of molybdenum ions, and particularly preferably 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester. The concentration in the extract is preferably 〇 lm 〇 1/1 or more. If the concentration is not reached, the extraction rate of the metal ions will become low, which is not preferable. The upper limit is not particularly limited, but is generally 2 〇 m 〇 1//1 or less, preferably 1.0 mol / 1 or less. The above extract may be used alone or in combination with a diluent or the like, or may be used in a suitable diluent. The diluent can be used as a grease such as kerosene 17 200900540 The organic solvent is a thinner, benzene, and ▼I #. In this case, L: Fangxiang 糸 thinner, etc. are insoluble in water. It is preferred to use kerosene. Since the price of kerosene is low, the cost of separation and recovery can be suppressed, and the phosphoric acid is not extracted on the shell, so there is an advantage of further efficient separation and recovery of phosphoric acid. Furthermore, although hunting uses aromatic thinners to enhance delamination, special attention must be paid to the reduction in extraction rate. : As long as it does not hinder the effects of the present invention, it is also possible to 'mix other known extractants (for example, neutral extractant, acid extractant 'alkaline extractant, etc.) in the i extract (5 4 In the step (2) of the invention, the extraction may be carried out by a continuous extraction method or a secondary extraction method. In order to increase the purification rate, a continuous stroke method is preferably used, specifically, for example, a step is taken. (2) The concentrated metal ion-containing phosphoric acid is appropriately diluted with water to form a phosphoric acid monoester represented by the above formula [1] and a phosphonium phosphate represented by the above formula [2]. The extract or the extract containing the monophosphoric acid represented by the above formula (1), the phosphodiester represented by the above formula [2], and the condensed phosphate is supplied to the agitator tank, and the above is also provided. The diluted phosphoric acid solution containing metal ions is stirred to mix the mixture, and then the mixture is separated from the stirring tank to the precipitation tank (resting tank) to be separated into an organic phase extract liquid phase and The aqueous phase extracts two layers of residual liquid phase. An extract liquid composed of a phosphoric acid monoester represented by the above formula [2] and a phosphoric acid diester represented by the above formula [2] with respect to a metal phase extracted to an organic phase or containing the above formula [1] The monoester of phosphoric acid, the discotic acid diester of the above formula [2] and the extract of the above condensed phosphate), the linonic acid 18 200900540 is not extracted to the organic phase and remains in the water In this way, the residual metal phase is extracted. In this way, the metal ions of the impurities are removed, and the highly purified disc acid is obtained in the form of an aqueous phase, which can be reused as the surname original. The above extraction step, if stirring is used. The sinking device can be continuously extracted. That is, the aspirator chamber is composed of a stirrer groove portion and a sinking groove portion, and the mixed liquid passes from the seeker tank to the sinking partition to Sinking tank, which can be continuously supplied, and the extract and the diluted metal ion-containing scaly acid are supplied to the stirring tank and stirred, and, in other words, the liquid moving to the sedimentation tank is left to stand by It is separated into an aqueous phase (bottom) and an organic phase (above) The organic phase of the separated upper layer and the extraction residual liquid of the lower layer can be separately recovered separately. By means of the device, whether continuous or batch, the extraction operation can be carried out. The well-known device, the operating conditions of the water phase, the organic phase, the supply rate, the supply speed, etc. can be appropriately ordered by the industry, and in order to enhance the extraction enthalpy, the organic extract phase may also contain an aqueous solution of phosphoric acid in the form of ions. The multi-stage countercurrent extraction method ', the == phase: multi-stage countercurrent (such as ... grade, etc.) extraction device can use the public extraction. Right using this method can be used for continuous extraction with extremely high efficiency: another of the present invention - The pattern is also a metal money engraving solution or a metal ion-containing phosphoric acid, which is used to remove the main ions to create a method of making a '丄'. (4) A fine metal I etching solution containing phosphoric acid or phosphoric acid In the step (3) and the present invention, the extract from the metal of 19 200900540 and the second ion in the above step (7) may be further added, and the (A) fluorine-containing aqueous solution 2 = weight water or (8) carbon number 3 or more may be used. Amine water soluble The extract and the regeneration step (3) of extracting metal ions (this will be referred to as reverse extraction) are extracted from the liquid and/or a wide range of the aqueous alkylamine solution of 3 or more. It is used to extract these components of the genus Mengzi. pri 士 * The knives, and 5, when used at the same time: only use the Qing), can also be used sequentially. For example, it is also possible to advance the reproduction step of ': and then carry out the regeneration step using the component (8). For this purpose, it can be: an aqueous gas-containing solution or an aqueous solution of oxalic acid, or a combination of the same. The component (β) may be a combination of a carbon number solution alone or a carbon number of 3 or more and an amine π 1 (4) water or the like. The aqueous solution of the pit-based amine may be used for the purpose of: using a fluorine-containing aqueous solution to preferably use hydrofluoric acid, and having a concentration of two or more, such that 1% by metal of metal ions may be back-extracted. If the weight loss is less than 2 weights, the reverse extraction of the V-genus ions (such as turning ions) will be deteriorated, but the concentration will be made selective to improve the stratification. The upper limit is not particularly limited. - at 2 or more. The concentration of the solution is not particularly limited, but in order to increase the difference, the ratio of t is more than G. 2%. If it is below (10), it will become stratified. The upper limit is limited by solubility. When the above == liquid and oxalic acid aqueous solution are used together, the respective concentrations are limited as follows:::::, but the concentration is excellent due to the solubility of oxalic acid. The viewpoint of the precipitation of the diarrhea I is determined to be... (10) There is no particular limitation on the aqueous gas-containing solution, and it can be used arbitrarily. 20 200900540 §Fluorine water mixture, especially hydrofluoric acid aqueous solution, although it can also extract molybdenum, two is particularly effective in extracting aluminum. On the other hand, the aqueous oxalic acid solution has a more effective effect than the :' Lu'. * The combination of chlorine, acid aqueous solution and oxalic acid aqueous solution can increase the respective effects, and can effectively extract aluminum and molybdenum, which can greatly increase the number of repeated use, and is very effective in effect. The above-mentioned barley amine having a carbon number of 3 or more may be, for example, monolinol, n-propanolamine 'triethylamine, sense methyldiethanolamine or 1 methylethanolamine temple. If the number of obstacles is less than 3 days, the stratification will be deteriorated and the volume change will become larger. The above-mentioned alkanolamine or alkylamine may be used singly or in combination. The concentration in the extract used for the reverse extraction is preferably equal to or higher than the molar concentration of the ruthenium 11 group having the metal ion-containing extract, and if it is not reached, the reverse extraction ratio is deteriorated. In the above-mentioned alkaloid amine solution and the aqueous solution of the alkylamine, the pin ion can be sufficiently reverse-extracted, but since the L-ion ion can not be reverse-extracted, it can be used by using the above-mentioned gas-containing aqueous solution. Separating and recovering the ionic ions from the cerium ions, the separated and recovered ones can be recycled and reused into valuable metals. In the above step (3), the extraction can be carried out by a continuous extraction method or a batch extraction method. In order to increase the refining rate, it is preferred to use a continuous extraction method. Specifically, for example, the extracting solution (the extract containing metal ions) obtained in the step (2) is supplied to the scramble tank using the agitator device, and is also supplied for the back extraction (4). An aqueous solution and / or grass & X: 3⁄4 or (Β) & number 3 or more of the aqueous solution of the alcohol amine and / or a carbonic acid aqueous solution of the carbon number of 3 or more, stirring, mixing, and then moving to the sinking 21 200900540 Tang set. Since the mixture is separated into an organic phase by mixing, and the operation is carried out by moving the water to the "mesh", so that the phase can be phased, and the water is composed of an aqueous solution of fluorine: The supply speed sub-building conditions can be adapted by the industry as a reverse extract - * 17 疋. The aqueous phase of hydrofluoric acid can be directly utilized ΓΓ for reuse, or as a general reagent to replace the fluorine-containing water The aqueous solution of the alcohol amine and the water of the octaamine are then taken with hydrofluoric acid::=:, only the indium ions are reversely extracted, and the sub-atoms are taken out, thereby pulling the l-ion ions and turning them apart.

For the separation and recovery of D organic, another aspect of the present invention is also a method for regenerating a liquid containing a metal ion by extracting metal ions from a human liquid by the above steps to extract from the metal. An organic extract of ions, an aqueous solution of fluorine and/or an aqueous solution of oxalic acid, or (B) a liquid having a carbon number of 3 or more and (4) and/or an alkylamine having a carbon number of 3 or more are removed from the precursor to the genus. The organic phase obtained in the above step (3), that is, the extract containing the above-mentioned vinegar vinegar can be supplied to the above step (2) as an extract, and the method of the present invention can extract the metal ion recycle. Further, in the range which does not impair the effects of the present invention, a phase separation accelerator such as nonylphenol may be mixed in the organic phase, and a salt such as a gasification may be mixed in the reverse extraction aqueous phase. In the regeneration method of the present invention, the metal ions of the impurities are removed as described above to obtain a highly purified phosphoric acid, and if necessary, it can be reused by mixing other acids or water such as acid or nitric acid as vinegar 22 200900540. [Examples] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. Removal of Volatile Impurities (Confirmation of Rejection of Recovery of Rice Cookery) Example 1 Filling the used etching solution in a distillation pot (the waste liquid after etching using M〇/A1/M〇 line: 63% phosphoric acid, acetic acid 3.8 %, nitric acid 8. 2%, the remainder is water) 'to 180. The heating of the crucible is carried out by simple distillation to remove the volatile stray shells (the volatiles from the tartaric acid, the cool acid, the water and the varnish of the acid varnish and the hydrophilic substance), and the A1 ion, M〇 remaining in the bottom of the pot is obtained. Ionic scalar acid. Nitric acid, acetic acid, and water were added to the obtained crude phosphoric acid to adjust the composition so that it had the same composition as the etching new liquid. An A1 single-film substrate having a film thickness of 1 Å was used, and the etching rate of the component was adjusted under the condition of 4 (TC), and the etching rate of A1 was calculated from the film thickness of 4 Point Probe. The results are shown in Table 1. Reference Example 1 The use of the unused raw materials, liquid, and engraving treatments was carried out in the same manner as in Example 1 to calculate the pure engraving rate. Reference Example 2 Reference Example 1 was used. The surname was used for the waste liquid after the Mo/A1/Mo line in the liquid crystal production line, and the silver etching process was carried out in the same manner as in Example 1 to calculate the etching rate. 23 200900540 The composition ratio of the tea test example 3 'Different use of the new material to make μ (four) 2)) (4) processing with the example! The same method is used to rate. Reference Example 4 f An etchant (made in the same manner) prepared from a new raw material was added to prepare a varnish-based resin so that the weight ratio was 2:1: = specific phase: dissolved. Then, using the method of (4) removing the remaining tree ==::: rate - TM" the same method as in Reference Example 5, the liquid obtained by 4, and heating, simple steaming to remove nitric acid, acetic acid, water and resin. Use the addition of broken:: the same composition as the used (four) liquid) to adjust the whole process to the law ===: liquid, the treatment is the same as the embodiment 1 • 1 π π residual rate . Example 6 Acids and fines The volatile impurities (nitric acid, vinegar 7 and the rice-blocking substances) removed by the first embodiment are dissolved in the engraving liquid recovered by the dish acid, and the rationale is the same as the implementation of you. The method was carried out, and the composition ratio of the composition of Example 7 was calculated. The etchant made of a new material (the same as Reference Example 6) was used for the etch process. The etching process was carried out in the same manner as in Example i. ; ; ; ;; New liquid for insect engraving 67 6.0 9.6 4.7x103 Reference example 2 Used aphid infusion 63 3.8 8.2 3.0χ103 Reference example 3 Composition liquid similar to Reference Example 63 3.8 8.2 3.8x103 Reference Example 4 and Reference Example 2 Resin-containing liquid of the same composition 63 3.8 8.2 3.4x103 Reference Example 5 Re-adjusted money engraving solution of Reference Example 4 3.8 8.2 3.8 χ 103 Reference Example 6 Waste liquid distillation recovery product 60 3.1 7.1 2.7 χ 103 Reference Example 7 and Reference Example 6 Liquid of the same composition 60 3.1 7.1 3.6χ103 If the first embodiment of Table 1 and the reference example 1, the reference In comparison with Examples 2 to 5 and Reference Examples 6 to 7, the composition ratios of the acids in the respective groups were the same, but the etching rates were different. Therefore, it was found that the etching rate was not slowed only by the composition ratio, but because it contained Some hinder the etching of the material and hinder the etching. One of the hindered etching materials, for example, when the reference example 2 and the reference examples 3 to 5 are compared, the resin component is different in content, and further, due to the hindrance substances, distillation and nitric acid, acetic acid, and water can be used. It is also volatilized, so it can be confirmed that it is a volatile impurity derived from a resin such as a monomer or a dimer. It can be seen that if only nitric acid, acetic acid, and water are removed, it cannot be reused as a refining solution, and as long as the obstructing etching material is surely removed from the used etching liquid, the same performance as the etching of the new liquid can be restored. Purification of acid-containing acid containing metal ions 25 200900540 Example 2 The concentration of the phosphoric acid aqueous solution by the vaporizer in Example 1 was adjusted to the concentration of the broad A1 ion and the M〇, and the A1 ion was changed to one. The metal of this adjustment liquid is U, and the W is made of A:, M〇 ion is a discussion. Use two. -ethylhexyl vinegar), dissolved: as::. The volume ratio of __ethylhexyl ester to · liquid is i ratio i = phase (9) liquid phase) and the organic phase (extracted, then, find the extract (four)?: the device mixes it to get refined in the flat The results are shown in Table 2. The calculation method of the extraction rate was as follows (1).

XV, if./(Corg.afxVorf • af. + CAq.af.XVAq.af.)xl〇〇 Ο) The symbols in the formula are as follows. Ccrg.af : concentration of metal ions in the organic phase after extraction equilibrium v0rg.af.: volume of organic phase after extraction equilibrium CAq.af.: concentration of metal ions in the aqueous phase after extraction equilibrium VAq.af.: after extraction equilibrium Aqueous phase volume Example 3 Dry % Xinhan changed mazonic acid simplex Β 畀螂 畀螂 Μ ' ' ' ' 均 均 ' ' ' ' ' ' ' ' ' ' ' ' The results are shown in Table 2. Example 4 - The extraction rate was determined by the same method except that the W 2 t extract was changed to squaric acid monoisoglycol g and _ _ diisoindole (iv). The results are shown in Table 26 200900540. Example 5 except that the extract of Example 2 was changed to mono(2-ethylhexyl phosphate) with di(2-ethylhexyl) phosphate and di(2-ethylhexyl) pyrophosphate. Except for the esters, the extraction rate was determined by the same method. The results are shown in Table 2. Comparative Examples 1 to 10 The same procedures as in Example 1 were carried out except that the extracts were changed to those shown in Table 2, and the extraction ratio was determined. The results are shown in Table 2. Further, Comparative Example 3 corresponds to the embodiment of Patent Document 3, and Comparative Example 4 corresponds to the embodiment of Patent Document 4.

[Table 2] Extractant name Extract concentration extraction rate (%) (mol/1) A1 ion Mo ion Example 2 Phosphate mono(2-ethylhexyl) 1.0 78.0 67.1 Di(2-ethylhexyl phosphate) 1.0 Example 3 Monodecyl phosphate 1.0 Didecyl phosphate 1.0 85.3 68.3 Example 4 Monoisodecyl phosphate 1.0 84.5 67.6 Diisodecyl phosphate 1.0 Mono(2-ethylhexyl) phosphate 0.8 Example 5 Phosphate II 2-ethylhexyl ester) 0.9 89.3 79.5 di(2-ethylhexyl) pyrophosphate 0.1 Comparative Example 1 Dibutyl phosphate 2.0 16.4 60.8 Comparative Example 2 Di(2-ethylhexyl phosphate) 2.0 5.6 61.9 Comparative Example 3 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester 2.0 9.4 87.4 Comparative Example 4 Di(2,4,4-trimethylpentyl) phosphonate 2.0 9.9 73.4 Comparative Example 5 Thiophosphoric acid di(2) 4,4-trimethylpentyl ester) 2.0 9.0 13.6 Comparative Example 6 Di(2-ethylhexyl) dithiophosphate 2.0 10.5 91.8 Comparative Example 7 Dithiophosphoric acid di(2,4,4-triterpene) Pentaerythritol) 2.0 14.5 96.3 Comparative Example 8 Monooctyl phosphate 2.0 - (emulsified) - (emulsified) Comparative Example 9 Monobutoxyethyl phosphate 1.0 Dibutyloxyethyl phosphate 1.0 Layered with organic phase (No Comparative Example 10 Acid-filled single oil vinegar 1.0 Phosphate oleate 1.0 Emulsified (non-layerable) 27 200900540 In Examples 2, 3, and 4, 3 A1 ions containing A1 ions and M() ion impurities can be used. And the phosphoric acid of the M 〇 ion, effectively removing ions and ions to obtain high-purity phosphoric acid. Further, the extraction ratio of the A1 ion of the longer alkyl chain of the phosphate ester tends to be higher. In Example 5, it is very useful to simultaneously increase the A1 ion and ion extraction rate by using 3, and s-disc acid esters. In Comparative Examples 2 and 2, it was found that the A cation was almost impossible to be extracted at the gate/density of phosphoric acid. In Comparative Example 3,

In the above, it was confirmed that even with the use of the phosphoric acid vinegar of Patent Documents 3 and 4, the A1 ion was hardly extracted at a high concentration of 5 m〇1 /1 phosphoric acid. In Comparative Example 5, 'A1 ion, M. The extraction rate of ions is low and is not suitable as an extractant. In Comparative Examples 6 and 7, although the extraction ratio of M〇 ions was quite high, it was not suitable as an extractant because of difficulty in female qualitative and reverse extraction. In Comparative Example 8~1, it can be seen that if the 驴赦 匕 匕 I I I I I I I I I I I I 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰It is layered with the organic phase and cannot be used as an extractant.

Example A 咪 ί in imolX 1 Temple ~ W q Hungarian ρριη, as a metal ion of Mg ions and Cr ions, Μη workers r ^ Ding Mn ions, Fe ions, Ni ions,

Except for Cu ions and zn ions, the extraction rate was determined by the same method as in Example 2 except that the blood scent was used. The results are shown in Table 4.

28 200900540. It is indeed possible to extract Fe ions particularly efficiently from a high concentration of phosphoric acid by using the present extractant. As for the other elements, although the extraction rate itself is low, it can also be removed, and it can be confirmed that the purification of phosphoric acid is effective. 1. The regeneration of the extract using reverse extraction is also the case of 6 9

In Example 2, an aqueous solution containing an A1 ion and an M〇 ion (an extract after the extraction step) was used, and a hydrofluoric acid aqueous solution was used as a reverse extract. = The volume ratio of the aqueous phase (reverse extract) to the organic phase (extracted extract after the extraction step) was 1:1, which was mixed by a shaker for reverse extraction. The reverse extraction rate was not obtained in the following manner. x, stratification evaluation, based on the following benchmarks. Moreover, those with smaller numbers have better stratification. 5: Layered in 5min 1 〇: layered at 1 Omin 20: layered at 20min

3〇 ·• Stratification in 30min The evaluation of volume change is based on the following benchmarks. The results are shown in the table.

40% or more of which is less than 40% of it φ>\\ Less than 2% Use the following formula (2) as the #逆~δΐ method of the reverse extraction rate. CA, afXVAq,, /(C〇rg.afXV〇r, af+CAqafXVAqaf)xl〇〇 (2) The symbols in the formula are as follows. 29 200900540 c〇rg.af.: metal concentration in the organic phase after extraction equilibrium V0rg.af.: organic phase volume after extraction equilibrium cAq.' metal concentration in the aqueous phase after extraction equilibrium vAq.af.: after extraction equilibrium Aqueous phase volume Example 1 0 to 12 In Example 2, except that an extract containing A1 and Mo ions was used, respectively (the aqueous solution of the oxalic acid aqueous solution or the hydrofluoric acid aqueous solution) and the aqueous oxalic acid solution were used as the inverse of the extraction liquid after the extraction step. Except for the use of the extract, the reverse extraction was carried out in the same manner as in Example 4, and the stripping ratio was determined to evaluate the layering property. The results are not shown in Table 5. Example 1 3 to 1 7 ^ In addition to Example 4 The reverse extract was changed to MIPA (monoisopropanol) NPA (n-propanolamine), TEA (triethylamine), mdea (n-mercaptodiethanolamine), MMEA (N-methylethanolamine) aqueous solution. In addition, the reverse extraction ratio was determined in the same manner, and the stratification was evaluated. The results are shown in Table 5. I Comparative Examples 11 to 1 5 Except that the stripping agent was changed to the substance of Table 5, respectively, In the same operation as in Example 4, the stripping rate was determined and the stratification was evaluated. The results are not shown in Table 5. In the table, MEA Represents monoethanolamine, NpA for n-propanolamine, TEA for triethylamine, MDEA for N-methyldiethanolamine, mmea for N-methylethanolamine, and countermarked with *mark to improve stratification Added NH4C1. 30 200900540 [Table 5] Reverse extractant concentration (w/w%, mol/l) Retrogression rate (%) Volume change layered A1 Mo Example 6 HF 2.1w/w% 100 95 No 10 Example 7 HF 4.2w/w% 100 100 No 10 Example 8 HF 12_5w/w% 100 100 No 10 Example 9 HF 0.5w/w% 100 13 No 30 Example 10 Oxalic acid lw/w% 10 69 No 10 Example 11 Oxalic acid 5w/w% 44 85 No 10 Example 12 Oxalic acid + HF 5w / w% ' 8w / w% 100 100 益", 5 Example 13 MIPA * 2.5mol / l 3 86 Medium 20 Example 14 NPA* 2.5 mol/l 0 72 medium 20 Example 15 TEA* 2.5 mol/l 0 87 Medium 10 Example 16 MDEA* 2.5 mol/l 0 52 Medium 10 Example 17 MMEA* 2.5 mol/l 0 72 Medium 5 Comparison Example 11 MEA* 3.5 mol/l 3 62 Large 20 Comparative Example 12 ΝΗ, ΟΗ* 2.5 mol/l 3 88 Intermediate emulsification Comparative Example 13 NaOH* 4.0 mol/l 76 84 Large 10 Comparative Example 14 HC1 18w/w% 15 1 Medium 5 Comparative Example 15 h, so4 74w/w% 0 0 Medium 10 ratio Example 16 Citric acid 5w/w% 2 28 No 10 Comparative Example 17 Acetic acid * 5w/w% 0 0 No 20 Comparative Example 18 Acetic acid 50%* 5w/w% 0 0 No 20 Comparative Example 19 Malonic acid * 5w/w % 0 0 No 20 Comparative Example 20 Succinic acid * 5w/w% 0 0 No 20 Comparative Example 21 Malic acid * 5w/w% 0 0 No 20 Comparative Example 22 Lactic acid * 5w/w% 4 0 No 20 Comparative Example 23 Ethanol Acid* 5w/w% 1 0 No. 20 Comparative Example 24 EDTA4Na hydrate 5w/w% 0 3 Precipitation formation 20 It was found that by using hydrofluoric acid, reverse extraction can be carried out efficiently, and the layering property is good. Moreover, by using MIPA and NPA and TEA and MDEA and MMEA, compared with the general alkali NaOH (Comparative Example 13) and NH4OH (Comparative Example 12), the stratification is further improved, and the volume change is also reduced, and Option 31 200900540 Separately recovers mg ions. It can be seen that if the alkanolamine having a carbon number of less than 3 is run (Comparative Example u), the volume change will become large. Furthermore, although it is suitable for the reverse extraction of hydrofluoric acid, at a concentration of 0 ice

The stratification is poor, and M 无法 cannot be reversely extracted. However, since A! can be sufficiently inversely extracted, it can be used for the selective separation method of metals, and stratification can be improved by adding a salt. In Comparative Examples 14 and 15 t, it was almost impossible to perform reverse extraction, and it was found that it was not suitable for the reverse extraction liquid. In Comparative Examples 16 to 24, it was almost impossible to carry out reverse extraction, and it was found that it was not suitable for the reverse extraction liquid. In the examples, although the back extraction rate of ruthenium was low-point', the layering property was good, and the volume was not changed, which was confirmed to be effective. In Example 12, when a mixed liquid of oxalic acid and hydrofluoric acid was used, it was confirmed that the reverse extraction ratio and the delamination property were very good, and it was more effective. Evaluation of the reverse extraction performance after repeated use Examples A1 to A 3 The metal ion extract was regenerated by the method of the present invention, and the reverse extraction performance at this time was used for evaluation by the following method. The results are shown in Figures 1 to 3. (Experimental operation and evaluation method) Examples A1 and A2 In Example 2, an extract containing μ ions and M 〇 ions (extract solution after the extraction step) was used, respectively, with a hydrofluoric acid 4 w/w% aqueous solution (Example A1) Oxalic acid 5w/w% aqueous solution (Example A2) is used as a reverse extract to make the volume ratio of the aqueous phase (reverse extract) to the organic phase (extraction after the extraction step) is 1 to 1' by means of a vibrating machine This was mixed and subjected to reverse extraction to obtain a reverse extraction ratio. The reverse extracting solution after the reverse extraction was again used, and in Example 32 200900540 2, the stem containing the A1 ion and the Mo ion was used, and the extract was extracted. Repeat the same job several times. Example A3 The volume of the aqueous phase (reverse stroke liquid) and the organic phase (extraction solution after the extraction step) is the same as that of the mixed solution of oxalic acid 5w/w% and hydrofluoric acid 8w//w%2. The same operation as in Example A was carried out except that the ratio was 1 to 2. The results are shown in Figure 3. From Fig. 1, it was confirmed that the hydrofluoric acid aqueous solution was used repeatedly, and the reverse extraction ratio of M〇 was lowered. Further, from Fig. 2, it was confirmed that the oxalic acid aqueous solution was used repeatedly, and the back extraction rate of A1 was lowered. However, it can be seen that by the increase in the number of stages of the reverse extraction, it is possible to use several times of repeated use, and it is also an effective counter-extraction liquid in terms of cost. From Fig. 3, it was confirmed that the mixture of oxalic acid and hydrofluoric acid was used as the back extract. Even if it was used repeatedly, the stripping rate did not change, which was very effective. Thereby, efficient and low-cost processing can be made possible by industrialization. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 ' shows a change in the reverse extraction performance after repeated use of Example A1. Fig. 2 is a graph showing the change in the reverse extraction performance after the repeated use of Example A2. Fig. 3' shows the change in the reverse extraction performance after the repeated use of Example A3. [Main component symbol description] Benefit 33

Claims (1)

200900540 X. Patent application scope: 1 · A method for regenerating a phosphoric acid-containing metal etching solution or phosphoric acid containing impurities> characterized in that it comprises the following steps: from a metal containing acid which contains volatile and hydrophilic impurities An etching solution or a phosphoric acid containing volatile and hydrophilic impurities and metal ions, by heating, decompressing or supplying gas or a combination of any two or three of them to remove volatile components; The residue containing phosphoric acid as a main component obtained in the step (i) is extracted by using a phosphate monoester represented by the following formula [1] and a phosphodiester represented by the following formula [2]. a liquid, a step (2) of further extracting metal ions containing impurities into the extract: Ri〇\ / Η0〆\ 0H R20 \ / R3〇7 X0H [1] [2] (wherein R1 is a saturated aliphatic group having a linear or side chain with a carbon number of 7 to 17 and having a linear chain Or an aliphatic group, an alicyclic group, an aryl group or an aralkyl group having a carbon-carbon double bond in the side chain; and the R2 and R3 groups are each independently a linear chain having a carbon number of 3 to 25 or a saturated fat having a side chain. An aliphatic group, an alicyclic group, an aryl group 34 200900540 aralkyl group containing a carbon-carbon double bond having a side chain, a linear chain or a side chain. 2. A metal etchant containing phosphoric acid or a method for regenerating phosphoric acid, characterized in that it comprises the steps of: containing an acid-containing metal etchant containing volatile and hydrophilic impurities or containing volatility and a step (1) of removing a volatile substance by heating, decompressing or supplying gas or a combination of any two or three of them as a hydrophilic impurity and a phosphoric acid of a metal ion; and from passing through the step (丨) The obtained residue containing a dish acid as a main component is a phosphate monoester represented by the following formula [丨], a phosphodiester represented by the following formula [2], and the following formula [3]. The extract liquid comprising the condensed phosphate ester and/or the condensed phosphate ester represented by the following formula [4], and the step (2) of extracting the metal ion containing the impurity into the extract liquid: RV / \ HO 0H R2〇/〇V/ / \ R3〇OH (R4)p(H)q(Pn03n+l) (R5)r(H)s(Pm03m) (wherein R1 is carbon number 7~ 17 ^ [11 [2] [3] [4] Linear or saturated with side chains 35 200900540 曰 Fat-free, linear or side chain-containing fat containing carbon-carbon double bonds a group, an alicyclic group, an aryl group or an aralkyl group; R 2 胄 R 3 , each independently a saturated aliphatic group having a linear or side chain having a carbon number of 3 to 25, having a linear or side chain An aliphatic group, an alicyclic group, an aryl group or an aralkyl group having a carbon-carbon double bond, and each of R and R5 is independently a saturated aliphatic group having a linear or side chain having a carbon number of 7 to 17 and having An aliphatic group, an alicyclic group, an aryl group or an aralkyl group having a carbon-carbon double bond in a linear or side chain; n and m are each an integer of 2 or more 'P and q are satisfying p+q=n An integer of +2, r and s satisfy an integer of r + s = m; where there are a plurality of R4 and R5, R4 and R5 may be the same or different). 3. A method for purifying a metal etchant containing a metal ion containing phosphoric acid or a phosphoric acid containing a metal ion, characterized in that a metal etchant containing phosphoric acid or a phosphoric acid containing a metal ion is used, and the following formula [1] is used. An extract composed of a phosphate monoester and a diacetate represented by the following formula [2], which is extracted into the extract: ί. [1] [2] \ P / \ HO 0H R20 /〇npX/ / \ R3〇OH (wherein R1 is a carbon number of 7 to 17 having a linear or side chain saturation 36 200900540 曰 aliphatic group, having a linear or side chain An aliphatic group, a aliphatic % group, an aryl group or an aralkyl group having a carbon-carbon double bond; and the R 2 and R 3 groups are each independently a saturated aliphatic group having a linear or side chain having a carbon number of 3 to 25; An aliphatic group, an alicyclic group, an aryl group or an aralkyl group having a carbon-carbon double bond in a linear or side chain. 4. A metal etchant containing a metal ion or a method for purifying a molybdenum acid containing a metal ion, characterized in that: from a metal etchant containing phosphoric acid or a phosphoric acid containing phosphoric acid, the following general formula [1] is used. a phosphoric acid monoester, a phosphodiester represented by the following formula [2], a condensed phosphate represented by the following formula [3], and/or a condensed acid represented by the following formula [4] An ester which is extracted into the extract: [1] Ri〇 \ H0〆 R2〇 \ R3〇7 [2] [3] [4] (R4)p(H)q(Pn〇3n+1) (R5)r(H)s(Pm〇3m) (wherein R1 has a carbon number of 7 to 17) a saturated aliphatic group of a linear or side chain, an aliphatic group having a carbon-carbon double bond having a linear or side chain, a 2009, 005, an alicyclic group, an aryl group or an aryl group; each of the R 2 and R 3 groups An aliphatic group having a linear or side chain saturated aliphatic group of 3 to 25, a carbon-carbon double bond having a straight or side chain, an alicyclic group, and an aromatic aryl group. An aliphatic group, an alicyclic group or an aryl group having a carbon-carbon cone bond having a linear or side chain, which is a saturated (tetra) group having a straight or large side chain, having a carbon number of 7 to 17 , aralkyl; n, m are respectively = above integer 'p and q satisfy the integer of p + q = n + 2, 4 S is an integer satisfying r + s = m; there are multiple ... and R5 , ... can be the same as rs or different). The method of any one of the above-mentioned claims, wherein the mono-phosphate phosphate monophosphate (2-ethylhexyl vinegar), the mono-phosphoric acid phosphate or the mono-phosphoric acid phosphate, the di-phosphoric acid phosphate Di(2-ethylhexanoacetate), diterpene phosphate or diisononyl phosphate. 6. The method of claim 2, wherein the condensed phosphate is selected from the group consisting of pyrophosphoric acid (mono-, di-, tri- or tetra-) 2-ethylhexyl ester, three-stone η acid (single- , two-, three-, four- or five-) 2-ethylhexyl ester, pyrophosphoric acid (mono-, di-, tri- or tetra-) decyl ester, triphosphate (single _, two _, three _, Four- or five-) hydrazine, pyrophosphoric acid (mono-, di-, tri- or tetra-) isodecyl esters and triphosphates (mono-, di-, ---, tetra- or penta-)isodecyl esters At least one of the group formed. 7. The method of any one of claims 1 to 4, wherein the step further comprises extracting a metal ion-containing extract extracted from the metal ion in the step (2), using (Α) An aqueous solution of fluorine and/or an aqueous solution of oxalic acid, or an aqueous solution of an alkanolamine having a carbon number of 3 or more and/or an alkylamine water/glutamine having a carbon number of 3 or more, and an extracting step of extracting the metal ions (3) . 38 200900540 8. If you are in the scope of the patent application, you can use the 3 虱 aqueous solution to draw the metal ion — the 仃 。 。 冬 冬 冬 冬 冬 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. 9. If the application of patent scope 7 is used, the v v is removed, in which the metal ion is extracted using the early hydrazine aqueous solution in the step (3). In the step (3), the metal ions are extracted by using a 3 aqueous solution and an aqueous solution of oxalic acid. 11. If the scope of the patent application is 7th, the right _ _ _ >, 10,000's of the 'fluorine-containing aqueous solution 3 has an aqueous solution of fluoric acid. 12. An aqueous solution of an alkanolamine according to item 7 of the patent application and/or a carbon number of 3 or more carbon number 3 or more., ^ An aqueous solution of an alkylamine having an anisotropy of 3 U, selected from n-propylamine, single At least one of a group consisting of isopropanolamine, di-N-methylethanolamine, and N-methyldiacetylthymidine-ethylamine. 13. As in the method of claim 4, in the bean, the metal containing phosphoric acid is called &&"" deficiency, and the acid & acid is selected from the group consisting of acetic acid and stone - an acid of at least one of the group consisting of. 14 · A phosphoric acid-recovering method by heating, reducing or supplying gas from a metal-containing etching solution containing a volatile and hydrophilic substance that hinders the etching of miscellaneous or miscellaneous materials. A combination of 2 or 3 types to remove volatile components. 15. The method of claim 14, wherein the phosphoric acid, and the liquid, in addition to the phosphoric acid, comprises at least one volatile acid selected from the group consisting of acetic acid and tribasic acid. 16. A method for regenerating an organic extract containing a metal ion, which is obtained by taking an organic extract containing the metal ion from a metal ion extracted from the extract, and using (A) a fluorine-containing aqueous solution and/or An aqueous solution of oxalic acid or (8) an aqueous solution of an alkanolamine having a carbon number of 3: and/or an aqueous solution of an alkylamine having a carbon number of 3 or more is used to extract and remove the metal ion. The method of claim 16, wherein the liquid system comprises a phosphate monoester and a phosphodiester. 1 In the method of claim 16 of the patent application, the liquid system contains (4) the single purpose and the condensed phosphoric acid s are intended to be formed by the machine. 19. In the scope of the patent application range u4, i6, the continuous type The method of culling, the method of going, or the batch extraction method is carried out 2 〇 · as in the case of any of the patent application scope. The metal ion is selected from, and wherein, h, (4), iron, 4 4 ion, magnesium ion, chromium ion, chain ionization, at least one of a group consisting of "titanium ions, scorpions and silver ions" One, the copper ion, the zinc ion 21, such as the aluminum ion and/or molybdenum ion of the second aspect of the patent application, / /, medium, metal ion, a metal etching solution containing a dish acid, Regeneration of the method of any one of items 1 to 4. From the scope of the patent application, the eleventh, round: as the next page 40