WO2018190461A1 - Method for preparing, from waste ito scraps, powder for high-purity ito target having high relative density by using nitric acid, and powder prepared thereby - Google Patents

Method for preparing, from waste ito scraps, powder for high-purity ito target having high relative density by using nitric acid, and powder prepared thereby Download PDF

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WO2018190461A1
WO2018190461A1 PCT/KR2017/005537 KR2017005537W WO2018190461A1 WO 2018190461 A1 WO2018190461 A1 WO 2018190461A1 KR 2017005537 W KR2017005537 W KR 2017005537W WO 2018190461 A1 WO2018190461 A1 WO 2018190461A1
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powder
ito
waste
nitric acid
relative density
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Korean (ko)
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이재용
송싱현
윤상혁
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(주)한청알에프
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
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    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C04B35/64—Burning or sintering processes
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/602—Making the green bodies or pre-forms by moulding
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Definitions

  • the present invention relates to a method for producing a high purity ITO target powder having high relative density from waste ITO scrap using nitric acid, and more particularly, to dissolving waste ITO scrap powder using a nitric acid (HNO3) solution.
  • HNO3 nitric acid
  • ITO (indium-tin composite oxide) film is widely used as a transparent electrode film of a display device centered on a liquid crystal display.
  • a method of forming this ITO film a method generally called a physical vapor deposition method such as a vacuum deposition method or a sputtering method is usually used.
  • the magnetron sputtering method is often used for operability and film stability.
  • the formation of the film by the sputtering method physically collides cations such as argon (Ar) ions with the target provided on the cathode, and releases the material constituting the target by the collision energy, thereby causing the surface of the target to face the substrate on the anode side. This is done by laminating films of approximately the same composition as the material.
  • the coating method by the sputtering method has a feature that it can form from the thin film of the Angstrom unit to the dozens of thick film at a stable film forming speed by adjusting the processing time and the power supply.
  • Indium (In) one of the materials of the transparent electrode, has an atomic number of 49 and is one of rare metals. It is a bright-gloss silver-white metal with good ductility and malleability and softness, so it has good workability and has a low melting point of 156.6.
  • tin another material, is mainly used for plating, compound preparation, etc., and is a metal having an atomic number of tin of 50, which is not easily oxidized in air, and is resistant to corrosion and does not react with water. It is mainly used for anti-corrosion plating and alloy of other metals, and is a metal used as the main constituent raw material of ITO together with indium.
  • indium oxide and tin oxide are used to make transparent electrodes of various flat panel devices including light emitting diodes (LEDs) and liquid crystal displays (LCD panels).
  • Indium tin oxide in which indium oxide and tin oxide are mixed is manufactured into a sintered body obtained by molding and sintering a raw material powder and used for a transparent conductive film.
  • one of the problems in forming a transparent conductive film using an ITO target is that the use efficiency of the ITO target is low, and the remaining ITO target after about 20-30% in general sputtering is scrapped. Recycling this scrap is very important in terms of utilizing scarce resources.
  • ITO powder from ITO scrap There are several ways to produce ITO powder from ITO scrap, one of which is to recover indium and tin as an oxidized powder, and then mix them at a predetermined ratio. This method has to recover the indium oxide powder and tin oxide powder separately, and the installation cost of the equipment is very large, there is a disadvantage that a lot of time for uniform mixing. Usually expensive indium is mainly recovered, and a method for selectively recovering indium from waste ITO scrap has already been proposed in the prior art.
  • Patent Document 1 Registered Patent No. 10-0850009
  • Patent Document 2 Prior Document 2: Registration No. 10-1002088
  • the present invention has been made to solve the above problems, and after dissolving the waste ITO scrap with nitric acid for the production method of high purity and high density ITO target powder obtained from the waste ITO scrap, the dissolved waste ITO solution is metatin acid, ITO
  • the residue is separated by an indium nitrate solution.
  • the indium nitrate solution is purified by removing impurities using a solvent extraction method to increase the purity.
  • the separated indium nitrate and ITO residue is neutralized with an indium nitrate liquid having high purity, and an alkaline liquid containing a dispersant, and the powder obtained by neutralization is washed and dried, and then the dried powder is calcined.
  • the present invention can solve the inconvenience, cost and process problems of recovering and mixing indium oxide powder and tin oxide powder, respectively, and further provide a method for producing a high density sintered ITO target.
  • the present invention dissolves waste ITO scrap with nitric acid, improves purity, neutralizes them with an alkaline liquid containing a dispersant, and uses high-density and high-density ITO having a high relative density of 99% or more using a powder obtained through neutralization. To provide a target.
  • the particle size of the waste ITO scrap of step (a) is characterized in that the powder form of 1 ⁇ 20.
  • reaction scheme in the dissolution step of preparing the mixed solution of step (a) is characterized in that the reaction of the following formula (1) and (2).
  • organic solvent used in the solvent extraction method in the step (c) is characterized in that selected from the group consisting of carboxylic acid, organic phosphoric acid and combinations thereof.
  • the organic solvent may be selected from the group consisting of tributyl phosphate, 2-ethylhexyl phosphoric acid, di- (2-ethylhexyl) phosphoric acid, and combinations thereof.
  • the alkaline solution is characterized in that any one or more of NaOH, KOH, NH 4 OH, NH 4 HCO 3 , CH 3 COONH 4 .
  • step (d) when the alkaline solution is NH 4 OH, it characterized in that following the reaction of the formula (3) and 4.
  • the pH is characterized in that the range of 9 to 11.
  • the heat treatment temperature of the step (f) is characterized in that the 300 ⁇ 900 range.
  • the content of the binder of the step (g) is characterized in that 1 to 5 parts by weight based on 100 parts by weight of the heat-treated powder.
  • the molded ITO target of step (i) is characterized in that the sintering in a high temperature oxygen atmosphere of 1500 ⁇ 1600.
  • ITO target powder is characterized in that it is obtained by a method for producing a high purity ITO target powder having a high relative density from waste ITO scrap using nitric acid as described above.
  • FIG. 1 is a schematic diagram of a method for producing a powder for high purity and high density ITO targets obtained from the waste ITO scrap of the present invention.
  • Figure 2 (a) is a scanning electron microscope image of the lung ITO scrap used according to the embodiment, (b) is an enlarged image.
  • 3 (a) and 3 (c) are scanning electron microscope images of meta-tartrate and ITO residues prepared according to the embodiment, and (b) and (d) are enlarged images.
  • 4 (a) and 4 (c) are scanning electron microscope images of the ITO oxide powder prepared according to the embodiment, and (b) and (d) are enlarged images.
  • a method for producing a high purity and high density ITO target powder obtained from waste ITO scrap is a) dissolving waste ITO scrap in nitric acid to produce indium nitrate solution and metatartrate, and producing a mixed liquid in which insoluble ITO residue remains.
  • step (a) the waste ITO scrap in the form of powder having a particle size of about 1 to 20 is added with 3-7 times the nitric acid to the scrap weight, so that In in the waste ITO scrap is indium nitrate (In (No 3 )). 3 ), allow meta-tartrate to be produced and insoluble ITO residues remain.
  • the reaction scheme for the dissolution process is as follows.
  • the mixed solution is filtered and separated into indium nitrate solution, meta-tartrate acid and ITO residue, respectively.
  • the indium nitrate solution obtained in the step (b) is purified by removing metal ion impurities that inhibit purity by using solvent extraction.
  • the organic solvent used in the solvent extraction method used to increase the purity in the step (c) is preferably selected from the group consisting of carboxylic acid, organic phosphoric acid, and combinations thereof, and specific examples are tributyl phosphate. , TBP), 2-ethylhexyl 2-ethylhexyl phosphonic acid (PC88A), di- (2-ethylhexyl) phosphonic acid (di- (2-ethyl hexyl) phosphonic acid, D2EHPA) and combinations thereof You can choose from the group consisting of.
  • an alkali containing OH ⁇ group is dissolved and diluted in ultrapure water, and the neutralized process is performed by adding a small amount of the separated indium nitrate solution, metatartrate acid and ITO residue.
  • a small amount of dispersant was added to the alkaline liquid in order to ensure uniform dispersibility and high sinterability of the powder during neutralization.
  • the pH is preferably in the range of about 9 to 11, and examples of the alkali that can be used include NaOH, KOH, NH 4 OH, NH 4 HCO 3 , CH 3 COONH 4 , and the like.
  • NH 4 OH can be used.
  • reaction scheme for the neutralization process is as follows.
  • the reason why the pH range is set to 9 to 11 is that when the pH is 9 or less, precipitation of the hydroxide powder produced after neutralization may be delayed, which may cause a problem in the washing step, and when the pH is 11 or more, the size of the hydroxide powder particles may be unevenly formed. It may be undesirable.
  • step (e) ultrapure water (DI water) is added to the product produced through the neutralization step of step (d), and decantation is used to remove ammonium nitrate and other salts in the product.
  • DI water ultrapure water
  • the product is hydroxide.
  • NH 4 OH to use the by-product produced in the neutralization reaction medium NH 4 NO 3 is the advantage of being soluble in water and from 0 118.3g / 100g, the solubility is very high, readily cleaned when removed from the 30 241.8g / 100g have.
  • step (e) the washed product is dried to remove moisture, and then crushed using a pulverization apparatus to powder it. This is because the pulverized and powdered form can perform a uniform heat treatment than the lumped product than the lumped product.
  • step (f) the powdered product is oxidized, and a calcined powder in angular form is formed.
  • the heat treatment temperature ranges from 300 to 900. If the heat treatment temperature is less than 300, the In (OH) 3 -Sn (OH) 4 precipitate is difficult to be converted to In 2 O 3 -SnO 2 , and if the heat treatment temperature is 900 or more, It is undesirable because the particle size can grow.
  • heat processing atmosphere can be performed in oxygen, argon, nitrogen, and air atmosphere.
  • the reaction scheme for the process is as follows.
  • step (g) by adding an appropriate amount of the binder to the heat-treated powder to increase the moldability of the heat-treated powder.
  • the content of the binder may be added 1 to 5 parts by weight based on 100 parts by weight of the heat-treated powder.
  • the content of the binder is 1 part by weight or less, the moldability of the oxidized powder may be lowered.
  • the content of the binder is 5 parts by weight or more, the moldability is increased, but the relative density is significantly lowered.
  • the powder having improved moldability obtained through the step (g) is put into a circular mold and press-molded to produce a cylindrical ITO target, and the cylindrical ITO target is sintered under oxygen pressure conditions at a high temperature of 1500 to 1600.
  • an ITO target having a relative density of at least 7.1 g / cm 3 is produced.
  • the powder for ITO target manufactured by the manufacturing method of the powder for high purity and high density ITO target obtained from waste ITO scrap can be obtained.
  • high purity and high density ITO targets can be produced using the powder for ITO targets.
  • the pulmonary ITO scrap was observed by the scanning electron microscope to determine the shape and size of the particles, as shown in Figure 1 to identify the powder having an angular form of about 1 micron.
  • 500 g of waste ITO scrap powder was added to 2 L of 60% nitric acid, dissolved at 110 to 20 hours, and filtered to separate indium nitrate, metatartrate and ITO residue.
  • the separated precipitate powder was observed with a scanning electron microscope, and it was confirmed that meta-tartrate and ITO residues coexist as shown in Example 1 of FIGS. 3 (a) and 3 (b).
  • Solvent extraction was carried out using PC88A, an organic solvent, to remove impurities contained in the filtered indium nitrate solution.
  • the washed hydroxide was dried for about 12 hours in an 80 oven to evaporate water, and then coarsely pulverized with a blender to obtain a hydroxide powder, and heat treated at 900 for 2.5 hours to obtain an oxidized powder. Observing the powder particles with a scanning electron microscope, it was confirmed that the particles of the angular form as shown in Example 1 of Figure 4 (a) and (b).
  • the binder was treated to 2% by weight of the powder to increase the moldability of the powder, and the binder-treated oxide powder was molded to prepare an ITO target, followed by sintering. After sintering, the relative density was measured and found to be 7.12 g / cm 3 , which was 99.46% of ITO.
  • Indium nitrate, meta-tartrate and ITO residues were added in small amounts to an alkaline solution containing a dispersant to reverse neutralization, and the neutralized hydroxide was washed six times with pure water.
  • the washed hydroxide was dried for about 16 hours in an 70 oven to evaporate moisture, and then coarsely pulverized with a blender to obtain a hydroxide powder, and heat treated at 900 for 2.5 hours to obtain an oxidized powder. Observing the powder particles with a scanning electron microscope, it was confirmed that the particles of the angular form as shown in Example 2 of Figure 4 (c) and (d).
  • the binder was treated with 2.5% by weight of the powder to increase the moldability of the powder, and the binder-treated oxide powder was molded to prepare an ITO target, followed by sintering. After sintering, the relative density measurement showed a value of 7.13 g / cm 3 , which was 99.58% compared to ITO.

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Abstract

The present invention relates to a method for preparing, from waste ITO scraps, a powder for a high-purity ITO target having a high relative density by using nitric acid, and the powder prepared thereby and, more specifically, to: a method for preparing, from waste ITO scraps, a powder for a high-purity ITO target having a high relative density by using nitric acid, the method being capable of recycling scarce resources when a high-purity ITO target powder, which is prepared by using a nitric acid (HNO3) solution so as to melt waste ITO scrap powder, thereby purifying and neutralizing the same in order to obtain a high-purity ITO target powder, and then performing a firing step, is used; and the powder prepared thereby. To this end, the present invention comprises: a) a melting step of melting waste ITO scraps in nitric acid so as to prepare a mixture solution in which an indium nitrate solution and metastannic acid are generated and insoluble ITO residue remains; b) a filtration step of separating, from the mixture solution, the indium nitrate solution, the metastannic acid, and the insoluble ITO; c) a purification step of removing, by a solvent extraction method, metal impurities from the indium nitrate solution separated in step b); d) a neutralization step of injecting, into an alkaline solution containing a dispersant, a small amount of a purified solution obtained in step c) and the metastannic acid and the insoluble ITO, which are obtained in step b), thereby neutralizing the same; e) washing and drying the product generated in step d), and then powdering the same by grinding; f) a firing step of heat treating the powder obtained in step e); g) a self-assembly step of increasing the formability of the powder by adding a binder to the heat-treated powder obtained in step f); h) preparing a molded ITO target by injecting, into a mold, the powder having increased formability, obtained in step g); and i) sintering the molded ITO target.

Description

질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법 및 그 분말 Manufacturing method of high purity ITO target powder having high relative density from waste ITO scrap using nitric acid and powder
본 발명은 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법 및 그 분말에 관한 것으로서, 좀 더 구체적으로는 폐 ITO스크랩 분말을 질산(HNO3) 용액을 이용하여 용해하고, 이를 통하여 고순도의 ITO 타겟분말을 얻기 위하여 이를 정제하고, 중화시키며, 이후 소성단계를 거쳐 제조된 고순도 ITO 타겟분말을 이용할 경우에 희소자원의 재활용이 가능한 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법 및 그 분말에 관한 것이다.The present invention relates to a method for producing a high purity ITO target powder having high relative density from waste ITO scrap using nitric acid, and more particularly, to dissolving waste ITO scrap powder using a nitric acid (HNO3) solution. In order to obtain high-purity ITO target powder, it is refined and neutralized, and then, when using a high-purity ITO target powder manufactured through a calcination step, high relative from waste ITO scrap using nitric acid which is capable of recycling scarce resources. A method for producing a powder for high purity ITO target having a density and a powder thereof.
ITO(인듐-주석의 복합산화물)막은 액정 디스플레이를 중심으로 하는 표시 디바이스의 투명 전극막으로서 널리 사용되고 있다. 이 ITO막을 형성하는 방법으로서 진공증착법이나 스퍼터링법 등 일반적으로 물리증착법이라고 하는 방법이 사용되는 것이 보통이다. ITO (indium-tin composite oxide) film is widely used as a transparent electrode film of a display device centered on a liquid crystal display. As a method of forming this ITO film, a method generally called a physical vapor deposition method such as a vacuum deposition method or a sputtering method is usually used.
특히, 조작성이나 피막의 안정성을 이유로 마그네트론 스퍼터링법을 사용하는 경우가 많다. 스퍼터링법에 의한 막의 형성은, 음극에 설치한 타겟에 아르곤(Ar)이온 등의 양이온을 물리적으로 충돌시키고, 그 충돌에너지로 타겟을 구성하는 재료를 방출시켜 대면하고 있는 양극측의 기판에 타겟의 재료와 거의 같은 조성의 막을 적층함으로써 행해진다. 스퍼터링법에 의한 피복법은 처리시간이나 공급전력 등을 조절함으로써 안정된 성막속도로 옹그스트롬단위의 엷은 막으로부터 수십 의 두꺼운 막까지 형성할 수 있는 특징을 갖는다.In particular, the magnetron sputtering method is often used for operability and film stability. The formation of the film by the sputtering method physically collides cations such as argon (Ar) ions with the target provided on the cathode, and releases the material constituting the target by the collision energy, thereby causing the surface of the target to face the substrate on the anode side. This is done by laminating films of approximately the same composition as the material. The coating method by the sputtering method has a feature that it can form from the thin film of the Angstrom unit to the dozens of thick film at a stable film forming speed by adjusting the processing time and the power supply.
투명 전극의 재료 중의 하나인 인듐(Indium, In)은 원자번호는 49이고, 희귀금속 중 하나이다. 밝은 광택이 나는 은백색의 금속으로, 연성과 전성이 우수하고 무르기 때문에 가공성이 좋으며, 녹는점이 156.6로 낮은 편이다. Indium (In), one of the materials of the transparent electrode, has an atomic number of 49 and is one of rare metals. It is a bright-gloss silver-white metal with good ductility and malleability and softness, so it has good workability and has a low melting point of 156.6.
인듐(In)을 포함한 여러 희토류 금속들은 현재 많은 양을 수입에 의존하고 있다. 이는 많은 비용이 발생하는 것을 의미하며, 수입 의존도를 낮추고 재활용률을 높이기 위해서 폐 자원에서의 효율적인 회수 방법이 필요하다.Several rare earth metals, including indium (In), currently rely heavily on imports. This means that a lot of costs are incurred, and efficient recovery from waste resources is needed to reduce import dependence and increase recycling rates.
또한, 다른 재료인 주석은 도금, 화합물 제조 등에 주로 사용되며, 주석의 원자번호 50의 금속으로 공기 중에서 쉽게 산화되지 않아 부식에 저항성이 있으며, 물과도 반응하지 않는다. 주로 다른 금속의 부식 방지 도금 및 합금의 용도로 사용되며, 인듐과 함께 ITO의 주요 구성 원료로 사용되는 금속이다. 이처럼 인듐산화물과 주석 산화물은 발광 다이오드 (LED), 액정 화면 (LCD 패널)을 비롯한 여러 평판 소자의 투명 전극을 만드는 데 이용된다.In addition, tin, another material, is mainly used for plating, compound preparation, etc., and is a metal having an atomic number of tin of 50, which is not easily oxidized in air, and is resistant to corrosion and does not react with water. It is mainly used for anti-corrosion plating and alloy of other metals, and is a metal used as the main constituent raw material of ITO together with indium. As such, indium oxide and tin oxide are used to make transparent electrodes of various flat panel devices including light emitting diodes (LEDs) and liquid crystal displays (LCD panels).
인듐산화물과 주석산화물이 혼합된 인듐 주석 산화물(Indium Tin Oxide)은 원료 분말을 성형, 소결하여 얻어낸 소결체로 제작하여 투명 전도성 막에 사용되고 있다. Indium tin oxide in which indium oxide and tin oxide are mixed is manufactured into a sintered body obtained by molding and sintering a raw material powder and used for a transparent conductive film.
그러나, ITO 타겟을 이용해 투명 전도성 막을 형성할 때의 문제점 중 하나로 ITO타겟의 사용 효율이 낮은 것을 들 수 있는데, 일반적인 스퍼터링에서 약 20~30% 정도를 사용한 후 남은 ITO 타겟은 폐 스크랩화된다. 이 스크랩의 재활용은 희소 자원을 활용한다는 측면에서 매우 중요하다고 할 수 있겠다.However, one of the problems in forming a transparent conductive film using an ITO target is that the use efficiency of the ITO target is low, and the remaining ITO target after about 20-30% in general sputtering is scrapped. Recycling this scrap is very important in terms of utilizing scarce resources.
폐 ITO스크랩에서 ITO분말을 제작하는 방법에는 여러 가지가 있는데, 그중 하나는 인듐과 주석을 각각 산화분말로 회수한 후 일정 비율로 혼합하는 방법이 있다. 이 방법은 인듐산화분말과 주석산화분말을 개별적으로 회수해야 하며, 그에 따른 설비의 설치비용이 매우 크며, 균일한 혼합을 위한 시간이 많이 필요하다는 단점이 있다. 대부분 고가인 인듐을 주로 회수하며, 폐 ITO스크랩에서 인듐을 선택적으로 회수하는 방법은 종래기술에 이미 제안되었다. lungs There are several ways to produce ITO powder from ITO scrap, one of which is to recover indium and tin as an oxidized powder, and then mix them at a predetermined ratio. This method has to recover the indium oxide powder and tin oxide powder separately, and the installation cost of the equipment is very large, there is a disadvantage that a lot of time for uniform mixing. Mostly expensive indium is mainly recovered, and a method for selectively recovering indium from waste ITO scrap has already been proposed in the prior art.
또한, 염산을 이용해 폐 ITO스크랩을 용해 후 일련의 공정을 거쳐 ITO분말을 만드는 방법이 있는데, 염산으로 용해시 염산에 포함되어 있는 염소 이온의 존재로 인하여 소결밀도에 영향을 줄 수 있다는 단점이 존재한다. 이를 개선하고자 염산으로 폐 ITO스크랩을 용해 후 산화제 처리, 용매추출 후 중화 및 소성하여 분말화한 뒤 질산을 투입하여 인듐을 선택적으로 회수하는 방법이 있다. 그렇지만 본 발명에 비하여 회수공정이 복잡하고 제조공정시간이 길다는 단점이 있다. In addition, there is a method of making ITO powder through a series of processes after dissolving the waste ITO scrap by using hydrochloric acid, there is a disadvantage that may affect the sintered density due to the presence of chlorine ions contained in hydrochloric acid when dissolved with hydrochloric acid do. To improve this, there is a method of dissolving waste ITO scrap with hydrochloric acid, followed by oxidizing agent treatment, solvent extraction, neutralization and sintering to powder and then nitric acid to selectively recover indium. However, compared with the present invention, the recovery process is complicated and the manufacturing process time is long.
따라서, 폐 ITO스크랩의 회수공정을 단순화하여 작업공정에 소요되는 시간을 단축 및 비용을 절감하는 방법이 절실하게 요구되고 있다.Therefore, there is an urgent need for a method of reducing the time required for the work process and reducing the cost by simplifying the recovery process of the waste ITO scrap.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 선행문헌 1 : 등록특허번호 제10-0850009호(Patent Document 1) Prior Document 1: Registered Patent No. 10-0850009
(특허문헌 2) 선행문헌 2 : 등록특허번호 제10-1002088호(Patent Document 2) Prior Document 2: Registration No. 10-1002088
본 발명은 상기한 문제점을 해결하기 위하여 안출된 것으로서, 폐 ITO스크랩으로부터 얻어지는 고순도 및 고밀도 ITO 타켓용 분말의 제조 방법을 위하여 폐 ITO스크랩을 질산으로 용해한 후, 용해된 폐 ITO 용액을 메타주석산, ITO잔사, 질산인듐액으로 분리한다. 이 중에서 질산인듐액은 용매추출법을 이용하여 불순물을 제거하여 순도를 높인다. 또한, 분리된 메타주석산 및 ITO잔사와 함께, 순도가 높아진 질산인듐액을 분산제가 포함된 알칼리액으로 중화하고, 중화를 통하여 얻어진 분말을 세척 및 건조를 수행한 후, 건조된 분말을 소성한다. 그 후 소성된 분말에 결합제를 첨가하여 이들을 금형에 투입하여 성형된 ITO 타켓을 제작하고, 제작된 타겟을 소결하여 99% 이상의 높은 상대밀도를 얻는 ITO 타켓을 얻을 수 있음을 발견하였다. 따라서, 본 발명은 인듐산화분말과 주석산화분말을 각각 회수하여 혼합하는 번거로움과 비용 및 공정 문제를 동시에 해결할 수 있고, 더욱이 고밀도의 소결된 ITO 타겟을 제조하는 방법을 제공하는 데 있다.The present invention has been made to solve the above problems, and after dissolving the waste ITO scrap with nitric acid for the production method of high purity and high density ITO target powder obtained from the waste ITO scrap, the dissolved waste ITO solution is metatin acid, ITO The residue is separated by an indium nitrate solution. Among these, the indium nitrate solution is purified by removing impurities using a solvent extraction method to increase the purity. In addition, the separated indium nitrate and ITO residue is neutralized with an indium nitrate liquid having high purity, and an alkaline liquid containing a dispersant, and the powder obtained by neutralization is washed and dried, and then the dried powder is calcined. Then, it was found that a binder was added to the calcined powder, and these were put into a mold to produce a molded ITO target, and the obtained target was sintered to obtain an ITO target having a high relative density of 99% or more. Accordingly, the present invention can solve the inconvenience, cost and process problems of recovering and mixing indium oxide powder and tin oxide powder, respectively, and further provide a method for producing a high density sintered ITO target.
또한, 본발명은 폐 ITO스크랩을 질산으로 용해하여, 순도를 높이고, 이들을 분산제가 포함된 알칼리액으로 중화하고, 중화를 통하여 얻어진 분말을 이용하여 99% 이상의 높은 상대밀도를 갖는 고순도 및 고밀도의 ITO 타켓을 제공하는데 있다.In addition, the present invention dissolves waste ITO scrap with nitric acid, improves purity, neutralizes them with an alkaline liquid containing a dispersant, and uses high-density and high-density ITO having a high relative density of 99% or more using a powder obtained through neutralization. To provide a target.
상기한 목적을 달성하기 위한 본 발명은, The present invention for achieving the above object,
a) 폐 ITO스크랩을 질산에 용해시켜 질산인듐액, 메타주석산이 생성되며, 불용 ITO잔사가 잔존하는 혼합액을 제조하는 용해단계; b) 상기 혼합액을 질산인듐액과 메타주석산, ITO잔사를 분리시키는 여과 단계; c) 상기 b)에서 분리된 질산인듐액으로부터 금속불순물을 용매추출법을 이용하여 제거하는 정제 단계; d) 상기 c) 단계에서 얻어진 정제액과 상기 b) 단계에서 얻어진 메타주석산 및 ITO잔사를 분산제가 포함된 알칼리 용액에 소량 투입하여 중화시키는 중화 단계; e) 상기 d) 단계에 생성된 생성물을 세척 및 건조한 후 이를 분쇄하여 분말화하는 단계; f) 상기 e) 단계에서 얻어진 분말을 열처리하는 소성 단계; g) 상기 f) 단계에서 얻어진 열처리된 분말에 결합제를 첨가하여 분말의 성형성을 증가시키는 자기 조립 단계; h) 상기 g) 단계에서 얻어진 성형성이 증가된 분말을 금형에 투입하여 성형된 ITO 타겟을 제조하는 단계; i) 상기 성형된 ITO 타겟을 소결처리하는 단계;를 포함하는 것을 특징으로 한다.a) a dissolving step of dissolving the waste ITO scrap in nitric acid to produce an indium nitrate solution and metatartrate, and a mixed solution in which an insoluble ITO residue remains; b) filtering the mixed solution to separate the indium nitrate solution, meta-tartrate and ITO residue; c) a purification step of removing metal impurities from the indium nitrate solution separated in b) by using a solvent extraction method; d) a neutralization step of neutralizing the purified liquid obtained in step c) and the metatartrate acid and ITO residue obtained in step b) into an alkaline solution containing a dispersant; e) washing and drying the product produced in step d) and then pulverizing the powder; f) calcining the powder obtained in step e); g) adding a binder to the heat-treated powder obtained in step f) to increase the moldability of the powder; h) preparing a molded ITO target by injecting a powder having increased moldability obtained in step g) into a mold; i) sintering the molded ITO target.
여기서, 상기 (a) 단계의 폐 ITO스크랩의 입자크기는 1~20의 분말 형태인 것을 특징으로 한다.Here, the particle size of the waste ITO scrap of step (a) is characterized in that the powder form of 1 ~ 20.
그리고, 상기 (a) 단계의 혼합액을 제조하는 용해단계에서의 반응식은 하기의 화학식 1 및 화학식 2의 반응을 거치는 것을 특징으로 한다.In addition, the reaction scheme in the dissolution step of preparing the mixed solution of step (a) is characterized in that the reaction of the following formula (1) and (2).
화학식 1 : 2In + 6HNO3 3H2+2In(NO3)3 Formula 1: 2In + 6HNO 3 3H 2 + 2In (NO 3 ) 3
화학식 2 : Sn+4HNO3 H2SnO3+4NO2+H2OFormula 2: Sn + 4HNO 3 H 2 SnO 3 + 4NO 2 + H 2 O
또한, 상기 (c) 단계에서의 용매추출법에 사용되는 유기용매는 카르복실산계, 유기 인산계 및 이들의 조합으로 이루어진 군에서 선택하는 것을 특징으로 한다.In addition, the organic solvent used in the solvent extraction method in the step (c) is characterized in that selected from the group consisting of carboxylic acid, organic phosphoric acid and combinations thereof.
그리고, 상기 유기 용매는 트리부틸 포스페이트, 2-에틸헥실 인산, di-(2-에틸헥실)인산 및 이들의 조합으로 이루어진 군으로부터 선택하는 것을 특징으로 한다.The organic solvent may be selected from the group consisting of tributyl phosphate, 2-ethylhexyl phosphoric acid, di- (2-ethylhexyl) phosphoric acid, and combinations thereof.
또한, 상기 (d) 단계에 있어서, 상기 알칼리 용액은 NaOH, KOH, NH4OH, NH4HCO3, CH3COONH4 중 어느 하나 이상인 것을 특징으로 한다.In addition, in the step (d), the alkaline solution is characterized in that any one or more of NaOH, KOH, NH 4 OH, NH 4 HCO 3 , CH 3 COONH 4 .
그리고, 상기 (d) 단계에 있어서, 상기 알칼리 용액은 NH4OH인 경우에는 하기의 화학식 3 및 4의 반응을 따르는 것을 특징으로 한다.And, in the step (d), when the alkaline solution is NH 4 OH, it characterized in that following the reaction of the formula (3) and 4.
화학식 3 : In(NO3)3+3NH4OHIn(OH)3+2NH4 ++3NO3 - Formula 3: In (NO 3) 3 + 3NH 4 OHIn (OH) 3 + 2NH 4 + + 3NO 3 -
화학식 4 : H2SnO3+4NH4OHSn(OH)4+4NH4+H2O+O2 Formula 4: H 2 SnO 3 +4 NH 4 OHSn (OH) 4 +4 NH 4 + H 2 O + O 2
또한, 상기 (d) 단계에 있어서, pH는 9 내지 11의 범위인 것을 특징으로 한다.In addition, in the step (d), the pH is characterized in that the range of 9 to 11.
그리고, 상기 (f)단계의 열치리 온도는 300~900 범위인 것을 특징으로 한다.And, the heat treatment temperature of the step (f) is characterized in that the 300 ~ 900 range.
또한, 상기 (g)단계의 상기 결합제의 함량은 열처리된 분말의 100중량부에 대하여 1~5중량부를 첨가하는 것을 특징으로 한다.In addition, the content of the binder of the step (g) is characterized in that 1 to 5 parts by weight based on 100 parts by weight of the heat-treated powder.
그리고, 상기 (i) 단계의 성형된 ITO 타겟을 소결처리하기 위하여 1500~1600의 고온의 산소분위기에서 소결하는 것을 특징으로 한다.And, in order to sinter the molded ITO target of step (i) is characterized in that the sintering in a high temperature oxygen atmosphere of 1500 ~ 1600.
한편, ITO 타겟용 분말은 질산을 이용하여 상기와 같은 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법에 의해 얻어지는 것을 특징으로 한다.On the other hand, ITO target powder is characterized in that it is obtained by a method for producing a high purity ITO target powder having a high relative density from waste ITO scrap using nitric acid as described above.
상기한 구성의 본 발명에 따르면, 기존의 인듐산화분말 및 주석산화분말을 각각 회수하여 혼합하는 방법에 비하여 공정을 단순화하여 시간단축 및 생산비용을 절감할 수 있는 장점이 있으며, 폐 ITO스크랩 용해시 발생하는 금속불순물을 효율적으로 제거가 가능하여 고순도의 ITO타겟분말을 제조가능하며, 최종적으로 소결 시 높은 상대밀도를 가질 수 있다는 장점을 가지고 있다.According to the present invention of the above configuration, there is an advantage that can simplify the process and reduce the time and production cost compared to the method of recovering and mixing the conventional indium oxide powder and tin oxide powder, respectively, when dissolving waste ITO scrap It is possible to efficiently remove the metal impurity generated to produce a high-purity ITO target powder, and finally has the advantage of having a high relative density when sintering.
또한, 종래기술을 사용 시 필연적으로 발생하는 염소 이온의 존재로 인하여 소결성이 떨어질 수 있는 문제점이 나타나고 있으나, 본 발명에서 염소 이온을 배제한 질산을 용매로 사용하여 산화분말을 제조하기 때문에 종래기술에 비해 소결성이 떨어질 수 있는 단점을 보완할 수 있다.In addition, there is a problem that the sinterability is deteriorated due to the presence of chlorine ions inevitably generated when using the prior art, but in the present invention compared to the prior art because the oxidation powder is prepared using a nitric acid excluding the chlorine ion as a solvent It can compensate for the disadvantage that the sinterability may be reduced.
도 1은 본 발명의 폐 ITO스크랩으로부터 얻어지는 고순도 및 고밀도 ITO 타켓용 분말의 제조 방법에 대한 개략도이다.1 is a schematic diagram of a method for producing a powder for high purity and high density ITO targets obtained from the waste ITO scrap of the present invention.
도 2의 (a)는 실시예에 따라 사용된 폐 ITO스크랩의 주사전자현미경 이미지이고, (b)는 확대이미지이다.Figure 2 (a) is a scanning electron microscope image of the lung ITO scrap used according to the embodiment, (b) is an enlarged image.
도 3의 (a), (c)는 실시예에 따라 제조된 메타주석산 및 ITO잔사를 촬영한 주사전자현미경 이미지이고, (b),(d)는 확대이미지이다.3 (a) and 3 (c) are scanning electron microscope images of meta-tartrate and ITO residues prepared according to the embodiment, and (b) and (d) are enlarged images.
도 4의 (a), (c)는 실시예에 따라 제조된 ITO 산화분말의 주사전자현미경 이미지이고, (b),(d)는 확대이미지이다.4 (a) and 4 (c) are scanning electron microscope images of the ITO oxide powder prepared according to the embodiment, and (b) and (d) are enlarged images.
본 발명에 의한 폐 ITO스크랩으로부터 얻어지는 고순도 및 고밀도 ITO 타켓용 분말의 제조 방법은 도 1에 제시한 바와 같이, 용해단계(1), 여과단계(2), 정제단계(3), 중화단계(4), 세척단계(5), 건조 및 분쇄단계(6), 소성단계(7), 조립단계(8), 성형 및 소결단계(9)를 포함할 수 있다. Method for producing a high purity and high density ITO target powder obtained from the waste ITO scrap according to the present invention, as shown in Figure 1, dissolution step (1), filtration step (2), purification step (3), neutralization step (4) A), washing step (5), drying and grinding step (6), firing step (7), assembling step (8), forming and sintering step (9).
더욱 자세하게는 폐 ITO스크랩으로부터 얻어지는 고순도 및 고밀도 ITO 타켓용 분말의 제조 방법은 a) 폐 ITO스크랩을 질산에 용해시켜 질산인듐액, 메타주석산이 생성되며, 불용 ITO잔사가 잔존하는 혼합액을 제조하는 용해단계; b) 상기 혼합액을 질산인듐액과 메타주석산, ITO잔사를 분리시키는 여과 단계; c) 상기 b)에서 분리된 질산인듐액으로부터 금속불순물을 용매추출법을 이용하여 제거하는 정제 단계; d) 상기 c) 단계에서 얻어진 정제액과 상기 b) 단계에서 얻어진 메타주석산 및 ITO잔사를 분산제가 포함된 알칼리 용액에 소량 투입하여 중화시키는 중화 단계; e) 상기 d) 단계에 생성된 생성물을 세척 및 건조한 후 이를 분쇄하여 분말화하는 단계; f) 상기 e) 단계에서 얻어진 분말을 열처리하는 소성 단계; g) 상기 f) 단계에서 얻어진 열처리된 분말에 결합제를 첨가하여 분말의 성형성을 증가시키는 자기 조립 단계; h) 상기 g) 단계에서 얻어진 성형성이 증가된 분말을 금형에 투입하여 성형된 ITO 타겟을 제조하는 단계; i) 상기 성형된 ITO 타겟을 소결처리하는 단계;를 포함한다.More specifically, a method for producing a high purity and high density ITO target powder obtained from waste ITO scrap is a) dissolving waste ITO scrap in nitric acid to produce indium nitrate solution and metatartrate, and producing a mixed liquid in which insoluble ITO residue remains. step; b) filtering the mixed solution to separate the indium nitrate solution, meta-tartrate and ITO residue; c) a purification step of removing metal impurities from the indium nitrate solution separated in b) by using a solvent extraction method; d) a neutralization step of neutralizing the purified liquid obtained in step c) and the metatartrate acid and ITO residue obtained in step b) into an alkaline solution containing a dispersant; e) washing and drying the product produced in step d) and then pulverizing the powder; f) calcining the powder obtained in step e); g) adding a binder to the heat-treated powder obtained in step f) to increase the moldability of the powder; h) preparing a molded ITO target by injecting a powder having increased moldability obtained in step g) into a mold; i) sintering the shaped ITO target.
여기서, 상기 (a) 단계에서는 1~20 정도의 입자크기를 가지는 분말 형태의 폐 ITO스크랩을 스크랩 중량 대비 3~7배의 질산을 투입하여 폐 ITO스크랩 내 In을 질산인듐(In(No3)3)으로 용해시키고, 메타주석산이 생성되도록 하며 불용 ITO잔사가 잔존하도록 한다.Here, in step (a), the waste ITO scrap in the form of powder having a particle size of about 1 to 20 is added with 3-7 times the nitric acid to the scrap weight, so that In in the waste ITO scrap is indium nitrate (In (No 3 )). 3 ), allow meta-tartrate to be produced and insoluble ITO residues remain.
상기 용해 공정에 대한 반응식은 다음과 같다.The reaction scheme for the dissolution process is as follows.
화학식 1 : 2In + 6HNO3 3H2+2In(NO3)3 Formula 1: 2In + 6HNO 3 3H 2 + 2In (NO 3 ) 3
화학식 2 : Sn+4HNO3 H2SnO3+4NO2+H2OFormula 2: Sn + 4HNO 3 H 2 SnO 3 + 4NO 2 + H 2 O
그리고, 상기 (b) 단계에서는 혼합액을 여과하여 이를 각각 질산인듐액과 메타주석산, ITO잔사로 분리하게 된다. In the step (b), the mixed solution is filtered and separated into indium nitrate solution, meta-tartrate acid and ITO residue, respectively.
또한, 상기 (c) 단계에서는 상기 (b)단계에서 얻은 질산인듐액을 용매추출을 이용하여 순도를 저해하는 금속이온 불순물을 제거하여 정제한다. 상기 (c) 단계에서 순도를 높이기 위해 사용되는 용매추출법에 사용되는 유기용매는 카르복실산계, 유기 인산계 및 이들의 조합으로 이루어진 군에서 선택하는 것이 바람직하며, 구체적인 예로는 트리부틸 포스페이트 (Tributyl phosphate, TBP), 2-에틸헥실 인산(2-ethylhexyl 2-ethylhexyl phosphonic acid, PC88A), di-(2-에틸헥실)인산 (di-(2-ethyl hexyl)phosphonic acid, D2EHPA) 및 이들의 조합으로 이루어진 군에서 선택할 수 있다. In the step (c), the indium nitrate solution obtained in the step (b) is purified by removing metal ion impurities that inhibit purity by using solvent extraction. The organic solvent used in the solvent extraction method used to increase the purity in the step (c) is preferably selected from the group consisting of carboxylic acid, organic phosphoric acid, and combinations thereof, and specific examples are tributyl phosphate. , TBP), 2-ethylhexyl 2-ethylhexyl phosphonic acid (PC88A), di- (2-ethylhexyl) phosphonic acid (di- (2-ethyl hexyl) phosphonic acid, D2EHPA) and combinations thereof You can choose from the group consisting of.
질산인듐액에 인듐을 추출하는 유기 용매를 첨가한 후, 실온에서 10 내지 30분 동안 추출하여 불순물이 제거된, 인듐을 포함하는 유기 용액을 얻었다. 이 유기 용액에 산을 첨가한 후 교반하여 인듐을 역추출하였다. 상기 공정에 의해 유기용액에 추출되어 있던 인듐이온은 산액으로 빠져나오게 된다.An organic solvent for extracting indium was added to the indium nitrate solution, followed by extraction for 10 to 30 minutes at room temperature to obtain an organic solution containing indium from which impurities were removed. Acid was added to this organic solution, followed by stirring to back extract indium. Indium ions extracted into the organic solution by the above process are released into the acid solution.
그리고, 상기 (d) 단계에서는 OH-기를 포함하는 알칼리를 초순수에 용해시켜 희석한 후, 상기 분리된 질산인듐액 및 메타주석산, ITO잔사 침전물을 소량씩 투입하여 중화공정을 진행한다. 알칼리액에는 중화시 분말의 균일한 분산성 및 높은 소결성을 확보하기 위하여 소량의 분산제를 투입하였다. pH는 9~11 정도의 범위가 적당하며, 사용 가능한 알칼리의 예로는 NaOH, KOH, NH4OH, NH4HCO3, CH3COONH4등이 있고, 이들 중에서 하나 이상 선택할 수 있다. 바람직하에는 NH4OH를 이용할 수 있다.In the step (d), an alkali containing OH − group is dissolved and diluted in ultrapure water, and the neutralized process is performed by adding a small amount of the separated indium nitrate solution, metatartrate acid and ITO residue. A small amount of dispersant was added to the alkaline liquid in order to ensure uniform dispersibility and high sinterability of the powder during neutralization. The pH is preferably in the range of about 9 to 11, and examples of the alkali that can be used include NaOH, KOH, NH 4 OH, NH 4 HCO 3 , CH 3 COONH 4 , and the like. Preferably NH 4 OH can be used.
상기 중화 공정에 대한 반응식은 다음과 같다.The reaction scheme for the neutralization process is as follows.
화학식 3 : In(NO3)3+3NH4OHIn(OH)3+2NH4 ++3NO3 - Formula 3: In (NO 3) 3 + 3NH 4 OHIn (OH) 3 + 2NH 4 + + 3NO 3 -
화학식 4 : H2SnO3+4NH4OHSn(OH)4+4NH4+H2O+O2 Formula 4: H 2 SnO 3 +4 NH 4 OHSn (OH) 4 +4 NH 4 + H 2 O + O 2
pH의 범위를 9~11로 설정한 이유로는, pH가 9 이하일 시 중화 후 생성된 수산화분말의 침전이 늦어져 세척 단계에서 문제가 발생할 수 있고, 11 이상일 시 수산화분말 입자의 크기가 불균일하게 형성될 수 있어 바람직하지 않다.The reason why the pH range is set to 9 to 11 is that when the pH is 9 or less, precipitation of the hydroxide powder produced after neutralization may be delayed, which may cause a problem in the washing step, and when the pH is 11 or more, the size of the hydroxide powder particles may be unevenly formed. It may be undesirable.
상기 (e) 단계에서의 세척과정은 상기 (d) 단계의 중화단계를 통하여 생성된 생성물에 초순수(DI water)를 투입하고, 데칸테이션(Decantation법을 사용하여 생성물내의 질산암모늄 및 기타 염을 제거하게 된다. 이때 생성물은 수산화물이다.In the washing process of step (e), ultrapure water (DI water) is added to the product produced through the neutralization step of step (d), and decantation is used to remove ammonium nitrate and other salts in the product. The product is hydroxide.
NH4OH를 사용시 중화반응 중간에 생성되는 부산물인 NH4NO3는 물에 대한 용해도가 0에서 118.3g/100g이며, 30에서는 241.8g/100g으로 용해도가 매우 높아 세척시 제거가 용이하다는 장점이 있다. NH 4 OH to use the by-product produced in the neutralization reaction medium NH 4 NO 3 is the advantage of being soluble in water and from 0 118.3g / 100g, the solubility is very high, readily cleaned when removed from the 30 241.8g / 100g have.
상기 (e)단계에서는 세척이 완료된 생성물을 건조하여 수분을 제거한 후 분쇄 장치를 이용해 파쇄하여, 이를 분말화하게 된다. 덩어리 형태의 생성물보다, 분쇄하여 분말화한 형태가 덩어리 형태의 생성물보다 균일한 열처리를 할 수 있기 때문이다.In step (e), the washed product is dried to remove moisture, and then crushed using a pulverization apparatus to powder it. This is because the pulverized and powdered form can perform a uniform heat treatment than the lumped product than the lumped product.
상기 (f)단계에서는 분말화한 생성물을 산화시키게 되는데, 각진 형태의 소성된 분말이 형성된다. 이 때, 열처리 온도는 300~900의 범위인데, 만일 열처리 온도가 300 미만일 경우 In(OH)3-Sn(OH)4침전물이 In2O3-SnO2로 전환되기 어렵고, 900 이상일 경우 열처리 후 입자크기가 성장할 수 있어서 바람직하지 못하다.In step (f), the powdered product is oxidized, and a calcined powder in angular form is formed. At this time, the heat treatment temperature ranges from 300 to 900. If the heat treatment temperature is less than 300, the In (OH) 3 -Sn (OH) 4 precipitate is difficult to be converted to In 2 O 3 -SnO 2 , and if the heat treatment temperature is 900 or more, It is undesirable because the particle size can grow.
또한, 열처리 분위기는 산소, 아르곤, 질소, 공기 분위기에서 실시할 수 있다. In addition, heat processing atmosphere can be performed in oxygen, argon, nitrogen, and air atmosphere.
상기 공정에 대한 반응식은 다음과 같다.The reaction scheme for the process is as follows.
2In(OH)3In2O3+3H2O 2 In (OH) 3 In 2 O 3 +3 H 2 O
Sn(OH)4SnO2+2H2OSn (OH) 4 SnO 2 + 2H 2 O
상기 (g) 단계에서는 열처리된 분말을 적량의 결합제를 첨가하여 열처리된 분말의 성형성을 증가시킬 수 있도록 한다.In the step (g), by adding an appropriate amount of the binder to the heat-treated powder to increase the moldability of the heat-treated powder.
이때, 결합제의 함량은 열처리된 분말의 100중량부에 대하여 1~5중량부를 첨가할 수 있다. 결합제의 함량이 1중량부 이하일 경우 산화분말의 성형성이 낮아질 수 있고, 5중량부 이상일 경우에는 성형성은 높아지지만 상대밀도가 현저히 저하되기 때문이다. 또한 결합제로는 아크릴에멀젼을 사용하는 것이 바람직하며, 이에 제한된 것은 아니다. At this time, the content of the binder may be added 1 to 5 parts by weight based on 100 parts by weight of the heat-treated powder. When the content of the binder is 1 part by weight or less, the moldability of the oxidized powder may be lowered. When the content of the binder is 5 parts by weight or more, the moldability is increased, but the relative density is significantly lowered. In addition, it is preferable to use an acrylic emulsion as a binder, but is not limited thereto.
이후에 (g) 단계를 통하여 얻어진 성형성이 향상된 분말을 원형의 금형에 투입하고 가압성형하여 원통형의 ITO타겟을 제작하게 되며, 제작된 원통형 ITO타겟을 1500~1600의 고온에서 산소가압조건으로 소결하여 7.1g/cm3이상의 상대밀도를 갖는 ITO타겟을 제작하게 된다.Thereafter, the powder having improved moldability obtained through the step (g) is put into a circular mold and press-molded to produce a cylindrical ITO target, and the cylindrical ITO target is sintered under oxygen pressure conditions at a high temperature of 1500 to 1600. To produce an ITO target having a relative density of at least 7.1 g / cm 3 .
또한, 본 발명에 따르면, 폐 ITO스크랩으로부터 얻어지는 고순도 및 고밀도 ITO 타켓용 분말의 제조 방법에 의해 제조되는 ITO 타겟용 분말을 얻을 수 있다.Moreover, according to this invention, the powder for ITO target manufactured by the manufacturing method of the powder for high purity and high density ITO target obtained from waste ITO scrap can be obtained.
또한, ITO 타겟용 분말을 이용하여 고순도 및 고밀도의 ITO 타겟을 제조할 수 있다.In addition, high purity and high density ITO targets can be produced using the powder for ITO targets.
이하에서 실시예를 통하여 본 발명을 구체적으로 설명하기로 한다. 그러나, 하기의 실시예는 오로지 본 발명의 구체적인 설명을 하기 위한 것으로 이들 실시예에 의해 본 발명의 범위를 한정한 것은 아니다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention by these examples.
[실시예 1]Example 1
폐 ITO스크랩을 주사전자현미경을 이용하여 입자의 형태 및 크기를 관찰하였고, 도 1에 나타난 바와 같이 1미크론 안팎의 각진 형태를 가지는 분말을 확인하였다. 폐 ITO스크랩 분말 500g을 60% 질산 2L에 투입, 110에서 20시간을 용해한 후 여과하여 질산인듐과 메타주석산 및 ITO잔사를 분리하였다. 분리한 침전물 분말을 주사전자현미경으로 관찰하였고, 도 3 (a) 및 (b)의 실시예 1에 나타난 바와 같이 메타주석산과 ITO잔사가 공존한다는 것을 확인하였다. 여과된 질산인듐액 내에 포함된 불순물을 제거하기 위하여 유기용매인 PC88A를 이용해 용매추출을 진행하였고, 아래의 표 1에서 제시한 바와 같이 용매추출 전후로 불순물의 함량이 크게 감소하는 것을 확인하였다. 소량의 분산제가 첨가된 알칼리액에 질산인듐 및 메타주석산, ITO잔사를 소량씩 투입하여 역중화를 실시하였고, 중화 완료된 수화물을 초순수를 이용해 순수를 사용해 세척을 5회 실시하였다.The pulmonary ITO scrap was observed by the scanning electron microscope to determine the shape and size of the particles, as shown in Figure 1 to identify the powder having an angular form of about 1 micron. 500 g of waste ITO scrap powder was added to 2 L of 60% nitric acid, dissolved at 110 to 20 hours, and filtered to separate indium nitrate, metatartrate and ITO residue. The separated precipitate powder was observed with a scanning electron microscope, and it was confirmed that meta-tartrate and ITO residues coexist as shown in Example 1 of FIGS. 3 (a) and 3 (b). Solvent extraction was carried out using PC88A, an organic solvent, to remove impurities contained in the filtered indium nitrate solution. As shown in Table 1 below, the content of impurities was significantly reduced before and after solvent extraction. In neutralization was performed by adding a small amount of indium nitrate, metatartrate and ITO residue to the alkali solution to which a small amount of dispersant was added. The neutralized hydrate was washed five times using pure water using ultrapure water.
세척이 완료된 수산화물을 80 오븐에서 12시간 가량 건조하여 수분을 증발시킨 후, 믹서기로 조분쇄하여 수산화분말을 얻었고, 900에서 2.5시간 열처리하여 산화분말을 얻었다. 주사전자현미경으로 분말입자를 관찰하여 도 4 (a) 및 (b)의 실시예 1에 나타난 바와 같이 각진 형태의 입자가 형성됨을 확인하였다.The washed hydroxide was dried for about 12 hours in an 80 oven to evaporate water, and then coarsely pulverized with a blender to obtain a hydroxide powder, and heat treated at 900 for 2.5 hours to obtain an oxidized powder. Observing the powder particles with a scanning electron microscope, it was confirmed that the particles of the angular form as shown in Example 1 of Figure 4 (a) and (b).
생성된 산화분말에 결합제를 분말중량대비 2%로 처리하여 분말의 성형성을 증대시켰고, 결합제 처리완료된 산화분말을 성형하여 ITO 타겟을 제작 후 소결처리하였다. 소결완료 후 상대밀도 측정 결과 7.12g/cm3의 수치가 확인되었고, 환산 결과 ITO 대비 99.46%였다.The binder was treated to 2% by weight of the powder to increase the moldability of the powder, and the binder-treated oxide powder was molded to prepare an ITO target, followed by sintering. After sintering, the relative density was measured and found to be 7.12 g / cm 3 , which was 99.46% of ITO.
[실시예 2]Example 2
실시예 1과 동일한 로트의 폐 ITO스크랩 분말 500g을 60% 질산 2L에 투입, 110에서 48시간을 용해한 후 여과하여 질산인듐과 메타주석산 및 ITO잔사를 분리하였다. 분리한 침전물 분말을 주사전자현미경으로 관찰하였고, 도 3(c) 및 (d)의 실시예 2에 나타난 바와 같이 메타주석산과 ITO잔사가 공존한다는 것을 확인하였다. 질산인듐액 내에 포함된 불순물을 제거하기 위하여 유기용매인 PC88A를 사용, 용매추출을 실시하였으며, 표 2에서 제시한 바와 같이 질산인듐액 내의 불순물이 크게 감소하였음을 확인하였다. 질산인듐액과 메타주석산 및 ITO잔사를 분산제가 포함된 알칼리액에 소량씩 투입하여 역중화를 실시하였고, 중화된 수산화물을 순수를 이용하여 6회 세척하였다. 세척이 완료된 수산화물을 70 오븐에서 16시간 가량 건조하여 수분을 증발시킨 후, 믹서기로 조분쇄하여 수산화분말을 얻었고, 900에서 2.5시간 열처리하여 산화분말을 얻었다. 주사전자현미경으로 분말입자를 관찰하여 도 4(c) 및 (d)의 실시예 2에 나타난 바와 같이 각진 형태의 입자가 형성됨을 확인하였다.500 g of waste ITO scrap powder of the same lot as in Example 1 was added to 2 L of 60% nitric acid, dissolved at 110 to 48 hours, and filtered to separate indium nitrate, metatartrate and ITO residue. The separated precipitate powder was observed with a scanning electron microscope, and it was confirmed that meta-tartrate and ITO residue coexist as shown in Example 2 of FIGS. 3 (c) and (d). In order to remove impurities contained in the indium nitrate solution, solvent extraction was carried out using the organic solvent PC88A, and as shown in Table 2, it was confirmed that the impurities in the indium nitrate solution were greatly reduced. Indium nitrate, meta-tartrate and ITO residues were added in small amounts to an alkaline solution containing a dispersant to reverse neutralization, and the neutralized hydroxide was washed six times with pure water. The washed hydroxide was dried for about 16 hours in an 70 oven to evaporate moisture, and then coarsely pulverized with a blender to obtain a hydroxide powder, and heat treated at 900 for 2.5 hours to obtain an oxidized powder. Observing the powder particles with a scanning electron microscope, it was confirmed that the particles of the angular form as shown in Example 2 of Figure 4 (c) and (d).
생성된 산화분말에 결합제를 분말중량대비 2.5%로 처리하여 분말의 성형성을 증대시켰고, 결합제 처리완료된 산화분말을 성형하여 ITO 타겟을 제작 후 소결처리하였다. 소결완료 후 상대밀도 측정 결과 7.13g/cm3의 수치가 확인되었고, 환산 결과 ITO 대비 99.58%였다.The binder was treated with 2.5% by weight of the powder to increase the moldability of the powder, and the binder-treated oxide powder was molded to prepare an ITO target, followed by sintering. After sintering, the relative density measurement showed a value of 7.13 g / cm 3 , which was 99.58% compared to ITO.
실시예 1에 따른 불순물 제거율 Impurity removal rate according to Example 1
분석항목Analysis item 단위unit 용매추출 전Before solvent extraction 용매추출 후After solvent extraction 제거율 (%)Removal rate (%)
FeFe ppmppm 8282 1One 98.78 98.78
CuCu 8383 22 97.59 97.59
AlAl 2323 0.30.3 98.70 98.70
PbPb 0.20.2 00 100.00 100.00
ZnZn 8.78.7 0.10.1 98.85 98.85
NiNi 7.77.7 0.20.2 97.40 97.40
CrCr 0.80.8 0.40.4 50.00 50.00
실시예 2에 따른 불순물 제거율Impurity Removal Rate According to Example 2
분석항목Analysis item 단위unit 용매추출 전Before solvent extraction 용매추출 후After solvent extraction 제거율 (%)Removal rate (%)
FeFe ppmppm 5656 22 96.43 96.43
CuCu 7575 1One 98.67 98.67
AlAl 1919 0.10.1 99.47 99.47
PbPb 1One 00 100.00 100.00
ZnZn 99 0.20.2 97.78 97.78
NiNi 5.45.4 0.30.3 94.44 94.44
CrCr 0.40.4 0.10.1 75.00 75.00
이상에서는 본 발명의 바람직한 실시 예를 설명하였으나, 본 발명의 권리범위는 이에 한정되지 않으며, 본 발명의 실시 예와 실질적으로 균등한 범위에 있는 것까지 본 발명의 권리범위가 미치는 것으로 본 발명의 정신을 벗어나지 않는 범위 내에서 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 다양한 변형 실시가 가능한 것이다.Although the preferred embodiment of the present invention has been described above, the scope of the present invention is not limited thereto, and the scope of the present invention extends to the scope of the present invention to be substantially equivalent to the embodiment of the present invention. Various modifications can be made by those skilled in the art without departing from the scope of the present invention.

Claims (12)

  1. a) 폐 ITO스크랩을 질산에 용해시켜 질산인듐액, 메타주석산이 생성되며, 불용 ITO잔사가 잔존하는 혼합액을 제조하는 용해단계; a) a dissolving step of dissolving the waste ITO scrap in nitric acid to produce an indium nitrate solution and metatartrate, and a mixed solution in which an insoluble ITO residue remains;
    b) 상기 혼합액을 질산인듐액과 메타주석산, ITO잔사를 분리시키는 여과 단계; b) filtering the mixed solution to separate the indium nitrate solution, meta-tartrate and ITO residue;
    c) 상기 b)에서 분리된 질산인듐액으로부터 금속불순물을 용매추출법을 이용하여 제거하는 정제 단계; c) a purification step of removing metal impurities from the indium nitrate solution separated in b) by using a solvent extraction method;
    d) 상기 c) 단계에서 얻어진 정제액과 상기 b) 단계에서 얻어진 메타주석산 및 ITO잔사를 분산제가 포함된 알칼리 용액에 소량 투입하여 중화시키는 중화 단계; d) a neutralization step of neutralizing the purified liquid obtained in step c) and the metatartrate acid and ITO residue obtained in step b) into an alkaline solution containing a dispersant;
    e) 상기 d) 단계에 생성된 생성물을 세척 및 건조한 후 이를 분쇄하여 분말화하는 단계e) washing and drying the product produced in step d) and pulverizing it to powder
    f) 상기 e) 단계에서 얻어진 분말을 열처리하는 소성 단계;f) calcining the powder obtained in step e);
    g) 상기 f) 단계에서 얻어진 열처리된 분말에 결합제를 첨가하여 분말의 성형성을 증가시키는 자기 조립 단계;g) adding a binder to the heat-treated powder obtained in step f) to increase the moldability of the powder;
    h) 상기 g) 단계에서 얻어진 성형성이 증가된 분말을 금형에 투입하여 성형된 ITO 타겟을 제조하는 단계;h) preparing a molded ITO target by injecting a powder having increased moldability obtained in step g) into a mold;
    i) 상기 성형된 ITO 타겟을 소결처리하는 단계;를 포함하는 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.i) sintering the molded ITO target; using a nitric acid, characterized in that it comprises a method for producing a high purity ITO target powder having a high relative density from waste ITO scrap.
  2. 제1항에 있어서, 상기 (a) 단계의 폐 ITO스크랩의 입자크기는 1~20의 분말 형태인 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The method of claim 1, wherein the particle size of the waste ITO scrap of the step (a) using a nitric acid, characterized in that the production of high purity ITO target powder having a high relative density from the waste ITO scrap, characterized in that Way.
  3. 제1항에 있어서, 상기 (a) 단계의 혼합액을 제조하는 용해단계에서의 반응식은 하기의 화학식 1 및 화학식 2의 반응을 거치는 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The reaction scheme in the dissolution step of preparing the mixed solution of step (a) has a high relative density from waste ITO scrap using nitric acid, characterized in that the reaction of the following formula (1) and (2). Method for producing a powder for high purity ITO target.
    화학식 1 : 2In + 6HNO3 3H2+2In(NO3)3 Formula 1: 2In + 6HNO 3 3H 2 + 2In (NO 3 ) 3
    화학식 2 : Sn+4HNO3 H2SnO3+4NO2+H2OFormula 2: Sn + 4HNO 3 H 2 SnO 3 + 4NO 2 + H 2 O
  4. 제1항에 있어서, 상기 (c) 단계에서의 용매추출법에 사용되는 유기용매는 카르복실산계, 유기 인산계 및 이들의 조합으로 이루어진 군에서 선택하는 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.According to claim 1, wherein the organic solvent used in the solvent extraction method in step (c) is selected from the group consisting of carboxylic acid, organic phosphoric acid and combinations thereof from waste ITO scrap using nitric acid Method for producing a high purity ITO target powder having a high relative density.
  5. 제4항에 있어서, 상기 유기 용매는 트리부틸 포스페이트, 2-에틸헥실 인산, di-(2-에틸헥실)인산 및 이들의 조합으로 이루어진 군으로부터 선택하는 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The waste ITO scrap of claim 4, wherein the organic solvent is selected from the group consisting of tributyl phosphate, 2-ethylhexyl phosphoric acid, di- (2-ethylhexyl) phosphoric acid, and combinations thereof. Method for producing a high purity ITO target powder having a high relative density from.
  6. 제1항에 있어서, 상기 (d) 단계에 있어서, 상기 알칼리 용액은 NaOH, KOH, NH4OH, NH4HCO3, CH3COONH4 중 어느 하나 이상인 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The waste ITO scrap of claim 1, wherein the alkaline solution is any one or more of NaOH, KOH, NH 4 OH, NH 4 HCO 3 , and CH 3 COONH 4 . Method for producing a high purity ITO target powder having a high relative density from.
  7. 제1항에 있어서, 상기 (d) 단계에 있어서, 상기 알칼리 용액은 NH4OH인 경우에는 하기의 화학식 3 및 4의 반응을 따르는 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The method according to claim 1, wherein in the step (d), the alkaline solution is NH 4 OH, the high relative density from the waste ITO scrap using nitric acid, characterized in that following the reaction of the following formulas (3) and (4) Eggplant manufacturing method for high purity ITO target.
    화학식 3 : In(NO3)3+3NH4OHIn(OH)3+2NH4 ++3NO3 - Formula 3: In (NO 3) 3 + 3NH 4 OHIn (OH) 3 + 2NH 4 + + 3NO 3 -
    화학식 4 : H2SnO3+4NH4OHSn(OH)4+4NH4+H2O+O2 Formula 4: H 2 SnO 3 +4 NH 4 OHSn (OH) 4 +4 NH 4 + H 2 O + O 2
  8. 제1항에 있어서, 상기 (d) 단계에 있어서, pH는 9 내지 11의 범위인 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The method of claim 1, wherein in the step (d), the pH is in the range of 9 to 11. A method for producing a high purity ITO target powder having high relative density from waste ITO scrap using nitric acid.
  9. 제1항에 있어서, 상기 (f)단계의 열치리 온도는 300~900 범위인 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The method of claim 1, wherein the thermal treatment temperature of step (f) is in the range of 300 to 900, using a nitric acid, a method for producing a high purity ITO target powder having high relative density from waste ITO scrap.
  10. 제1항에 있어서, 상기 (g)단계의 상기 결합제의 함량은 열처리된 분말의 100중량부에 대하여 1~5중량부를 첨가하는 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.According to claim 1, wherein the content of the binder of the step (g) has a high relative density from the waste ITO scrap by using nitric acid, characterized in that 1 to 5 parts by weight based on 100 parts by weight of the heat-treated powder Method for producing a powder for high purity ITO target.
  11. 제1항에 있어서, 상기 (i) 단계의 성형된 ITO 타겟을 소결처리하기 위하여 1500~1600의 고온의 산소분위기에서 소결하는 것을 특징으로 하는 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법.The high purity having high relative density from waste ITO scrap using nitric acid, according to claim 1, wherein the molded ITO target of step (i) is sintered in a high temperature oxygen atmosphere of 1500-1600. Method for producing powder for ITO target.
  12. 제1항 내지 제11항 중 어느 한 항의 질산을 이용하여 폐 ITO스크랩으로부터 높은 상대밀도를 가지는 고순도 ITO타겟용 분말의 제조방법에 의해 제조되는 ITO 타겟용 분말.The powder for ITO target manufactured by the manufacturing method of the powder for high purity ITO target which has a high relative density from waste ITO scrap using the nitric acid of any one of Claims 1-11.
PCT/KR2017/005537 2017-04-13 2017-05-26 Method for preparing, from waste ito scraps, powder for high-purity ito target having high relative density by using nitric acid, and powder prepared thereby WO2018190461A1 (en)

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