KR102178251B1 - Vapor phase decomposition method, analysis method, quality control method, production method, and container - Google Patents

Abstract

The present invention relates to a gas phase decomposition method for preventing mixing of metal impurities and/or non-metal impurities derived from a decomposition liquid into a decomposed organic material. The gas phase decomposition method includes a preparation step of accommodating the organic material and the decomposition liquid in a sealed container so that the organic material and the decomposition liquid for decomposing the organic material do not come into contact, and pressurization by heating the inside of the sealed container to obtain the organic material. And a decomposition step in which the decomposition liquid is decomposed by the decomposition liquid gas vaporized.

Description

Vapor phase decomposition method, analysis method, quality control method, manufacturing method and container {VAPOR PHASE DECOMPOSITION METHOD, ANALYSIS METHOD, QUALITY CONTROL METHOD, PRODUCTION METHOD, AND CONTAINER}

The present invention relates to a gas phase decomposition method for decomposing an organic material, a method for analyzing the decomposed organic material, a method for quality control of the analyzed organic material, a manufacturing method using the analyzed organic material, and a container for decomposing organic material It is about.

As a method of analyzing impurities contained in organic substances, the pressure decomposition method described in Non-Patent Document 1 is known. According to the method described in Non-Patent Document 1, a polymer material is immersed in an acid solution such as nitric acid, heated and pressurized to dissolve organic substances in the acid solution to obtain a measurement sample solution. Then, impurities containing a metallic element (hereinafter referred to as metallic impurities) and/or impurities containing a non-metallic element (hereinafter referred to as non-metallic impurities) contained in the measurement sample are detected.

Non-Patent Document 1: Fujikura Giho, No. 101, pp. 57~60, 2001,'Analysis of trace elements in composite materials by pressure decomposition method'

However, according to the method described in Non-Patent Document 1, since the polymer material and the acid solution directly contact each other, impurities contained in the acid solution are contained in the measurement sample solution, and contamination of the measurement sample solution occurs. In addition, impurities adhering to the inner wall of the container containing the acid solution and metals and/or non-metals contained as impurities on the inner wall contact the acid solution to elute into the acid solution and mix into the measurement sample solution.

In recent years, the application of an organic material as an electronic material has entered the field of view, and a higher purity organic material is required. Therefore, it is necessary to more accurately analyze the metallic impurities and/or non-metal impurities contained in the organic material, and the incorporation of trace impurities during analysis, which has not been a problem in the past, becomes a problem.

The present invention has been made in view of the above problems, and its object is to prevent the incorporation of impurities derived from the decomposition solution, and to more accurately analyze metallic impurities and/or non-metal impurities in organic materials, a gas phase decomposition method, decomposed It is to provide a method for analyzing organic materials, a method for quality control of analyzed organic materials, a manufacturing method using the analyzed organic materials, and a container for decomposing organic materials.

The gas phase decomposition method according to the present invention includes a preparation step of accommodating the organic material and the decomposition solution in a sealed container so that the organic material and the decomposition solution for decomposing the organic material do not come into contact, and pressurization by heating the inside of the sealed container. And a decomposition step of decomposing the organic material by the decomposition liquid gas vaporized by the decomposition liquid.

Further, in the gas phase decomposition method according to the present invention, the organic material contained in the sealed container is preferably 0.001 mg or more and 500 mg or less.

In addition, the gas phase decomposition method according to the present invention includes an alkali metal, an alkaline earth metal, a lanthanoid, an actinoid, a transition metal, a boron group, a carbon group, and a nick from the organic material decomposed in the decomposition step. It is preferable to further include a recovery step of recovering a measurement sample containing at least one element belonging to pnictogen or chalcogen.

The analysis method according to the present invention is characterized by including an analysis step of detecting impurities in a measurement sample obtained by decomposing an organic material by any one of the gas phase decomposition methods described above.

The quality control method according to the present invention includes an analysis process for detecting impurities in a measurement sample obtained by decomposing an organic material by any one of the gas phase decomposition methods, and an organic material in which the amount of impurities detected in the analysis process is less than a predetermined reference amount. It characterized in that it comprises an extraction process for extracting the material.

The manufacturing method according to the present invention includes an analysis process for detecting impurities in a measurement sample obtained by decomposing an organic material by any one of the gas phase decomposition methods, and an organic material in which the amount of impurities detected in the analysis process is less than or equal to a predetermined reference amount. It characterized in that it comprises an extraction process of extracting the, and a manufacturing process of manufacturing an organic electronic device using the organic material extracted in the extraction process.

The container according to the present invention is a container for decomposing an organic material, and has a closed space for accommodating a decomposition solution for decomposing the organic material therein, and is pressure resistant to the pressure for decomposing the organic material. A phosphorus outer container and an inner container provided in the outer container, formed of a material resistant to the decomposition liquid, and receiving the organic material from an open top, the inner container When the decomposition solution is accommodated in the outer container, it is characterized in that it is provided so that the decomposition solution does not come into contact with the inner wall.

The gas phase decomposition method according to the present invention includes a preparation step of accommodating the organic material and the decomposition solution in a sealed container so that the organic material and the decomposition solution for decomposing the organic material do not come into contact, and pressurization by heating the inside of the sealed container. Thus, since a decomposition step of decomposing the organic material by the decomposition liquid gas vaporized by the decomposition liquid is included, it is possible to prevent impurities derived from the decomposition liquid from being mixed in the decomposed organic material.

1 is a cross-sectional view showing a container for decomposing an organic material according to an embodiment of the present invention.

[Measure decomposition method]

The gas phase decomposition method of an organic material according to the present invention includes a preparation step of accommodating the organic material and the decomposition solution in a sealed container so that the organic material and the decomposition solution for decomposing the organic material do not come into contact, and the inside of the sealed container And a decomposition step of pressurizing by heating to decompose the organic material with a decomposition liquid gas vaporized by the decomposition liquid.

According to the present invention, an organic material is decomposed by a decomposition liquid gas in which the decomposition liquid vaporizes. Therefore, it is possible to prevent impurities contained in the decomposition liquid from being mixed in the measurement sample obtained by decomposing the organic material.

The organic material is a material containing an organic material and includes an organic electronic material. The organic electronic material is an organic material used as a material constituting an electronic device, and includes, for example, an organic thin film solar cell material, an organic EL material, an organic transistor (semiconductor) material, and the like. According to the gas phase decomposition method according to the present invention, since the occurrence of contamination by impurities contained in the decomposition liquid is suppressed, it is possible to provide a measurement sample after decomposition for accurate analysis even if the organic material to be decomposed is small. Therefore, the gas phase decomposition method according to the present invention is also suitable for decomposition of expensive organic electronic materials.

In addition, organic metal complexes are also contained in the organic material. Further, the organic material includes a thin film formed by depositing or applying an organic material, for example, and an organic material solution in which the thin film is dissolved. Here, the thin film refers to, for example, a thin film formed by vapor deposition or a thin film formed by coating, but the formation method is not particularly limited.

As an organic material, for example, an aromatic hydrocarbon, a polycyclic aromatic hydrocarbon, a heteroaromatic hydrocarbon containing a hetero atom in the skeleton, or a compound derived from a polycyclic heteroaromatic hydrocarbon, a compound in which rings are linked through a covalent bond, fullerene. And compounds containing a skeleton, a compound containing porphyrin and phthalocyanine, a metal complex compound containing these structures, and oligomers and polymers containing these structures.

According to the gas phase decomposition method according to the present invention, even a non-decomposable organic material having a benzene ring can be decomposed in a gas phase very efficiently, and such an organic material having a benzene ring can be subjected to gas phase decomposition.

The decomposition solution is a solution that decomposes organic materials, and may be a solution that evaporates by heating and pressurization to generate decomposition gas, at least one selected from the group consisting of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, aqueous hydrogen peroxide, and perchloric acid. An acid solution containing an acid of can be used. In addition, the decomposition liquid may be an aqueous acid solution of at least one of the above-described acids and water.

(Preparation process)

In the preparation step, the organic material and the decomposition liquid are accommodated in a sealed container so that the organic material and the decomposition liquid for decomposing the organic material do not come into direct contact. For example, the decomposition liquid is directly accommodated in a sealed container, and an organic material contained in an inner container having an opening is accommodated in the sealed container. At this time, the opening of the inner container containing the organic material may be accommodated so that the opening of the inner container is positioned above the liquid level of the decomposition solution, so that the organic material and the decomposition solution do not come into contact.

In addition, an inner container containing an organic material and an inner container containing a decomposition liquid may be respectively accommodated in a sealed container. In addition, an inner container containing organic material may be placed on a table provided in a sealed container, and the decomposition liquid may be stored under the table. The inner container containing the organic material and the inner container containing the decomposition liquid are adjacent to the table. You can do it. Further, an inner container containing the decomposition liquid may be placed on a table, and an inner container containing an organic material may be placed under the table. That is, the organic material and the decomposition liquid do not come into direct contact in the sealed container, and may be accommodated in the sealed container so that the organic material is exposed to the decomposition liquid gas vaporized by the decomposition liquid.

The organic material contained in the sealed container is preferably 0.001 mg or more and 500 mg or less, more preferably 0.1 mg or more and 500 mg or less, and most preferably 1 mg or more and 50 mg or less. According to the gas phase decomposition method according to the present invention, since the organic material and the decomposition liquid do not directly contact each other, contamination by impurities contained in the decomposition liquid is suppressed from occurring in a measurement sample obtained by decomposing the organic material. Therefore, it is possible to provide a measurement sample obtained by using a small amount of organic material for accurate analysis.

Although the amount of the decomposition liquid contained in the sealed container is not particularly limited, for example, when the volume of the sealed container is 100%, if the decomposition liquid is contained in an amount of 1% or more and 40% or less of the sealed container volume, it is effective. It is preferable because it can decompose organic materials. In addition, the amount of the decomposition liquid contained in the sealed container may be an amount capable of sufficiently decomposing the organic material. Therefore, for example, 5 ml or more and 20 ml or less of the decomposition liquid may be accommodated per 500 mg of the organic material to be decomposed.

The organic material contained in the sealed container may be bulk, may be a thin film formed by vapor deposition or a thin film formed by coating. After containing the organic material and the decomposition liquid in the sealed container, the sealed container is sealed.

(Decomposition process)

In the decomposition step, the inside of the sealed container is heated to pressurize, and the organic material is decomposed by the decomposition liquid gas vaporized by the decomposition liquid. That is, the organic material and the decomposition liquid are accommodated and pressurized by heating the inside of the sealed container. Pressurization and heating in the sealed container can be appropriately performed by a conventionally known method.

As will be described later, the heating temperature of the sealed container may be a temperature at which desired pressurization is possible and the decomposition liquid is vaporized, but it is preferably 100°C or more and 240°C or less, more preferably 150°C or more and 240°C or less, and 200 It is most preferable that it is more than or equal to 240 degreeC. Further, the heating time of the sealed container is preferably 1 hour or more and 72 hours or less per 500 mg of organic material, more preferably 1 hour or more and 48 hours or less, and most preferably 1 hour or more and 24 hours or less.

The pressure applied in the sealed container by heating to the above-described temperature is the pressure at which the organic material can be decomposed by the vaporized decomposition liquid, and is preferably 1 MPa or more and 15 MPa or less, more preferably 5 MPa or more and 15 MPa or less, It is most preferably 7 MPa or more and 15 MPa or less.

When heating the sealed container, it is preferable to heat the entire sealed container. In addition, in particular, when heat is applied to the upper part of the sealed container, it is possible to prevent the occurrence of contamination by falling droplets aggregated on the upper wall of the sealed container onto the organic material.

In this way, by heating and pressurizing the inside of the sealed container containing the organic material and the decomposition liquid, the organic material is gas-phase decomposed by the decomposition liquid gas vaporized by the decomposition liquid. Therefore, it is possible to prevent impurities contained in the decomposition liquid or impurities adhering to the inner wall of the sealed container from being mixed in the measurement sample obtained by decomposing the organic material. As a result, trace amounts of metallic impurities and/or non-metallic impurities contained in the organic material can be provided for analysis so that they can be detected more accurately.

(Recovery process)

The gas phase decomposition method according to the present invention comprises at least one element belonging to an alkali metal, an alkaline earth metal, a lanthanoid, an actinoid, a transition metal, a boron group, a carbon group, a nicktogen or a chalcogen from an organic material decomposed in the decomposition process. You may further include a recovery step of recovering the measurement sample containing?

In the decomposition process, the organic material is gas-phase decomposed by the decomposition liquid gas to sublimate, and metallic elements and/or non-metallic elements contained in the organic material remain. In the recovery step, a metal element and/or a non-metal element remaining after the organic material is decomposed is recovered as a measurement sample. The metal elements and/or non-metal elements remaining after decomposition of the organic material are impurities contained in the organic material, that is, metal impurities and/or non-metal impurities.

Here, the metal impurity refers to an impurity containing at least one metal element belonging to an alkali metal, alkaline earth metal, lanthanide, actinoid or transition metal, and the non-metal impurity refers to an alkali metal, alkaline earth metal, lanthanoid, It does not contain at least one metal element belonging to an actinoid or transition metal, and refers to an impurity containing at least one non-metal element belonging to a boron group, a carbon group, a nictogen or a chalcogen.

For the recovery of metal elements and/or non-metal elements, a conventionally known recovery solution may be used, and the recovery solution includes at least one selected from the group consisting of nitric acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, aqueous hydrogen peroxide and perchloric acid. An acid solution containing an acid can be used.

In the recovery step, for example, a recovery solution is dripped into an internal container that has been decomposed by containing an organic material, and metallic elements and/or non-metallic elements adhering to the inner wall of the internal container are dissolved. At this time, metal elements and/or non-metal elements may be recovered by heating the internal container to which the recovery liquid was dropped again.

According to the gas phase decomposition method according to the present invention, since decomposition by a high temperature at which metallic impurities and/or non-metal impurities contained in organic materials are volatilized is not performed, alkali metals, alkaline earth metals, lanthanoids, and actioids contained in organic materials are not performed. At least one element belonging to a noid, a transition metal, a boron group, a carbon group, a nicktogen, or a chalcogen may be recovered as a metallic impurity and/or a non-metal impurity. That is, it can be provided to analyze whether these elements are contained in the organic material. In particular, in the recovery process, elements such as Na, K, Zn, Cu, Ag, Cd, Sn, Sb and Pb can be preferably recovered as metallic impurities and/or non-metal impurities.

Alkali metals recoverable in the recovery process include Li, Na, K, Cs, and Rb. Further, examples of alkaline earth metals recoverable in the recovery process include Be, Mg, Ca, Sr, and Ba. In addition, as lanthanoids recoverable in the recovery process, La, Ce, Lu, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb may be mentioned. In addition, Th and U can be mentioned as actinoids recoverable in the recovery process. In addition, transition metals recoverable in the recovery process include Fe, Co, Ni, Ti, Sc, V, Cr, Mn, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W , Re, Os, Ir, Pt, Au, Zn, and Cd. In addition, examples of the boron group recoverable in the recovery step include Ga, In, Tl, B, and Al. Further, examples of the carbon groups recoverable in the recovery step include Si, Ge, Sn, and Pb. In addition, P, As, Sb, and Bi may be mentioned as the nictogen recoverable in the recovery process. In addition, the chalcogens recoverable in the recovery process include S, Se and Te.

In addition, according to the gas phase decomposition method according to the present invention, it is possible to very efficiently decompose non-decomposable organic materials, such as having a benzene ring, so that organic materials are decomposed and provided for analysis without repeating the decomposition process. Metal impurities or non-metal impurities can be recovered.

According to the conventional dry ashing method for decomposing organic material, since the organic material is decomposed by ashing at high temperature, elements that volatilize at high temperature could not be recovered and thus cannot be provided for analysis (for example, Reference 1 (See Commentary on Hygiene Test Method 2005, compilation of the Japanese Pharmacopoeia, P391). In addition, in the conventional microwave method for decomposing organic materials, it is difficult to decompose non-decomposable organic materials such as having a benzene ring, and depending on the material, it is necessary to change the combination of acids used or repeat the decomposition process. (For example, see Reference 2 (Niigata Prefectural Institute of Industrial Technology Industrial Technology Research Report, ``Establishment of a Sample Decomposition Method Using a Microwave Sample Decomposition Device, P86-88)). In addition, in the microwave method, since the sample is in contact with sulfuric acid, there is a problem that poorly soluble sulfates of sulfuric acid such as Ca, Sr, Ba, Ag and Pb are generated in the measurement sample recovered after decomposition (e.g., Reference 3 (Refer to the Tokyo Metropolitan Industrial Technology Research Center Research Report, No. 4,'Efficient Chemical Analysis Pretreatment by Microwave Heat Decomposition Treatment', P92~93).

According to the gas phase decomposition method according to the present invention, it is possible to recover metal impurities and/or non-metal impurities that are difficult to recover by the conventional decomposition method, and also, a hardly decomposable organic material that is difficult to decompose by the conventional decomposition method. It is also possible to disassemble. Further, according to the gas phase decomposition method according to the present invention, it is possible to more accurately analyze the metallic impurities and/or non-metal impurities in the organic material by preventing the impurities derived from the decomposition liquid from being mixed in the decomposed organic material.

[Analysis method]

The method for analyzing an organic material according to the present invention includes an analysis step of detecting metallic impurities and/or non-metallic impurities in a measurement sample obtained by decomposing the organic material by the gas phase decomposition method according to the present invention described above.

In the analysis process, the organic material is decomposed by the gas phase decomposition method according to the present invention, and the remaining metallic and/or non-metallic elements are recovered as metallic impurities and/or non-metallic impurities, and the elements are used as a measurement sample by a conventionally known measurement method. Analyze. As a method of elemental analysis of the measurement sample, for example, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectrometry (ICP-AES), atomic absorption spectrometry (AAS), and the like can be cited.

As described above, according to the analysis method according to the present invention, metal impurities and/or non-metal impurities contained in the organic material can be more accurately detected by analyzing the measurement sample obtained by gas-phase decomposition of the organic material.

[Quality Control Method]

The quality control method according to the present invention includes an analysis process for detecting metallic impurities and/or non-metallic impurities in a measurement sample obtained by decomposing an organic material by the gas phase decomposition method according to the present invention described above, and a metal detected in the analysis process. And an extraction process of extracting an organic material having an amount of impurities and/or non-metallic impurities equal to or less than a predetermined reference amount.

In the analysis process, the organic material is decomposed by the gas phase decomposition method according to the present invention, and the remaining metallic and/or non-metallic elements are recovered as metallic impurities and/or non-metallic impurities, and the elements are used as a measurement sample by a conventionally known measurement method. Analyze. As a method of elemental analysis of the measurement sample, for example, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectrometry (ICP-AES), atomic absorption spectrometry (AAS), and the like can be cited.

Then, in the extraction process, an organic material in which the amount of metal impurities and/or non-metal impurities detected in the analysis process is equal to or less than a predetermined reference amount is extracted. That is, the organic material is selected based on the amount of metallic impurities and/or non-metallic impurities detected in the analysis process. On the other hand, in the extraction process, the organic material may be selected based on the type of the metal element contained in the metal impurity detected in the analysis process or the type of the nonmetal element contained in the nonmetallic impurity.

As described above, according to the quality control method according to the present invention, since metallic impurities and/or non-metallic impurities contained in the organic material can be accurately detected, the quality of the organic material is uniformly selected by selecting the organic material based on the detection result. Can be maintained. Accordingly, the quality control method according to the present invention is also suitable for quality control of organic materials used in the manufacture of organic electronic products that require more accurate quality control.

[Manufacturing method]

The manufacturing method according to the present invention includes an analysis process for detecting metallic impurities and/or nonmetallic impurities in a measurement sample obtained by decomposing an organic material by the gas phase decomposition method according to the present invention described above, and a metal impurity detected in the analysis process. And/or an extraction process of extracting an organic material having an amount of non-metallic impurities equal to or less than a predetermined reference amount, and a manufacturing process of manufacturing an organic electronic device using the organic material extracted in the extraction process.

In the analysis process, the organic material is decomposed by the gas phase decomposition method according to the present invention, and the remaining metallic and/or non-metallic elements are recovered as metallic impurities and/or non-metallic impurities, and the elements are used as a measurement sample by a conventionally known measurement method. Analyze. As a method of elemental analysis of the measurement sample, for example, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma emission spectrometry (ICP-AES), atomic absorption spectrometry (AAS), and the like can be cited.

Next, in the extraction process, an organic material in which the amount of metal impurities and/or non-metal impurities detected in the analysis process is equal to or less than a predetermined reference amount is extracted. That is, the organic material is selected based on the amount of metallic impurities and/or non-metallic impurities detected in the analysis process. On the other hand, in the extraction process, the organic material may be selected based on the type of the metal element contained in the metal impurity detected in the analysis process or the type of the nonmetal element contained in the nonmetallic impurity.

And, in the manufacturing process, an organic electronic product (organic electronic device) is manufactured using the organic material extracted in the extraction process. Examples of organic electronic products include organic thin-film solar cells, organic EL and organic transistors (semiconductors).

In the manufacturing method according to the present invention, since the amount of metallic impurities and/or non-metallic impurities contained in the organic material extracted in the extraction process is less than the reference amount, it is possible to manufacture high-quality organic electronic products, and the product yield of the product is improved. Can be improved.

[Container (10)]

The container according to the present invention is a container for decomposing an organic material, and has a closed space for accommodating a decomposition solution for decomposing the organic material therein, an external container that is pressure resistant to pressure for decomposing the organic material, and the It is provided in an outer container, is formed of a material resistant to the decomposition liquid, and includes an inner container in which the organic material is accommodated from an open top, wherein the inner container is accommodated in the outer container. It is provided so that the decomposition liquid does not come into contact with the inner wall thereof.

Hereinafter, an embodiment of a container according to the present invention will be described in detail with reference to FIG. 1. 1 is a cross-sectional view showing a container for decomposing an organic material according to an embodiment of the present invention. As shown in FIG. 1, the container 10 includes an outer container 1 and an inner container 4. The container 10 is used to decompose the organic material 5. The container 10 may further include a support (not shown) provided with a table on which the inner container 4 is placed. In this embodiment, as shown in FIG. 1, the inner container 4 containing the organic material 5 is immersed in the decomposition liquid 6 accommodated in the outer container 1.

(Outer container (1))

The outer container 1 has a closed space in which the organic material 5 and a decomposition liquid 6 for decomposing the organic material 5 are accommodated. The outer container 1 is pressure resistant to pressure applied to decompose the organic material 5 contained therein. Further, it is preferable that the outer container 1 is heat resistant to heat applied to decompose the organic material 5 contained therein.

Here, the pressure resistance to the pressure applied to decompose the organic material 5 means that when pressure is applied to decompose the organic material 5, it is difficult to expand or soften, and it is not deformed by maintaining a constant shape. Intend to do. In addition, heat resistance to heat applied to decompose the organic material 5 is intended to be difficult to elute or soften when heated to decompose the organic material 5, and to maintain a constant shape and not deform.

<Inner tube part (3)>

The outer container 1 has a double-walled structure of the inner cylinder 3 and the outer cylinder 2 on the outside. The inner cylinder portion 3 is made of a material that is in contact with the closed space and is resistant to the decomposition solution 6. When the decomposition solution 6 is accommodated in the closed space, the inner cylinder portion 3 is made of a material that is resistant to the decomposition solution 6 because it directly contacts the decomposition solution 6. The material that is resistant to the decomposition solution (6) is intended to be a material with little elution of metal components and/or nonmetallic components to the decomposition solution (6), and the metal component and/or nonmetallic component to the decomposition solution (6). It is more preferable that it is a material that does not elute.

As a material resistant to the decomposition liquid 6, for example, a fluororesin, platinum, or ceramic material may be mentioned. Examples of the fluorine resin include PTFE (polytetrafluoroethylene) (tetrafluoroethylene), PFA (tetrafluoroethylene) perfluoroalkyl vinyl ether copolymer, and PVDF (polyvinylidene fluoride) (difluoride). , PCTFE (polychlorotrifluoroethylene) (trifluoride), and the like. Examples of the ceramic material include alumina, zirconia, carcia, magnesia, and yttria.

The shape of the inner cylinder portion 3 is not particularly limited, and an airtight space is present inside, and the organic material 5 and the decomposition liquid 6 may be accommodated. The inner cylinder portion 3 is divided into two members, a lower portion and a cover portion, and accommodates the decomposition liquid 6 in the lower portion, and may be sealed by placing a cover portion so as to block it from the upper portion. The thickness of the lower wall, the side wall, and the upper wall of the inner cylinder 3 is not particularly limited as long as it is a thickness capable of preventing the outflow of the accommodated decomposition liquid 6 and sealing the inner space.

<External cylinder part (2)>

The outer cylinder portion 2 is located outside the inner cylinder portion 3 and is provided to surround the inner cylinder portion 3. Further, the outer cylinder portion 2 is pressure resistant to the pressure for dissolving the organic material 5. Therefore, even if the inner cylinder 3 is deformed by heating and pressure to decompose the organic material 5 contained therein, since the outer cylinder 2 has pressure resistance, deformation of the entire outer container 1 is prevented. Can be prevented. In addition, it is preferable that the outer cylinder portion 2 is heat resistant to heat applied to dissolve the organic material 5. Accordingly, deformation of the outer container 1 due to heat can be prevented.

The outer cylinder portion 2 may have pressure resistance and heat resistance against pressure and heat for dissolving the organic material 5, and is formed of, for example, stainless steel. The outer cylinder portion 2 may be provided so as to surround the inner cylinder portion 3 at least when pressing and heating. That is, the outer cylinder portion 2 is divided into two members, a lower portion and a cover portion, and accommodates the inner cylinder portion 3 in the lower portion, and the cover portion may be put on and sealed to prevent this from the upper portion, thereby providing for pressurization and heating. The thickness of the lower wall, the side wall, and the upper wall of the outer cylinder portion 2 is not particularly limited as long as it is a thickness at which desired pressure resistance and heat resistance are obtained.

In the outer container (1), the inner cylinder portion (3) is in contact with the sealed space in which the decomposition solution (6) is accommodated, and the outer cylinder portion (2) and the decomposition solution (6) do not come into contact with each other. Metal impurities and/or non-metallic impurities are prevented from being eluted in the decomposition solution 6 to cause contamination, and elution of the metal impurities and/or non-metallic impurities into the decomposition solution 6 can be suppressed. On the other hand, the inner cylinder portion 3 may have a two-layer structure again to more reliably prevent the metal impurities and/or non-metallic impurities originating from the outer cylinder portion 2 from eluting into the decomposition liquid 6.

(Inner container (4))

The inner container 4 is formed of a material resistant to the decomposition liquid 6 and is a columnar container with an open top. The organic material 5 is accommodated in the inner container 4 from the upper open part. The inner container 4 is provided in the outer container 1 so that the decomposition liquid 6 does not come into contact with its inner wall. Since the inner container 4 is exposed to the decomposition liquid gas in which the decomposition liquid 6 has been vaporized, the elution of metal components and/or non-metallic components with respect to the decomposition liquid 6 is small, or with respect to the decomposition liquid 6 Metal components and/or non-metal components need to be formed by a material that does not elute.

As a material that is resistant to the decomposition liquid 6 constituting the inner container 4, for example, a fluororesin, platinum, or ceramic material may be mentioned. Examples of the fluorine resin include PTFE (polytetrafluoroethylene) (tetrafluoroethylene), PFA (tetrafluoroethylene) perfluoroalkyl vinyl ether copolymer, and PVDF (polyvinylidene fluoride) (difluoride). , PCTFE (polychlorotrifluoroethylene) (trifluoride), and the like. Examples of the ceramic material include alumina, zirconia, carcia, magnesia, and yttria.

In the inner container 4, for example, the inner container 4 is placed on a table (not shown) provided in the outer container 1 and disassembled under the table positioned above the liquid level of the decomposition solution 6 The liquid 6 may be accommodated. At this time, the table is provided with a hole through which the decomposition liquid gas passes, or the inner diameter of the table is made smaller than the inner diameter of the inner cylinder 3 so that a gap is created between the table and the inner wall of the inner cylinder 3 It is preferable to provide a gas flow path. In addition, a table may be provided on the top of a stand (not shown) provided to protrude from the bottom surface of the outer container 1, and a support pin (not shown) provided to protrude from at least two places of the sidewall of the inner cylinder 3 Thus, you may provide so as to support the table from below. The height of the stand or the position of the support pin may be configured to be changeable.

Further, the inner container 4 and the decomposition liquid container (not shown) in which the decomposition liquid 6 is accommodated may be placed adjacent to each other on the table. Further, the inner container 4 may be placed under the table, and the decomposition liquid container in which the decomposition liquid is accommodated may be placed above the table. That is, in the inner container 4, the decomposition liquid 6 does not come into contact with the inner wall thereof, and the organic material 5 in the inner container 4 is exposed to the decomposition liquid gas vaporized by the decomposition liquid 6. On the other hand, as the decomposition liquid container, one formed of a material resistant to the decomposition liquid 6 and containing the decomposition liquid from the open top can be used.

A plurality of inner containers 4 may be provided in the outer container 1, and accordingly, it is possible to simultaneously decompose a plurality of organic materials 5. The size of the inner container 4 is not particularly limited as long as the accommodated organic material 5 is sufficiently exposed to the decomposition liquid gas vaporized by the decomposition liquid 6. Further, a small container having a smaller capacity than the inner container 4 may be accommodated in the inner container 4, and the organic material 5 may be accommodated in the small container to be provided for decomposition.

As described above, when the container 10 is used, the organic material 5 is accommodated in the inner container 4 provided in the pressure-resistant outer container 1 for accommodating the decomposition solution 6, and the outer container 1 By heating and pressurizing, the organic material 5 is gas-phase decomposed by the decomposition liquid gas vaporized by the decomposition liquid 6. Accordingly, metal impurities and/or non-metallic impurities contained in the decomposition liquid 6, or metal impurities adhering to the inner wall of the outer container 1 (the inner wall of the inner cylinder 3) and the inner wall of the inner container 4 and/or Alternatively, it is possible to prevent non-metallic impurities from being mixed in the measurement sample obtained by decomposing the organic material 5. As a result, when the organic material 5 is decomposed using the container 10, a trace amount of metallic impurities and/or non-metallic impurities contained in the organic material 5 can be provided for analysis so as to more accurately detect.

Example

[Example 1: Blank test]

The blank test of the gas phase decomposition method according to the present invention was performed. In the blank test, by performing a treatment such as gas phase decomposition using the container described in the embodiment without using an organic material, metal impurities and/or non-metal impurities contained in the decomposition liquid, and metal impurities adhering to the inner wall of the outer container, and / Or it was investigated to what extent non-metallic impurities were mixed in the measurement sample.

A mixed acid solution of 40% hydrofluoric acid and 68% nitric acid (1:1) was used as the decomposition liquid. The inside of the inner container was made empty, the decomposition liquid was exposed to the vaporized decomposition liquid gas, and the inside of the outer container was heated at 200°C for 5 hours to obtain a high temperature pressurized condition. A SUS container was used as the outer cylinder part, and a PTFE container was used as the inner cylinder part. Two inner containers made of PTFE (VPD-1 and VPD-2) were placed in the outer container. The internal container was taken out, nitric acid was added dropwise to recover metallic impurities and/or non-metallic impurities in each of the internal containers to obtain a measurement sample.

The measurement sample was measured by ICP-MS (manufactured by Parkin Elma). As a result, the amount of metal impurities and the amount of non-metal impurities contained in the measurement sample were as shown in Table 1. On the other hand, the values shown in Table 1 were calculated by multiplying the concentration (ng/g) measured by ICP-MS by the amount of liquid adjusted to the liquid (g). In the other examples described below, it was similarly described.

[Example 2: Fullerene]

Gas phase decomposition was performed using fullerene as an organic material. 7 mg of fullerene was accommodated in the container described in the embodiment and gas phase decomposition was performed. A mixed acid solution of 68% nitric acid and 96% sulfuric acid was used as the decomposition liquid. It was set as high temperature pressurization conditions by heating at 230 degreeC. After the decomposition treatment, the inner container was taken out, nitric acid was added dropwise to dissolve by heating, and the metallic impurities and/or non-metal impurities in the inner container were recovered to obtain a measurement sample.

The measurement sample was measured by ICP-MS (manufactured by Parkin Elma). As a result, the measured values of the sample were as shown in Table 2. In the table, the symbol of'<' indicates that the measured value is smaller than the numerical value described on the right side of this symbol. Hereinafter, it is similarly shown in other tables.

[Example 3: 5,6,11,12-tetraphenyl naphthacene]

Using 5,6,11,12-tetraphenyl naphthacene (rubrene) as an organic material, it was decomposed by the gas phase decomposition method according to the present invention and the microwave method as a comparative example.

First, 10 mg of rubrene was accommodated in the container described in the embodiment, and gas phase decomposition was carried out in the same manner as in Example 2. After the decomposition treatment, the inner container was taken out, nitric acid was added dropwise to heat dissolution, and the metallic impurities and/or non-metallic impurities in the inner container were recovered to obtain a measurement sample of the example.

Next, 96% sulfuric acid was added to 10 mg of rubrene, followed by microwave heating. Microwave heating was performed using a microwave sample pretreatment device (manufactured by Milstone General Corporation). After the decomposition treatment, further 68% nitric acid was added and microwave heating was repeated. After the sample solution after decomposition was subjected to heat treatment, nitric acid was added and dissolved by heating to obtain a measurement sample of a comparative example.

Each of the above measurement samples was measured by ICP-MS (manufactured by Parkin Elma). As a result, the measured values of the sample were as shown in Table 3.

[Example 4: N,N'-diphenyl-N,N'-di(m-thryl)benzidine]

Gas phase decomposition was performed using N,N'-diphenyl-N,N'-di(m-thryl)benzidine (TPD) as an organic material. 9 mg of TPD was accommodated in the container described in the embodiment, and gas phase decomposition was performed in the same manner as in Example 2. After the decomposition treatment, the inner container was taken out, nitric acid was added dropwise to heat dissolution, and the metallic impurities and/or non-metallic impurities in the inner container were recovered to obtain a measurement sample.

The measurement sample was measured by ICP-MS (manufactured by Parkin Elma). As a result, the measured values of the sample were as shown in Table 4.

[Example 5: Tris (8-hydroxyquinolinate) aluminum (III)]

Gas phase decomposition was performed using tris(8-hydroxyquinolinate)aluminum(III)(Alq3) as an organic material. 10 mg of Alq3 was accommodated in the container described in the embodiment, and gas phase decomposition was performed in the same manner as in Example 2. After the decomposition treatment, the inner container was taken out, nitric acid was added dropwise to heat dissolution, and metallic impurities and/or non-metallic impurities in the inner container were recovered to obtain a measurement sample.

The measurement sample was measured by ICP-MS (manufactured by Parkin Elma). As a result, the measured values of the sample were as shown in Table 5.

[Example 6: Comparison of sample decomposition]

The gas phase decomposition method according to the present invention and the decomposition properties of organic materials by the microwave method as a comparative example were compared. When a precipitate was generated after decomposition, it could be determined that the decomposition of the organic material was insufficient, and it was evaluated whether or not a precipitate derived from the organic material was generated after decomposition by each decomposition method.

First, in a container shown in the embodiment, 10 mg of each organic material shown in Table 6 was accommodated and gas-phase decomposed. As the decomposition liquid, a 68% nitric acid or a mixed acid solution of 68% nitric acid and 96% sulfuric acid was used. It was set as high temperature pressurization conditions by heating at 230 degreeC. After the decomposition treatment, the inner container was taken out, nitric acid was added dropwise, and the presence or absence of a precipitate in the inner container was visually checked.

Next, 68% nitric acid or a mixed acid solution of 68% nitric acid and 96% sulfuric acid was added to 10 mg of the organic material shown in Table 6, followed by microwave heating. Microwave heating was performed using a microwave sample pretreatment device (made by Milstone General Corporation). After the sample solution after decomposition was heat-treated, nitric acid was added to dissolve by heating, and it was made into a constant volume with water, and the presence or absence of a precipitate was visually checked.

Table 6 shows the results. In Table 6, the case where no precipitate was formed is indicated as'○', and the case where the precipitate was formed was indicated as'×'.

The present invention is not limited to each of the above-described embodiments, and various modifications are possible within the scope described in the claims, and the technical scope of the present invention is also for an embodiment obtained by appropriately combining the technical means disclosed in each of the other embodiments. Included in

〈Industrial availability〉

The present invention can be used for analysis of metallic impurities and/or non-metallic impurities in organic materials used in various fields.

1 External container (closed container)
2 External cylinder
3 inner tube
4 inner container
5 organic material
6 Decomposition liquid

Claims (11)

A preparation step of accommodating the organic material and the decomposition liquid in a sealed container so that the organic material and the decomposition liquid for decomposing the organic material do not come into contact,
And a decomposition step in which the inside of the sealed container is pressurized by heating, and the organic material is sublimated by gas phase decomposition using decomposition liquid gas in which the decomposition liquid vaporizes. The method of claim 1,
The vapor phase decomposition method, wherein the organic material contained in the sealed container is 0.001 mg or more and 500 mg or less. The method according to claim 1 or 2,
From the organic material decomposed in the decomposition step, a measurement sample containing at least one element belonging to an alkali metal, an alkaline earth metal, a lanthanide, an actinoid, a transition metal, a boron group, a carbon group, a nicktogen or a chalcogen Gas phase decomposition method, characterized in that it further comprises a recovery step of recovering. A preparation step of accommodating the organic material and the decomposition solution in a sealed container so that the organic material and the decomposition solution for decomposing the organic material do not come into contact, and the organic material is vaporized by heating the sealed container to pressurize the organic material. By a gas phase decomposition method including a decomposition step of sublimating by gas phase decomposition with one decomposition liquid gas
An analysis method for organic material comprising an analysis step of detecting impurities in a measurement sample obtained by decomposing the organic material. A preparation step of accommodating the organic material and the decomposition liquid in a sealed container so that the organic material and the decomposition liquid for decomposing the organic material do not come into contact, and a decomposition liquid in which the decomposition liquid is vaporized by heating the sealed container By a gas phase decomposition method including a decomposition step of sublimating the organic material with gas by gas phase decomposition,
An analysis process for detecting impurities in a measurement sample obtained by decomposing an organic material, and an extraction process for extracting an organic material in which the amount of the impurities detected in the analysis process is less than or equal to a predetermined reference amount. Management method. A preparation step of accommodating the organic material and the decomposition liquid in a sealed container so that the organic material and the decomposition liquid for decomposing the organic material do not come into contact,
Measurement obtained by decomposing the organic material by a gas phase decomposition method including a decomposition step of sublimating the organic material by gas phase decomposition by pressurization by heating the inside of the sealed container and the decomposition liquid gas vaporized by the decomposition liquid An analysis process for detecting impurities in the sample, and
An extraction step of extracting an organic material whose amount of impurities detected in the analysis step is less than or equal to a predetermined reference amount,
And a manufacturing process of manufacturing an organic electronic device using the organic material extracted in the extraction process. As a container for decomposing organic materials,
An external container having a closed space inside for accommodating a decomposition solution for decomposing the organic material, and having a pressure resistance to a pressure for decomposing the organic material,
An inner container provided in the outer container, formed of a material resistant to the decomposition liquid, and receiving the organic material from an open top,
The inner container is provided so that when the decomposition liquid is accommodated in the outer container, the decomposition liquid does not contact with the inner wall thereof,
A container, further comprising a heating device for heating the entire container. The method of claim 1,
The decomposition liquid is an acid solution containing at least one acid selected from the group consisting of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, and perchloric acid, or an aqueous solution of at least one of the acids and water. Way.
The method of claim 4,
The decomposition liquid is an acid solution containing at least one acid selected from the group consisting of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, and perchloric acid, or an aqueous solution of at least one of the acids and water. Method of analysis.
The method of claim 5,
The decomposition liquid is an acid solution containing at least one acid selected from the group consisting of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, and perchloric acid, or an aqueous solution of at least one of the acids and water. How to make the device.
The method of claim 6,
The decomposition liquid is an acid solution containing at least one acid selected from the group consisting of hydrofluoric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, and perchloric acid, or an aqueous solution of at least one of the acids and water. How to make the device.

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