WO2024106303A1

WO2024106303A1 - Iodohydrocarbon mixture, method for producing iodohydrocarbon mixture, and container filled with iodohydrocarbon mixture

Info

Publication number: WO2024106303A1
Application number: PCT/JP2023/040411
Authority: WO
Inventors: 弘康佐藤; 宏貴山内
Original assignee: 住友精化株式会社
Priority date: 2022-11-18
Filing date: 2023-11-09
Publication date: 2024-05-23

Abstract

This iodohydrocarbon mixture contains an iodohydrocarbon and moisture. The moisture concentration in this iodohydrocarbon mixture is 140 ppm by mass or less.

Description

Iodinated hydrocarbon mixture, method for producing the same, and container for filling the same

The present invention relates to an iodinated hydrocarbon mixture, a method for producing an iodinated hydrocarbon mixture, and a container for filling the iodinated hydrocarbon mixture.

Iodohydrocarbons are compounds that are widely used industrially as chemical raw materials and solvents. In recent years, they have also come to be used in various processes in semiconductor manufacturing. Unlike the plastic and glass containers that are generally used as storage containers for chemical raw material applications, metal containers such as metal high-pressure containers (cylinders) or metal canisters are used as storage containers for these iodinated hydrocarbons used in various processes in semiconductor manufacturing.

However, it is known that the purity of iodinated hydrocarbons can decrease depending on factors such as storage conditions, and this property remains a major issue for the industry.
As a solution to this problem, for example, Patent Document 1 listed below discloses a method of arranging a stabilizing material for iodinated hydrocarbons inside an iodinated hydrocarbon storage container, the stabilizing material having a contact surface with the iodinated hydrocarbon liquid and a contact surface with the iodinated hydrocarbon gas made of metallic copper, metallic silver, or the like.

JP 2005-24073 A

Incidentally, when iodinated hydrocarbons are used, for example, in the application of forming semiconductor films, they may be stored in metal containers at high temperatures (for example, at a temperature of 100° C. or higher) for the purpose of increasing the vapor pressure in order to ensure the supply of iodinated hydrocarbons to semiconductor manufacturing equipment or the like.
However, the iodinated hydrocarbon described in Patent Document 1 has room for improvement in terms of suppressing deterioration of the quality of the iodinated hydrocarbon, particularly at high temperatures.
In addition, since iodinated hydrocarbons contain trace amounts of water and other impurities, strictly speaking they are mixtures rather than pure substances. For this reason, in this specification, "iodinated hydrocarbons" will be referred to as "iodinated hydrocarbon mixtures."

The present invention was made in consideration of the above problems, and aims to provide an iodized hydrocarbon mixture that can suppress quality deterioration even when stored at high temperatures, a method for producing the iodized hydrocarbon mixture, and a container for filling the iodized hydrocarbon mixture.

As a result of extensive research into solving the above problems, the inventors discovered that the above problems could be solved by reducing the water concentration in the iodinated hydrocarbon mixture to a specific value or less, and thus completed the present invention.

That is, one aspect of the present invention provides an iodohydrocarbon mixture containing an iodohydrocarbon and moisture, wherein the concentration of the moisture in the iodohydrocarbon mixture is 140 ppm by mass or less.
This iodinated hydrocarbon mixture can suppress deterioration in quality even when stored at high temperatures.

Another aspect of the present invention provides a method for producing the above-mentioned iodinated hydrocarbon mixture, comprising a dehydration step of dehydrating a raw material containing iodinated hydrocarbon and moisture.
According to this method for producing an iodinated hydrocarbon mixture, it is possible to produce an iodinated hydrocarbon mixture that can suppress deterioration in quality even when stored at high temperatures.

Yet another aspect of the present invention provides an iodo-hydrocarbon mixture-filled container comprising a container and an iodo-hydrocarbon mixture filled in the container, the iodo-hydrocarbon mixture containing an iodo-hydrocarbon and moisture, wherein the moisture concentration in the iodo-hydrocarbon mixture is 140 ppm by mass or less.
According to this container filled with an iodohydrocarbon mixture, deterioration in the quality of the iodohydrocarbon mixture can be suppressed even when the container is filled with the iodohydrocarbon mixture and stored at high temperatures.

In the above iodinated hydrocarbons, the hydrocarbon group may have 1 to 4 carbon atoms and 1 to 3 iodines.

The iodinated hydrocarbon may be an iodinated saturated hydrocarbon.

The iodinated hydrocarbon may be diiodomethane.

In the present invention, iodinated hydrocarbon refers to a compound represented by RI (R represents a hydrocarbon group, and I represents iodine), or a compound in which some of the hydrogen atoms contained in R of this compound have been replaced with iodine.

The present invention provides an iodized hydrocarbon mixture that can suppress quality deterioration even when stored at high temperatures, a method for producing the iodized hydrocarbon mixture, and a container for filling the iodized hydrocarbon mixture.

1 is a partial cross-sectional view showing a schematic diagram of one embodiment of an iodinated hydrocarbon mixture filling container of the present invention.

The following describes in detail an embodiment of the present invention.

<Iodohydrocarbon mixture>
First, an embodiment of an iodinated hydrocarbon mixture according to one aspect of the present invention will be described.
The iodinated hydrocarbon mixture contains an iodinated hydrocarbon and moisture. The concentration of moisture in the iodinated hydrocarbon mixture is 140 ppm by mass or less.
This iodinated hydrocarbon mixture can suppress deterioration in quality even when stored at high temperatures.

　Hereafter, we will explain in detail about iodinated hydrocarbons and moisture.

(Iodohydrocarbons)
Although the iodinated hydrocarbon is not particularly limited, for example, when the iodinated hydrocarbon is used for the purpose of forming a semiconductor film, the iodinated hydrocarbon is preferably an iodinated hydrocarbon having a high vapor pressure from the viewpoint of handling. As the iodinated hydrocarbon having a high vapor pressure, an iodinated hydrocarbon having a hydrocarbon group with a carbon number of 1 to 8 and an iodine number of 1 to 4 is preferable, and an iodinated hydrocarbon having a hydrocarbon group with a carbon number of 1 to 4 and an iodine number of 1 to 3 is more preferable. These iodinated hydrocarbons exist in a liquid or solid state at room temperature, but among the above-mentioned iodinated hydrocarbons having a high vapor pressure, an iodinated hydrocarbon that exists in a liquid state at room temperature is preferable from the viewpoint of handling.
The iodinated hydrocarbon may be an iodinated saturated hydrocarbon or an iodinated unsaturated hydrocarbon, i.e., the hydrocarbon group of the iodinated hydrocarbon may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
An example of the iodinated saturated hydrocarbon is diiodomethane.

(moisture)
The water concentration of the iodinated hydrocarbon may be 140 ppm by mass or less, but is preferably 120 ppm by mass or less, more preferably 100 ppm by mass or less, even more preferably 80 ppm by mass or less, still more preferably 50 ppm by mass or less, and particularly preferably 30 ppm by mass or less.
The water concentration of the iodinated hydrocarbon may be 0.1 ppm by mass or more, 0.5 ppm by mass or more, 1.0 ppm by mass or more, 5.0 ppm by mass or more, 10 ppm by mass or more, 15 ppm by mass or more, or 20 ppm by mass or more.

Here, the water concentration in the iodinated hydrocarbon mixture is a value measured by a Karl Fischer moisture meter. Specifically, when measuring the water concentration in the iodinated hydrocarbon mixture, a moisture concentration meter sold by a measuring device manufacturer can be used. An example of such a moisture concentration meter is the coulometric titration Karl Fischer moisture meter manufactured by Hiranuma Corporation.

<Method for producing iodinated hydrocarbon mixture>
Next, an embodiment of a method for producing an iodinated hydrocarbon mixture according to another aspect of the present invention will be described.

The method for producing an iodized hydrocarbon mixture according to the present invention is a method for producing an iodized hydrocarbon mixture containing iodized hydrocarbons and moisture, the moisture concentration of which is 140 mass ppm or less, and includes a dehydration step of dehydrating a raw material containing iodized hydrocarbons and moisture.

(Dehydration process)
The raw material may be a mixture containing an iodinated hydrocarbon and water, and the water concentration in the raw material is not particularly limited.
The moisture concentration in the raw material may be 1000 ppm by mass or less, or may be 200 ppm by mass or less.

The dehydration method is not particularly limited as long as it is a method capable of reducing the moisture concentration in the raw material, which is the iodinated hydrocarbon mixture before dehydration. Examples of the dehydration method include distillation of the iodinated hydrocarbon mixture before dehydration and a method of dehydrating the iodinated hydrocarbon mixture before dehydration by contacting it with a moisture adsorbent.

The type of moisture adsorbent is not particularly limited, but examples of the moisture adsorbent include zeolite, activated carbon, and silica gel. Here, the type of zeolite is not particularly limited, and the molar ratio of _SiO2 and _Al2O3 contained in the _zeolite ( _SiO2 _/ _Al2O3 ratio) and the pore size of the zeolite are also not particularly limited. However, the zeolite is preferably a zeolite that does not react with iodinated hydrocarbons. Such a zeolite is, for example, molecular sieve 4A.

After the dehydration step, the dehydrated raw material may be mixed with water to adjust the water concentration in the iodinated hydrocarbon mixture.

The water concentration in the iodinated hydrocarbon mixture finally obtained by the method for producing an iodinated hydrocarbon mixture according to the present invention may be 140 ppm by mass or less, but the water concentration is preferably 120 ppm by mass or less, more preferably 100 ppm by mass or less, even more preferably 80 ppm by mass or less, still more preferably 50 ppm by mass or less, and particularly preferably 30 ppm by mass or less.
The water concentration in the iodinated hydrocarbon mixture may be 0.1 ppm by mass or more, 0.5 ppm by mass or more, 1.0 ppm by mass or more, 5.0 ppm by mass or more, 10 ppm by mass or more, 15 ppm by mass or more, or 20 ppm by mass or more.

<Container filled with iodinated hydrocarbon mixture>
Next, an embodiment of a container filled with an iodinated hydrocarbon mixture according to yet another aspect of the present invention will be described with reference to Fig. 1. Fig. 1 is a partial cross-sectional view that shows a schematic view of one embodiment of a container filled with an iodinated hydrocarbon mixture according to the present invention.

As shown in Fig. 1, the iodinated hydrocarbon mixture filling container 100 includes a container 10 and an iodinated hydrocarbon mixture 20 filled in the container 10. The iodinated hydrocarbon mixture 20 contains iodinated hydrocarbons and moisture, and the moisture concentration in the iodinated hydrocarbon mixture 20 is 140 ppm by mass or less.
According to this iodinated hydrocarbon mixture filled container 100, even if the container 10 is filled with the iodinated hydrocarbon mixture 20 and stored at high temperatures, deterioration in the quality of the iodinated hydrocarbon mixture 20 can be suppressed.

The container 10 will now be described.
<Container>
Although there are no particular limitations on the material constituting the container 10, it is preferable to use a material that can ensure airtightness and has excellent pressure resistance. Examples of such materials include alloy steels such as manganese steel, stainless steel, and chromium-molybdenum steel, carbon steel, and metals such as aluminum alloys, and composite materials such as fiber-reinforced plastics.

The container 10 includes a cylindrical body 11 having an inner surface 10a. Specifically, as shown in Fig. 1, the container 10 further includes a bottom 12 provided at the lower end of the cylindrical body 11, a lid 13 provided at the upper end side of the cylindrical body 11, and a valve 14 provided on the lid 13. In this embodiment, the valve 14 includes a valve for filling the iodinated hydrocarbon mixture 20 and a valve for discharging the iodinated hydrocarbon mixture 20. The valve 14 may be a single valve. In this case, the valve 14 serves both as a valve for filling the iodinated hydrocarbon mixture 20 and a valve for discharging the iodinated hydrocarbon mixture 20.
The container 10 may be constructed of a single layer, or may be constructed of a laminate of two or more layers.
The container 10 is preferably pressure resistant, so that the iodinated hydrocarbon mixture 20 can be stored in a pressurized state.

<Method of manufacturing container filled with iodinated hydrocarbon>
Next, an embodiment of the method for producing a container filled with an iodinated hydrocarbon mixture of the present invention will be described.

The method for manufacturing the container 100 filled with an iodinated hydrocarbon mixture includes a step of filling the container 10 with an iodinated hydrocarbon mixture 20 to manufacture the container 100 filled with an iodinated hydrocarbon mixture.

In general, iodized hydrocarbon mixtures are highly reactive. For this reason, it is preferable that the iodized hydrocarbon mixture 20 is filled in a light-shielded and dehumidified environment to prevent the inclusion of air when filling the container. For example, the iodized hydrocarbon mixture 20 is introduced into the container 10 in an inert gas atmosphere, and the container 10 is sealed and filled with the iodized hydrocarbon mixture 20. From the viewpoint of preventing the inclusion of air when filling the container 10, it is more preferable to connect the iodized hydrocarbon mixture supply source and the container 10 with piping and fill the container 10 with the iodized hydrocarbon mixture 20 in a closed system that minimizes the possibility of air inclusion. For example, the iodized hydrocarbon mixture supply source may be connected with piping to the container 10 that has been previously depressurized, and the iodized hydrocarbon mixture 20 may be filled into the container 10 by utilizing the pressure difference between the container 10 and the iodized hydrocarbon mixture supply source.

After the iodinated hydrocarbon mixture 20 is filled into the container 10, an inert gas may be sealed inside the container 10 and the iodinated hydrocarbon mixture 20 may be stored under normal pressure or under pressure, or an iodinated hydrocarbon mixture supply source may be connected by piping to the container 10 in which an inert gas has already been sealed, and the iodinated hydrocarbon mixture 20 may be pumped with the inert gas and filled into the container 10.

The present invention will be explained in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

Example 1
The diiodomethane mixture as the raw material was dehydrated by contacting it with molecular sieve 4A (manufactured by Tosoh Corporation, product name: Zeorum A-4) to prepare a mixture of diiodomethane as an iodinated hydrocarbon and water as a diiodomethane mixture. The water concentration in the diiodomethane mixture was measured with a Karl Fischer moisture meter (manufactured by HIRANUMA Corporation, product name: AQ-2200S, coulometric titration method) and was found to be 24 ppm by mass, as shown in Table 1.

Example 2
The diiodomethane mixture obtained in Example 1 was mixed with water to prepare a diiodomethane mixture having a water concentration of 47 ppm by mass, as shown in Table 1.

Example 3
The diiodomethane mixture obtained in Example 1 was mixed with water to prepare a diiodomethane mixture having a water concentration of 94 ppm by mass as shown in Table 1.

(Comparative Example 1)
As shown in Table 1, a diiodomethane mixture having a water concentration of 165 ppm by mass was prepared.

<Preparation of test samples>
First, a metal container was prepared as follows.
First, a cylindrical pipe made of SUS316L (inner diameter 6.35 mm × length 100 mm × thickness 1.0 mm) with female nuts on both ends was prepared as a cylindrical body, and a SUS316 cap was attached to the lower end of the pipe as a bottom part using a Swagelok (registered trademark) tube joint. In this way, the main body of the metal container was obtained.
Next, 0.75 mL of the diiodomethane mixture prepared as described above (about half the volume of the container) was placed in the main body of the metal container under a dry _N2 atmosphere, and then a SUS316 cap was attached to the top end of the pipe as a lid for the main body of the metal container using a Swagelok (registered trademark) tube joint to seal it. Thus, a test sample was obtained.

<Confirmation test for quality deterioration prevention effect>
The above test samples were subjected to a test for confirming the effect of inhibiting deterioration of quality caused by a diiodomethane mixture as described below.
That is, first, the purity of the diiodomethane mixture, the concentration of iodomethane in the diiodomethane mixture, and the concentrations of other components (components other than diiodomethane and iodomethane) of the above test samples were measured as the purity or concentration before storage using a GC-FID (manufactured by Shimadzu Corporation, product name: GC-2014). The results are shown in Table 1.
Next, the test sample was placed in a constant temperature bath and stored at 130° C. After storing the test sample for 13 days, it was removed from the constant temperature bath and allowed to cool to 20-25° C., after which the purity of the diiodomethane mixture, the concentration of iodomethane in the diiodomethane mixture, and the concentrations of other components (components other than diiodomethane and iodomethane) were measured using the GC-FID. The results are shown in Table 1.

The purity of the diiodomethane mixture is calculated according to the following formula.
Purity of diiodomethane mixture (%)
= 100% - iodomethane concentration (%) - other component concentration (%)
Here, the unit % of purity and concentration is GC area % (area % of the obtained GC chart).

As shown in Table 1, in Examples 1 to 3, the increase in iodomethane concentration was smaller before and after storage at high temperatures than in Comparative Example 1, and the decrease in purity of the diiodomethane mixture was smaller. This indicates that the deterioration of the quality of the diiodomethane mixture is suppressed even when stored at high temperatures.

This confirms that the iodinated hydrocarbon mixture of the present invention can suppress quality deterioration even when stored at high temperatures.

10...container, 10a...inner surface, 11...cylindrical body, 12...bottom, 13...lid, 14...valve, 20...iodinated hydrocarbon mixture, 100...container filled with iodinated hydrocarbon.

Claims

An iodinated hydrocarbon mixture containing an iodinated hydrocarbon and moisture,
The iodinated hydrocarbon mixture has a moisture concentration of 140 ppm by mass or less.
The iodized hydrocarbon mixture according to claim 1, wherein the number of carbon atoms in the hydrocarbon group in the iodized hydrocarbon is 1 to 4, and the number of iodines is 1 to 3.
The iodinated hydrocarbon mixture of claim 1, wherein the iodinated hydrocarbon is an iodinated saturated hydrocarbon.
The iodinated hydrocarbon mixture of claim 3, wherein the iodinated saturated hydrocarbon is diiodomethane.
2. A method for producing the iodinated hydrocarbon mixture of claim 1, comprising the steps of:
A method for producing an iodinated hydrocarbon mixture, comprising a dehydration step of dehydrating a raw material containing iodinated hydrocarbon and moisture.
The method for producing an iodized hydrocarbon mixture according to claim 4, wherein the number of carbon atoms in the hydrocarbon group in the iodized hydrocarbon is 1 to 4 and the number of iodines is 1 to 3.
The method for producing an iodinated hydrocarbon mixture according to claim 6, wherein the iodinated hydrocarbon is an iodinated saturated hydrocarbon.
The method for producing an iodized hydrocarbon mixture according to claim 7, wherein the iodized saturated hydrocarbon is diiodomethane.
A container;
an iodinated hydrocarbon mixture filled container comprising an iodinated hydrocarbon mixture containing an iodinated hydrocarbon and water, the iodinated hydrocarbon mixture being filled in the container,
A container filled with an iodinated hydrocarbon mixture, wherein the water concentration in the iodinated hydrocarbon mixture is 140 ppm by mass or less.
The container for filling an iodized hydrocarbon mixture according to claim 9, wherein the number of carbon atoms in the hydrocarbon group in the iodized hydrocarbon is 1 to 4, and the number of iodines is 1 to 3.
The container for filling an iodinated hydrocarbon mixture according to claim 10, wherein the iodinated hydrocarbon is an iodinated saturated hydrocarbon.
The container filled with an iodinated hydrocarbon mixture according to claim 11, wherein the iodinated saturated hydrocarbon is diiodomethane.