JP6208929B2 - Package formed by packaging an ionic compound containing a fluorine atom or an ionic compound-containing composition containing a fluorine atom - Google Patents

Description

  The present invention relates to a package in which an ionic compound containing a fluorine atom is packaged with good storage stability.

  Ionic compounds containing fluorine atoms, such as salts of fluorosulfonylimide, are electrolytes, additives to fuel cell electrolytes, selective electrophilic fluorinating agents, photoacid generators, thermal acid generators, near-infrared absorbing dyes It is known to be useful as an antistatic agent, a reaction catalyst, etc. (for example, Patent Document 1).

  An ionic compound containing a fluorine atom tends to generate hydrofluoric acid upon hydrolysis. Hydrofluoric acid is a strong acid and may damage the storage container. In addition, since the presence of water has an adverse effect in battery applications and the like, the amount of water in the ionic compound must be reduced as much as possible.

International Publication No. 2009/123328 Pamphlet

  As described above, ionic compounds containing fluorine atoms may generate hydrofluoric acid due to the presence of water. However, when these ionic compounds are stored or transported, they may be stored or transported in any form. However, the conventional technique does not provide a solution for such a problem. Therefore, in the present invention, it has been raised as an object to find a package that can store or transport an ionic compound containing a fluorine atom in an environment that does not cause hydrolysis.

  The present invention is a package formed by packaging a ionic compound containing a fluorine atom or a composition containing an ionic compound containing a fluorine atom with a packaging material, the packaging material comprising at least one metal layer. It is a package of the ionic compound characterized by including.

  The metal layer is preferably an aluminum layer and / or a stainless steel layer.

  Moreover, it is also preferable that the water content in an ionic compound or a composition is 1000 ppm or less.

  In a preferred embodiment of the present invention, the ionic compound is a fluorosulfonylimide represented by the following general formula (I) or a composition containing a fluorosulfonylimide represented by the following general formula (I). is there.

（式（Ｉ）中、Ｍは有機または無機カチオン、Ｘは有機基を表す。）

(In formula (I), M represents an organic or inorganic cation, and X represents an organic group.)

  In the above general formula (I), M is an alkali metal ion or alkaline earth metal ion, X is F, and M is Li are all preferred embodiments of the present invention.

  It is preferable that the said package is preserve | saved at 50 degrees C or less.

  In the present invention, an ionic compound containing a fluorine atom having a moisture content of 1000 ppm or less, or an ionic compound containing a fluorine atom having a moisture content of 1000 ppm or less, which is packaged by a packaging material containing at least one metal layer. Also included are compound-containing compositions.

  According to the present invention, hydrolysis of ionic compounds containing fluorine atoms can be suppressed as much as possible, and these ionic compounds can be stored with good stability.

  The package of the present invention is obtained by packaging an ionic compound containing a fluorine atom or a composition containing the ionic compound in a packaging material containing at least one metal layer. That is, the package of the present invention means a product distributed in the market.

[Packaging materials and packages]
The packaging material for packaging the ionic compound containing a fluorine atom of the present invention or a composition containing the ionic compound (ionic compound-containing composition) includes at least one metal layer. This metal layer suppresses moisture and water from entering from the outside. As the metal layer, an aluminum layer and / or a stainless steel layer is preferable. When the packaging material is a flexible laminate, a laminate having an aluminum layer is preferable, and a sealable bag formed from a laminate in which both sides of the aluminum layer are protected with a resin film is preferable. In this case, usable resin films include polyolefin such as polyethylene and polypropylene; polyester such as polyethylene terephthalate and polybutylene terephthalate; nylon; polystyrene and the like. When the packaging material is a laminate including an aluminum layer, it may be composed of any number of layers, and three or more layers are preferable.

  Although the total thickness as a laminated body is not specifically limited, 50 micrometers-200 micrometers are preferable, and about 5 micrometers-20 micrometers are preferable among these aluminum layers. If the aluminum layer is too thin, the film strength may decrease and pinholes may occur, and if it is too thick, the flexibility of the film will decrease and it will be difficult to handle. The production of the above laminate includes a method of attaching a resin film to an aluminum foil through an adhesive as appropriate, a method of laminating the resin on the aluminum foil while extruding the resin, depositing aluminum on the resin film, and further laminating the resin film. The method etc. are mentioned, It does not specifically limit. Moreover, as a method of sealing these laminated bodies, means such as heat sealing and ultrasonic welding are used using a chuck formed in advance in a bag.

  In addition, when transferring an ionic compound containing a fluorine atom or an ionic compound-containing composition on a larger scale, the packaging material may be a cardboard box or a plastic case containing a bag made of the above laminate. it can. Furthermore, when transporting on a large scale of 100 kg or more, a packaging material such as a drum can made of stainless steel can be employed.

  From the viewpoint of moisture proofing, it is preferable to use a plurality of bags, and it is preferable to fill them with dry inert gas or dry air, or to make a vacuum. A resin bag, a resin container, or a glass container may be used inside or outside the metal layer. Examples of the resin that can be used for the resin bag or the resin container include fluororesin, polyethylene, polypropylene, polystyrene, polycarbonate, nylon, polyester (polyethylene terephthalate, etc.), and the like. Good. In particular, when the ionic compound containing a fluorine atom or the composition containing this ionic compound (ionic compound-containing composition) is in a liquid state, a resin container or a glass container is used inside the metal layer. It is preferable.

  In addition, a package protected by a plurality of bags can be further stored in a drum can, a cardboard box, a plastic case, etc. for storage and transport, or the bag can be damaged from the outside and the ionic compound can absorb moisture. This is a preferred embodiment. Such an embodiment is also included in the package of the present invention.

  The package of this invention points out the thing of the state in which the ionic compound containing a fluorine atom or the ionic compound containing composition was packaged with the said packaging material. Since the package of the present invention prevents moisture and water from entering from the outside, hydrolysis of the ionic compound can be suppressed. Furthermore, as a result of the suppression of hydrolysis, the generation of hydrofluoric acid is also suppressed, so that the deterioration of the packaging material itself can be prevented, and the ionic compound or the ionic compound-containing composition is almost in the state immediately before packaging. It can be stored and transported as it is.

  In order to prevent hydrolysis and thermal decomposition, the package of the present invention is desirably stored or transported at a relatively low temperature, preferably stored (transferred) at 50 ° C. or less, more preferably 40 ° C. or less, and still more preferably. Is preferably stored (transferred) at 30 ° C. or lower. When the temperature exceeds 50 ° C., the progress of hydrolysis and thermal decomposition is accelerated. Therefore, it is preferable to perform storage and transport in extreme heat (especially in a car) or in a tropical region while cooling to 50 ° C. or less.

[Packaging method of ionic compound containing fluorine atom]
When the ionic compound containing a fluorine atom is a powder at room temperature, the packaging operation is an operation of charging the packaging material by inserting the powder into a resin container, bag or drum. For ionic compounds with high hygroscopicity, packaging is performed in a dry room. It is preferable to package after adjusting the water content in the ionic compound to 1000 ppm (mass basis; the same shall apply hereinafter) or less. More preferably, it is 800 ppm or less, More preferably, it is 500 ppm or less, Most preferably, it is 100 ppm or less. If the initial moisture is 1000 ppm or less, the generation of F ^- and SO ₄ ^2- is reduced, the decomposition of the ionic compound is suppressed even during long-term storage (transfer), and corrosion of the container can be prevented. Furthermore, when the initial moisture is 100 ppm or less, the present inventors have found that hydrolysis of the ionic compound hardly occurs if it is possible to prevent external moisture from entering the package after packaging. . Therefore, at least the drying step of the ionic compound and the subsequent packaging step are preferably performed in a closed system (water-free system) so that the ionic compound before packaging does not absorb moisture. Of course, it is desirable to carry out the synthesis process and the purification process in a closed system.

  Specifically, after the ionic compound is sufficiently dried to have a water content of 1000 ppm or less, the obtained ionic compound may be charged into the packaging material in a dry room or glove box in a dry environment. After charging, it is preferable that the inside of the packaging material is sealed with dry air or a dry inert gas, or vacuumed. When a double or triple resin bag is placed inside the packaging material of the present invention, the ionic compound (or ionic compound-containing composition) is enclosed in the innermost bag as described above. This bag is sealed in the next bag, and the resulting double bag is sealed together with dry air and dry inert gas in the packaging material having the metal layer of the present invention. Dry air or dry inert gas may be sealed in the second bag, and the bag may be four or more layers. Moreover, you may put a bag in a drum can. As a dry environment, the dew point is preferably -50 ° C or lower. More preferably, the dew point is −60 ° C. or lower. In addition, when encapsulating the ionic compound (or ionic compound-containing composition), if the moisture of the ionic compound (or ionic compound-containing composition) can be maintained at 1000 ppm or less, it is temporarily non-drying environment. You may have the process in.

[Packaging Method for Composition Containing Ionic Compound Containing Fluorine Atom]
The ionic compound-containing composition containing a fluorine atom only needs to contain an ionic compound having a fluorine atom, and may contain other compositions. When the content is a composition containing an ionic compound having a fluorine atom, the ionic compound having a fluorine atom in the composition is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably. Is 8% by mass or more, particularly preferably 10% by mass or more. Other compositions are not particularly limited, such as solvents, other ionic compounds, and other powders, and can be appropriately blended depending on the application. When the ionic compound containing a fluorine atom is a powder at normal temperature, it becomes easy to handle by dissolving in a solvent, which is a particularly preferred embodiment. As a solvent, it is more preferable to use an aprotic solvent. Specifically, carbonate solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate; dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3- Ether solvents such as dioxane and 4-methyl-1,3-dioxolane; ester solvents such as methyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl propionate, γ-butyrolactone, γ-valerolactone; Amide solvents such as N, N-dimethylformamide; Nitrile solvents such as acetonitrile, butyronitrile, isobutyronitrile, valeronitrile, and benzonitrile; Nitro such as nitromethane and nitrobenzene System solvents; sulfur solvents such as sulfolane, 3-methylsulfolane, dimethyl sulfoxide; N-methyloxazolidinone and the like. These solvents may be used alone or in combination of two or more. The solvent is preferably a dry solvent or an anhydrous solvent.

It is preferable to package after adjusting the water content in the composition to 1000 ppm or less. More preferably, it is 800 ppm or less, More preferably, it is 500 ppm or less, Most preferably, it is 100 ppm or less. If the initial moisture is 1000ppm or less, generation of F ^- and SO ₄ ^2- is reduced, decomposition of ionic compounds in the composition is suppressed even during long-term storage (transfer), and corrosion of the container is also prevented. Can do. Furthermore, when the initial water content is 100 ppm or less, hydrolysis of the ionic compound in the composition hardly occurs if it is possible to prevent external moisture from entering the package after packaging. Therefore, at least the ionic compound drying process, the packaging process, and the mixing / dissolving process with other compositions should be performed in a closed system (water-free system) so that the ionic compound-containing composition before packaging does not absorb moisture. preferable. Of course, it is desirable to carry out the synthesis process and the purification process in a closed system.

  Specifically, after sufficiently drying the ionic compound to reduce the water content to 1000 ppm or less, the composition is obtained by mixing or dissolving the obtained ionic compound with other components in a dry room or glove box in a dry environment. It is better to insert the product into the packaging material. After charging, it is preferable that the inside of the packaging material is sealed with dry air or a dry inert gas, or vacuumed.

[Preservation method]
In order to prevent hydrolysis and thermal decomposition, the package of the present invention is desirably stored or transported at a relatively low temperature, preferably stored (transferred) at 50 ° C. or less, more preferably 40 ° C. or less, and still more preferably. Is preferably stored (transferred) at 30 ° C. or lower. When the temperature exceeds 50 ° C., the progress of hydrolysis and thermal decomposition is accelerated. Therefore, it is preferable to perform storage and transport in extreme heat (especially in a car) or in a tropical region while cooling to 50 ° C. or less. By keeping the storage temperature to 50 ° C. or less, for a long time such as 3 months and 6 months, F ^- the occurrence of or SO ₄ ^2-like decomposition products that cause the nonwoven can be suppressed. In particular, when used as an ion conductive material for various electrochemical devices, the content of these decomposition products is preferably less than 4000 ppm. For this purpose, the storage temperature of the package is preferably kept at 50 ° C. or lower. More preferably, the content of the decomposition product is less than 1000 ppm. For this purpose, it is necessary to store at 30 ° C. or lower.

[Ionic compounds containing fluorine atoms]
In the package of the present invention, what is packaged by the packaging material and becomes the contents is an ionic compound having a fluorine atom or an ionic compound-containing composition. Since an ionic compound having a fluorine atom is hydrolyzed by moisture in the air and generates hydrofluoric acid, it is necessary to prevent moisture permeation during storage and transportation.

Specific examples of the ionic compound containing a fluorine atom include alkali metal salts and alkaline earth metal salts of trifluoromethanesulfonic acid such as LiCF ₃ SO ₃ , NaCF ₃ SO ₃ , KCF ₃ SO ₃ ; LiC (CF ₃ SO ₂ ) ₃ , LiN (CF ₃ CF ₂ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN (FSO ₂ ) _{2 and} other alkali metal salts and alkaline earth metal salts of perfluorosulfonic acid imides; LiPF alkali metal salts of LiAsF _6, LiSbF _6, NaAsF _6, and the like; tetrafluoroborate salt LiBF _4, NaBF _4, and the like; _6, NaPF _6, alkali metal salts and alkaline earth metal salts of Hexal fluoro phosphate KPF ₆ and the like; _{(C 2 H 5) 4 NBF} 4, (C 2 H 5) 3 (CH 3) quaternary ammonium salts of tetrafluoroborate of ₄ such _{NBF, (C 2 H 5)} 4 NP Quaternary ammonium salts of _6, such _{as; (CH 3) 4 P ·} BF 4, include quaternary phosphonium salts such as _{(C 2 H 5) 4 P} · BF 4.

  As an ionic compound containing a fluorine atom, a fluorosulfonylimide salt represented by the following general formula (I) is suitable as a packaging object of the present invention. This is because these fluorosulfonylimide salts have high hygroscopicity and may generate sulfuric acid in addition to hydrofluoric acid by hydrolysis, and it is necessary to package with a packaging material that can reliably prevent moisture permeation. In the case of fluorosulfonylimide, whether or not hydrolysis has occurred can be determined by quantitative determination (ion chromatography) of fluorine ions and sulfate ions.

（式（Ｉ）中、Ｍは有機または無機カチオン、Ｘは有機基を表す。）

(In formula (I), M represents an organic or inorganic cation, and X represents an organic group.)

  Examples of the organic group represented by X include a haloalkyl group, a cyano group, an alkoxy group, a nitro group, a hydroxyl group, an aliphatic group, and an aromatic group. X is preferably fluorine or a fluorinated alkyl group having 1 to 6 carbon atoms. When X is fluorine, the above formula (I) represents a bis (fluorosulfonyl) imide salt, and when X is a fluorinated alkyl group, N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide salt and Become. “Fluoroalkyl” means an alkyl group having 1 to 6 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms. For example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group. Group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group and the like are included.

As the organic cation, an onium cation is preferable. As the onium cation, general formula (II); L ⁺ -Rs (wherein L represents C, Si, N, P, S or O. R is the same or different, and represents a hydrogen atom, a fluorine atom, Or when it is an organic group and R is an organic group, these may be bonded to each other, s is 2, 3 or 4, and is a value determined by the valence of the element L. The bond represented by R may be a single bond or a double bond.

  The “organic group” represented by R means a group having at least one carbon atom. The “group having at least one carbon atom” only needs to have at least one carbon atom, and may have another atom such as a halogen atom or a hetero atom, a substituent, or the like. Good. Specific examples of the substituent include an amino group, an imino group, an amide group, a group having an ether bond, a group having a thioether bond, an ester group, a hydroxyl group, an alkoxy group, a carboxyl group, a carbamoyl group, a cyano group, and a disulfide. Group, nitro group, nitroso group, sulfonyl group and the like.

  Specific examples of the onium cation represented by the general formula (II) include the following general formula:

(Wherein R is the same as in general formula (II)) is preferred. Such onium cations may be used alone or in combination of two or more. Among these, the following onium cations are preferable.

  (1) The following general formula:

で表される９種類の複素環オニウムカチオンの内の１種。

One of nine heterocyclic onium cations represented by

  (2) The following general formula:

で表される５種類の不飽和オニウムカチオンの内の１種。

One of five types of unsaturated onium cations represented by

  (3) The following general formula:

で表される１０種類の飽和環オニウムカチオンの内の１種。

1 type of 10 types of saturated ring onium cations represented by these.

In the general formula, R ^{1 to} R ¹² are the same or different and are a hydrogen atom, a fluorine atom, or an organic group, and in the case of an organic group, these may be bonded to each other.

(4) R is hydrogen, C ₁ alkyl group -C _8, aryl group having C ₆ -C ₁₂ or C ₇ -C ₁₃ chain onium cations aralkyl group,. Among them, those in which L is N in the general formula (II) are preferable.

For example, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraheptylammonium, tetrahexylammonium, tetraoctylammonium, triethylmethylammonium, methoxyethyldiethylmethylammonium, trimethylphenylammonium, benzyltrimethylammonium, benzyltributylammonium Quaternary ammoniums such as benzyltriethylammonium, dimethyldistearylammonium, diallyldimethylammonium, 2-methoxyethoxymethyltrimethylammonium, tetrakis (pentafluoroethyl) ammonium, trimethylammonium, triethylammonium, tributylammonium, Tertiary ammonium such as ruammonium, dimethylethylammonium and dibutylmethylammonium, secondary ammoniums such as dimethylammonium, diethylammonium and dibutylammonium, methylammonium, ethylammonium, butylammonium, hexylammonium and octylammonium Examples include primary ammoniums, N-methoxytrimethylammonium, N-ethoxytrimethylammonium, N-propoxytrimethylammonium, and ammonium compounds such as NH ₄ . Among these exemplified chain onium cations, preferred chain onium cations are ammonium, trimethylammonium, triethylammonium, tributylammonium, triethylmethylammonium, tetraethylammonium and diethylmethyl (2-methoxyethyl) ammonium.

  Among the onium cations of the above (1) to (4), preferred are the following general formulas:

(Wherein R ^{1 to} R ¹² are the same as above), and the chain onium cation of (4) above. R ^{1 to} R ¹² are a hydrogen atom, a fluorine atom, or an organic group, and examples of the organic group include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, fluorine Group etc. are preferable, More preferably, they are a C1-C8 saturated or unsaturated hydrocarbon group, and a fluorocarbon group. These organic groups are hydrogen atom, fluorine atom, nitrogen atom, oxygen atom, sulfur atom, amino group, imino group, amide group, ether group, ester group, hydroxyl group, carboxyl group, carbamoyl group, cyano group, sulfone. A functional group such as a group or sulfide group may be contained. More preferably, R ^{1 to} R ¹² have one or more of a hydrogen atom, a fluorine atom, a cyano group and a sulfone group. When two or more organic groups are bonded, the bond may be formed between the main skeleton of the organic group, or between the main skeleton of the organic group and the functional group described above, or It may be formed between the functional groups.

  When M in the formula (I) is an inorganic cation, an alkali metal ion or an alkaline earth metal ion is preferred. Examples of the alkali metal include Li, Na, and K, and examples of the alkaline earth metal include Ca and Mg. A more common compound is lithium fluorosulfonylimide where M is Li.

[Method for producing fluorosulfonylimide salt]
It is recommended to produce the fluorosulfonylimide salt by the method described below.

  A step of fluorinating chlorosulfonylimide or a salt thereof in the presence of a reaction solvent (fluorination step), a step of exchanging a cation of fluorosulfonylimide generated in the fluorination step with a desired cation (cation exchange step) A method comprising is preferred. First, the fluorination process will be described.

[Fluorination process]
In the fluorination step, fluorination reaction of chlorosulfonylimide or a salt thereof is performed. As the chlorosulfonylimide as a starting material, a commercially available product may be used, or a chlorosulfonylimide synthesized by a known method may be used.

  As a method of synthesizing chlorosulfonylimide, for example, after reacting cyanic chloride with sulfuric anhydride, reacting the product (chlorosulfonyl isocyanate) with chlorosulfonic acid, reacting amidosulfuric acid with thionyl chloride. Thereafter, a method of further reacting chlorosulfonic acid (a method for synthesizing bis (chlorosulfonyl) imide); a method of reacting chlorosulfonyl isocyanate and fluorinated alkylsulfonic acid or fluorosulfonic acid (N- (chlorosulfonyl)- N- (fluoroalkylsulfonyl) imide or N- (chlorosulfonyl) -N- (fluorosulfonyl) imide synthesis method);

  Next, a fluorination reaction of chlorosulfonylimide is performed. The timing of the fluorination reaction is not particularly limited. An embodiment in which fluorination reaction of chlorosulfonylimide (proton) is performed; after cation exchange reaction of chlorosulfonylimide, fluorination reaction of chlorosulfonylimide salt is performed. Any of the embodiments may be used.

As a method of fluorinating the above chlorosulfonylimide (proton) or a salt thereof (hereinafter referred to as chlorosulfonylimides), a fluorinating agent (AsF ₃ , SbF ₃ ) is used, and the chlorosulfonylimide is halogenated. A method of exchanging, a method of fluorinating di (chlorosulfonyl) imide using an ionic fluoride of a monovalent cation such as KF or CsF as a fluorinating agent, a chlorosulfonylimide, an alkali metal fluoride, Fluoride containing at least one element selected from the group consisting of elements of Group 11 to Group 15 and Period 4 to Period 6 (preferably CuF ₂ , ZnF ₂ , SnF ₂ , PbF _2, BiF _3, etc.) ). Fluoride containing at least one element selected from the group consisting of elements of Group 11 to Group 15 and Period 4 to Period 6 (preferably CuF ₂ , ZnF ₂ , SnF ₂ , PbF _2, BiF _3, etc.) ) To fluorinate di (chlorosulfonylimide) in terms of reaction yield. Further, the method of fluorinating di (chlorosulfonylimide) using an alkali metal fluoride such as KF, LiF, or NaF as a fluorinating agent is preferable because an alkali metal salt of fluorosulfonylimide can be obtained in one step.

  In the fluorination step, an aprotic solvent is preferably used as the reaction solvent. Specifically, carbonate solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate; dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3- Ether solvents such as dioxane and 4-methyl-1,3-dioxolane; ester solvents such as methyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl propionate, γ-butyrolactone, γ-valerolactone; Amide solvents such as N, N-dimethylformamide; Nitrile solvents such as acetonitrile, butyronitrile, isobutyronitrile, valeronitrile, and benzonitrile; Nitro such as nitromethane and nitrobenzene System solvents; sulfur solvents such as sulfolane, 3-methylsulfolane, dimethyl sulfoxide; N-methyloxazolidinone and the like. These solvents may be used alone or in combination of two or more. From the viewpoint of smoothly proceeding the fluorination reaction, it is recommended to use a polar solvent, and among the solvents exemplified above, ester solvents and / or nitrile solvents are preferable, and in particular, butyronitrile, isobutyronitrile, valero Nitrile, ethyl acetate, isopropyl acetate and butyl acetate are preferred. From the viewpoint of workability during purification, a solvent having a low boiling point and capable of forming a two-layer state with water is preferable.

The completion of the fluorination reaction can be confirmed by, for example, ¹⁹ F-NMR. That is, a peak appears in the chemical shift derived from fluorine as the reaction proceeds, and the relative intensity (integrated value) of the peak increases. Therefore, the completion of the fluorination reaction may be confirmed while tracking the progress of the reaction by ¹⁹ F-NMR. In addition, when reaction time is too long, since the production | generation of a by-product becomes remarkable, at the time (for example, about 0.5 to 24 hours from the start of reaction) when the relative intensity of the peak of a target object becomes the maximum. The fluorination reaction is preferably terminated.

[Cation exchange process]
Next, the cation exchange step will be described. Cation exchange can be performed by reacting chlorosulfonylimide or fluorosulfonylimide or a salt thereof (hereinafter sometimes referred to as fluorosulfonylimide) with a salt containing M of the formula (I). For example, fluorosulfonylimide alkali metal salt, alkaline earth metal salt, or onium salt is used as an ion conductor material for various electrochemical devices by melting at high temperature or dissolving in an appropriate organic solvent. can do.

Examples of the salt containing an alkali metal include hydroxides such as LiOH, NaOH, KOH, RbOH, and CsOH, and carbonic acids such as Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , Rb ₂ CO ₃ , and Cs ₂ CO _3. Salts, bicarbonates such as LiHCO ₃ , NaHCO ₃ , KHCO ₃ , RbHCO ₃ , CsHCO ₃ , chlorides such as LiCl, NaCl, KCl, RbCl, CsCl, fluorides such as LiF, NaF, KF, RbF, CsF, Examples thereof include alkali metal salts such as alkoxide compounds such as CH ₃ OLi and EtOLi, and alkyllithium compounds such as EtLi, BuLi and t-BuLi (where Et represents an ethyl group and Bu represents a butyl group).

  Salts containing alkaline earth metals include Mg, Ca, Sr, Ba hydroxide, fluoride, carbonate, bicarbonate, nitrate, sulfate, hydrochloride, phosphate, acetate, oxalate And borate.

  When M in the formula (I) is an onium cation, cation exchange can be performed on the fluorosulfonylimides by reacting the onium cation halide, hydroxide, carbonate, bicarbonate, or the like. .

  Examples of the solvent that can be used in the cation exchange step include those exemplified in the fluorination step.

  The implementation time of the cation exchange step is not particularly limited, and can be carried out at any stage depending on the situation. For example, it may be carried out before the fluorination step or after the fluorination step, but preferably after the fluorination step.

  Further, the number of times of performing the cation exchange step is not limited, and it may be repeated once or twice or more. For example, the cation of chlorosulfonylimides or fluorosulfonylimides may be exchanged with a desired cation represented by M by a single cation exchange step.

  In both the fluorination step and the cation exchange step, the concentration of the fluorosulfonylimide salt contained in the reaction solution is preferably 1% by mass to 70% by mass. If the concentration is too high, the reaction may be non-uniform, while if too low, the productivity per batch is low and not economical. More preferably, it is 3 mass%-60 mass%, More preferably, it is 5 mass%-50 mass%.

[Concentration process]
The concentration step is a step of removing the solvent from the reaction solution after the cation exchange step and concentrating a solution of the generated fluorosulfonylimide salt (hereinafter simply referred to as fluorosulfonylimide). In the present invention, the concentration step is preferably carried out by (1) a method of bubbling a gas into the reaction solution (a bubbling method) and / or (2) a thin film distillation method.

  In the present invention, the concentration step refers to removing a part of the solvent from the obtained fluorosulfonylimide solution (reaction solution), and from the reaction solution until the target fluorosulfonylimide is obtained as a solid. It also includes distilling off the solvent. Therefore, the product obtained in the concentration step is a concentrated solution of fluorosulfonylimide, a solid (powder) of fluorosulfonylimide, or a concentrated solution (slurry solution) in which a part of fluorosulfonylimide exists in a solid state. It is.

  First, (1) the concentration step employing the bubbling method will be described. In the bubbling method, the evaporation area can be increased by flowing a gas through the reaction solution, so that the evaporation of the reaction solvent is promoted and the reaction solvent can be quickly removed from the reaction solution. In this case, the reaction apparatus that can be used for the concentration step is not particularly limited as long as it is provided with a means for introducing gas into the reaction solution and a means for discharging the reaction solvent out of the system. For example, a tank reactor, a tank reactor capable of depressurization, and the like can be mentioned.

  As the gas to be circulated (bubbled) in the reaction solution, an inert gas such as helium, nitrogen and argon, dry air, and a mixed gas thereof can be used. From the viewpoint of product quality and safety, nitrogen gas is preferred. The flow rate of the gas to the reaction solution may be appropriately determined according to the concentration of the fluorosulfonyl compound in the reaction solution. For example, 0.001 mL / min to 10000 mL / min per 1 g of the fluorosulfonylimide solution. Is preferred. More preferably, it is 0.005 mL / min-1000 mL / min, More preferably, it is 0.05 mL / min-100 mL / min. From the viewpoint of promoting the evaporation of the reaction solvent, it is preferable that the gas bubbles supplied to the reaction solution have a smaller diameter. The means for forming bubbles is not particularly limited. For example, bubbles may be formed by passing the supply gas through a filter such as a glass filter, or a gas generator such as a fine gas generator may be used. Also good.

  Next, (2) the concentration step employing the thin film distillation method will be described. The thin film distillation method is a method in which a thin film of a liquid to be processed is formed and heated to separate components contained in the liquid to be processed into an evaporated component and a non-evaporated component. Therefore, in the concentration step employing the thin film distillation method, the solvent is separated from the reaction solution after the cation exchange step by thin film distillation, and the fluorosulfonylimide solution is concentrated.

  In this case, the concentration step is performed using a thin film distiller. The thin-film distiller includes means for forming a thin film of the reaction solution, means for heating the formed thin film, means for recovering the evaporated component (reaction solvent), and means for recovering the non-evaporated component (fluorosulfonylimide). Any device may be used. Moreover, you may provide the circulation means which returns the concentrate extracted from the thin film distiller to the thin film distiller again. Thereby, it can concentrate repeatedly.

  The method for forming the thin film is not particularly limited, and any conventionally known method such as a flow-down method, a centrifugal method, a stirring method, a rotating method, a blade method, and an ascending method can be employed. Specific thin-film distillers include, for example, “short stroke distillation apparatus” (manufactured by UIC GmbH), “Wiperen (registered trademark)”, “Exeva (registered trademark)” (above, manufactured by Shinko Environmental Solution Co., Ltd.), “Contro”, “Inclined Wing Contro”, “Cebucon (registered trademark)” (manufactured by Hitachi Plant Technology Co., Ltd.), “High Evaporator (registered trademark)” (manufactured by Sakai Seisakusho Co., Ltd.), “Viscon”, “Film Truder” (made by Kimura Chemical Co., Ltd.), “Hi-U Blusher”, “Evariactor”, “Recovery” (made by Kansai Chemical Machinery Manufacturing Co., Ltd.), “NRH” ( Nichinan Machinery Co., Ltd.), “Evapol (registered trademark)” (manufactured by Ogawara Seisakusho Co., Ltd.), and the like.

  Further, in order to further increase the concentration efficiency of fluorosulfonylimide, the concentration step may be performed while gas is circulated in the thin film still. As the gas, it is preferable to use an inert gas such as nitrogen or argon, more preferably nitrogen.

  Other conditions in the concentration step by thin film distillation are not particularly limited. For example, the supply rate of the reaction solution into the thin film distiller may be appropriately determined according to the size of the apparatus to be used and the concentration of fluorosulfonylimide in the reaction solution.

  In addition, in order to further enhance the concentration efficiency of fluorosulfonylimide, the concentration step may be performed while heating the reaction solution when either the bubbling method or the thin film distillation method is employed. The heating temperature may be appropriately set according to the reaction solvent to be used, but is preferably 30 ° C. or higher and 150 ° C. or lower from the viewpoint of suppressing the decomposition of fluorosulfonylimide. A more preferable temperature is 50 ° C. or higher, and more preferably 120 ° C. or lower. If the temperature is too low, the removal efficiency of the reaction solvent cannot be obtained. On the other hand, if the temperature is too high, the fluorosulfonylimide may be decomposed.

  In either case of employing a bubbling method or a thin film distillation method, the concentration step may be performed under reduced pressure from the viewpoint of carrying out an efficient concentration step. By controlling the degree of vacuum, the reaction solvent can be efficiently removed even at low temperatures, and the decomposition of fluorosulfonylimide by heat can also be prevented. The degree of reduced pressure is not particularly limited as long as it is appropriately adjusted according to the type of the reaction solvent, but is preferably 40 kPa or less, for example. More preferably, it is 15 kPa or less, More preferably, it is 5 kPa or less.

  When the amount of the reaction solvent is large, a part of the reaction solvent may be removed before the concentration step. It is possible that the reaction between the fluorosulfonylimide and the solvent becomes significant and the removal of the reaction solvent from the reaction solution is difficult since the amount of the reaction solvent relative to the fluorosulfonylimide is 150% by mass or less. This is because the concentration step can be efficiently performed by reducing the amount of the reaction solution as much as possible. Moreover, you may implement a concentration process, stirring a reaction solution. In the concentration step, both the bubbling method and the thin film distillation method may be performed in order (the order of execution is not particularly limited), or either one may be performed alone. In addition, from the viewpoint of preventing thermal decomposition of fluorosulfonylimide, a thin film distillation method that can carry out the concentration step in a shorter time is preferable.

  From the viewpoint of preventing the decomposition of the fluorosulfonylimide due to heating in the concentration step, the amount of heat applied in the concentration step is 1,000,000 J or less per 1 g of the fluorosulfonylimide, regardless of whether the above bubbling method or thin film distillation method is employed. Preferably, it is 500,000 J or less, and more preferably 100,000 J or less. The amount of heat does not include the amount of heat given to the reaction solution in order to remove a part of the reaction solvent before being subjected to the concentration step.

  In the present invention, the amount of heat given to the reaction solution in the concentration step is set as the amount of heat given to the fluorosulfonylimide. In addition, the said calorie | heat amount should just be calculated | required based on the power consumption (apparatus maker's nominal value should be referred to) of the apparatus used at a concentration process, the quantity of fluorosulfonyl imide contained in a reaction solution, and heating time, and is concrete. For this, the amount of heat given to the reaction solution in the concentration step may be calculated and converted to the amount of heat given per 1 g of fluorosulfonylimide.

[Drying and powdering process]
The fluorosulfonylimide concentrate obtained in the concentration step can be used as a product as it is, but in order to increase the stability during storage and facilitate the distribution of the product, the fluorosulfonylimide may be powdered. Good (powdering and drying process). In addition, when the fluorosulfonylimide in a solid state is obtained in the concentration step, the obtained solid may be dried as it is with a drying device, or after the fluorosulfonylimide is dissolved in a soluble solvent, You may use for a drying and powdering process.

  The method for drying and pulverizing the fluorosulfonylimide is not particularly limited. (1) The above-described concentration step is continued until the fluorosulfonylimide is precipitated, and this is separated, dried and pulverized. 2) A method in which the concentrated solution obtained in the concentration step is left as it is or while being cooled to 30 ° C. or lower as needed to precipitate fluorosulfonylimide, which is separated, dried and pulverized. (3) A method in which a solvent is added to the concentrated liquid to precipitate fluorosulfonylimide, which is separated by filtration, dried, and powdered.

  Next, the precipitated fluorosulfonylimide is separated from the reaction solvent or the like by a gradient method, a centrifugal separation method, a filtration method or the like and dried. The drying method of fluorosulfonylimide is not specifically limited, A conventionally well-known drying apparatus can be used. The temperature during drying is preferably 0 ° C to 100 ° C. More preferably, it is 10 degreeC or more, More preferably, it is 20 degreeC or more, More preferably, it is 80 degreeC or less, More preferably, it is 60 degreeC or less.

  Moreover, you may perform drying of fluorosulfonyl imide, supplying gas to a drying apparatus. Examples of usable gases include those used in the concentration step, and examples thereof include inert gases such as nitrogen and argon, and dry air.

  The fluorosulfonylimide obtained by the above method may be subjected to a purification step for further improving the purity as necessary. Any conventionally known purification method can be adopted as the purification step. The purification step is preferably performed in a dry atmosphere using a low moisture or anhydrous solvent.

  Hereinafter, the present invention will be described more specifically with reference to experimental examples.However, the present invention is not limited by the following experimental examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

[NMR measurement]
^{The 19} F-NMR measurement was performed using “Unity Plus-400” manufactured by Varian (internal standard substance: trifluoromethylbenzene, solvent: deuterated acetonitrile, integration number: 16 times).

[ICP emission spectroscopy]
A multi-type ICP emission spectrophotometer (“ICPE-9000” manufactured by Shimadzu Corporation) was prepared by using an aqueous solution having a concentration of 1% by mass obtained by mixing 0.1 g of a fluorosulfonylimide salt obtained in the following example with 9.9 g of ultrapure water. ")It was used.

Experimental example 1
[Fluorination process]
1800 g of butyl acetate was added to a Pyrex (registered trademark) reaction vessel A (internal volume 10 L) equipped with a stirrer under a nitrogen stream, and 200 g (934 mmol) of bis (chlorosulfonyl) imide was added thereto at room temperature (25 ° C.). It was dripped at.

  To the resulting bis (chlorosulfonyl) imide solution in butyl acetate, 101 g of zinc fluoride (982 mmol, 1.05 equivalents relative to bis (chlorosulfonyl) imide) was added in one portion at room temperature until this was completely dissolved. Stir at room temperature for 6 hours.

[Cation Exchange Step 1-Synthesis of Ammonium Salt]
To a Pyrex (registered trademark) reaction vessel B (with an internal volume of 10 L) equipped with a stirrer, 540 g (7928 mmol, 8.49 equivalents based on bis (chlorosulfonyl) imide) of 25% by mass ammonia water was added. The reaction solution in the reaction vessel A was added dropwise to the reaction vessel B at room temperature with stirring of aqueous ammonia. After completion of the addition of the reaction solution, stirring was stopped, and the aqueous layer containing by-products such as zinc chloride was removed from the reaction solution divided into two layers, an aqueous layer and a butyl acetate layer, and ammonium bis (fluoro A butyl acetate solution of sulfonyl) imide was obtained. ¹⁹ F-NMR (solvent: deuterated acetonitrile) was measured using the obtained organic layer as a sample. In the obtained chart, the amount of trifluoromethylbenzene added as an internal standard substance, and the comparison between the integrated value of the peak derived from this and the integrated value of the peak derived from the target product, was included in the organic layer. The crude yield of ammonium bis (fluorosulfonyl) imide was determined (756 mmol).
¹⁹ F-NMR (solvent: deuterated acetonitrile): δ 56.0

[Cation Exchange Step 2-Synthesis of Lithium Salt]
To the ammonium bis (fluorosulfonyl) imide contained in the obtained organic layer, 242 g of a 15% by mass lithium hydroxide aqueous solution (1516 mmol as Li) was added so that the amount of lithium was 2 equivalents. Stir for minutes. Thereafter, the aqueous layer was removed from the reaction solution to obtain a butyl acetate solution of lithium bis (fluorosulfonyl) imide.

  Using the obtained organic layer as a sample, it was confirmed by ICP emission spectroscopy that the ammonium cation of fluorosulfonylimide was exchanged for lithium ions. The concentration of lithium bis (fluorosulfonyl) imide in the organic layer was 7% by mass (yield: 127 g, yield: 73%).

The concentration of fluorosulfonylimide was measured by ¹⁹ F-NMR (solvent: deuterated acetonitrile) using the obtained organic layer as a sample, and the amount of trifluoromethylbenzene added as an internal standard substance in the measurement result chart. And a comparison between the integrated value of the peak derived therefrom and the integrated value of the peak derived from the target product.

[Concentration process]
The lithium bis (fluorosulfonyl) imide solution obtained in the cation exchange step is added to a rotary evaporator (“REN-1000”, manufactured by IWAKI), the solvent is distilled off under reduced pressure, and the lithium bis (fluorosulfonyl) imide solution 282 g was obtained (concentration: 45% by mass).

  Next, a flask (capacity) containing 200 g of a butyl acetate solution of lithium bis (fluorosulfonyl) imide having a concentration of 45% by mass in a rotary evaporator (“REN-1000”, manufactured by IWAKI) equipped with a gas introduction tube and a decompression device. : 500 mL). While nitrogen gas was blown into the liquid in the flask at 500 mL / min, rotation was started while heating in a constant temperature water bath set at 60 ° C. (100 rpm). Next, the pressure in the apparatus was gradually reduced to 933 Pa, and a concentration process was performed for 12 hours. The concentration of the obtained solution was 72% by mass. The amount of heat applied in the concentration step was 72,000 J with respect to 1 g of lithium bis (fluorosulfonyl) imide.

[Powdering and drying process]
125 g of toluene was added to 125 g of the obtained concentrated liquid, and the mixture was allowed to stand at 25 ° C. for 1 hour to precipitate a solid of lithium bis (fluorosulfonyl) imide (LiFSI). The obtained solid was collected by filtration and dried in vacuo at 50 ° C. to obtain dry LiFSI (powder) (yield: 68 g, yield: 76% (from the concentration step)).

Experimental example 2 , Comparative experimental example 1
When the moisture content of the dry LiFSI obtained in Experimental Example 1 was measured with a Karl Fischer coulometric titrator (AQ-2000; manufactured by Hiranuma Sangyo Co., Ltd.), the water content was 86 ppm. Fluorine ions (F ⁻ ) and sulfate ions (SO ₄ ²⁻ ) were quantified with an ion chromatography system (ICS-3000; manufactured by Nippon Dionex). F ⁻ was 37 ppm, and SO ₄ ²⁻ was 3 ppm.

  Dried in dozens of high-density polyethylene bottles (NALGENE (registered trademark of NALGENE); with screw cap) in a dry room with a dew point of -50 ° C or less (relative humidity 0.157% or less) 30 g each of LiFSI was enclosed.

A plurality of the bottles were taken out of the dry room and the screw stoppers were opened to forcibly absorb moisture. The screw cap was closed after 5 minutes and 10 minutes, and then returned to the dry room and shaken vigorously. When the moisture content of this LiFSI was measured, they were 378 ppm and 1332 ppm (Comparative Experimental Example 1) .

  The bottle containing the dried LiFSI and the bottle after the moisture absorption were put into a lamizip (registered trademark; produced by Production Japan) AL and heat-sealed. The lami zip is a bag composed of a laminated film having a five-layer structure made of 12 μm polyethylene terephthalate / 15 μm adhesive polyethylene / 7 μm aluminum foil / 20 μm adhesive polyethylene / 60-80 μm polyethylene.

These samples were stored at 25 ° C, 40 ° C, 50 ° C, 60 ° C. Table 1 shows the quantitative results of F ⁻ , SO ₄ ²⁻ after 1 month, 3 months and 6 months.

In the bottle with an initial moisture content of 86 ppm, hydrolysis hardly progressed at 25 ° C., but the amount of F ⁻ and SO ₄ ²⁻ gradually increased as the storage temperature increased. When the storage temperature reached 60 ° C., the increase in the amount of SO ₄ ²⁻ increased. This tendency was also observed in a bottle having an initial water content of 378 ppm. In the bottle (Comparative Experimental Example 1) whose initial moisture content was 1332 ppm, hydrolysis hardly progressed until 3 months when stored at 25 ° C., but after 6 months, there was a marked increase in each ion. Admitted. In addition, when stored at 40 ° C. to 60 ° C., the amount of F ⁻ and SO ₄ ²⁻ rapidly increased after one month. However, after one month, the increase in the amount of F ⁻ and SO ₄ ²⁻ is moderate, and the value of about 1000 ppm to 2000 ppm is maintained. This is probably because the hydrolysis was hardly progressed after one month as a result of the consumption of water by the hydrolysis.

Comparative Experiment Example 2
30 g of dry LiFSI obtained in Experimental Example 1 (water content: 86 ppm) was put into a PE bag (100 μm) manufactured by Taiyo Co., Ltd. and a PET / PE laminate bag (16/40 μm) manufactured by Yamamoto Seisakusho, respectively, and heat-sealed. Then, it was sealed and stored in a constant temperature and humidity chamber at a room temperature of 23 ° C. and a relative humidity of 50%. Two weeks later, the package was opened and the water content was measured. As a result, moisture was absorbed at 37157 ppm and 59782 ppm, respectively. The appearance of LiFSI was not a powder, but was deliquescent in both bags to form a slurry.

Comparative Experiment Example 3
F ^- The amount 206 ppm, SO ₄ ^2-quantity 11 ppm, even bottles containing the LiFSI moisture content 645Ppm, heat sealed and put on the Ramijippu AL, 25 ℃, 40 ℃, 50 ℃, at 60 ° C., 1 month, 3 Stored for 6 months.

Table 2 shows the amount of increase in the amount of F ⁻ and SO ₄ ²⁻ in Experimental Example 2 , Comparative Experimental Example 1, and Comparative Experimental Example 3. By keeping the water content at 1000 ppm or less and the storage temperature at 50 ° C. or less, the increase in the amount of F ⁻ and SO ₄ ²⁻ can be suppressed to 4000 ppm or less.

Experimental Example 4
In Experimental Example 1, sodium bis (fluorosulfonyl) imide (NaFSI) was obtained in the same manner using sodium hydroxide instead of lithium hydroxide (74 g).

Experimental Example 5
In Experimental Example 1, potassium bis (fluorosulfonyl) imide (KFSI) was obtained in the same manner using potassium hydroxide instead of lithium hydroxide (80 g).

Comparative Experiment Example 4
Lithium bis (fluorosulfonyl) imide solution 1814 g (containing 127 g of LiFSI) obtained in the same manner as in [Cation Step 2—Synthesis of Lithium Salt] in Experimental Example 1 and 130 g of ethylmethylimidazolium bromide into 130 g of ultrapure water Dissolved aqueous solution was added. The aqueous layer was removed by liquid separation, and the organic layer was separated and washed twice with 130 g of ultrapure water. The obtained organic layer was put into a rotary evaporator (“REN-1000”, manufactured by IWAKI), and the solvent was distilled off under reduced pressure to obtain an ethylmethylimidazolium bis (fluorosulfonyl) imide (EMImFSI) solution ( 106 g).

Experimental Example 7 and Comparative Experimental Examples 5-7
The preservation experiment of NaFSI, KFSI, and EMImFSI obtained in Experimental Example 4 , Experimental Example 5, and Comparative Experimental Example 4 was performed. For NaFSI, the initial moisture content in the bottle is 85 ppm and 1409 ppm (Comparative Experiment 5) , and for KFSI, the initial moisture content in the bottle is 82 ppm and 653 ppm (Comparative Experiment 6). For EMImFSI (Comparative Experimental Example 7) , an initial water content in the bottle of 10 ppm was prepared. Storage temperatures were 25 ° C., 50 ° C., and 60 ° C., and the samples were stored for one month. F ^- The amount, the measurement of SO ₄ ^2-amount, Table 3 (NaFSI), Table 4 (KFSI), Table 5 (EMImFSI), F ^- amount, the amount of increase from the initial value of SO ₄ ^2-amount Table 6 (NaFSI) and Table 7 (KFSI). EMImFSI did not increase the amount of F ⁻ and SO ₄ ²⁻ even when stored for 1 month at each temperature, so the table of increase was omitted.

  Since the package of the present invention can suppress moisture absorption of ionic compounds containing fluorine atoms having high hygroscopicity as much as possible, hydrolysis progresses during the distribution in the market and the ionic compounds deteriorate. There is no. Moreover, hydrolysis of the ionic compound during storage and transport can be suppressed by setting the initial water content of the ionic compound (or ionic compound-containing composition) to a predetermined amount or less. And as a result of suppressing hydrolysis, since generation | occurrence | production of hydrofluoric acid is also suppressed, deterioration of packaging material itself can be prevented, and an ionic compound (or ionic compound containing composition) is almost immediately before packaging. It can be stored and transported as it is. Furthermore, since the water content of the ionic compound (or ionic compound-containing composition) is packaged with an extremely small amount, even if the ionic compound of the present invention is used in various batteries such as a lithium battery, Adverse effects can be suppressed. Therefore, it is useful as an ionic compound for various electrochemical devices.

Claims (12)

A packaging body for storing or transporting an ionic compound containing a fluorine atom and packaging the ionic compound containing a fluorine atom with a packaging material, wherein the ionic compound has a moisture content. A package of an ionic compound, which is a bisfluorosulfonylimide represented by the following general formula (I), which is a powder of 500 ppm or less, and wherein the packaging material includes at least one metal layer.

(In formula (I), M represents an alkali metal ion and X represents F.)   The package according to claim 1, wherein the metal layer is an aluminum layer and / or a stainless steel layer.   The package according to claim 1 or 2, wherein in the general formula (I), M is Li.   The package according to any one of claims 1 to 3, wherein the total thickness of the packaging material is 50 to 200 µm. The package according to any one of claims 1 to 4, wherein the metal layer includes an aluminum layer having a thickness of 5 to 20 µm.   The package according to any one of claims 1 to 5, further comprising a resin bag, a resin container, or a glass container inside or outside the metal layer of the packaging material.   The package according to claim 6, wherein the resin used for the resin bag or the resin container is a fluororesin, polyethylene, polypropylene, polystyrene, polycarbonate, nylon or polyester.   The package according to any one of claims 1 to 7, which has dry air or dry inert gas inside the package.   The package according to any one of claims 1 to 7, wherein the inside of the package is vacuum. The package according to any one of claims 1 to 9, wherein the amount of the decomposition product of the ionic compound when the package is stored at 30 ° C or less for 6 months is less than 1000 ppm.   It preserve | saves at 50 degrees C or less, The preservation | save method of the package in any one of Claims 1-10 characterized by the above-mentioned.   It transfers at 50 degrees C or less, The transfer method of the package in any one of Claims 1-10 characterized by the above-mentioned.