JP7001861B1 - Fluorine-based ionic liquid and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-based ionic liquid capable of suppressing coloring in a high temperature environment and enabling long-term hue stability, and a method for producing the same. SOLUTION: A fluorine-based ionic liquid is an ionic liquid represented by the following formula (1) consisting of a pair of cation K + and anion A-, in which the cation K + is an imidazolium cation, a pyrrolidinium cation, and a pyridinium. One or more selected from the group consisting of cations, ammonium cations, pyrrolinium cations and morpholinium cations, the anion A- is a fluoroan anion, and the total amine value in the potential differential titration method is 0.013. It is as follows. Equation (1): K + A- [Selection diagram] None

Description

The present invention relates to a fluorine-based ionic liquid and a method for producing the same.

In recent years, electronic products using flat panel displays such as LCD TVs, personal computers, mobile phones, smartphones equipped with touch panels, and car navigation systems have become widespread. Televisions are becoming larger, and mobile and in-vehicle displays tend to have higher image quality and higher functionality. Among these, the problem of static electricity becomes a bigger problem, and the larger the size, the higher the risk of charging, and the higher the performance of the component, the greater the influence of troubles such as failure. Against this background, the development of antistatic agents that are more effective in preventing static electricity, that is, can reduce resistance by adding a small amount, is, for example, adhesives (polarizing plates, protective films, semiconductors, etc.). It is required in a wide range of electronic material fields such as UV curable hard coating agents (AR film, AG film, etc.) and OA rolls.

Conventionally, as the main antistatic agent, a surfactant, an inorganic filler, and a conductive polymer are used. These materials have problems such as difficulty in sustaining performance due to humidity dependence and wiping, poor appearance such as haze, and inability to maintain resin performance due to a large amount of addition. On the other hand, ionic liquids are attracting attention as materials that can solve these problems, and are being applied to electronic members.

However, since ionic liquids are sparingly volatile, they cannot be purified by distillation. Therefore, its high purity is regarded as one of the major issues, and various developments have been made for the high purification of ionic liquids (see Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2010-184902 Japanese Patent No. 4499594

The phenomenon of yellowing, haze, and reflectivity of optically transparent materials over time and the environment in which they are used is not desirable in many applications. Especially in optical materials, discoloration in a high temperature environment is a big problem. For example, ionic liquids used as antistatic agents are also required to suppress coloring in a high temperature environment, and high purification is required.

Conventional high-purification methods have been carried out by purifying raw materials and devising quaternizing agents, but the purification method is limited depending on the type of alkyl chain or amine, and the coloring component is specified and specially removed. It has not been possible to take a refined purification method. In order to suppress coloring in a high temperature environment, it is required to identify the coloring component in the ionic liquid and remove the coloring component.

In view of the above points, it is an object of the present invention to provide a fluorine-based ionic liquid and a method for producing the same, which suppresses coloring in a high temperature environment and enables long-term hue stability.

式（２）中、Ｒ^１～Ｒ^９は、それぞれ独立に、置換されているかもしくは非置換の炭素数１～２０の飽和もしくは不飽和の直鎖状、分枝状もしくは環状の脂肪族炭化水素基、置換されているかもしくは非置換の炭素数６～３０のアリール基、または置換されているかもしくは非置換の炭素数７～３１のアリールアルキル基であり、但しＲ^５～Ｒ^９はそれぞれ独立に水素原子でもよく、前記脂肪族炭化水素基、前記アリール基または前記アリールアルキル基が置換されている場合は、ハロゲン原子、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アクリロイル基、メタクリロイル基、アシルオキシ基、アシル基、ヒドロキシ基、カルボキシ基、ホルミル基、メルカプト基、スルホ基、メシル基、ｐ－トルエンスルホニル基、シアノ基、トリフルオロメチル基、トリクロロメチル基、およびトリメチルシリル基からなる群から選択される少なくとも一種で置換されており、ｎは１～５の整数であり、式（ｆ）で表される化合物は、Ｘで表される酸素原子または硫黄原子を１つ以上含む４～７員環の飽和もしくは不飽和の複素環式化合物である。
［２］ 光学材料の添加剤として使用される、［１］に記載のフッ素系イオン性液体。 The present invention includes embodiments shown below.
[1] An ionic liquid represented by the following general formula (1) consisting of a pair of cation K ⁺ and anion A ⁻ , wherein the cation K ⁺ is selected from the group represented by the following general formula (2). A fluorine-based ionic liquid having one or more of these, the anion A ⁻ being a fluorine-based anion, and a total amine value of 0.013 or less in the potential difference titration method.
General formula (1) ^: K ⁺ A-
General formula (2):

In formula (2), R ¹ to R ⁹ are independently substituted or unsubstituted saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbons having 1 to 20 carbon atoms. A group, an substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, where R ⁵ to R ⁹ are independent of each other. It may be a hydrogen atom, and when the aliphatic hydrocarbon group, the aryl group or the arylalkyl group is substituted, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acryloyl group, a methacryloyl group, an acyloxy group. , Aryl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, cyano group, trifluoromethyl group, trichloromethyl group, and trimethylsilyl group. Substituted with at least one, n is an integer of 1 to 5, and the compound represented by the formula (f) is a 4- to 7-membered ring containing one or more oxygen or sulfur atoms represented by X. It is a saturated or unsaturated heterocyclic compound.
[2] The fluorine-based ionic liquid according to [1], which is used as an additive for optical materials.

[3] The method for producing a fluorinated ionic liquid according to [1] or [2].
Fluoroionic ionicity, which comprises reacting the compound containing the cation K ⁺ with the compound containing the anion A ⁻ to generate a fluoroionic ionic liquid, and contacting the obtained fluoroionic liquid with an acid. Liquid manufacturing method.
[4] The method for producing a fluorinated ionic liquid according to [3], wherein the fluorinated ionic liquid is brought into contact with an acid at 50 ° C. or higher.

[5] The method for producing a fluorinated ionic liquid according to [1] or [2].
The amine is reacted with a quaternizing agent to produce the compound containing the cation K ⁺ , the compound containing the cation K ⁺ is brought into contact with the acid, and then the compound containing the cation K ⁺ and the anion A ⁻ are contained. A method for producing a fluoroionic liquid, which comprises reacting with a compound to produce a fluoroionic liquid.
[6] The method for producing a fluorine-based ionic liquid according to [5], wherein the compound containing the cation K ⁺ is brought into contact with an acid at 50 ° C. or higher.

According to the embodiment of the present invention, it is possible to suppress coloring in a high temperature environment and obtain long-term hue stability.

In order to obtain color suppression in a high temperature environment, the present inventors need to remove impurities remaining in the fluorine-based ionic liquid, and removal of a trace amount of residual primary to tertiary amines is the most effective. I found that it was a target. For example, it has been clarified that a fluorine-based ionic liquid containing an amine derived from a raw material as an impurity gradually causes coloring at a high temperature. Therefore, the present inventors decided to remove the amine remaining in the fluorinated ionic liquid as much as possible, and the numerical value of the total amine value in the potential difference drip method was 0.013 or less, so that the fluorinated ionic liquid could be used. It has been found that coloring can be suppressed in a high temperature environment and hue stability can be maintained for a long period of time.

The fluorine-based ionic liquid (hereinafter, may be simply referred to as an ionic liquid) according to the present embodiment is a compound represented by the following general formula (1), and is composed of a pair of cation K ⁺ and anion A ⁻ . .. Here, the ionic liquid means an ion pair compound having a melting point of 100 ° C. or lower.
General formula (1) ^: K ⁺ A-

As the cation K ⁺ , one kind or two or more kinds selected from the group represented by the following general formula (2) is used.
General formula (2):

In formula (2), R ¹ to R ⁴ are independently substituted or unsubstituted saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbons having 1 to 20 carbon atoms. A group, an substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. Each of ^R5 to ^R9 is an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, or a hydrogen atom, respectively.

The aliphatic hydrocarbon group is a monovalent aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, and may be a linear or branched chain type, a cyclic (that is, an alicyclic) group, or a cyclic group. May have a branched chain. The aliphatic hydrocarbon group has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. The carbon number of the aliphatic hydrocarbon group referred to here does not include the number of carbon atoms contained in the substituent when the aliphatic hydrocarbon group has a substituent described later.

The aryl group has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. The carbon number of the aryl group referred to here does not include the number of carbon atoms contained in the substituent when the aryl group has a substituent described later.

The arylalkyl group has 7 to 31 carbon atoms, preferably 7 to 21 carbon atoms, and more preferably 7 to 11 carbon atoms. When the arylalkyl group has a substituent described later, the carbon number of the arylalkyl group referred to here does not include the number of carbon atoms contained in the substituent.

With respect to the above aliphatic hydrocarbon groups, aryl groups and arylalkyl groups, "substituted or unsubstituted" means that even if one or more hydrogen atoms of those groups are substituted with a substituent, they are substituted. It means that it does not have to be. Examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acryloyl group, a methacryloyl group, an acyloxy group, an acyl group, a hydroxy group, a carboxy group, a formyl group, a mercapto group, a sulfo group and a mesyl group. Examples thereof include a p-toluenesulfonyl group, a cyano group, a trifluoromethyl group, a trichloromethyl group, and a trimethylsilyl group, which may be introduced as a substituent by any one or a combination of two or more.

N in the formula (b) represents an integer of 1 to 5, so that the compound represented by the formulas (2)-(b) is a saturated heterocyclic compound having a 5- to 9-membered ring containing one nitrogen atom. Is. n is preferably 1 or 2.

X in the formula (f) represents an oxygen atom or a sulfur atom, and the compound represented by the formula (f) is a 4- to 7-membered ring containing one or more oxygen atom or sulfur atom represented by X. It is preferably a saturated or unsaturated heterocyclic compound (preferably a 5- to 6-membered ring).

Specific examples of the imidazolium cation represented by the formula (a) include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, and 1-butyl-3. -Methyl imidazolium, 1-hexyl-3-methyl imidazolium, 1-methyl-3-octyl imidazolium, 1-dodecyl-3-methyl imidazolium, 1,3-diethyl imidazolium, 1-ethyl-3-propyl Imidazolium, 1-butyl-3-ethyl imidazolium, 1-ethyl-3-hexyl imidazolium, 1-ethyl-3-octyl imidazolium, 1-dodecyl-3-ethyl imidazolium, 1,3-dipropyl imidazolium Rium, 1-butyl-3-propylimidazolium, 1-hexyl-3-propylimidazolium, 1-octyl-3-propylimidazolium, 1-dodecyl-3-propylimidazolium, 1-allyl-3-methylimidazolium Rium, 1,3-diallyl imidazolium, 1,2,3-trimethyl imidazolium, 1-ethyl-2,3-dimethylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-butyl-2, 3-Dimethylimidazolium, 1-hexyl-2,3-dimethylimidazolium, 1,2-dimethyl-3-octylimidazolium, 1-dodecyl-2,3-dimethylimidazolium, 1,3-diethyl-2- Methyl imidazolium, 1-ethyl-2-methyl-3-propyl imidazolium, 1-butyl-3-ethyl-2-methyl imidazolium, 1-ethyl-3-hexyl-2-methyl imidazolium, 1-ethyl- 2-Methyl-3-octylimidazolium, 1-dodecyl-3-ethyl-2-methylimidazolium, 2-methyl-1,3-dipropylimidazolium, 1-butyl-2-methyl-3-propylimidazolium , 1-Hexyl-2-methyl-3-propylimidazolium, 1-octyl-2-methyl-3-propylimidazolium, 1-dodecyl-2-methyl-3-propylimidazolium, 1-allyl-2,3 -Methyl imidazolium, 1,3-diallyl-2-methyl imidazolium and the like can be mentioned. These can be used alone or in combination of two or more.

Specific examples of the cation represented by the formula (b) include 1,1-dimethylpyrrolidinium, 1-ethyl-1-methylpyrrolidinium, 1-methyl-1-propylpyrrolidinium, and 1-butyl-. 1-Methylpyrrolidinium, 1-Methyl-1-hexylpyrrolidinium, 1-Methyl-1-octylpyrrolidinium, 1-dodecyl-1-methylpyrrolidinium, 1,1-diethylpyrrolidinium, 1 -Ethyl-1-propylpyrrolidinium, 1-butyl-1-ethylpyrrolidinium, 1-ethyl-1-hexylpyrrolidinium, 1-ethyl-1-octylpyrrolidinium, 1-dodecyl-1-ethyl Pyrrolidinium, 1,1-dipropylpyrrolidinium, 1-butyl-1-propylpyrrolidinium, 1-propyl-1-hexylpyrrolidinium, 1-propyl-1-octylpyrrolidinium, 1-dodecyl -1-propylpyrrolidinium, 1,1-dibutylpyrrolidinium, 1-butyl-1-hexylpyrrolidinium, 1-butyl-1-octylpyrrolidinium, 1-butyl-1-dodecylpyrrolidinium, 1,1-Dihexylpyrrolidinium, 1-hexyl-1-octylpyrrolidinium, 1-dodecyl-1-hexylpyrrolidinium, 1,1-dioctylpyrrolidinium, 1-dodecyl-1-octylpyrrolidinium , 1,1-Didodecylpyrrolidinium and other pyrrolidinium cations; 1,1-dimethylpiperidinium, 1-ethyl-1-methylpiperidinium, 1-methyl-1-propylpiperidinium, 1-butyl-1 -Methylpiperidinium, 1-methyl-1-hexylpiperidinium, 1-methyl-1-octylpiperidinium, 1-dodecyl-1-methylpiperidinium, 1,1-diethylpiperidinium, 1-ethyl-1-propylpi Peridinium, 1-Butyl-1-ethylpiperidinium, 1-ethyl-1-hexylpiperidinium, 1-ethyl-1-octylpiperidinium, 1-dodecyl-1-ethylpiperidinium, 1,1-dipropylpiperidinium , 1-Butyl-1-propylpiperidinium, 1-propyl-1-hexylpiperidinium, 1-propyl-1-octylpiperidinium, 1-dodecyl-1-propylpiperidinium, 1,1-dibutylpiperidinium, 1 -Butyl-1-hexylpiperidinium, 1-butyl-1-octylpiperidinium, 1-butyl-1-dodecylpiperidinium , 1,1-dihexylpiperidinium, 1-hexyl-1-octylpiperidinium, 1-dodecyl-1-hexylpiperidinium, 1,1-dioctylpiperidinium, 1-dodecyl-1-octylpiperidinium, 1,1 -Examples include piperidinium cations such as piperidinium cations such as didodecyl piperidinium. These can be used alone or in combination of two or more.

Specific examples of the pyridinium cation represented by the formula (c) include 1-methylpyridinium, 1-ethylpyridinium, 1-propylpyridinium, 1-butylpyridinium, 1-pentylpyridinium, 1-hexylpyridinium, and 1-octylpyridinium. , 1-dodecylpyridinium, 1-methyl-4-methylpyridinium, 1-ethyl-4-methylpyridinium, 1-butyl-4-methylpyridinium, 1-hexyl-4-methylpyridinium, 1-octyl-4-methylpyridinium , 1-dodecyl-4-methylpyridinium, 1-methyl-3-methylpyridinium, 1-ethyl-3-methylpyridinium, 1-butyl-3-methylpyridinium, 1-hexyl-3-methylpyridinium, 1-octyl- 3-Methylpyridinium, 1-dodecyl-3-methylpyridinium, 1-methyl-2-methylpyridinium, 1-ethyl-2-methylpyridinium, 1-butyl-2-methylpyridinium, 1-hexyl-2-methylpyridinium, Examples thereof include 1-octyl-2-methylpyridinium and 1-dodecyl-2-methylpyridinium. These can be used alone or in combination of two or more.

Specific examples of the ammonium cation represented by the formula (d) include tetramethylammonium, tetraethylammonium, tetrabutylammonium, tetraoctylammonium, ethyltrimethylammonium, butyltrimethylammonium, trimethyloctylammonium, trimethyldodecylammonium, and diethyldimethylammonium. , Butylethyldimethylammonium, ethyldimethyloctylammonium, ethyldodecyldimethylammonium, dibutyldimethylammonium, butyldimethyloctylammonium, butyldodecyldimethylammonium, dodecyldimethyloctylammonium, didodecyldimethylammonium, triethylmethylammonium, butyldiethylmethylammonium, diethyl Methyloctylammonium, dodecyldiethylmethylammonium, dibutylethylmethylammonium, butylethylmethyloctylammonium, butyldodecylethylmethylammonium, ethylmethyldioctylammonium, dodecylethylmethyloctylammonium, tributylmethylammonium, dibutylmethyloctylammonium, dibutyldodecylmethylammonium , Butylmethyldioctylammonium, Butyldodecylmethyloctylammonium, Butyldidodecylmethylammonium, Methyltrioctylammonium, Dodecylmethyldioctylammonium, Didodecylmethyloctylammonium, Tridodecylmethylammonium and other alkylammonium cations; benzyltrimethylammonium, benzyltriethyl Ammonium, benzyltributylammonium, benzyltrioctylammonium, benzylethyldimethylammonium, benzylbutyldimethylammonium, benzyldimethyloctylammonium, benzyldimethyldodecylammonium, benzyldiethylmethylammonium, benzylbutylethylmethylammonium, benzylethylmethyloctylammonium, benzylethyl Dodecylmethylammonium, benzyldibutylmethylammonium, benzylbutylmethyloctylammonium, benzylbutyldodecylmethylammonium, benzyldodecylmethyloctylammonium, benzyldidodecylmethylammonium, benzylbutyldiethylammonium, benzyldi Ethyloctylammonium, benzyldodecyldiethylammonium, benzyldibutylethylammonium, benzylbutylethyloctylammonium, benzylbutyldodecylethylammonium, benzylethyldioctylammonium, benzyldodecylethyloctylammonium, benzyldibutyloctylammonium, benzyldibutyldodecylammonium, benzylbutyldioctylam. Benzylalkylammonium cations such as ammonium, benzylbutyldodecyloctylammonium, benzylbutyldidodecylammonium, benzyldodecyldioctylammonium, benzyldidodecyloctylammonium; allyltrimethylammonium, allyltriethylammonium, allyltributylammonium, allyltrioctylammonium, allylethyl Dimethylammonium, allylbutyldimethylammonium, allyldimethyloctylammonium, allyldimethyldodecylammonium, allyldiethylmethylammonium, allylbutylethylmethylammonium, allylethylmethyloctylammonium, allylethyldodecylmethylammonium, allyldibutylmethylammonium, allylbutylmethyloctyl Ammonium, Allylbutyldodecylmethylammonium, Allyldodecylmethyloctylammonium, Allyldidodecylmethylammonium, Allylbutyldiethylammonium, Allyldiethyloctylammonium, Allyldodecyldiethylammonium, Allyldibutylethylammonium, Allylbutylethyloctylammonium, Allylbutyldodecylethyl Ammonium, allylethyldioctylammonium, allyldodecylethyloctylammonium, allyldibutyloctylammonium, allyldibutyldodecylammonium, allylbutyldioctylammonium, allylbutyldodecyloctylammonium, allylbutyldidodecylammonium, allyldodecyldioctylammonium, allyldidodecyloctylammonium , Allylalkylammonium cations such as diallyldimethylammonium, diallylethylmethylammonium, diallylbutylmethylammonium, diallyloctylammonium, diallyldodecylammonium; 2-acryloyloxyethyl-trimethylammo Nium, 2-acryloyloxyethyl-triethylammonium, 2-acryloyloxyethyl-tributylammonium, 2-acryloyloxyethyl-trioctylammonium, 2-acryloyloxyethyl-ethyldimethylammonium, 2-acryloyloxyethyl-butyldimethylammonium, 2-Acryloyloxyethyl-dimethyloctylammonium, 2-acryloyloxyethyl-dimethyldodecylammonium, 2-acryloyloxyethyl-diethylmethylammonium, 2-acryloyloxyethyl-butylethylmethylammonium, 2-acryloyloxyethyl-ethylmethyloctyl Ammonium, 2-acryloyloxyethyl-ethyldodecylmethylammonium, 2-acryloyloxyethyl-dibutylmethylammonium, 2-acryloyloxyethyl-butylmethyloctylammonium, 2-acryloyloxyethyl-butyldodecylmethylammonium, 2-acryloyloxyethyl -Dodecylmethyloctylammonium, 2-acryloyloxyethyl-didodecylmethylammonium, 2-acryloyloxyethyl-butyldiethylammonium, 2-acryloyloxyethyl-diethyloctylammonium, 2-acryloyloxyethyl-dodecyldiethylammonium, 2-acryloyl Oxyethyl-dibutylethylammonium, 2-acryloyloxyethyl-butylethyloctylammonium, 2-acryloyloxyethyl-butyldodecylethylammonium, 2-acryloyloxyethyl-ethyldioctylammonium, 2-acryloyloxyethyl-dodecylethyloctylammonium, 2-Acryloyloxyethyl-dibutyloctylammonium, 2-acryloyloxyethyl-dibutyldodecylammonium, 2-acryloyloxyethyl-butyldioctylammonium, 2-acryloyloxyethyl-butyldodecyloctylammonium, 2-acryloyloxyethyl-butyldidodecyl 2-Acryloyloxyethyl-alkylammonium cations such as ammonium, 2-acryloyloxyethyl-dodecyldioctylammonium, 2-acryloyloxyethyl-didodecyloctylammonium; 2-methacryloyloxyethyl-trimethylammonium Monium, 2-methacryloyloxyethyl-triethylammonium, 2-methacryloyloxyethyl-tributylammonium, 2-methacryloyloxyethyl-trioctylammonium, 2-methacryloyloxyethyl-ethyldimethylammonium, 2-methacryloyloxyethyl-butyldimethylammonium, 2-Methylloyloxyethyl-dimethyloctylammonium, 2-metharyloxyethyl-dimethyldodecylammonium, 2-methacryloyloxyethyl-diethylmethylammonium, 2-methacryloyloxyethyl-butylethylmethylammonium, 2-methacryloxyethyl-ethylmethyl Octylammonium, 2-methacryloxyethyl-ethyldodecylmethylammonium, 2-methacryloyloxyethyl-dibutylmethylammonium, 2-methacryloxyethyl-butylmethyloctylammonium, 2-methacryloxyethyl-butyldodecylmethylammonium, 2-methacryloyloxy Ethyl-dodecylmethyloctylammonium, 2-methacryloyloxyethyl-didodecylmethylammonium, 2-methacryloyloxyethyl-butyldiethylammonium, 2-methacryloyloxyethyl-diethyloctylammonium, 2-methacryloyloxyethyl-dodecyldiethylammonium, 2- Methacyoyloxyethyl-dibutylethylammonium, 2-methacryloyloxyethyl-butylethyloctylammonium, 2-methacryloyloxyethyl-butyldodecylethylammonium, 2-methacryloxyethyl-ethyldioctylammonium, 2-methacryloxyethyl-dodecylethyloctylammonium , 2-Methylloyloxyethyl-dibutyloctylammonium, 2-methacryloyloxyethyl-dibutyldodecylammonium, 2-methacryloyloxyethyl-butyldioctylammonium, 2-methacryloyloxyethyl-butyldodecyloctylammonium, 2-methacryloyloxyethyl-butyldi 2-Methylloyloxyethyl-alkylammoni such as dodecylammonium, 2-methacryloxyethyl-dodecyldioctylammonium, 2-methacryloyloxyethyl-didodecyloctylammonium Umm cations can be mentioned. These can be used alone or in combination of two or more.

Specific examples of the Helicobacter pylori cation represented by the formula (e) include 1,1-dimethylpylorium, 1-ethyl-1-methylpyrrorium, 1-methyl-1-propylpyrrorium, and 1-butyl-1. -Methylpyrorium, 1-Methyl-1-hexylpyrorium, 1-Methyl-1-octylpyrorium, 1-dodecyl-1-methylpyrorium, 1,1-diethylpyrorium, 1-ethyl-1-propyl Helicobacter pylori, 1-butyl-1-ethylpyrorium, 1-ethyl-1-hexylpyrorium, 1-ethyl-1-octylpyrorium, 1-dodecyl-1-ethylpyrorium, 1,1-dipropylpyrori Um, 1-butyl-1-propylpyrorium, 1-propyl-1-hexylpyrrorium, 1-propyl-1-octylpyrorium, 1-dodecyl-1-propylpyrorium, 1,1-dibutylpyrorium, 1-butyl-1-hexylpyrorium, 1-butyl-1-octylpyrorium, 1-butyl-1-dodecylpyrorium, 1,1-dihexylpyrorium, 1-hexyl-1-octylpyrorium, 1- Examples thereof include Helicobacter pylori cations such as Dodecyl-1-hexylpyrorium, 1,1-dioctylpyrorium, 1-dodecyl-1-octylpyrorium, and 1,1-didodecylpyrorium. These can be used alone or in combination of two or more.

Specific examples of the cation represented by the formula (f) include 4,4-dimethylmorpholinium, 4-ethyl-4-methylmorpholinium, 4-methyl-4-propylmorpholinium, and 4-butyl-. 4-Methylmorpholinium, 4-hexyl-4-methylmorpholinium, 4-methyl-4-octylmorpholinium, 4-dodecyl-4-methylmorpholinium, 4,4-diethylmorpholinium, 4 -Ethyl-4-propylmorpholinium, 4-butyl-4-ethylmorpholinium, 4-ethyl-4-hexylmorpholinium, 4-ethyl-4-octylmorpholinium, 4-dodecyl-4-ethyl Morphorinium, 4,4-dipropylmorpholinium, 4-butyl-4-propylmorpholinium, 4-hexyl-4-propylmorpholinium, 4-octyl-4-propylmorpholinium, 4-dodecyl -4-propylmorpholinium, 4,4-dibutylmorpholinium, 4-butyl-4-hexylmorpholinium, 4-butyl-4-octylmorpholinium, 4-butyl-4-dodecylmorpholinium, 4,4-Dihexylmorpholinium, 4-hexyl-4-octylmorpholinium, 4-dodecyl-4-hexylmorpholinium, 4,4-dioctylmorpholinium, 4-dodecyl-4-octylmorpholinium , 4,4-Didodecylmorpholinium and other morpholinium cations; 4,4-dimethylthiomorpholinium, 4-ethyl-4-methylthiomorpholinium, 4-methyl-4-propylthiomorpholinium, 4-Butyl-4-methylthiomorpholinium, 4-hexyl-4-methylthiomorpholinium, 4-methyl-4-octylthiomorpholinium, 4-dodecyl-4-methylthiomorpholinium, 4,4-diethyl Thiomorpholinium, 4-ethyl-4-propylthiomorpholinium, 4-butyl-4-ethylthiomorpholinium, 4-ethyl-4-hexylthiomorpholinium, 4-ethyl-4-octylthiomol Holinium, 4-dodecyl-4-ethylthiomorpholinium, 4,4-dipropylthiomorpholinium, 4-butyl-4-propylthiomorpholinium, 4-hexyl-4-propylthiomorpholinium, 4-octyl-4-propylthiomorpholinium, 4-dodecyl-4-propylthiomorpholinium, 4,4-dibutylthiomorpholinium, 4-butyl-4-hexylthiomorpholinium , 4-Butyl-4-octylthiomorpholinium, 4-butyl-4-dodecylthiomorpholinium, 4,4-dihexylthiomorpholinium, 4-hexyl-4-octylthiomorpholinium, 4-dodecyl -4-Hexylthiomorpholinium, 4,4-dioctylthiomorpholinium, 4-dodecyl-4-octylthiomorpholinium, 4,4-didodecylthiomorpholinium and other thiomorpholinium cations Can be mentioned. These can be used alone or in combination of two or more.

As the anion A ⁻ , a fluorine-based anion is used. The fluorine-based anion is not particularly limited, and is, for example, an inorganic fluorine-based anion such as tetrafluoroborate (BF _4- ⁾ or hexafluorophosphate (PF _6- ^{) ;} RSO _3- such as CF ₃ SO _3- ⁽ in the formula). , R represents a fluoroalkyl group); (CF ₃ SO ₂ ) ₂ N ⁻ (ie, TFSI anion), (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , etc. (RSO ₂ ) Fluoroalkanesulfonylimide anion represented by ₂ N- ⁽ in the formula, R represents a fluoroalkyl group); (FSO ₂ ) ₂ N- ⁽ ie, FSI anion); (CF ₃ SO ₂ ) ₃ C ^- etc. RSO ₂ ) ₃ C- ⁽ in the formula, R represents a fluoroalkyl group) fluoroalkane sulfonyl carboanion; CF ₃ CO _2- ^, C ₃ F ₇ CO _2- ^, etc. ^RCOO- (in the formula, R is Fluorocarboxylate anionic acid represented by) (representing a fluoroalkyl group) and the like can be mentioned. These can be used alone or in combination of two or more.

The ionic liquid according to this embodiment has a total amine value of 0.013 or less in the potentiometric titration method. When the total amine value is 0.013 or less, coloring in a high temperature environment can be suppressed, and long-term hue stability can be obtained. The total amine value of the ionic liquid is represented by the mg number of perchloric acid and equivalent potassium hydroxide required to neutralize the total basic nitrogen contained in 1 g of the sample (ionic liquid), and is an unnamed number. .. The total amine value of the ionic liquid is preferably 0.010 or less. Since the smaller the total amine value is, the more preferable it is, the lower limit is not particularly limited.

An ionic liquid having a total amine value of 0.013 or less can be obtained by removing impurities of primary to tertiary amines derived from raw materials. In the method for producing an ionic liquid obtained by reacting a compound containing a cation K ⁺ with a compound containing an anion A ⁻ , as a method for removing primary to tertiary amines, for example, after the reaction of the ionic liquid is generated, or At the stage of the raw material (that is, the compound containing the cation K ⁺ ) before the reaction, a method of contacting the remaining primary to tertiary amines with an acid to remove the primary to tertiary amines can be mentioned. However, as long as the primary to tertiary amines can be removed so that the total amine value is 0.013 or less, the method is not limited to the method of contacting with such an acid.

One method for producing an ionic liquid according to an embodiment is to react a compound containing a cation K ⁺ with a compound containing an anion A ⁻ to generate an ionic liquid, and bring the obtained ionic liquid into contact with an acid. including. For example, a method including the following steps 1 to 3 can be mentioned.
-Step 1: A step of reacting an amine with a quaternizing agent to produce a compound containing a cation K ⁺ .
Step 2: A step of reacting the obtained compound containing the cation K ⁺ with the compound containing the anion A ⁻ to form an ionic liquid, and
-Step 3: A step of bringing the obtained ionic liquid into contact with an acid.

Examples of the amine used in step 1 include amines corresponding to the above cation K ⁺ , preferably tertiary amines. Examples of the quaternizing agent for quaternizing the amine include alkyl halides such as methyl chloride, methyl bromide and octyl bromide, dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, dipropyl sulfate and dihexyl sulfate, and propyl methanesulfonate. , Alkyl methanesulfonic acid such as methyl methanesulphonate, trialkylphosphoric acid such as trimethylphosphoric acid, benzyl halide, glycidyl ether compound, epichlorohydrin and the like. By reacting the amine with the quaternary agent, a quaternary ammonium salt can be obtained as a compound containing the cation K ⁺ .

In step 2, the compound containing the cation K ⁺ and the compound containing the anion A ⁻ are reacted. Specifically, an alkali metal salt of anion A ^- is used as a compound containing anion A-, ^and the quaternary ammonium salt is mixed with the alkali metal salt in an equivalent amount in water or a solvent for salt exchange. The ionic liquid represented by the above general formula (1) can be obtained.

In step 3, the ionic liquid layer separated after the above reaction is taken out, and an acid is added to the ionic liquid layer to bring the ionic liquid into contact with the acid. Specifically, by mixing an ionic liquid and an aqueous solution of an acid, the primary to tertiary amines remaining in the ionic liquid are brought into contact with the acid for reaction, and then separated into two layers to form an ionic liquid layer. Take out. By repeating such treatment and separation with an acid once or two or more times, the ionic liquid taken out can be washed with water to remove by-products.

The acid to be brought into contact with the ionic liquid is not particularly limited, and for example, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitrate and phosphoric acid, sulfonic acid such as methanesulfonic acid and p-toluenesulfonic acid, and acetic acid. , Cyclic acid, carboxylic acid such as oxalic acid, etc. may be mentioned, and any one or two or more of them may be combined.

The number of repetitions of the treatment with the acid and the separation is not particularly limited, and the treatment with the acid and the separation may be repeated until the total amine value of the ionic liquid becomes 0.013 or less.

The temperature at which the ionic liquid and the acid are brought into contact (that is, the treatment temperature with the acid) is preferably 50 ° C. or higher. By treating at 50 ° C. or higher, the efficiency of removing the remaining primary to tertiary amines can be increased, and the number of repetitions of the above-mentioned acid treatment and separation can be reduced. The upper limit of the treatment temperature with an acid is not particularly limited, but is preferably 90 ° C. or lower.

After washing with water as described above, the ionic liquid according to the embodiment can be obtained by, for example, vacuum drying.

In the above embodiment, it was decided to remove the primary to tertiary amines using an acid after the reaction between the compound containing the cation K ⁺ and the compound containing the anion A ⁻ , but the treatment with the acid is the stage of the raw material before the reaction. It may be carried out at both the raw material stage before the reaction and the post-reaction stage.

That is, in the method for producing an ionic liquid according to another embodiment, a step of reacting an amine with a quaternizing agent to produce a compound containing a cation K ⁺ , and a step of producing a compound containing the obtained cation K ⁺ with an acid are used. It includes a step of contacting, a step of reacting a compound containing a cation K ⁺ with a compound containing an anion A ⁻ to generate an ionic liquid, and a step of washing the produced ionic liquid with water.

As a method of contacting a compound containing cation K ⁺ with an acid, a compound containing cation K ⁺ is produced by a reaction between an amine and a quaternizing agent, and then the compound containing cation K ⁺ alone, or methanol or isopropanol. Alcohol such as, carboxylic acid ester such as ethyl acetate and butyl acetate, organic solvent such as toluene Diluting conditions, or water diluting condition, the compound containing cation K ⁺ is brought into contact with the acid. The by-product of contacting the remaining primary to tertiary amines in the compound containing cation K ⁺ with an acid and reacting the compound is an ionic liquid obtained by reacting the compound containing cation K ⁺ with the compound containing anion A ⁻ . After the step of producing the ionic liquid, the generated ionic liquid is removed by the step of washing with water.

The temperature at which the compound containing the cation K ⁺ and the acid are brought into contact with each other (that is, the treatment temperature with the acid) is preferably 50 ° C. or higher. By treating at 50 ° C. or higher, the efficiency of removing the remaining primary to tertiary amines can be improved. The upper limit of the treatment temperature with an acid is not particularly limited, but is preferably 90 ° C. or lower.

The use of the ionic liquid according to the embodiment is not particularly limited, and can be used in various fields of electrical and electronic materials. According to this embodiment, since coloring in a high temperature environment can be suppressed, high performance is applied to various electrochemical devices, particularly applications for optical materials (for example, an in-vehicle display that requires heat resistance). It is possible to provide a fluorine-based ionic liquid showing the above.

In one embodiment, the ionic liquid is preferably used as an additive for optical materials. Examples of the additive include antistatic agents, conductivity-imparting agents, surface treatment agents, flame retardants, plasticizers, bactericides, solubilizers, CO ₂ absorbers, lubricants and the like, and are derived from these additives. It is possible to improve the coloring over time.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

The raw materials used in Examples and Comparative Examples are shown below.

[Evaluation methods]
・ Total amine value:
The sample was dissolved in acetic acid to prepare an analytical sample. Potentiometric titrator COM-1700A manufactured by HIRANUMA Co., Ltd. (Indicator electrode manufactured by HIRANUMA Co., Ltd .: Glass electrode GE-101B, Reference electrode manufactured by HIRANUMA Co., Ltd .: 4M-KCl internal electrode RE-201, Titration solution manufactured by Kishida Chemical Co., Ltd .: 0.01 mol / The total amine value was measured by the following formula.
Total amine value = 56.11 x titration (mL) x titration concentration 0.01 (mol / L) x titer titer ÷ sample mass (g)

・ Number of colors APHA:
The sample was taken in a colorimetric tube, and the Hazen color number (APHA) was measured with a petroleum product measuring device OEM-2000 (manufactured by Nippon Denshoku Kogyo).

[Example 1]
100 g (0.52 mol) of n-octyl bromide and 40 g of isopropyl alcohol were placed in a 500 mL four-necked flask equipped with a stirrer, a dropping funnel, a cooling tube and a thermometer, and heated to 80 ° C. 48.2 g (0.52 mol) of γ-picoline was slowly added dropwise thereto. After further reacting at 80 ° C. for 6 hours, the mixture was added to 300 g of ion-exchanged water and dissolved. The pressure was reduced to 60 ° C. or lower to remove isopropyl alcohol, and then the mixture was diluted with ion-exchanged water to obtain 281.6 g of an aqueous solution of 1-octyl-4-methylpyridinium / bromide salt having a solid content of 50% by mass.

Next, a mixture of 107.8 g of potassium bis (fluorosulfonyl) imide dissolved in 107.8 g of ion-exchanged water was added to 281.6 g of the obtained aqueous solution of 1-octyl-4-methylpyridinium / bromide salt at room temperature. Stirred. The lower layer separated into two layers was separated. A 10 mass% citric acid aqueous solution was added to the lower layer, and the mixture was stirred at 50 ° C. and the lower layer separated into two layers was separated again. After performing this operation three times, by-products are removed by washing with ion-exchanged water at 50 ° C., and vacuum drying is performed to obtain 1-octyl-4-methylpyridinium = bis (fluorosulfonyl) imide 171. 0 g was obtained. In the obtained ionic liquid, the cation K ⁺ is represented by the formula (2)-(c) (R ¹ = n-octyl, R ⁷ = methyl, R ⁵ , R ⁶ , R ⁸ , R ⁹ = H). , Anion A ⁻ is an FSI anion. The total amine value of the ionic liquid was measured. In addition, in order to confirm the color suppression effect in a high temperature environment, a test was conducted in which the color was left in an atmosphere of 85 ° C for 3 weeks, and the number of colors APHA before and after the test was measured, and the difference between the two was measured. The ratio of (Δ) to the number of colors after the test to the number of colors before the test (after test / before test) was calculated. The results are shown in Table 1 below.

[Example 2]
The ionic liquid was prepared by the same operation as in Example 1 except that the number of washings with the 10 mass% citric acid aqueous solution was set to 2 times. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Example 3]
In Example 1, after obtaining an aqueous solution of 1-octyl-4-methylpyridinium / bromide salt, nitric acid was added so as to be 1% by mass, a reaction was carried out at 50 ° C., and the acid treatment was carried out in this manner 1 The ionic liquid was operated in the same manner as in Example 1 except that an aqueous solution of octyl-4-methylpyridinium / bromide salt was used and washing with a 10 mass% citric acid aqueous solution was not performed. Was prepared. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Comparative Example 1]
The ionic liquid was prepared by the same operation as in Example 1 except that the washing with a 10 mass% citric acid aqueous solution was not carried out. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Example 4]
32.8 g (0.40 mol) of 1-methylimidazole and 40 mL of toluene were placed in a 200-four-necked flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, and heated to 40 ° C. 61.6 g (0.40 mol) of diethyl sulfate was slowly added dropwise thereto. After further reacting at 50 ° C. for 1 hour, the mixture was added to 150 g of ion-exchanged water and dissolved. After depressurizing at 70 ° C. or lower to remove toluene, dilute with ion-exchanged water to dilute with 50% by mass of solid-content ion-exchanged water, and then dilute with 50% by mass of solid-content 1-ethyl-3-methylimidazolium. 175.6 g of an aqueous solution of ethyl sulfate was obtained.

Next, to 175.6 g of the obtained aqueous solution of 1-ethyl-3-methylimidazolium ethyl sulfate, a mixture of 81.4 g of potassium bis (fluorosulfonyl) imide dissolved in 81.4 g of ion-exchanged water was added, and the mixture was added to room temperature. Was stirred with. The lower layer separated into two layers was separated. A 10 mass% citric acid aqueous solution was added to the lower layer, and the mixture was stirred at 50 ° C. and the lower layer separated into two layers was separated again. After performing this operation three times, by-products are removed by washing with ion-exchanged water at 50 ° C. and vacuum-drying to perform 1-ethyl-3-methylimidazolium = bis (fluorosulfonyl) imide 75. 0.7 g was obtained. In the obtained ionic liquid, the cation K ⁺ is represented by the formula (2)-(a) (R ¹ = ethyl, R ² = methyl, R ³ = H), and the anion A ⁻ is an FSI anion. For the ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Example 5]
The number of washings with the 10 mass% citric acid aqueous solution was set to 2 times, and the ionic liquid was prepared by the same operation as in Example 4 except for the washing. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Comparative Example 2]
The ionic liquid was prepared by the same operation as in Example 4 except that the washing with a 10 mass% citric acid aqueous solution was not carried out. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Example 6]
A mixture of 100 mL of ethyl acetate and 60.0 g of lithium bis (fluorosulfonyl) imide dissolved in 60.0 g of ion-exchanged water is added to 200.0 g of an aqueous solution of tri-n-butylbenzylammonium chloride salt having a solid content of 50% by mass. , Stirred at room temperature. The lower layer separated into two layers was separated. A 10 mass% citric acid aqueous solution was added to the lower layer, and the mixture was stirred at 50 ° C. and the lower layer separated into two layers was separated again. After performing this operation three times, by-products were removed by washing with ion-exchanged water at 50 ° C., and vacuum drying was performed to obtain an alkylbenzylammonium = bis (fluorosulfonyl) imide. In the obtained ionic liquid, the cation K ⁺ is represented by the formula (2)-(d) (R ¹ = benzyl, R ² , R ³ , R ⁴ = n-butyl), and the anion A ^- is an FSI anion. be. For the ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Comparative Example 3]
The ionic liquid was prepared by the same operation as in Example 6 except that the washing with a 10 mass% citric acid aqueous solution was not carried out. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 85 ° C. for 3 weeks was measured. The results are shown in Table 1.

[Example 7]
85.9 g (0.52 mol) of n-hexyl bromide instead of 100 g (0.52 mol) of n-octyl bromide, 141.2 g of lithium bis (trifluoromethanesulfonyl) imide instead of 107.8 g of potassium bis (fluorosulfonyl) imide An ionic liquid was prepared by the same operation as in Example 2 except that the above was used. In the obtained ionic liquid, the cation K ⁺ is represented by the formula (2)-(c) (R ¹ = n-hexyl, R ⁷ = methyl, R ⁵ , R ⁶ , R ⁸ , R ⁹ = H). , Anion A ^- is a TFSI anion. For the ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2 below.

[Comparative Example 4]
The ionic liquid was prepared by the same operation as in Example 7 except that the washing with a 10 mass% citric acid aqueous solution was not carried out. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2.

[Example 8]
An ionic liquid was prepared by the same procedure as in Example 4 except that 106.6 g of lithium bis (trifluoromethanesulfonyl) imide was used instead of 81.4 g of potassium bis (fluorosulfonyl) imide. In the obtained ionic liquid, the cation K ⁺ is represented by the formula (2)-(a) (R ¹ = ethyl, R ² = methyl, R ³ = H), and the anion A ⁻ is a TFSI anion. For the ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2 below.

[Example 9]
The ionic liquid was prepared by the same operation as in Example 8 except that the number of washings with the 10 mass% citric acid aqueous solution was set to 2 times. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2.

[Comparative Example 5]
The ionic liquid was prepared by the same operation as in Example 8 except that the washing with a 10 mass% citric acid aqueous solution was not carried out. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2.

[Example 10]
Instead of 200.0 g of an aqueous solution of tri-n-butylbenzylammonium chloride salt having a 50% by mass solid content, 151.2 g of an aqueous solution of tri-n-butylmethylammonium chloride salt having a 50 mass% solid content, lithium bis (fluorosulfonyl) Using 92.1 g of lithium bis (trifluoromethanesulfonyl) imide instead of 60.0 g of the imide, the ionic liquid was prepared by the same operation as in Example 6 except that the number of washings with the 10 mass% ammonium citrate aqueous solution was 3 times. Prepared. In the obtained ionic liquid, the cation K ⁺ is represented by the formula (2)-(d) (R ¹ , R ² , R ³ = n-butyl, R ⁴ = methyl), and the anion A ^- is a TFSI anion. be. For the ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2.

[Example 11]
The ionic liquid was prepared by the same operation as in Example 10 except that the number of washings with the 10 mass% citric acid aqueous solution was set to 2 times. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2.

[Comparative Example 6]
The ionic liquid was prepared by the same operation as in Example 10 except that the washing with a 10 mass% citric acid aqueous solution was not carried out. For the obtained ionic liquid, the total amine value was measured, and the number of colors APHA before and after the test at 115 ° C. for 2 weeks was measured. The results are shown in Table 2.

[Comparative Example 7]
An ionic liquid was prepared by the same operation as in Example 2 except that the washing operation with a 10 mass% citric acid aqueous solution was changed from 50 ° C. to 25 ° C. The total amine value of the obtained ionic liquid was measured and found to be 0.029, which was lower than that of Example 2. It is considered that the total amine value can be reduced to 0.013 or less by increasing the number of washings, but it was found that the washing efficiency is lower when washing at 25 ° C than when washing at 50 ° C.

As shown in Tables 1 and 2, the ionic liquids subjected to the acid cleaning of Examples 1 to 11 are all under higher temperature than the ionic liquids not subjected to the acid cleaning of Comparative Examples 1 to 6. The change in the number of colors after long-term storage was small, and coloring was suppressed. This tendency is related to the total amine value of the ionic liquid (1st to 3rd grade amines remaining in a trace amount), and by setting the total amine value to 0.013 or less, the effect of suppressing the change in coloring with time can be obtained. rice field.

Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments, omissions, replacements, changes, etc. thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.

Claims (6)

An ionic liquid having a pair of cation K ⁺ and anion A ⁻ represented by the following general formula (1), wherein the cation K ⁺ is selected from the group represented by the following general formula (2). Or two or more, the anion A ^- is at least one of a fluoroalcan sulfonylimide anion or (FSO ₂ ) ₂ N- ^, and the total amine value in the potential differential titration method is 0.013 or less, which is a fluoroionic ionic property. liquid.
General formula (1) ^: K ⁺ A-
General formula (2):

In formula (2), R ¹ to R ⁹ are independently substituted or unsubstituted, saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbons having 1 to 20 carbon atoms. A group, an substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, where R ⁵ to R ⁹ are independent of each other. It may be a hydrogen atom, and when the aliphatic hydrocarbon group, the aryl group or the arylalkyl group is substituted, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acryloyl group, a methacryloyl group or an acyloxy group. , Acrylic group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, cyano group, trifluoromethyl group, trichloromethyl group, and trimethylsilyl group. Substituted with at least one, n is an integer of 1 to 5, and the compound represented by the formula (f) is a 4- to 7-membered ring containing one or more oxygen or sulfur atoms represented by X. Saturated or unsaturated heterocyclic compound , in formula (d) whether at least one of R ¹ to R ⁴ is substituted or unsubstituted, an aryl group having 6 to 30 carbon atoms or substituted. Alternatively, it is an unsubstituted arylalkyl group having 7 to 31 carbon atoms . The fluorine-based ionic liquid according to claim 1, which is used as an additive for an optical material. The method for producing a fluorinated ionic liquid according to claim 1 or 2.
Fluoroionic ionicity, which comprises reacting the compound containing the cation K ⁺ with the compound containing the anion A ⁻ to generate a fluoroionic ionic liquid, and contacting the obtained fluoroionic liquid with an acid. Liquid manufacturing method. The method for producing an ionic liquid according to claim 3, wherein the fluorinated ionic liquid is brought into contact with an acid at 50 ° C. or higher. An ionic liquid having a pair of cation K ⁺ and anion A ⁻ represented by the following general formula (1), wherein the cation K ⁺ is selected from the group represented by the following general formula (2). Alternatively, it is a method for producing a fluorine-based ionic liquid, which is two or more kinds, the anion A ⁻ is a fluorine-based anion, and the total amine value in the potential differential titration method is 0.013 or less .
The amine is reacted with the quaternizing agent to produce the compound containing the cation K ⁺ , the compound containing the cation K ⁺ is brought into contact with the acid, and then the compound containing the cation K ⁺ and the anion A ⁻ are formed. A method for producing a fluorine-based ionic liquid, which comprises reacting with a containing compound to generate a fluorine-based ionic liquid.
General formula (1) ^: K ⁺ A-
General formula (2):

In formula (2), R ¹ to R ⁹ are independently substituted or unsubstituted saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbons having 1 to 20 carbon atoms. A group, an substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or an substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, where R ⁵ to R ⁹ are independent of each other. It may be a hydrogen atom, and when the aliphatic hydrocarbon group, the aryl group or the arylalkyl group is substituted, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acryloyl group, a methacryloyl group, an acyloxy group. , Aryl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, cyano group, trifluoromethyl group, trichloromethyl group, and trimethylsilyl group. Substituted with at least one, n is an integer of 1 to 5, and the compound represented by the formula (f) is a 4- to 7-membered ring containing one or more oxygen or sulfur atoms represented by X. It is a saturated or unsaturated heterocyclic compound. The method for producing a fluorine-based ionic liquid according to claim 5, wherein the compound containing the cation K ⁺ is brought into contact with an acid at 50 ° C. or higher.