TWI501948B - Onium salt composition - Google Patents

Description

Bismuth salt composition

The present invention relates to an onium salt composition.

An onium salt having a phosphorus hexafluoride (PF ₆ ^- ) anion is widely used in an electrolyte for an electrochemical element such as an electric double layer capacitor, a surfactant, a phase transfer catalyst, an antistatic agent, a bactericide, and the like. However, since the cerium salt is easily hygroscopic and is also liable to cause hydrolysis, it may be hydrolyzed due to the inability to avoid the incorporation of trace amounts of water during storage and treatment, and may cause toxicity and corrosiveness to metals or resins. The problem of hydrogen fluoride.

As a good storage stability of PF6 ^- salts are, in Japanese Laid-Open Patent Publication No. 2001-48846, although PF ₆ is disclosed having a particular non-solvent to the coating ^- the onium salts, but with the particular coating solvent PF ₆ ^- When the salt is at 60 ° C or higher, it is also hydrolyzed by a trace amount of water, so it cannot be said that it has sufficient stability.

The present invention provides the following <1> to <8>:

<1> an onium salt composition containing a phosphonium salt represented by the formula (1) and a composition of an organic base,

Formula 1):

Q ⁺ ‧A ^- (1)

(wherein Q ⁺ represents a cesium ion and A ^- represents PF ₆ ^- );

<2> a salt composition of <1>, which further comprises a solvent;

<3> a salt composition of <1> or <2>, wherein the cerium ion is a quaternary ammonium cation or a quaternary phosphonium cation;

<4> The bismuth salt composition according to any one of <1> to <3> wherein the organic base is a tertiary amine or a phosphine;

<5> The salt composition of <4>, wherein the tertiary amine is selected from the group consisting of aliphatic tertiary amines, aromatic tertiary amines, pyridin and imidazol. At least one

The salt composition of any one of <1> to <5>, wherein the content of the organic base is 10 to 5000 ppm with respect to the onium salt represented by the formula (1);

<7> A method for stabilization of a cerium salt, which is characterized by mixing a cerium salt and an organic base represented by the formula (1);

<8> A method for preserving a cerium salt, which is characterized in that the cerium salt represented by the formula (1) is preserved in the presence of an organic base.

Best form for implementing the invention

In the formula of the onium salt (hereinafter referred to as the onium salt (1)) represented by the formula (1), examples of the onium ion represented by Q ⁺ include a quaternary ammonium cation and a quaternary phosphonium cation.

Examples of the quaternary ammonium cation include a tetraalkylammonium cation, a pyrrolidinium cation, a morpholinium cation, an imidazolium cation, a tetrahydropyrimidinium cation, Piperazinium cation, piperidinium cation, pyridinium cation, and the like. Examples of the fourth-order phosphonium cation include a tetraalkyl phosphonium cation.

Examples of the tetraalkylammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, tetraamylammonium cation, tetrahexylammonium cation, and tetraheptyl group. Ammonium cation, tetraoctyl ammonium cation, tetradecylammonium cation, tetradecylammonium cation, tetrakis(dodecyl)ammonium cation, ethyltrimethylammonium cation, diethyldimethylammonium cation, triethyl Methyl ammonium cation, tetraethyl ammonium cation, trimethyl propyl ammonium cation, trimethyl isopropyl ammonium cation, ethyl dimethyl propyl ammonium cation, ethyl dimethyl isopropyl ammonium cation, Diethylmethylpropylammonium cation, diethylmethylisopropylammonium cation, dimethyldipropylammonium cation, dimethylpropylisopropylammonium cation, dimethyldiisopropylammonium cation , triethyl propyl ammonium cation, butyl trimethyl ammonium cation, isobutyl trimethyl ammonium cation, tertiary butyl trimethyl ammonium cation, triethyl isopropyl ammonium cation, ethyl methyl two Propyl ammonium cation, ethyl methyl diisopropyl ammonium cation, butyl Ethyl dimethyl ammonium cation, isobutyl ethyl dimethyl ammonium cation, tertiary butyl ethyl dimethyl ammonium cation, diethyl dipropyl ammonium cation, diethyl propyl isopropyl ammonium cation , diethyldiisopropylammonium cation, methyltripropylammonium cation, methyldipropylisopropylammonium cation, methylpropyldiisopropylammonium cation, butyltriethylammonium cation, different Butyl triethylammonium cation, tertiary butyl triethylammonium cation, dibutyldimethylammonium cation, diisobutyldimethylammonium cation, di-tertiary butyldimethylammonium cation, butyl Isobutyl dimethyl ammonium cation, butyl tertiary butyl dimethyl ammonium cation, isobutyl tertiary butyl dimethyl ammonium cation, trioctylmethyl ammonium cation, and the like.

Examples of the pyrrolidinium cation include a 1,1-dimethylpyrrolidinium cation, a 1-ethyl-1-methylpyrrolidinium cation, a 1,1-diethylpyrrolidinium cation, and 1 1,1,3-trimethylpyrrolidinium cation, 1,1,3-trimethylpyrrolidinium cation, 1-ethyl-1,2-dimethylpyrrolidinium cation, 1-ethyl-1 , 3-dimethylpyrrolidinium cation, 2-ethyl-1,1-dimethylpyrrolidinium cation, 3-ethyl-1,1-dimethylpyrrolidinium cation, 1,1-di Ethyl-2-methylpyrrolidinium cation, 1,1-diethyl-3-methylpyrrolidinium cation, 1,2-diethyl-1-methylpyrrolidinium cation, 1,3- Diethyl-1-methylpyrrolidinium cation, 1,1,2-triethylpyrrolidinium cation, 1,1,3-triethylpyrrolidinium cation, 1,1,2,2-tetra Methyl pyrrolidinium cation, 1,1,2,3-tetramethylpyrrolidinium cation, 1,1,2,4-tetramethylpyrrolidinium cation, 1,1,2,5-tetramethyl Pyrrolidinium cation, 1,1,3,4-tetramethylpyrrolidinium cation, 1,1,3,3-tetramethylpyrrolidinium cation, 1,1-dimethylpyrrolidinium cation, 1 -ethyl-1-methylpyrrolidinium Ionic, 1,1-diethylpyrrolidinium cation, 1,1,2-trimethylpyrrolidinium cation, 1,1,3-trimethylpyrrolidinium cation, 1-ethyl-1,2 - dimethylpyrrolidinium cation, 1-ethyl-1,3-dimethylpyrrolidinium cation, 2-ethyl-1,1-dimethylpyrrolidinium cation, 3-ethyl-1, 1-dimethylpyrrolidinium cation, 1,1-diethyl-2-methylpyrrolidinium cation, 1,1-diethyl-3-methylpyrrolidinium cation, 1,2-diethyl 1,1-methylpyrrolidinium cation, 1,3-diethyl-1-methylpyrrolidinium cation, 1,1,2-triethylpyrrolidinium cation, 1,1,3-triethyl Pyrrolidinium cation, 1,1,2,2-tetramethylpyrrolidinium cation, 1,1,2,3-tetramethylpyrrolidinium cation, 1,1,2,4-tetramethylpyrrole Alkane cation, 1,1,2,5-tetramethylpyrrolidinium cation, 1,1,3,4-tetramethylpyrrolidinium cation, 1,1,3,3-tetramethylpyrrolidinium Cation, 2-ethyl-1,1,2-trimethylpyrrolidinium cation, 2-ethyl-1,1,3-trimethylpyrrolidinium cation, 3-ethyl-1,1,2 -trimethylpyrrolidinium cation, 3-ethyl-1,1,3-trimethylpyrrolidinium Ionic, 2-ethyl-1,1,4-trimethylpyrrolidinium cation, 4-ethyl-1,1,2-trimethylpyrrolidinium cation, 2-ethyl-1,1,5 - trimethylpyrrolidinium cation, 5-ethyl-1,1,2-trimethylpyrrolidinium cation, 3-ethyl-1,1,4-trimethylpyrrolidinium cation, 4-B 1,1-trimethylpyrrolidinium cation, 1-ethyl-1,2,2-trimethylpyrrolidinium cation, 1-ethyl-1,2,3-trimethylpyrrole Alkane cation, 1-ethyl-1,3,3-trimethylpyrrolidinium cation, 1-ethyl-1,2,4-trimethylpyrrolidinium cation, 1-ethyl-1,2 , 5-trimethylpyrrolidinium cation, 1-ethyl-1,3,4-trimethylpyrrolidinium cation, 2,2-diethyl-1,1-dimethylpyrrolidinium cation, 2,3-diethyl-1,1-dimethylpyrrolidinium cation, 3,3-diethyl-1,1-dimethylpyrrolidinium cation, 2,4-diethyl-1, a 1-dimethylpyrrolidinium cation, a 2,5-diethyl-1,1-dimethylpyrrolidinium cation, a 3,4-diethyl-1,1-dimethylpyrrolidinium cation, 1,2-diethyl-1,2-dimethylpyrrolidinium cation, 1,2-diethyl-1,3-dimethylpyrrolidinium cation, 1,3- Ethyl-1,2-dimethylpyrrolidinium cation, 1,3-diethyl-1,3-dimethylpyrrolidinium cation, 1,2-diethyl-1,4-dimethyl Pyrrolidinium cation, 1,4-diethyl-1,2-dimethylpyrrolidinium cation, 1,2-diethyl-1,5-dimethylpyrrolidinium cation, 1,5-di Ethyl-1,2-dimethylpyrrolidinium cation, 1,3-diethyl-1,4-dimethylpyrrolidinium cation, 1,1,2,2,3-pentamethylpyrrolidine Ruthenium cation, 1,1,2,2,4-pentamethylpyrrolidinium cation, 1,1,2,2,5-pentamethylpyrrolidinium cation, 1,1,2,3,4-five Methyl pyrrolidinium cation, 1,1,2,3,5-pentamethylpyrrolidinium cation, 1,1,3,3,4-pentamethylpyrrolidinium cation, 1,1,3,3 , 5-pentamethylpyrrolidinium cation, 1-ethyl-1,2,2,3-tetramethylpyrrolidinium cation, 1-ethyl-1,2,2,4-tetramethylpyrrolidine Ruthenium cation, 1-ethyl-1,2,2,5-tetramethylpyrrolidinium cation, 1-ethyl-1,2,3,4-tetramethylpyrrolidinium cation, 1-ethyl- 1,2,3,5-tetramethylpyrrolidinium cation, 1-ethyl-1,2,4,5-tetramethylpyrrolidinium cation, 1-ethyl-1,3,3,4- Tetramethylpyrrolidine cation 1-ethyl-1,3,3,5-tetramethylpyrrolidinium cation, 1-ethyl-1,3,4,5-tetramethylpyrrolidinium cation, 2-ethyl-1,1 , 2,3-tetramethylpyrrolidinium cation, 2-ethyl-1,1,2,4-tetramethylpyrrolidinium cation, 2-ethyl-1,1,2,5-tetramethyl Pyrrolidinium cation, 2-ethyl-1,1,3,3-tetramethylpyrrolidinium cation, 2-ethyl-1,1,3,4-tetramethylpyrrolidinium cation, 2-B 1,2-,3,5-tetramethylpyrrolidinium cation, 2-ethyl-1,1,4,4-tetramethylpyrrolidinium cation, 2-ethyl-1,1,4, 5-tetramethylpyrrolidinium cation, 2-ethyl-1,1,5,5-tetramethylpyrrolidinium cation, 3-ethyl-1,1,2,2-tetramethylpyrrolidinium Cation, 3-ethyl-1,1,2,3-tetramethylpyrrolidinium cation, 3-ethyl-1,1,2,4-tetramethylpyrrolidinium cation, 3-ethyl-1 , 1,2,5-tetramethylpyrrolidinium cation, 3-ethyl-1,1,3,4-tetramethylpyrrolidinium cation, 3-ethyl-1,1,4,4-tetra a methylpyrrolidine cation, a 3-ethyl-1,1,4,5-tetramethylpyrrolidinium cation, a 1,1,2,2,3,3-hexamethylpyrrolidinium cation, 1, 1,2,2,3,4-hexamethylpyrrolidinium cation, 1,1,2,2, 3,5-hexamethylpyrrolidinium cation, 1,1,2,2,4,4-hexamethylpyrrolidinium cation, 1,1,2,2,4,5-hexamethylpyrrolidinium a cation, a 1,1,2,2,5,5-hexamethylpyrrolidinium cation, a 1,1,2,3,3,4-hexamethylpyrrolidinium cation, 1,1,2,3, 3,5-hexamethylpyrrolidinium cation, 1,1,2,3,4,4-hexamethylpyrrolidinium cation, 1,1,2,3,5,5-hexamethylpyrrolidinium a 1,1-dialkylpyrrolidinium cation having an alkyl group at a carbon atom of the pyrrolidine ring, such as a cation, a 1,1,2,3,4,5-hexamethylpyrrolidinium cation.

Examples of the morpholinium cation include a 4,4-dimethylmorpholinium cation, a 4-ethyl-4-methylmorpholinium cation, a 4,4-diethylmorpholinium cation, and 3 , 4,4-trimethylmorpholinium cation, 2,4,4-trimethylmorpholinium cation, 3-ethyl-4,4-dimethylmorpholinium cation, 3,4-dimethyl 4-ethylmorpholinium cation, 2,4-dimethyl-4-ethylmorpholinium cation, 3-methyl-4,4-diethylmorpholinium cation, 2,4-di Methyl-4-ethylmorpholinium cation, 2-methyl-4,4-diethylmorpholinium cation, 3,4-diethyl-4-methylmorpholinium cation, 2,4- Diethyl-4-methylmorpholinium cation, 3,4,4-triethylmorpholinium cation, 2,4,4-triethylmorpholinium cation, 3,3,4,4-tetra Methylmorpholinium cation, 2,3,4,4-tetramethylmorpholinium cation, 2,4,4,5-tetramethylmorpholinium cation, 3,4,4,5-tetramethyl Morpholinium cation, 2,2,4,4-tetramethylmorpholinium cation, 2,4,4,6-tetramethylmorpholinium cation, 2,4,4-trimethyl-3-B Pyrazoline cation, 2-ethyl-3,4,4-trimethylmorpholinium cation, 2,4,4-trimethyl-5-ethylmorpholinium cation 2-ethyl-4,4,5-trimethylmorpholinium cation, 3-ethyl-4,4,6-trimethylmorpholinium cation, 2-ethyl-4,4,5-three Methylmorpholinium cation, 2-ethyl-4,4,6-trimethylmorpholinium cation, 2,3-dimethyl-4,4-diethylmorpholinium cation, 2,5- Dimethyl-4,4-diethylmorpholinium cation, 3,5-dimethyl-4,4-diethylmorpholinium cation, 2,6-dimethyl-4,4-di Pyrazoline cation, 2,4-dimethyl-3,4-diethylmorpholinium cation, 2,4-diethyl-3,4-dimethylmorpholinium cation, 2,4- Dimethyl-4,5-diethylmorpholinium cation, 2,4-diethyl-4,5-dimethylmorpholinium cation, 3,4-diethyl-4,5-dimethyl Pyrazoline cation, 2,4-diethyl-4,6-dimethylmorpholinium cation, 2,3-diethyl-4,4-dimethylmorpholinium cation, 2,5- Diethyl-4,4-dimethylmorpholinium cation, 3,5-diethyl-4,4-dimethylmorpholinium cation, 2,6-diethyl-4,4-dimethyl Pyrazoline cation, 2,3,4,4,6-pentamethylmorpholinium cation, 2,3,4,4,5-pentamethylmorpholinium cation, 2,6,4,4- Tetramethyl-3-ethylmorpholinium cation, 2,4,4,5-tetramethyl-3 -ethylmorpholinium cation, 2-ethyl-3,4,4,6-tetramethylmorpholinium cation, 2-ethyl-3,4,4,5-tetramethylmorpholinium cation, A 2,3,4,4,5,6-hexamethylmorpholinium cation or the like having an alkyl 4-alkylmorpholinium cation on the carbon atom of the morpholine ring.

Examples of the imidazolinium cation include 1,3-dimethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1,3-diethylimidazolium cation, and 1 , 2,3-trimethylimidazolinium cation, 1,3,4-trimethylimidazolinium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-ethyl-3 , 4-dimethylimidazolinium cation, 1-ethyl-3,5-dimethylimidazolium cation, 2-ethyl-1,3-dimethylimidazolium cation, 4-ethyl- 1,3-Dimethylimidazolinium cation, 1,2-diethyl-3-methylimidazolinium cation, 1,4-diethyl-3-methylimidazolium cation, 1,5- Diethyl-3-methylimidazolinium cation, 1,3-diethyl-2-methylimidazolinium cation, 1,3-diethyl-4-methylimidazolinium cation, 1,2 , 3-triethylimidazolium cation, 1,3,4-triethylimidazolium cation, 1,2,3,4-tetramethylimidazolium cation, 1-ethyl-2,3, 4-trimethylimidazolinium cation, 1-ethyl-2,3,5-trimethylimidazolinium cation, 1-ethyl-3,4,5-trimethylimidazolium cation, 2- Ethyl-1,3,4-trimethylimidazolinium Cation, 4-ethyl-1,2,3-trimethylimidazolinium cation, 1,2-diethyl-3,4-dimethylimidazolium cation, 1,3-diethyl-2 , 4-dimethylimidazolium cation, 1,4-diethyl-2,3-dimethylimidazolium cation, 2,4-diethyl-1,3-dimethylimidazolium cation , 4,5-diethyl-1,3-dimethylimidazolium cation, 1,2,3-triethyl-4-methylimidazolinium cation, 1,2,4-triethyl- 3-methylimidazolinium cation, 1,2,5-triethyl-3-methylimidazolinium cation, 1,3,4-triethyl-2-methylimidazolinium cation, 1,3 , 4-triethyl-5-methylimidazolinium cation, 1,4,5-triethyl-3-methylimidazolinium cation, 1,2,3,4,5-pentamethylimidazoline An anthracene cation, a 1-methyl-3-propylimidazolium cation or the like has an alkyl group of a 1,3-dialkylimidazolinium cation on the carbon atom of the imidazole ring.

Examples of the tetrahydropyrimidinium cation include 1,3-dimethyltetrahydropyrimidinium cation, 1-ethyl-3-methyltetrahydropyrimidinium cation, and 1,3-diethyltetrahydropyrimidine. Ruthenium cation, 1,2,3-trimethyltetrahydropyrimidinium cation, 1,3,4-trimethyltetrahydropyrimidinium cation, 1,3,5-trimethyltetrahydropyrimidinium cation, 1- Ethyl-2,3-dimethyltetrahydropyrimidinium cation, 1-ethyl-3,4-dimethyltetrahydropyrimidinium cation, 1-ethyl-3,5-dimethyltetrahydropyrimidine Cation, 1-ethyl-3,6-dimethyltetrahydropyrimidinium cation, 2-ethyl-1,3-dimethyltetrahydropyrimidinium cation, 4-ethyl-1,3-dimethyl Tetrahydropyrimidinium cation, 5-ethyl-1,3-dimethyltetrahydropyrimidinium cation, 1,2,3,4-tetramethyltetrahydropyrimidinium cation, 1,2,3,5-tetra Methyltetrahydropyrimidine cation, 1-ethyl-2,3,4-trimethyltetrahydropyrimidinium cation, 1-ethyl-2,3,5-trimethyltetrahydropyrimidinium cation, 1- Ethyl-2,3,6-trimethyltetrahydropyrimidinium cation, 2-ethyl-1,3,4-trimethyltetrahydropyrimidinium cation, 2-ethyl-1,3,5-three Methyltetrahydropyrimidine cation, 4-ethyl-1,2, 3-trimethyltetrahydropyrimidinium cation, 4-ethyl-1,3,5-trimethyltetrahydropyrimidinium cation, 4-ethyl-1,3,6-trimethyltetrahydropyrimidinium cation , 5-ethyl-1,2,3-trimethyltetrahydropyrimidinium cation, 5-ethyl-1,3,4-trimethyltetrahydropyrimidinium cation, 1,2-diethyl-3 , 4-dimethyltetrahydropyrimidinium cation, 1,2-diethyl-3,5-dimethyltetrahydropyrimidinium cation, 1,2-diethyl-3,6-dimethyltetrahydro Pyrimidine cation, 1,3-diethyl-2,4-dimethyltetrahydropyrimidinium cation, 1,3-diethyl-2,5-dimethyltetrahydropyrimidinium cation, 1,4- Diethyl-2,3-dimethyltetrahydropyrimidinium cation, 1,4-diethyl-3,5-dimethyltetrahydropyrimidinium cation, 1,4-diethyl-3,6- Dimethyltetrahydropyrimidine cation, 1,5-diethyl-2,3-dimethyltetrahydropyrimidinium cation, 1,5-diethyl-3,4-dimethyltetrahydropyrimidinium cation 1,5-diethyl-3,6-dimethyltetrahydropyrimidinium cation, 2,4-diethyl-1,3-dimethyltetrahydropyrimidinium cation, 2,5-diethyl -1,3-dimethyltetrahydropyrimidinium cation, 4,5-diethyl-1,3-dimethyltetrahydropyrimidinium cation, 4, 6-Diethyl-1,3-dimethyltetrahydropyrimidinium cation, 1,2,3,4,5-pentamethyltetrahydropyrimidinium cation, 1,2,3,4,6-penta a tetrahydrotetrapyrimidine cation, an 1,2,3,4,5,6-hexamethyltetrahydropyrimidinium cation or the like having an alkyl group of 1,3-dialkyltetrahydrogen at a carbon atom of a tetrahydropyrimidine ring Pyrimidine cation.

Examples of the piperazinium cation include 1,1,4,4-tetramethylpiperazinium cation, 1-ethyl-1,4,4-trimethylpiperazinium cation, and 1 , 1-diethyl-4,4-dimethylpiperazinium cation, 1,1,4-triethyl-4-methylpiperazinium cation, 1,1,4,4-tetraethylper Pyridinium cation, 1,1,2,4,4-pentamethylpiperazinium cation, 1,1,3,4,4-pentamethylpiperazinium cation, 1,1,2,3,4, 4-hexamethylpiperazinium cation, 1,1,2,4,4,5-hexamethylpiperazinium cation, 1,1,2,4,4,6-hexamethylpiperazinium cation, 1,1,3,4,4,5-hexamethylpiperazinium cation, 1-ethyl-1,2,4,4-tetramethylpiperazinium cation, 1-ethyl-1,3, 4,4-tetramethylpiperazinium cation, 2-ethyl-1,1,4,4-tetramethylpiperazinium cation, 1-ethyl-1,2,4,4-tetramethylper Pyridinium cation, 1-ethyl-1,3,4,4-tetramethylpiperazinium cation, 1,1-diethyl-2,4,4-trimethylpiperazinium cation, 1,4 -diethyl-1,2,4-trimethylpiperazinium cation, 1,2-diethyl-1,4,4-trimethylpiperazinium cation, 1,3-diethyl-1 , 4,4-trimethylpiperazinium cation, etc., having an alkyl group 1,1,4 on the carbon atom of the piperazine ring , 4-tetraalkyl piperazine cation.

Examples of the piperidinium cation include 1,1-dimethylpiperidinium cation, 1-ethyl-1-methylpiperidinium cation, and 1,1-diethylpiperidinium. a cation, a 1,1,2-trimethylpiperidinium cation, a 1,1,3-trimethylpiperidinium cation, a 1,1,4-trimethylpiperidinium cation, 1,1,2, 2-tetramethylpiperidinium cation, 1,1,2,3-tetramethylpiperidinium cation, 1,1,2,4-tetramethylpiperidinium cation, 1,1,2,5- Tetramethylpiperidinium cation, 1,1,2,6-tetramethylpiperidinium cation, 1,1,3,3-tetramethylpiperidinium cation, 1,1,3,4-tetra Keipridinium cation, 1,1,3,5-tetramethylpiperidinium cation, 1-ethyl-1,2-dimethylpiperidinium cation, 1-ethyl-1,3-dimethyl Isopiperidinium cation, 1-ethyl-1,4-dimethylpiperidinium cation, 1-ethyl-1,2,3-trimethylpiperidinium cation, 1-ethyl-1,2 , 4-trimethylpiperidinium cation, 1-ethyl-1,2,5-trimethylpiperidinium cation, 1-ethyl-1,2,6-trimethylpiperidinium cation, 1 -ethyl-1,3,4-trimethylpiperidinium cation, 1-ethyl-1,3,5-trimethylpiperidinium cation, 1,1-diethyl-2-methyl Pyridinium cation, 1,1-diethyl-3-methylpiperidinium cation, 1,1-diethyl-4-methylpiperidinium cation, 1,1-diethyl-2,3- Dimethylpiperidinium cation, 1,1-diethyl-2,4-dimethylpiperidinium cation, 1,1-diethyl-2,5-dimethylpiperidinium cation, 1, 1-diethyl-2,6-dimethylpiperidinium cation, 1,1-diethyl-3,4-dimethylpiperidinium cation, 1,1-diethyl-3,5- Dimethylpiperidinium cation, 2-ethyl-1,1,3-trimethylpiperidinium cation, 2-ethyl-1, 1,4-trimethylpiperidinium cation, 2-ethyl -1,1,5-trimethylpiperidinium cation, 2-ethyl-1,1,6-trimethylpiperidinium cation, 3-ethyl-1,1,2-trimethylpiperidine Ruthenium cation, 3-ethyl-1,1,4-trimethylpiperidinium cation, 3-ethyl-1,1,5-trimethylpiperidinium cation, 3-ethyl-1,1, 6-trimethylpiperidinium cation, 4-ethyl-1,1,2-trimethylpiperidinium cation, 4-ethyl-1,1,3-trimethylpiperidinium cation, 1, 2-Diethyl-1,3-dimethylpiperidinium cation, 1-ethyl-1,2,4-trimethylpiperidinium cation, 1,2-diethyl-1,5-di Methylpiperidinium cation, 1,2-diethyl-1, 6-dimethylpiperidinium cation, 1,3-diethyl-1,5-dimethylpiperidinium cation, 1,3-diethyl-1,4-dimethylpiperidinium cation, 1,3-Diethyl-1,5-dimethylpiperidinium cation, 1,3-diethyl-1,6-dimethylpiperidinium cation, 1,4-diethyl-1, 2-dimethylpiperidinium cation, 1,4-diethyl-1,3-dimethylpiperidinium cation, 1,1,2-triethyl-3-methylpiperidinium cation, 1 1,2-triethyl-4-methylpiperidinium cation, 1,1,2-triethyl-5-methylpiperidinium cation, 1,1,2-triethyl-6- Isopiperidinium cation, 1,1,3-triethyl-2-methylpiperidinium cation, 1,1,3-triethyl-4-methylpiperidinium cation, 1,1,3- Diethyl-5-methylpiperidinium cation, 1,1,3-triethyl-6-methylpiperidinium cation, 1,1,4-triethyl-2-methylpiperidinium cation 1,1,4-diethyl-3-methylpiperidinium cation, 2-ethyl-1,1-dimethylpiperidinium cation, 3-ethyl-1,1-dimethylper Pyridinium cation, 4-ethyl-1,1-dimethylpiperidinium cation, 2,3-diethyl-1,1-dimethylpiperidinium cation, 2,4-diethyl-1 , 1-dimethylpiperidinium cation, 2,5- Ethyl-1,1-dimethylpiperidinium cation, 2,6-diethyl-1,1-dimethylpiperidinium cation, 3,4-diethyl-1,1-dimethyl Piperidinium cation, 3,5-diethyl-1,1-dimethylpiperidinium cation, 1,2-diethyl-1-methylpiperidinium cation, 1,3-diethyl- 1-methylpiperidinium cation, 1,4-diethyl-1-methylpiperidinium cation, 1,2,3-triethyl-1-methylpiperidinium cation, 1,2,4 -Triethyl-1-methylpiperidinium cation, 1,2,5-triethyl-1-methylpiperidinium cation, 1,2,6-triethyl-1-methylpiperidinium Cation, 1,3,4-triethyl-1-methylpiperidinium cation, 1,3,5-triethyl-1-methylpiperidinium cation, 1,1,2-triethylper a pyridine cation, a 1,1,2-triethylpiperidinium cation, a 1,1,4-triethylpiperidinium cation, a 1,1,2,3-tetraethylpiperidinium cation, 1, 1,2,4-tetraethylpiperidinium cation, 1,1,2,5-tetraethylpiperidinium cation, 1,1,2,6-tetraethylpiperidinium cation, 1,1, a 1,1-dialkylpiperidinium having an alkyl group at a carbon atom of a piperidine ring, such as a 3,4-tetraethylpiperidinium cation, a 1,1,3,5-tetraethylpiperidinium cation or the like. cation.

Examples of the pyridinium cation include 1-methylpyridinium cation, 1-ethylpyridinium cation, 1-propylpyridinium cation, 1-butylpyridinium cation, and 1-pentylpyridine. Ruthenium cation, 1-hexylpyridinium cation, 1-heptylpyridinium cation, 1-octylpyridinium cation, 1-mercaptopyridinium cation, 1-mercaptopyridinium cation, 1,2-dimethylpyridine Ruthenium cation, 1,3-dimethylpyridinium cation, 1,4-dimethylpyridinium cation, 1-ethyl-2-methylpyridinium cation, 2-ethyl-1-methylpyridinium cation , 1-ethyl-3-methylpyridinium cation, 3-ethyl-1-methylpyridinium cation, 1-ethyl-4-methylpyridinium cation, 4-ethyl-1-methylpyridine Ruthenium cation, 1,2-diethylpyridinium cation, 1,3-diethylpyridinium cation, 1,4-diethylpyridinium cation, 1,2,3-trimethylpyridinium cation, 1 , 2,4-trimethylpyridinium cation, 1,3,4-trimethylpyridinium cation, 1,3,5-trimethylpyridinium cation, 1,2,5-trimethylpyridinium cation 1,2,6-trimethylpyridinium cation, 1-B Benzyl-2,3-dimethylpyridinium cation, 1-ethyl-2,4-dimethylpyridinium cation, 1-ethyl-2,5-dimethylpyridinium cation, 1-ethyl- 2,6-lutidine cation, 1-ethyl-3,4-dimethylpyridinium cation, 1-ethyl-3,5-dimethylpyridinium cation, 2-ethyl-1, 3-dimethylpyridinium cation, 2-ethyl-1,4-dimethylpyridinium cation, 2-ethyl-1,5-dimethylpyridinium cation, 2-ethyl-1,6- Dimethylpyridinium cation, 3-ethyl-1,2-dimethylpyridinium cation, 3-ethyl-1,4-dimethylpyridinium cation, 3-ethyl-1,5-dimethyl Pyridinium cation, 3-ethyl-1,6-dimethylpyridinium cation, 4-ethyl-1,2-dimethylpyridinium cation, 4-ethyl-1,3-dimethylpyridine Ruthenium cation, 1,2-diethyl-3-methylpyridinium cation, 1,2-diethyl-4-methylpyridinium cation, 1,2-diethyl-5-methylpyridinium cation 1,2-diethyl-6-methylpyridinium cation, 1,3-diethyl-2-methylpyridinium cation, 1,3-diethyl-4-methylpyridinium cation, 1 , 3-diethyl-5-methylpyridinium cation, 1,3-diethyl-6- Methylpyridinium cation, 1,4-diethyl-2-methylpyridinium cation, 1,4-diethyl-3-methylpyridinium cation, 2,3-diethyl-1-methyl Pyridinium cation, 2,4-diethyl-1-methylpyridinium cation, 2,5-diethyl-1-methylpyridinium cation, 2,6-diethyl-1-methylpyridinium Cation, 3,4-diethyl-1-methylpyridinium cation, 3,5-diethyl-1-methylpyridinium cation, 1,2,3,4,5-pentamethylpyridinium cation 1,2,3,4,6-pentamethylpyridinium cation, 1,2,3,5,6-pentamethylpyridinium cation, 1,2,3,4,5,6-hexamethyl Pyridinium cation, 1-methyl-4-methylpyridinium cation, 1-ethyl-4-methylpyridinium cation, 1-propyl-4-methylpyridinium cation, 1-butyl-4- Methylpyridinium cation, 1-pentyl-4-methylpyridinium cation, 1-hexyl-4-methylpyridinium cation, 1-heptyl-4-methylpyridinium cation, 1-octyl-4 a 1-alkylpyridinium group having an alkyl group at a carbon atom of the pyridine ring, such as a methylpyridinium cation, a 1-mercapto-4-methylpyridinium cation, a 1-mercapto-4-methylpyridinium cation or the like cation.

Examples of the tetraalkyl phosphonium cation include a tetramethyl phosphonium cation, a tetraethyl phosphonium cation, a tetrapropyl phosphonium cation, a tetrabutyl phosphonium cation, a tetrapentyl phosphonium cation, a tetrahexyl phosphonium cation, and a tetraheptyl group. Ruthenium cation, tetraoctylphosphonium cation, tetradecylphosphonium cation, tetramethylhydrazine cation, tetraphenylphosphonium cation, 1,1,1-tributyl-1-octylphosphonium cation, 1,1,1 a tributyl-1-indenyl cation, a 1,1,1-tributyl-1-indenyl cation, a 1,1,1-tributyl-1-undecylphosphonium cation, 1, 1,1-tributyl-1-dodecylphosphonium cation, 1,1,1-tributyl-1-tridecylphosphonium cation, 1,1,1-tributyl-1-tetradecyl Alkyl phosphonium cation, 1,1,1-tributyl-1-pentadecyl phosphonium cation, 1,1,1-tributyl-1-hexadecyl sulfonium cation, 1,1,1-three a butyl-1-heptadecylphosphonium cation, a 1,1,1-tributyl-1-octadecylphosphonium cation, a 1,1,1-tributyl-1-nonylalkylphosphonium cation, 1,1,1-tributyl-1-eicosylphosphonium cation, 1,1,1-tripentyl-1-octylphosphonium cation, 1,1,1-tripentyl-1-fluorenyl Ruthenium cation, 1,1,1-tripentyl-1-indenyl cation, 1 1,1,1-tripentyl-1-undecylphosphonium cation, 1,1,1-tripentyl-1-dodecylphosphonium cation, 1,1,1-tripentyl-1-deca Trialkylsulfonium cation, 1,1,1-tripentyl-1-tetradecylphosphonium cation, 1,1,1-tripentyl-1-pentadecylsulfonium cation, 1,1,1- Triamyl-1-hexadecylphosphonium cation, 1,1,1-tripentyl-1-heptadecylphosphonium cation, 1,1,1-tripentyl-1-octadecylphosphonium cation 1,1,1-Tripentyl-1-nonadecylphosphonium cation, 1,1,1-tripentyl-1-eicosylphosphonium cation, 1,1,1-trihexyl-1- Octyl cation, 1,1,1-trihexyl-1-indenyl cation, 1,1,1-trihexyl-1-indenyl cation, 1,1,1-trihexyl-1-111 Alkyl phosphonium cation, 1,1,1-trihexyl-1-dodecylphosphonium cation, 1,1,1-trihexyl-1-tridecylphosphonium cation, 1,1,1-trihexyl- 1-pentadecylphosphonium cation, 1,1,1-trihexyl-1-hexadecylphosphonium cation, 1,1,1-trihexyl-1-heptadecylphosphonium cation, 1,1,1 - trihexyl-1-octadecylphosphonium cation, 1,1,1-trihexyl-1-nonylalkylphosphonium cation, 1,1,1-trihexyl-1-eicosylphosphonium cation, 1 1,1-triheptyl-1-octylhydrazine Ionic, 1,1,1-triheptyl-1-indenyl cation, 1,1,1-triheptyl-1-indenyl cation, 1,1,1-triheptyl-1-111 Alkyl phosphonium cation, 1,1,1-triheptyl-1-dodecyl sulfonium cation, 1,1,1-triheptyl-1-tridecyl sulfonium cation, 1,1,1-three a heptyl-1-tetradecylphosphonium cation, a 1,1,1-triheptyl-1-pentadecylsulfonium cation, a 1,1,1-triheptyl-1-hexadecylphosphonium cation, 1,1,1-triheptyl-1-heptadecylphosphonium cation, 1,1,1-triheptyl-1-octadecylphosphonium cation, 1,1,1-triheptyl-1- Pentadecylphosphonium cation, 1,1,1-triheptyl-1-eicosylphosphonium cation, 1,1,1,1-tetraoctylphosphonium cation, 1,1,1-trioctyl- 1-indenyl cation, 1,1,1-trioctyl-1-indenyl cation, 1,1,1-trioctyl-1-undecylphosphonium cation, 1,1,1-three An octyl-1-dodecylphosphonium cation, a 1,1,1-trioctyl-1-tridecylsulfonium cation, a 1,1,1-trioctyl-1-tetradecylphosphonium cation, 1,1,1-trioctyl-1-pentadecylsulfonium cation, 1,1,1-trioctyl-1-hexadecylphosphonium cation, 1,1,1-trioctyl-1- Heptadecylphosphonium cation, 1,1,1-trioctyl-1-octadecyl cation Child, 1,1,1-octyl-1-phosphonium cations, nonadecyl, eicosyl 1,1,1-octyl-1-phosphonium cation.

Among these cesium ions, trioctylmethylammonium cation, 1-methyl-3-propylimidazolium cation, 1-hexyl-4-methylpyridinium cation, 1-octyl-4-methyl The pyridinium cation and the 1-octylpyridinium cation are preferred.

A ^- shown anion, hexafluorophosphate anion (PF ₆ ^- ; hexafluoro phosphate anion), as a sulfonium salt (1), trioctylmethylammonium = hexafluorophosphoric acid, 1-methyl-3-propanol Imidazolinium hydrazine=hexafluorophosphoric acid, 1-hexyl-4-methylpyridinium=hexafluorophosphoric acid, 1-octyl-4-methylpyridinium=hexafluorophosphorus, and 1-octylpyridinium=hexafluoro Phosphoric acid is preferred.

The bismuth salt (1), for example, can be obtained by the formula (2):

Q ⁺ ‧X ^- (2)

(wherein, Q ⁺ represents the same meaning as described above, and X ^- represents a halogen ion.)

Show 鎓 = halide, and formula (3):

M ⁺ ‧A ^- (3)

(wherein M ⁺ represents a hydrogen ion or an alkali metal ion, and A ^- represents the same meaning as described above.)

It is produced by an ion exchange reaction of an acid or an alkali metal salt thereof. This ion exchange reaction can be carried out according to a conventional method.

Examples of the organic base include organic nitrogen compounds such as primary amines, secondary amines, and tertiary amines, and organic phosphorus compounds such as tertiary phosphines. Among them, tertiary amines and tertiary phosphines are preferred. The tertiary amine may, for example, be trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, tridecylamine, An aliphatic tertiary amine such as tridecylamine, an aromatic tertiary amine such as N,N-dimethylaniline, N,N-diethylaniline or N-benzyl-N-ethylaniline, pyridine, 2- Methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-lutidine, 3,5-lutidine, 2,3,5-collidine (ie, 2 , 3,5-trimethylpyridine; 2,3,5-Collidine), 3,5-diethylpyridine, 2,2'-bipyridine, 2,4'-bipyridine, 4,4'-linked Pyridines such as pyridine and imidazoles such as 1-methylimidazole. The tertiary phosphine may, for example, be trioctylphosphine or triphenylphosphine. Among them, tributylamine, trioctylamine, N-benzyl-N-ethylaniline, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 3,5-diethyl Pyridine, 2,2'-bipyridine, 1-methylimidazole, trioctylphosphine, and triphenylphosphine are preferred.

The onium salt composition of the present invention contains a phosphonium salt (1) and an organic base. The content of the organic base is usually 1 ppm or more, preferably 10 to 5,000 ppm, more preferably 10 to 1,000 ppm based on the cerium salt (1).

The onium salt composition of the present invention can be produced, for example, by adding an organic base to the onium salt (1), by a mixing method or the like. The temperature at which the organic base is added is not particularly limited as long as the temperature of both of them can be uniformly mixed, and is usually 10 ° C or more, preferably 15 ° C to 100 ° C, and particularly preferably 20 ° C to 50 ° C.

The onium salt composition of the present invention may contain a solvent. The solvent may be any one of the sulfonium salt (1) and the organic base, and is not particularly limited. Specific examples thereof include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, and decane; and methanol. Alcohol solvent such as ethanol, butanol, pentanol or hexanol; ester solvent such as methyl acetate or ethyl acetate; ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; benzene, toluene and xylene The aromatic hydrocarbon solvent or the like is preferably an ester solvent, and ethyl acetate is more preferable. These solvents may be used singly or in combination of two or more. When the cerium salt composition of the present invention contains a solvent, the content of the solvent is usually from 1 to 100% by weight, preferably from 1 to 50% by weight based on the cerium salt (1).

Example

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Meanwhile, in the following examples, the moisture was measured using a Karl-Fisher moisture measuring device (MKA-520) manufactured by Kyoto Electronics Manufacturing Co., Ltd., and the fluoride ion (F ^- ) was an ion chromatography analyzer (DX-made by Dionex). 100) Measurement (measurement limit is 10 ppm).

Manufacturing example 1

Trioctylmethylammonium chloride = 39.6 g of chloride, 51.3 g of water, 18.0 g of potassium = hexafluorophosphate, and 51.3 g of methyl ethyl ketone. The resulting mixture was stirred at 25 ° C for 1 hour and allowed to react. After the end of the reaction, the organic layer was separated from the obtained reaction mixture by a liquid separation operation. The resulting organic layer was washed twice with 32.2 g of water. The resulting organic layer was concentrated. The obtained concentrated residue was dried under reduced pressure to give 40.3 g of trioctylmethylammonium (hereinafter referred to as TOMA-PF6) (yield 98%, moisture: 400 ppm).

Manufacturing Example 2

In Production Example 1, except that 1-methyl-3-propylimidazolinium oxime = bromide was substituted for trioctylmethylammonium = chloride, and methyl ethyl ketone was replaced with dichloromethane. In the same manner as in Example 1, 24.2 g of 1-methyl-3-propylimidazolinium = hexafluorophosphoric acid (hereinafter abbreviated as MPIM-PF6) (yield 91%, moisture: 900 ppm) was obtained.

Manufacturing Example 3

In Production Example 2, the same procedure as in Production Example 2 was carried out except that 1-hexyl-4-methylpyridinium bromide was used instead of 1-methyl-3-propylimidazolinium oxime bromide. 1-hexyl-4-methylpyridinium=hexafluorophosphoric acid (hereinafter abbreviated as HMPy-PF6) 30.6 g (yield 96%, moisture 600 ppm).

Manufacturing Example 4

In Production Example 2, the same procedure as in Production Example 2 was carried out except that 1-octyl-4-methylpyridinium bromide was used instead of 1-methyl-3-propylimidazolinium oxime bromide. 1-octyl-4-methylpyridinium=hexafluorophosphoric acid (hereinafter abbreviated as OMPy-PF6) 33.5 g (yield 97%, moisture 600 ppm) was obtained.

Manufacturing Example 5

In Production Example 2, 1-octyl was obtained in the same manner as in Production Example 2 except that 1-octylpyridinium bromide was used instead of 1-methyl-3-propylimidazolinium oxime bromide. Pyridinium = hexafluorophosphoric acid (hereinafter abbreviated as OPy-PF6) 32.1 g (yield 97%, moisture 200 ppm).

Example 1

After weighing 100 g of TOMA-PF6 and 0.05 g of trioctylamine into a glass container, it was sealed in the atmosphere, and mixed at room temperature for 1 hour by a rotary rotary mixer to prepare a product containing TOMA-PF6 and trioctylamine. Barium salt composition. The glass container containing the obtained cerium salt composition was stored in a thermostat at 80 °C. A predetermined amount of sample is taken every day to measure the concentration of fluoride ion (F ^- ) in the sample. The results are shown in Table 1.

Example 2

In the same manner as in Example 1, except that 4-methylpyridine was used instead of trioctylamine, a hydrazine salt composition containing TOMA-PF6 and 4-methylpyridine was prepared. In the same manner as in Example 1, the glass container containing the obtained cerium salt composition was stored in a thermostatic chamber at 80 °C. A predetermined amount of sample is taken every day to measure the concentration of fluoride ion (F ^- ) in the sample. The results are shown in Table 1.

Example 3

In Example 1, except that MPIM-PF6 was used instead of TOMA-PF6, and 1-methylimidazole was substituted for trioctylamine, the same procedure as in Example 1 was carried out to prepare a solution containing MPIM-PF6 and 1-methylimidazole. Barium salt composition. In the same manner as in Example 1, the glass container containing the obtained cerium salt composition was stored in a thermostatic chamber at 80 °C. A predetermined amount of the sample is taken every day, and the concentration of F ^- in the sample is measured. The results are shown in Table 1.

Example 4

In Example 3, a ruthenium salt composition containing MPIM-PF6 and 4-methylpyridine was prepared in the same manner as in Example 3 except that 4-methylpyridine was used instead of 1-methylimidazole. In the same manner as in Example 3, the glass container containing the obtained cerium salt composition was stored in a thermostatic chamber at 80 °C. A predetermined amount of sample is taken every day to determine the F ^- concentration in the sample. The results are shown in Table 1.

Example 5

In Example 4, a ruthenium salt composition containing HMPy-PF6 and 4-methylpyridine was prepared in the same manner as in Example 4 except that HMPy-PF6 was used instead of MPIM-PF6. In the same manner as in Example 4, the glass container containing the obtained cerium salt composition was stored in a thermostatic chamber at 80 °C. A predetermined amount of the sample is taken every day, and the concentration of F ^- in the sample is measured. The results are shown in Table 1.

Example 6

In the same manner as in Example 4 except that OMPy-PF6 was used instead of MPIM-PF6, a sulfonium salt composition containing OMPy-PF6 and 4-methylpyridine was prepared. In the same manner as in Example 4, the glass container containing the obtained cerium salt composition was stored in a thermostatic chamber at 80 °C. A predetermined amount of the sample is taken every day, and the concentration of F ^- in the sample is measured. The results are shown in Table 1.

Example 7

In Example 1, except that OPY-PF6 was used instead of TOMA-PF6, and 3,5-diethylpyridine was substituted for trioctylamine, the same procedure as in Example 1 was carried out, and the preparation contained OPy-PF6 and 3,5. - a quinone salt composition of lutidine. In the same manner as in Example 1, the glass container containing the obtained cerium salt composition was stored in a thermostatic chamber at 80 °C. A predetermined amount of the sample is taken every day, and the concentration of F ^- in the sample is measured. The results are shown in Table 1. Meanwhile, in Table 1, respectively, "F ^- detect the number of days" means that F is detected in more than 1000ppm ^- A sample stored for several days, "F ^- concentration" is a time of F ^- concentration measurement.

As is clear from Table 1, the onium salt composition of the present invention was stable at 80 ° C for 30 days even in the presence of a trace amount of water.

Comparative example 1

In Example 1, except that trioctylamine was not used, the same procedure as in Example 1 was carried out, and a predetermined amount of the sample was taken every day to measure the concentration of F ^{- in} the sample. The results are shown in Table 2. Meanwhile, in Table 2, the number of sample storage days at which the F ^- concentration of 1000 ppm or more was detected is indicated by "F ^- detection day number", and "(F ^- concentration)" is the measured value of the F ^- concentration at that time.

Comparative example 2

In Example 3, except that 1-methylimidazole was not used, the same procedure as in Example 3 was carried out, and a predetermined amount of the sample was taken every day to measure the concentration of F ^{- in} the sample. The results are shown in Table 2.

Comparative example 3

In Example 5, except that 4-methylpyridine was not used, the same procedure as in Example 5 was carried out, and a predetermined amount of the sample was taken every day to measure the concentration of F ^{- in} the sample. The results are shown in Table 2.

Comparative example 4

In Example 6, except that 4-methylpyridine was not used, the same procedure as in Example 6 was carried out, and a predetermined amount of the sample was taken every day to measure the concentration of F ^{- in} the sample. The results are shown in Table 2.

Comparative Example 5

In Example 7, except that 3,5-diethylpyridine was not used, the same procedure as in Example 7 was carried out, and a predetermined amount of the sample was taken every day to measure the concentration of F ^{- in} the sample. The results are shown in Table 2.

Examples 8 to 18

In the same manner as in Example 5 except that the organic base described in Table 3 was used instead of 4-methylpyridine, the sulfonium salt composition was prepared. The glass vessel containing the obtained cerium salt composition was stored in a thermostat at 80 °C. A predetermined amount of the sample is taken every day, and the concentration of F ^- in the sample is measured. As a result, even after 30 days, the F ^- concentration was below the detection limit. From this result, it is understood that the onium salt composition of the present invention is stable even within 30 days at 80 ° C even if a trace amount of water is present.

Comparative Examples 6 to 12

In Example 5, except that the compound described in Table 4 was substituted for 4-methylpyridine, the same procedure as in Example 5 was carried out to prepare a cerium salt composition for comparison. The glass container containing the obtained cerium salt composition for comparison was stored in a thermostat at 80 °C. A predetermined amount of the sample is taken every day to determine the F ^- concentration in the sample. The results are shown in Table 4. At the same time, in Table 4, the number of sample storage days at which F ^- concentration of 1000 ppm or more is detected is indicated by "F ^- number of detection days", and "(F ^- concentration)" is a measured value indicating the F ^- concentration at that time.

Example 19

100 g of HMPy-PF6, 0.05 g of 4-methylpyridine and 50 g of ethyl acetate were weighed into a glass container, sealed in the air, and mixed at room temperature for 1 hour by a rotary rotary mixer to prepare HMPy-PF6. A salt composition with 4-methylpyridine. The glass container containing the obtained cerium salt composition was stored in a thermostat at 60 °C. A predetermined amount of sample is taken every day to measure the concentration of fluoride ion (F ^- ) in the sample. The results are shown in Table 5. At the same time, in Table 5, the number of sample storage days at which F ^- concentration of 1000 ppm or more is detected is indicated by "F ^- number of detection days", and "(F ^- concentration)" is a measured value indicating the F ^- concentration at that time.

Example 20

In Example 19, the same procedure as in Example 19 was carried out except that the amount of 4-methylpyridine used was changed to 0.01 g, and the results are shown in Table 5.

Comparative Example 13

In Example 19, the same procedure as in Example 19 was carried out except that 4-methylpyridine was not used, and the results are shown in Table 5.

Comparative Example 14

In Example 19, the same procedure as in Example 19 was carried out except that 4-methylpyridine was not used, and the amount of ethyl acetate used was changed to 25 g, and the results are shown in Table 5.

Comparative Example 15

In Comparative Example 14, the same procedure as in Comparative Example 14 was carried out except that isopropyl alcohol was used instead of ethyl acetate, and the results are shown in Table 5.

Examples 21 to 24

In the same manner as in Example 5 except that the amount of the 4-methylpyridine used was changed from the amount shown in Table 6, the composition containing the sulfonium salt of HMPy-PF6 and 4-methylpyridine was prepared. In the same manner as in Example 5, the glass container containing the obtained cerium salt composition was stored in a thermostat at 80 °C. A predetermined amount of the sample is taken every day, and the concentration of F ^- in the sample is measured. The results are shown in Table 6. At the same time, in Table 6, the "F ^- test days" indicates the number of sample storage days at which F ^- concentration of 1000 ppm or more was detected, and "(F ^- concentration)" indicates that F- at that time ^. The measured value of the concentration.

Industrial availability

Since the onium salt composition of the present invention is difficult to be hydrolyzed by a trace amount of water and heating, stability can be maintained in terms of handling and long-term storage. Further, according to the method of the present invention, by containing an organic base, hydrolysis due to a trace amount of moisture and heating of the cerium salt (1) can be suppressed, and the cerium salt (1) can be stably stored.

Claims (4)

An onium salt composition containing a phosphonium salt represented by the formula (1), and a composition of an organic nitrogen compound or an organophosphorus compound, wherein an organic nitrogen compound or an organic phosphorus compound is represented with respect to the onium salt represented by the formula (1). The content of the organic nitrogen compound is at least one selected from the group consisting of aliphatic tertiary amines, aromatic tertiary amines, and pyridines, and the organophosphorus compound is a tertiary phosphine, and the formula (1): Q ⁺ ‧A ^- (1) (wherein Q ⁺ represents a quaternary ammonium cation or a quaternary phosphonium cation, and A ^- represents PF ₆ ^- ). For example, the bismuth salt composition of claim 1 of the patent scope contains a solvent. A method for the stabilization of a cerium salt, which is characterized by mixing an onium salt and an organic nitrogen compound or an organic phosphorus compound represented by the formula (1) of claim 1 of the patent application. A method for preserving a cerium salt, which is characterized in that the cerium salt represented by the formula (1) of the first aspect of the patent application is preserved in the presence of an organic nitrogen compound or an organic phosphorus compound.