JP6908400B2 - An onium salt having an isocyanate group, an ionic polymer containing the onium salt, and an antistatic agent containing the onium salt. - Google Patents

Description

The present invention relates to an onium salt having an isocyanate group, an ionic polymer containing the onium salt, and an antistatic agent containing the onium salt.

As a method of imparting antistatic properties to a resin product, a method of blending an ionic liquid into the resin is known. For example, in Patent Document 1, 1-hexyl-4-methylpyridinium = bis (trifluoromethanesulfonyl) imide is blended as an ionic liquid in a pressure-sensitive adhesive based on an acrylic resin to impart antistatic properties. .. However, ionic liquids that do not have reactive functional groups, such as 1-hexyl-4-methylpyridinium-bis (trifluoromethanesulfonyl) imide, do not chemically bond to polymer molecules, causing the ionic liquid to bleed out of the resin. do. The ionic liquid bleeding out of the resin is washed away by the water immersion treatment of the resin, and the antistatic property of the resin surface is lowered, so that it is not suitable for applications requiring washing with water.

The present inventors compounded 1-hexyl-4-methylpyridinium-bis (trifluoromethanesulfonyl) imide with an acrylic resin to prepare an acrylic resin composition, and the antistatic property of the obtained acrylic resin composition was subjected to a water immersion test. As a result of the evaluation, the antistatic property was greatly reduced, and a satisfactory result was not obtained (see the comparative example described later).

Japanese Unexamined Patent Publication No. 2006-182716

An object of the present invention is to provide a novel onium salt capable of imparting antistatic properties to a resin, an ionic polymer having the structure of the onium salt as a partial skeleton, and an antistatic agent containing the ionic polymer. And. Another object of the present invention is to provide an antistatic agent and a resin composition having a small decrease in antistatic property even by water immersion treatment.

As a result of diligent studies by the present inventor in order to solve the above problems, the structure of the onium salt obtained by reacting the onium salt represented by the formula (1) with an acrylic resin composition having a hydroxy group is partially defined. It has been found that the ionic polymer having a skeleton has antistatic properties and the decrease in antistatic properties is small even by water immersion treatment, and the present invention has been completed.

That is, the present invention relates to the following [1] to [13].

[1] An onium salt represented by the formula (1).

Equation (1):

（式中、Ｌは置換基を有していてもよいアルキレン基又は置換基を有していてもよいアリーレン基、Ａ⁻はフッ素原子を有するアニオン、Ｂ^＋はアンモニウムカチオン、ピリジニウムカチオン、イミダゾリウムカチオン又はホスホニウムカチオン、ＤはＯ、ＮＨ又はＳを表す。）

(In the formula, L is an alkylene group which may have a substituent or an arylene group which may have a substituent, A ⁻ is an anion having a fluorine atom, and B ⁺ is an ammonium cation, a pyridinium cation, or an imidazolium. Cation or phosphonium cation, D represents O, NH or S)

[2] The ammonium cation is of the formula (2):

（式中、Ｒ^１〜Ｒ^３は炭素数１〜２０のアルキル基を表し、Ｒ^１とＲ^２は互いに末端で結合してピペリジン環又はピロリジン環を形成してもよい。ａは１〜２０の整数である。）
で示されるアンモニウムカチオンであり、前記ピリジニウムカチオンが式（３）：

(In the formula, R ^{1 to} R ³ represent an alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other at the terminal to form a piperidine ring or a pyrrolidine ring. A is 1 to 20. Is an integer of.)
It is an ammonium cation represented by, and the pyridinium cation is the formula (3) :.

（式中、Ｒ^４は水素原子又は炭素数１〜２０のアルキル基を表す。ｂは１〜２０の整数である。）
で示されるピリジニウムカチオンであり、前記イミダゾリウムカチオンが式（４）：

(In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. B is an integer of 1 to 20.)
It is a pyridinium cation represented by, and the imidazolium cation is the formula (4) :.

（式中、Ｒ^５は炭素数１〜２０のアルキル基を表す。ｃは１〜２０の整数である。）
で示されるイミダゾリウムカチオンであり、前記ホスホニウムカチオンが式（５）：

(In the formula, R ⁵ represents an alkyl group having 1 to 20 carbon atoms. C is an integer of 1 to 20.)
It is an imidazolium cation represented by the above, and the phosphonium cation is the formula (5) :.

（式中、Ｒ^６〜Ｒ^８は炭素数１〜２０のアルキル基を表す。ｄは１〜２０の整数である。）
で示されるホスホニウムカチオンである［１］に記載のオニウム塩。

(In the formula, R ^{6 to} R ⁸ represent an alkyl group having 1 to 20 carbon atoms. D is an integer of 1 to 20.)
The onium salt according to [1], which is a phosphonium cation represented by.

[3] The anion having a fluorine atom is a trifluoromethanesulfonic acid anion, a bis (trifluoromethanesulfonyl) imide anion, a bis (fluorosulfonyl) imide anion, a tetrafluoroborate anion, or a hexafluorophosphate anion [1] or [2]. ] The onium salt described in.

[4] Equation (6):
^{HD-B + X - (6} )
(In the formula, B and D are the same as above ^{. X −} represents a halogen anion.)
Halide salt and formula (7):
M ⁺ A ^- (7)
(In the formula, M ⁺ represents a hydrogen ion or an alkali metal ion ^{. A −} is the same as described above.)
By the anion exchange reaction with the alkali metal compound represented by, the formula (8):
^{HD-B + A - (8} )
(Wherein, D, ^{B +} or A ^- is as defined above.)
The onium salt represented by is synthesized, and further formula (9):
OCN-L-NCO (9)
(In the formula, L is the same as above.)
The method for producing an onium salt according to any one of [1] to [3], which is reacted with the diisocyanate represented by.

[5] An ionic polymer having a structural unit represented by the following formula (10).

Equation (10):

（式中、Ｌ、Ｄ、Ｂ^＋又はＡ⁻は前記に同じである。Ｒ^９〜Ｒ^１１は水素原子又は炭素数１〜２０のアルキル基、Ｒ^１２は炭素数１〜２０のアルキル基又は炭素数３〜２０のシクロアルキル基を表す。ｘ及びｎは１以上の整数、ｙ及びｚは０又は１以上の整数である。Ｅは下記式（１１）又は式（１２）で表される結合である。

(In the formula, L, D, B ⁺ or A ⁻ are the same as described above. R ^{9 to} R ¹¹ are hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and R ¹² is an alkyl group having 1 to 20 carbon atoms. It represents a cycloalkyl group having 3 to 20 carbon atoms. X and n are integers of 1 or more, y and z are 0 or integers of 1 or more. E is represented by the following formula (11) or formula (12). It is a bond.

Equation (11):

Equation (12):

（式中、Ｇは置換基を有していてもよい炭素数１〜２０のアルキレン基である。））

(In the formula, G is an alkylene group having 1 to 20 carbon atoms which may have a substituent.))

[6] The ionic polymer according to [5], wherein y and z are integers of 1 or more.

[7] A method for producing an ionic polymer in which an acrylic polymer having a hydroxyl group is reacted with at least one onium salt according to any one of [1] to [3].

[8] The acrylic polymer having a hydroxyl group is a polymer obtained from an acrylic monomer composition containing at least one of a hydroxyalkyl acrylate compound represented by the formula (13) or an acrylic acid compound represented by the formula (14). The method for producing an ionic polymer according to [7].

Equation (13):

（式中、Ｇは前記に同じ、Ｒ^１３は水素原子又は炭素数１〜２０のアルキル基を表す。）

(In the formula, G is the same as above, and R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

Equation (14):

（式中、Ｒ^１４は水素原子又は炭素数１〜２０のアルキル基を表す。）

(In the formula, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

[9] The seventh aspect of claim 7, wherein the acrylic polymer having a hydroxyl group is a polymer obtained from an acrylic monomer composition containing a hydroxyalkyl acrylate compound represented by the formula (13) and an acrylic acid compound represented by the formula (14). Method for producing an ionic polymer.

[10] The method for producing an ionic polymer according to [8] or [9], which further comprises an alkyl acrylate compound represented by the formula (15) in the acrylic monomer composition.
Equation (15):

（式中、Ｒ^１５は水素原子又は炭素数１〜２０のアルキル基を表す。Ｒ^１６は炭素数１〜２０のアルキル基又は炭素数３〜２０のシクロアルキル基である。）

(In the formula, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ¹⁶ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.)

[11] At least 0.1 mol of at least one onium salt according to any one of [1] to [3] is reacted with 1 mol of the hydroxyl group in the acrylic polymer having a hydroxyl group. The method for producing an ionic polymer according to any one of [6] to [8].

[12] An antistatic agent containing the ionic polymer according to [5] or [6].

[13] A resin composition containing the antistatic agent according to [12] and another resin.

According to the present invention, it is possible to provide a novel onium salt capable of imparting antistatic properties to a resin, an ionic polymer having the structure of the onium salt as a partial skeleton, and an antistatic agent containing the ionic polymer. Further, it is possible to provide an antistatic agent and a resin composition in which the decrease in antistatic property due to water immersion is small.

Hereinafter, the present invention will be specifically described.

The onium salt of the present invention (hereinafter referred to as onium salt (1)) is represented by the following formula (1). Equation (1):

In the formula (1), L is an alkylene group which may have a substituent or an arylene group which may have a substituent, and the alkylene group which may have a substituent is butylene. Group, hexamethylene group, decamethylene group, 2-methylhexamethylene group, 3-methylhexamethylene group, 2,4-dimethylhexamethylene group, 2,2,4-trimethylhexamethylene group, 2,4,4-trimethyl Examples thereof include a hexamethylene group, a 2-ethyldecamethylene group and a 1,1,4,4-tetramethyl-1,4-butylene group, preferably a butylene group, a hexamethylene group and a 3-methylhexamethylene group, and hexamethylene. Groups are particularly preferred. Examples of the arylene group which may have a substituent include an m-phenylene group, a p-phenylene group, a 2-methyl-m-phenylene group, a 4-methyl-m-phenylene group, a methylenedi-p-phenylene group, and 1 , 5-Naphthalene group, 1,3-cyclopentylene group and 1,4-cyclohexylene group are mentioned, and p-phenylene group, methylenedi-p-phenylene group and 4-methyl-m-phenylene group are preferable.

A ⁻ is an anion having a fluorine atom, and examples thereof include a trifluoromethanesulfonic anion, a bis (trifluoromethanesulfonyl) imide anion, a bis (fluorosulfonyl) imide anion, a tetrafluoroborate anion, and a hexafluorophosphate anion. Phosphate anions, bis (trifluoromethanesulfonyl) imide anions, and bis (fluorosulfonyl) imide anions are preferred, with bis (trifluoromethanesulfonyl) imide anions being particularly preferred.

B ⁺ is an ammonium cation, a pyridinium cation, an imidazolium cation or a phosphonium cation. D represents O, NH or S, with O or NH being preferred and O being more preferred.

The ammonium cation includes the formula (2):

（式中、Ｒ^１〜Ｒ^３は炭素数１〜２０のアルキル基を表し、Ｒ^１とＲ^２は互いに末端で結合してピペリジン環又はピロリジン環を形成してもよい。ａは１〜２０の整数である。）
で示されるアンモニウムカチオンが挙げられ、炭素数１〜２０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基等が挙げられ、メチル基、エチル基、プロピル基及びブチル基が好ましく、メチル基が特に好ましい。ａは１〜２０の整数であり、好ましくは２〜１２の整数であり、より好ましくは２〜６の整数である。

(In the formula, R ^{1 to} R ³ represent an alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other at the terminal to form a piperidine ring or a pyrrolidine ring. A is 1 to 20. Is an integer of.)
Examples of the ammonium cation represented by (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and the like, and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group and a propyl group. And Butyl groups are preferred, and methyl groups are particularly preferred. a is an integer of 1 to 20, preferably an integer of 2 to 12, and more preferably an integer of 2 to 6.

The pyridinium cation includes the formula (3):

（式中、Ｒ^４は水素原子又は炭素数１〜２０のアルキル基を表す。ｂは１〜２０の整数である。）
で示されるピリジニウムカチオンが挙げられ、炭素数１〜２０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基等が挙げられ、メチル基、エチル基、プロピル基及びブチル基が好ましく、メチル基が特に好ましい。ｂは１〜２０の整数であり、好ましくは２〜１６の整数であり、より好ましくは２〜１２の整数である。

(In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. B is an integer of 1 to 20.)
Examples of the pyridinium cation represented by (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and the like, and examples thereof include a methyl group, an ethyl group and a propyl group. And Butyl groups are preferred, and methyl groups are particularly preferred. b is an integer of 1 to 20, preferably an integer of 2 to 16, and more preferably an integer of 2 to 12.

The imidazolium cation includes the formula (4):

（式中、Ｒ^５は炭素数１〜２０のアルキル基を表す。ｃは１〜２０の整数である。）
で示されるイミダゾリウムカチオンが挙げられ、炭素数１〜２０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基等が挙げられ、メチル基、エチル基、プロピル基及びブチル基が好ましく、メチル基が特に好ましい。ｃは１〜２０の整数であり、好ましくは２〜１２の整数であり、より好ましくは２〜６の整数である。

(In the formula, R ⁵ represents an alkyl group having 1 to 20 carbon atoms. C is an integer of 1 to 20.)
Examples of the imidazolium cation represented by (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and the like, and examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group and a propyl group. A group and a butyl group are preferable, and a methyl group is particularly preferable. c is an integer of 1 to 20, preferably an integer of 2 to 12, and more preferably an integer of 2 to 6.

The phosphonium cation includes the formula (5):

（式中、Ｒ^６〜Ｒ^８は炭素数１〜２０のアルキル基を表す。ｄは１〜２０の整数である。）
で示されるホスホニウムカチオンが挙げられ、炭素数１〜２０のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基等が挙げられ、メチル基、エチル基、プロピル基及びブチル基が好ましく、ブチル基が特に好ましい。ｄは１〜２０の整数であり、好ましくは２〜１２の整数であり、より好ましくは２〜６の整数である。

(In the formula, R ^{6 to} R ⁸ represent an alkyl group having 1 to 20 carbon atoms. D is an integer of 1 to 20.)
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and the like, and examples thereof include a methyl group, an ethyl group and a propyl group. And a butyl group is preferable, and a butyl group is particularly preferable. d is an integer of 1 to 20, preferably an integer of 2 to 12, and more preferably an integer of 2 to 6.

Specific examples of the onium salt (1) include 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (6-isocyanatohexyl)). Carbamoyloxy] ethyltriethylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyltripropylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (6) -Isocyanatohexyl) carbamoyloxy] ethyltributylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyltrihexylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyltrioctylammonium = bis (trifluoromethanesulfonyl) imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltrimethylammonium = bis (trifluoromethanesulfonyl) imide ) Imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltriethylammonium = bis (trifluoromethanesulfonyl) imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltripropylammonium = Bis (trifluoromethanesulfonyl) imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] Hexyltributylammonium = bis (trifluoromethanesulfonyl) imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] Hexyltrihexylammonium = bis (trifluoromethanesulfonyl) imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltrioctylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (6-isosia) Nathexyl) carbamoyloxy] ethyltrimethylammonium = bis (fluorosulfonyl) imide, 2- [N- (6-isosianatohexyl) carbamoyloxy] ethyltriethylammonium = bis (fluorosulfonyl) imide, 2- [N- (6) -Isocyanatohexyl) carbamoyloxy] ethyltributylammonium = bis (fluorosulfonyl) Imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltrimethylammonium = bis (fluorosulfonyl) imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltriethylammonium = bis (fluoro) Sulfonyl) imide, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltributylammonium = bis (fluorosulfonyl) imide, 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyltrimethylammonium = hexa Fluorophosphate, 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyltriethylammonium = hexafluorophosphate, 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyltributylammonium = hexafluorophosphate, 6 -[N- (6-isocyanatohexyl) carbamoyloxy] hexyltrimethylammonium = hexafluorophosphate, 6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyltriethylammonium = hexafluorophosphate, 6- [N- (6-Isocyanatohexyl) Carbamoyloxy] Hexyltributylammonium = hexafluorophosphate,

1-Methyl-1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) piperidinium-bis (trifluoromethanesulfonyl) imide, 1-methyl-1- (6- [N- (6-isocyanate)) Natohexyl) carbamoyloxy] hexyl) piperidinium = bis (trifluoromethanesulfonyl) imide, 1-methyl-1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) pyrrolidinium = bis (trifluoromethanesulfonyl) Imide, 1-methyl-1- (6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyl) pyrrolidinium = bis (trifluoromethanesulfonyl) imide,

1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-methylimidazolium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl)) Carbamoyloxy] ethyl) -3-ethylimidazolium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (6-isosianatohexyl) carbamoyloxy] ethyl) -3-propylimidazolium = bis (trifluo) Lomethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-butylimidazolium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6) −Isocyanatohexyl) carbamoyloxy] ethyl) -3-hexylmidazolium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-octyl imidazole Rium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-methylimidazolium = bis (fluorosulfonyl) imide, 1- (2- [ N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-methylimidazolium = hexafluorophosphate, 1- (6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyl) -3-methylimidazole) Rium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyl) -3-ethylimidazolium = bis (trifluoromethanesulfonyl) imide, 1- (6-) [N- (6-isocyanatohexyl) carbamoyloxy] hexyl) -3-propylimidazolium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyl) -3-Butylimidazolium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyl) -3-hexyl imidazolium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (6-isocyanatohexyl) carbamoyloxy] hexyl) -3-octyl imidazolium = bis (trifluoromethanesulfo) Nil) imide,

2- [N- (3-Isocyanato-4-methylphenyl) carbamoyloxy] ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyltriethyl Ammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyltripropylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (3-isocyanato) -4-Methylphenyl) carbamoyloxy] ethyltributylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyltrihexylammonium = bis (trifluoromethanesulfonyl) Imide, 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyltrioctylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy ] Ethyltrimethylammonium = bis (fluorosulfonyl) imide, 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyltrimethylammonium = hexafluorophosphate, 2- [N- (4-isocyanatophenyl) Carbamoyloxy] ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyltriethylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (4-isocyanatophenyl) Isocyanatophenyl) carbamoyloxy] ethyltripropylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyltributylammonium = bis (trifluoromethanesulfonyl) imide, 2- [ N- (4-Isocyanatophenyl) carbamoyloxy] ethyltrihexylammonium = bis (trifluoromethanesulfonyl) imide, 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyltrioctylammonium = bis (trifluoromethanesulfonyl) imide ) Imide, 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl trime Tyrammonium = bis (fluorosulfonyl) imide, 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyltrimethylammonium = hexafluorophosphate, 2- {N- [4-[(4-isocyanatophenyl) methyl) ] Phenyl] carbamoyloxy} ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide, 2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyltriethylammonium = bis (trifluoromethanesulfonyl) ) Imide, 2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyltripropylammonium = bis (trifluoromethanesulfonyl) imide, 2- {N- [4-[(4) -Isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl tributylammonium = bis (trifluoromethanesulfonyl) imide, 2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyltrihexyl Ammonium = bis (trifluoromethanesulfonyl) imide, 2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyltrioctyl ammonium = bis (trifluoromethanesulfonyl) imide, 2- {N − [4-[(4-Isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyltrimethylammonium = bis (fluorosulfonyl) imide, 2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] Carbamoyloxy} ethyltrimethylammonium = hexafluorophosphate,

1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) pyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -2-Methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -4-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (6-isocyanatohexyl) carbamoyloxy] Ethyl) -2-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -4-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (6-isocyanatohexyl) carbamoyl) carbamoyl Oxy] Ethyl) -2-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-propylpyridinium = bis (trifluoromethanesulfonyl) Imid, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -4-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl)) ) Carbamoyloxy] ethyl) -2-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-butylpyridinium = bis (trifluoromethane) Sulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -4-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isosia) Nathexyl) Carbamoyloxy] Ethyl) -2-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N-] (6-Isocyanatohexyl) carbamoyloxy] ethyl) -3-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -4-hexyl Pyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -2-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [ N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -3-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) -4 -Octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) pyridinium = bis (fluorosulfonyl) imide, 1- (2- [N- ( 6-Isocyanatohexyl) carbamoyloxy] ethyl) pyridinium = hexafluorophosphate, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) pyridinium = bis (trifluoromethanesulfonyl) imide, 1-( 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -2-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (4-isosianatophenyl) carbamoyloxy] ethyl ) -3-Methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -4-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1 -(2- [N- (4-Isocyanatophenyl) carbamoyloxy] ethyl) -2-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (4-isocyanatophenyl) carbamoyloxy) ] Ethyl) -3-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -4-ethylpyridinium = bis (trifluoromethanesulfonyl) imide , 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -2-p Lopilpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isosianatophenyl) carbamoyloxy] ethyl) -3-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2) -[N- (4-Isocyanatophenyl) carbamoyloxy] ethyl) -4-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -2-Butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -3-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-Isocyanatophenyl) carbamoyloxy] ethyl) -4-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] Ethyl) -2-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -3-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -4-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (4-isocyanatophenyl) carbamoyl) Oxy] ethyl) -2-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -3-octylpyridinium = bis (trifluoromethanesulfonyl) Imide, 1- (2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl) -4-octylpyridinium-bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (4-isocyanatophenyl)) ) Carbamoyloxy] ethyl) pyridinium = bis (fluorosulfonyl) imide, 1-(2- [N- (4-isosianatophenyl) carbamoyloxy] ethyl) pyridinium = hexafluorophosphate,

1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) pyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) -2-Methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) -3-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) -4-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] Hexyl) -2-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isosianatophenyl) carbamoyloxy] hexyl) -3-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) -4-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyl) Oxy] hexyl) -2-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) -3-propylpyridinium = bis (trifluoromethanesulfonyl) Imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) -4-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl)) ) Carbamoyloxy] hexyl) -2-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(6- [N- (4-isosianatophenyl) carbamoyloxy] hexyl) -3-butylpyridinium = bis (trifluoromethane) Sulfonyl) imide, 1- (6- [N- (4-isosianatophenyl) carbamoyloxy] hexyl) -4-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isosia) Natophenyl) carbamoyloxy] hexyl) -2-hexylpyridinium = bis (trifluoromethanesulfoni) Le) imide, 1- (6- [N- (4-isosianatophenyl) carbamoyloxy] hexyl) -3-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isosia) Natophenyl) carbamoyloxy] hexyl) -4-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isosianatophenyl) carbamoyloxy] hexyl) -2-octylpyridinium = bis ( Trifluoromethanesulfonyl) imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) -3-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (6- [N- (4) −Isocyanatophenyl) carbamoyloxy] hexyl) -4-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) pyridinium = bis (fluorosulfonyl) ) Imide, 1- (6- [N- (4-isocyanatophenyl) carbamoyloxy] hexyl) pyridinium = hexafluorophosphate, 1- (2- [N- (3-isocyanatophenyl) carbamoyloxy] Ethyl) pyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -2-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1 -(2- [N- (3-Isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -3-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (3-Isocyanato-4) -Methylphenyl) carbamoyloxy] ethyl) -4-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -2-ethyl Pyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -3-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-( 2- [N- (3-Isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -4-ethylpyridinium = Bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -2-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2) -[N- (3-Isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -3-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (3-Isocyanato-4-methylphenyl) ) Carbamoyloxy] ethyl) -4-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -2-butylpyridinium = bis (Trifluoromethanesulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -3-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [ N- (3-Isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -4-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyl) Oxy] ethyl) -2-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -3-hexylpyridinium = bis (trifluo) Lomethanesulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -4-hexylpyridinium-bis (trifluoromethanesulfonyl) imide, 1- (2- [N-] (3-Isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -2-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] Ethyl) -3-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) -4-octylpyridinium = bis (trifluoromethanesulfonyl) sulfonyl ) Imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) pyri Dinium = bis (fluorosulfonyl) imide, 1- (2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyl) pyridinium = hexafluorophosphate,

1- (2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) pyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4- [4- [ (4-Isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -2-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl) ] Phenyl] carbamoyloxy} ethyl) -3-methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -4-Methylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -2-ethylpyridinium = bis ( Trifluoromethanesulfonyl) imide, 1- (2-{N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -3-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-Isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -4-ethylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4) − [(4-Isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -2-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) phenyl) ) Methyl] phenyl] carbamoyloxy} ethyl) -3-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} Ethyl) -4-propylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -2-butylpyridinium = Bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -3-butylpyridinium = bis (trifluoromethanesulfonyl) ) Imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -4-butylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2-) {N- [4-[(4-Isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -2-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[( 4-Isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -3-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl] Phenyl] carbamoyloxy} ethyl) -4-hexylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-(2- {N- [4-[(4-isosianatophenyl) methyl] phenyl] carbamoyloxy} ethyl)- 2-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1- (2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -3-octylpyridinium = bis (trifluo) Lomethanesulfonyl) imide, 1-(2-{N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) -4-octylpyridinium = bis (trifluoromethanesulfonyl) imide, 1-( 2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl) pyridinium = bis (fluorosulfonyl) imide, 1- (2- {N- [4-[(4-isosia) Natophenyl) methyl] phenyl] carbamoyloxy} ethyl) pyridinium = hexafluorophosphate,

Triethyl (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) phosphonium = bis (trifluoromethanesulfonyl) imide, tripropyl (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) phosphonium = Bis (trifluoromethanesulfonyl) imide, tributyl (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) phosphonium = bis (trifluoromethanesulfonyl) imide, trihexyl (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) Hexyl) carbamoyloxy] ethyl) phosphonium = bis (trifluoromethanesulfonyl) imide, trioctyl (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) phosphonium = bis (trifluoromethanesulfonyl) imide, tributyl (2-) [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) phosphonium = bis (fluorosulfonyl) imide, tributyl (2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl) phosphonium = hexafluorophosphate, etc. Can be mentioned.

Next, a method for producing the onium salt (1) will be described.

The onium salt (1) is expressed by the formula (6):

^{HD-B + X - (6} )
(In the formula, B and D are the same as above ^{. X −} represents a halogen anion.)
Halide salt (hereinafter referred to as halide salt (6)) and formula (7):
M ⁺ A ^- (7)
(In the formula, M ⁺ represents a hydrogen ion or an alkali metal ion ^{. A −} is the same as described above.)
By an anion exchange reaction with the alkali metal compound represented by (hereinafter referred to as alkali metal compound (7)), the formula (8):
^{HD-B + A - (8} )
(Wherein, D, ^{B +} or A ^- is as defined above.)
The onium salt represented by (hereinafter referred to as onium salt (8)) is synthesized, and the formula (9):
OCN-L-NCO (9)
(In the formula, L is the same as above.)
It can be produced by reacting the diisocyanate represented by (hereinafter referred to as diisocyanate (9)). A catalyst may be used for the reaction between the diisocyanate (9) and the onium salt (8).

First, the production of the onium salt (8) by the anion exchange reaction between the halide salt (6) and the alkali metal compound (7) will be described.

Specific examples of the halide salt (6) include (2-hydroxyethyl) trimethylammonium chloride, (2-hydroxyethyl) trimethylammonium bromide, (2-hydroxyethyl) triethylammonium chloride, and (2-hydroxyethyl) triethylammonium bromide. , (2-Hydroxyethyl) tripropylammonium chloride, (2-hydroxyethyl) tripropylammonium bromide, (2-hydroxyethyl) tributylammonium chloride, (2-hydroxyethyl) tributylammonium bromide, (2-hydroxyethyl) tri Hexylammonium chloride, (2-hydroxyethyl) trihexylammonium bromide, (2-hydroxyethyl) trioctylammonium chloride, (2-hydroxyethyl) trioctylammonium bromide, (6-hydroxyhexyl) trimethylammonium chloride, (6-hydroxyhexyl) Hydroxyhexyl) trimethylammonium bromide, (6-hydroxyhexyl) triethylammonium chloride, (6-hydroxyhexyl) triethylammonium bromide, (6-hydroxyhexyl) tripropylammonium chloride, (6-hydroxyhexyl) tripropylammonium bromide, (6-hydroxyhexyl) 6-Hydroxyhexyl) tributylammonium chloride, (6-hydroxyhexyl) tributylammonium bromide, (6-hydroxyhexyl) trihexylammonium chloride, (6-hydroxyhexyl) trihexylammonium bromide, (6-hydroxyhexyl) trioctylammonium Chloride, (6-hydroxyhexyl) trioctylammonium bromide,

1-Methyl-1- (2-hydroxyethyl) piperidinium chloride, 1-methyl-1- (2-hydroxyethyl) piperidinium bromide, 1-methyl-1- (6-hydroxyhexyl) piperidinium chloride , 1-Methyl-1- (6-hydroxyhexyl) piperidinium bromide, 1-methyl-1- (2-hydroxyethyl) pyrrolidinium chloride, 1-methyl-1- (2-hydroxyethyl) pyrrolidinium Bromide, 1-methyl-1- (6-hydroxyhexyl) pyrrolidinium chloride, 1-methyl-1- (6-hydroxyhexyl) pyrrolidinium bromide,

1- (2-Hydroxyethyl) -3-methylimidazolium chloride, 1- (2-hydroxyethyl) -3-methylimidazolium bromide, 1- (2-hydroxyethyl) -3-ethylimidazolium chloride, 1- (2-Hydroxyethyl) -3-ethylimidazolium bromide, 1- (2-hydroxyethyl) -3-propylimidazolium chloride, 1- (2-hydroxyethyl) -3-propylimidazolium bromide, 1- (2) -Hydroxyethyl) -3-butylimidazolium chloride, 1- (2-hydroxyethyl) -3-butylimidazolium bromide, 1- (2-hydroxyethyl) -3-hexyl imidazolium chloride, 1- (2-hydroxy) Ethyl) -3-hexyl imidazolium bromide, 1- (2-hydroxyethyl) -3-octyl imidazolium chloride, 1- (2-hydroxyethyl) -3-octyl imidazolium bromide, 1- (6-hydroxyhexyl) -3-Methylimidazolium chloride, 1- (6-hydroxyhexyl) -3-Methylimidazolium bromide, 1- (6-hydroxyhexyl) -3-ethylimidazolium chloride, 1- (6-hydroxyhexyl) -3 -Ethylimidazolium bromide, 1- (6-hydroxyhexyl) -3-propylimidazolium chloride, 1- (6-hydroxyhexyl) -3-propylimidazolium bromide, 1- (6-hydroxyhexyl) -3-butyl Imidazolium chloride, 1- (6-hydroxyhexyl) -3-butyl imidazolium bromide, 1- (6-hydroxyhexyl) -3-hexyl midazolium chloride, 1- (6-hydroxyhexyl) -3-hexyl imidazolium Bromide, 1- (6-hydroxyhexyl) -3-octyl imidazolium chloride, 1- (6-hydroxyhexyl) -3-octyl imidazolium bromide,

1- (2-Hydroxyethyl) pyridinium chloride, 1- (2-hydroxyethyl) pyridinium bromide, 1- (2-hydroxyethyl) -2-methylpyridinium chloride, 1- (2-hydroxyethyl) -2-methylpyridinium Bromide, 1- (2-hydroxyethyl) -3-methylpyridinium chloride, 1- (2-hydroxyethyl) -3-methylpyridinium bromide, 1- (2-hydroxyethyl) -4-methylpyridinium chloride, 1-( 2-Hydroxyethyl) -4-methylpyridinium bromide, 1- (2-hydroxyethyl) -2-ethylpyridinium chloride, 1- (2-hydroxyethyl) -2-ethylpyridinium bromide, 1- (2-hydroxyethyl) -3-Ethylpyridinium chloride, 1- (2-hydroxyethyl) -3-ethylpyridinium bromide, 1- (2-hydroxyethyl) -4-ethylpyridinium chloride, 1- (2-hydroxyethyl) -4-ethylpyridinium Bromide, 1- (2-hydroxyethyl) -2-propylpyridinium chloride, 1- (2-hydroxyethyl) -2-propylpyridinium bromide, 1- (2-hydroxyethyl) -3-propylpyridinium chloride, 1-( 2-Hydroxyethyl) -3-propylpyridinium bromide, 1- (2-hydroxyethyl) -4-propylpyridinium chloride, 1- (2-hydroxyethyl) -4-propylpyridinium bromide, 1- (2-hydroxyethyl) -2-Butylpyridinium chloride, 1- (2-hydroxyethyl) -2-butylpyridinium bromide, 1- (2-hydroxyethyl) -3-butylpyridinium chloride, 1- (2-hydroxyethyl) -3-butylpyridinium Bromide, 1- (2-hydroxyethyl) -4-butylpyridinium chloride, 1- (2-hydroxyethyl) -4-butylpyridinium bromide, 1- (2-hydroxyethyl) -2-hexylpyridinium chloride, 1-( 2-Hydroxyethyl) -2-hexylpyridinium bromide, 1- (2-hydroxyethyl) -3-hexylpyridinium chloride, 1- (2-hydroxyethyl) -3-hexylpyridinium bromide, 1- (2-hydroxyethyl) -4-hexylpyridinium chloride, 1- (2-hydroxyethyl) -4-hexylpyridinium bromide, 1- (2-hydro Xyethyl) -2-octylpyridinium chloride, 1- (2-hydroxyethyl) -2-octylpyridinium bromide, 1- (2-hydroxyethyl) -3-octylpyridinium chloride, 1- (2-hydroxyethyl) -3- Octylpyridinium bromide, 1- (2-hydroxyethyl) -4-octylpyridinium chloride, 1- (2-hydroxyethyl) -4-octylpyridinium bromide, 1- (6-hydroxyhexyl) pyridinium chloride, 1- (6-) Hydroxyhexyl) pyridinium bromide, 1- (6-hydroxyhexyl) -2-methylpyridinium chloride, 1- (6-hydroxyhexyl) -2-methylpyridinium bromide, 1- (6-hydroxyhexyl) -3-methylpyridinium chloride , 1- (6-Hydroxyhexyl) -3-methylpyridinium bromide, 1- (6-hydroxyhexyl) -4-methylpyridinium chloride, 1- (6-hydroxyhexyl) -4-methylpyridinium bromide, 1- (6) -Hydroxyhexyl) -2-ethylpyridinium chloride, 1- (6-hydroxyhexyl) -2-ethylpyridinium bromide, 1- (6-hydroxyhexyl) -3-ethylpyridinium chloride, 1- (6-hydroxyhexyl)- 3-Ethylpyridinium bromide, 1- (6-hydroxyhexyl) -4-ethylpyridinium chloride, 1- (6-hydroxyhexyl) -4-ethylpyridinium bromide, 1- (6-hydroxyhexyl) -2-propylpyridinium chloride , 1- (6-Hydroxyhexyl) -2-propylpyridinium bromide, 1- (6-hydroxyhexyl) -3-propylpyridinium chloride, 1- (6-hydroxyhexyl) -3-propylpyridinium bromide, 1- (6) -Hydroxyhexyl) -4-propylpyridinium chloride, 1- (6-hydroxyhexyl) -4-propylpyridinium bromide, 1- (6-hydroxyhexyl) -2-butylpyridinium chloride, 1- (6-hydroxyhexyl)- 2-butylpyridinium bromide, 1- (6-hydroxyhexyl) -3-butylpyridinium chloride, 1- (6-hydroxyhexyl) -3-butylpyridinium bromide, 1- (6-hydroxyhexyl) -4-butylpyridinium chloride , 1- (6-Hydroxyhexyl) -4-butylpi Lidinium bromide, 1- (6-hydroxyhexyl) -2-hexylpyridinium chloride, 1- (6-hydroxyhexyl) -2-hexylpyridinium bromide, 1- (6-hydroxyhexyl) -3-hexylpyridinium chloride, 1 -(6-Hydroxyhexyl) -3-hexylpyridinium bromide, 1- (6-hydroxyhexyl) -4-hexylpyridinium chloride, 1- (6-hydroxyhexyl) -4-hexylpyridinium bromide, 1- (6-hydroxy) Hexil) -2-octylpyridinium chloride, 1- (6-hydroxyhexyl) -2-octylpyridinium bromide, 1- (6-hydroxyhexyl) -3-octylpyridinium chloride, 1- (6-hydroxyhexyl) -3-3 Octylpyridinium bromide, 1- (6-hydroxyhexyl) -4-octylpyridinium chloride, 1- (6-hydroxyhexyl) -4-octylpyridinium bromide,

Triethyl (2-hydroxyethyl) phosphonium chloride, triethyl (2-hydroxyethyl) phosphonium bromide, tripropyl (2-hydroxyethyl) phosphonium chloride, tripropyl (2-hydroxyethyl) phosphonium bromide, tributyl (2-hydroxyethyl) phosphonium Chloride, tributyl (2-hydroxyethyl) phosphonium bromide, trihexyl (2-hydroxyethyl) phosphonium chloride, trihexyl (2-hydroxyethyl) phosphonium bromide, trioctyl (2-hydroxyethyl) phosphonium chloride, trioctyl (2-hydroxyethyl) phosphonium Bromid, triethyl (6-hydroxyhexyl) phosphonium chloride, triethyl (6-hydroxyhexyl) phosphonium bromide, tripropyl (6-hydroxyhexyl) phosphonium chloride, tripropyl (6-hydroxyhexyl) phosphonium bromide, tributyl (6-hydroxyhexyl) ) Phosphonium chloride, tributyl (6-hydroxyhexyl) phosphonium bromide, trihexyl (6-hydroxyhexyl) phosphonium chloride, trihexyl (6-hydroxyhexyl) phosphonium bromide, trioctyl (6-hydroxyhexyl) phosphonium chloride, trioctyl (6-hydroxyhexyl) ) Phosphonium bromide and the like.

Examples of the alkali metal compound (7) include bis (trifluoromethanesulfonyl) imide, lithium = bis (trifluoromethanesulfonyl) imide, potassium = bis (trifluoromethanesulfonyl) imide, sodium = bis (trifluoromethanesulfonyl) imide, and lithium = bis. (Fluorosulfonyl) imide, potassium = bis (fluorosulfonyl) imide, sodium = bis (fluorosulfonyl) imide, lithium = hexafluorophosphate, potassium = hexafluorophosphate, sodium = hexafluorophosphate, lithium = tetrafluoroborate, potassium = Examples thereof include tetrafluoroborate, sodium = tetrafluoroborate, trifluoromethanesulfonic acid, lithium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, sodium trifluoromethanesulfonate and the like.

The amount of the alkali metal compound (7) used is usually 0.8 mol or more, preferably 0.9 to 1.5 mol, more preferably 0.95 to 1.2 mol, based on 1 mol of the halide salt (6). It is a mole.

The anion exchange reaction is usually carried out in a solvent. As the solvent, water, methanol, dichloromethane, toluene or a mixed solvent thereof is used. The amount of the solvent used is not particularly limited, but is usually 20 parts by weight or less, preferably 0.5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, based on 1 part by weight of the halide salt (6). be.

The anion exchange reaction is usually stirred at 10 to 80 ° C., preferably 15 to 60 ° C., particularly preferably 20 to 40 ° C., usually for 15 minutes or longer, preferably 30 minutes to 2 hours, particularly preferably 45 minutes to 1 hour. If it is completed.

The mixing order of the halide salt (6), the alkali metal compound (7) and the solvent is not particularly limited, and the alkali metal compound (7) may be added after the halide salt (6) and the solvent are mixed, or the alkali metal. The halide salt (6) may be added after mixing the compound (7) and the solvent.

In the reaction mixture after completion of the reaction, the onium salt (8), which is a reaction product of the hydrophobic halide salt (6) and the alkali metal compound (7), is a liquid at a temperature above the melting point and below the melting point. Since it is separated as a solid, the onium salt (8) is separated by a desired separation means such as separation in the case of a liquid and filtration in the case of a solid, then washed with water as desired, and the obtained solid is dried. ) Is obtained. If necessary, an organic solvent (for example, ethyl acetate, methylene chloride, etc.) may be added to the reaction mixture during or after the reaction to extract the onium salt (8) into the organic solvent. The layer is washed with water if desired, and then the organic solvent is distilled off to obtain an onium salt (8) as a residue.

Next, the reaction between the onium salt (8) and the diisocyanate (9) will be described.

In formula (9), L is the same as described above. Examples of the diisocyanate (9) include butylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, 1,4-diisocyanate-2-butene, 1,2-diisocyanate ethene, and 2,5-di. Isocyanate-2,5-dimethylhexane, 1,6-diisocyanate-2,2,4-trimethylhexane, 1,3-diisocyanate-cyclopentane, 1,4-diisocyanate-cyclohexane, isophorondi Isocyanate, (methylenebis-p-phenylene) diisocyanate, 1,4-phenylenedi isocyanate, 1,3-phenylenedi isocyanate, 2,4-tolylene diisocyanate and the like, hexamethylene diisocyanate, etc. , 1,6-diisocyanate-2,2,4-trimethylhexane, (methylenebis-p-phenylene) diisocyanate, 1,4-phenylenediisocyanate and 2,4-tolylene diisocyanate are preferred. Methylene diisocyanate and 2,4-tolylene diisocyanate are more preferred.

The amount of diisocyanate (9) used is usually 0.8 to 20.0 mol, preferably 0.9 to 1.5 mol, more preferably 0.95 to 1.2 mol, based on the onium salt (8). Is.

Triethylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4. 0] -7-undecene, potassium iodide, zinc acetate, bismas octanoate, dibutyltin dilaurate and the like, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, potassium iodide , Dibutyltin dilaurate is preferable, 1,8-diazabicyclo [5.4.0] -7-undecene, and dibutyltin dilaurate are more preferable.

The amount of the catalyst used is usually 0.0001 to 0.20 mol, preferably 0.001 to 0.10 mol, more preferably 0.002 to 0.05 mol, based on 1 mol of the onium salt (8). be.

The reaction between the onium salt (8) and the diisocyanate (9) may or may not use a solvent, and examples of the solvent when the solvent is used include acetonitrile, tetrahydrofuran, toluene and the like. The amount of the solvent used is not particularly limited, but is usually 20 parts by weight or less, preferably 5 to 10 parts by weight, based on 1 part by weight of the onium salt (8).

In order to carry out the reaction of the onium salt (8) and the diisocyanate (9), a mixture of the onium salt (8), the diisocyanate (9) and, if necessary, a catalyst and a solvent is preferably mixed at 25 ° C. or higher. Is dropped at 40 to 80 ° C. for usually 1 hour or longer, preferably over 2 to 3 hours, and further usually at 25 ° C. or higher, preferably at 40 to 80 ° C. for usually 2 hours or longer, preferably over 3 to 5 hours. It may be stirred and mixed.

After obtaining the reaction mixture containing the onium salt (1) as described above, the obtained reaction mixture is filtered, concentrated to dryness, or the like to obtain a reaction product. The obtained reaction product is washed with a solvent (for example, ethyl ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, hexane, etc.) to remove unreacted raw materials contained in the reaction product, and an onium salt (1). ).

The onium salt (1) of the present invention can be used as an antistatic agent with little decrease in antistatic property even by water immersion treatment by reacting with an acrylic resin having a hydroxyl group to form an ionic polymer. In (1), the onium salt (1) can be used as it is as an antistatic agent without reacting with the acrylic resin having a hydroxyl group. In this case, the antistatic property can be imparted to the resin by blending the antistatic agent containing the onium salt (1) with the other resin. Examples of the resin include urethane resin, polycarbonate resin, acrylic resin and silicone resin, and acrylic resin is preferable.

When the antistatic agent containing the onium salt (1) is blended in the resin, the resin may be heated and melted and kneaded, or an appropriate solvent (for example, dichloromethane, ethyl acetate, toluene, etc.) and the resin and the onium salt may be added. After preparing a solution by mixing the above, the resin may be molded by a method such as applying the solution and removing the solvent. In the case of a photocurable resin, after applying the resin containing the onium salt (1) or a solution thereof, the coated surface may be cured by irradiation with ultraviolet rays.

The amount of the onium salt (1) added to the resin is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, particularly preferably 0.1 part by weight, based on 1 part by weight of the resin. Is 0.5 to 10% by weight.

Next, the ionic polymer of the present invention will be described.

The ionic polymer can be produced by reacting an acrylic polymer having a hydroxyl group with an onium salt (1). The ionic polymer preferably has a structural unit represented by the following formula (10).

Equation (10):

（式中、Ｌ、Ｄ、Ｂ^＋又はＡ⁻は前記に同じである。Ｒ^９〜Ｒ^１１は水素原子又は炭素数１〜２０のアルキル基、Ｒ^１２は炭素数１〜２０のアルキル基又は炭素数３〜２０のシクロアルキル基を表す。ｘ及びｎは１以上の整数、ｙ及びｚは０又は１以上の整数である。Ｅは下記式（１１）又は式（１２）で表示される結合である。

(In the formula, L, D, B ⁺ or A ⁻ are the same as described above. R ^{9 to} R ¹¹ are hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and R ¹² is an alkyl group having 1 to 20 carbon atoms. Represents a cycloalkyl group having 3 to 20 carbon atoms. X and n are integers of 1 or more, y and z are 0 or integers of 1 or more. E is represented by the following formula (11) or formula (12). It is a bond.

Equation (11):

Equation (12):

（式中、Ｇは置換基を有していてもよい炭素数１〜２０のアルキレン基である。））

(In the formula, G is an alkylene group having 1 to 20 carbon atoms which may have a substituent.))

In formula (10), L, D, B ⁺ or A ⁻ is the same as described above. R ^{9 to} R ¹¹ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. R ¹² is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably. It is an alkyl group having 1 to 2 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, and a 2-ethylhexyl group. Examples thereof include a stearyl group, and a methyl group, an ethyl group, a butyl group and a 2-ethylhexyl group are preferable, and a methyl group and an ethyl group are particularly preferable. Cycloalkyl groups having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, adamantyl group, isobornyl group and tricyclo. Examples thereof include a decyl group and a decahydronaphthyl group, and a cyclopentyl group, a cyclohexyl group and an adamantyl group are preferable. x and n are integers of 1 or more. y and z are 0 or an integer of 1 or more, and preferably an integer of 1 or more. E is a combination represented by equation (11) or equation (12).

In the formula (12), G is an alkylene group having 1 to 20 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 6 carbon atoms which may have a substituent, and particularly preferably. Is an alkylene group having 1 to 4 carbon atoms which may have a substituent. The substituent is preferably a hydrocarbon group, more preferably an alkyl group. Examples of the alkylene group having 1 to 20 carbon atoms which may have a substituent include a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, a decamethylene group, a 2-methylhexamethylene group and a 3-methylhexa. Methylene group, 2,4-dimethylhexamethylene group, 2,2,4-trimethylhexamethylene group, 2,4,4-trimethylhexamethylene group, 2-ethyldecamethylene group, 1,1,4,4-tetra Examples thereof include a methyl-1,4-butylene group, and a methylene group, an ethylene group, a propylene group, a butylene group, and a hexamethylene group are preferable, and a methylene group, an ethylene group, a propylene group, and a butylene group are particularly preferable.

In the present invention, the acrylic polymer having a hydroxyl group is not particularly limited as long as it has a hydroxyl group, but is a hydroxyalkyl acrylate compound represented by the following formula (13) (hereinafter referred to as hydroxyalkyl acrylate compound (13)). Alternatively, it is preferably a polymer obtained from an acrylic monomer composition containing at least one of an acrylic acid compound represented by the following formula (14) (hereinafter referred to as acrylic acid compound (14)).

Equation (13):

（式中、Ｇは前記に同じ、Ｒ^１３は水素原子又は炭素数１〜２０のアルキル基を表す）

(In the formula, G is the same as above, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)

Equation (14):

（式中、Ｒ^１４は水素原子又は炭素数１〜２０のアルキル基を表す。）

(In the formula, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

More preferably, it is a polymer obtained from an acrylic monomer composition containing a hydroxyalkyl acrylate compound (13) and an acrylic acid compound (14).

Further, the acrylic monomer composition may further contain an alkyl acrylate compound represented by the formula (15) (hereinafter, referred to as an alkyl acrylate compound (15)), and preferably contains an alkyl acrylate compound (15). ..

Equation (15):

（式中、Ｒ^１５は水素原子又は炭素数１〜２０のアルキル基を表す。Ｒ^１６は炭素数１〜２０のアルキル基又は炭素数３〜２０のシクロアルキル基である。）

(In the formula, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ¹⁶ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.)

In formula (13), G is the same as described above. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. Alkyl having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, 2-ethylhexyl group and stearyl group. Examples thereof include a methyl group, an ethyl group, a butyl group and a 2-ethylhexyl group, and a methyl group and an ethyl group are particularly preferable.

Examples of the hydroxyalkyl acrylate compound (13) include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, and 10-hydroxydecyl. Acrylate, 12-hydroxylauryl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, Examples thereof include 10-hydroxydecyl (meth) acrylate and 12-hydroxylauryl (meth) acrylate, and 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are preferable, and 2-hydroxyethyl acrylate is more preferable.

In the formula (14), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. Alkyl having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, 2-ethylhexyl group and stearyl group. Examples thereof include a methyl group, an ethyl group, a butyl group and a 2-ethylhexyl group, and a methyl group and an ethyl group are particularly preferable.

Examples of the acrylic acid compound (14) include acrylic acid, methacrylic acid, ethacryllic acid and the like, and acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable.

In the formula (15), R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom. R ₁₆ An alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably carbon. It is an alkyl group of number 1-2. Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a lauryl group, and a 2-ethylhexyl group. Examples thereof include a stearyl group, and a methyl group, an ethyl group, a butyl group and a 2-ethylhexyl group are preferable, and a methyl group and an ethyl group are particularly preferable. Cycloalkyl groups having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, adamantyl group, isobornyl group and tricyclo. Examples thereof include a decyl group and a decahydronaphthyl group, and a cyclopentyl group, a cyclohexyl group and an adamantyl group are preferable.

Examples of the alkyl acrylate compound (15) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, and 2 -Ethylhexyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate. , Hexyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate and the like. , Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, iso Nonyl acrylate, decyl acrylate, and dodecyl acrylate are preferable, and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, and t-butyl acrylate are more preferable.

When an acrylic monomer composition containing a hydroxyalkyl acrylate compound (13), an acrylic acid compound (14) and an alkyl acrylate compound (15) is used in the acrylic monomer composition, the acrylic acid compound (13) is compared with the hydroxyalkyl acrylate compound (13). The amount of the acrylic acid compound (14) and the alkyl acrylate compound (15) used is not particularly limited, but preferably 0.005 to 1 part by weight of the acrylic acid compound (14) and alkyl with respect to 1 part by weight of the hydroxyalkyl acrylate compound (13). 5 to 50 parts by weight of the acrylate compound (15), more preferably 0.01 to 0.1 parts by weight of the acrylic acid compound (14) and the alkyl acrylate compound (15) 10 with respect to 1 part by weight of the hydroxyalkyl acrylate compound (13). ~ 25 parts by weight, particularly preferably 0.02 to 0.06 parts by weight of the acrylic acid compound (14) and 16 to 20 parts by weight of the alkyl acrylate compound (15) with respect to 1 part by weight of the hydroxyalkyl acrylate compound (13). ..

When the acrylic monomer composition is polymerized, the polymerization reaction of the acrylic monomer composition is usually carried out in the presence of a polymerization initiator.

Examples of the polymerization initiator used for the polymerization of the acrylic monomer composition include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 4,4'-azobis. Examples thereof include azo-based initiators such as (4-cyanovaleric acid) and 2,2'-azobis (4-hydroxybutyl 2-methylpropionate), and organic peroxides such as benzoyl peroxide and lauroyl peroxide. 2,2'-azobisisobutyronitrile and benzoyl peroxide are preferable, and 2,2'-azobisisobutyronitrile is more preferable. The amount of the polymerization initiator used is usually 0.001 to 2 parts by weight, preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 parts by weight, based on 1 part by weight of the acrylic monomer composition. It is a part by weight.

When polymerizing an acrylic monomer composition, it is usually carried out by adding the acrylic monomer composition to a solvent to prepare a solution, and then adding a polymerization initiator to the solution. The solvent is not particularly limited as long as it does not affect the reaction, and examples thereof include methanol, ethanol, isopropyl alcohol, acetone, acetonitrile, ethyl acetate and the like, and ethyl acetate is preferable.

In the polymerization reaction, the amount of the solvent used is not particularly limited, but is usually 100 parts by weight or less, preferably 1 to 30 parts by weight, more preferably 1 to 3 parts by weight, based on 1 part by weight of the acrylic monomer composition. 10 parts by weight.

The reaction temperature during the polymerization of the acrylic monomer composition is not particularly limited, but is usually 25 to 100 ° C, preferably 40 to 80 ° C. The reaction time is usually 10 hours or more, preferably 20 to 30 hours.

The reaction mixture containing the polymer of the acrylic monomer composition obtained as described above may be used as it is as an acrylic polymer having a hydroxyl group in the reaction with the onium salt (1), but if necessary, it may be used. It may be further diluted with a solvent (for example, acetone, acetonitrile, ethyl acetate, etc.), or the obtained reaction mixture may be concentrated and used.

Next, the reaction between the acrylic polymer having a hydroxyl group and the onium salt (1) will be described.

The amount of the onium salt (1) used is usually 1 mol 1 or less, preferably 0.1 to 1 mol, more preferably 0.1 to 0, based on 1 mol of the hydroxyl group in the acrylic polymer having a hydroxyl group. It is 3 mol.

Triethylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [ 5.4.0] -7-undecene, potassium iodide, zinc acetate, bismas octanoate, dibutyltin dilaurate and the like, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, etc. , Potassium iodide and dibutyltin dilaurate are preferable, and 1,8-diazabicyclo [5.4.0] -7-undecene and dibutyltin dilaurate are more preferable.

The amount of the catalyst used is usually 0.0001 to 0.20 mol, preferably 0.001 to 0.10 mol, more preferably 0.002 to 0.05 mol, based on 1 mol of the onium salt (1). be.

The reaction between the onium salt (1) and the acrylic polymer having a hydroxyl group is usually carried out in a solvent. As the solvent, for example, acetone, acetonitrile, ethyl acetate, toluene or a mixed solvent thereof is used. The amount of the solvent used is not particularly limited, but is usually 10 parts by weight or less, preferably 1 to 8 parts by weight, and more preferably 3 to 5 parts by weight with respect to 1 part by weight of the acrylic polymer having a hydroxyl group. ..

In order to react the onium salt (1) with the acrylic polymer having a hydroxyl group, for example, a mixture of the onium salt (1), the acrylic polymer having a hydroxyl group, a catalyst and a solvent is usually heated at 25 ° C. or higher, preferably 40. It may be stirred and mixed at ~ 80 ° C. for usually 3 hours or more, preferably 4 to 6 hours.

The ionic polymer of the present invention can be obtained by concentrating the reaction mixture obtained by the above reaction, but if necessary, react with a solvent immiscible with the ionic polymer (for example, hexane, heptane, benzene, toluene, etc.). The mixture may be washed. Further, the reaction mixture can be used as it is as an antistatic agent or an antistatic acrylic resin composition without isolating the ionic polymer from the reaction mixture.

The ionic polymer of the present invention can be used as an antistatic agent or an antistatic acrylic resin composition by blending an arbitrary solvent and additives. The antistatic acrylic resin composition can be suitably used as an adhesive composition.

Further, an antistatic agent containing the ionic polymer of the present invention can be blended with another resin to obtain a resin composition having antistatic properties. Examples of other resins include polycarbonate resins, urethane resins, acrylic resins, silicone resins and the like.

When blending an ionic polymer with another resin, it may be melted by heating and kneaded, or it may be mixed with an appropriate solvent (for example, dichloromethane, ethyl acetate, etc.) to prepare a solution, and then the solution is applied. Then, the resin may be molded by a method such as removing the solvent. In the case of a photocurable resin, after applying a resin containing an ionic polymer or a solution thereof, the coated surface may be cured by irradiation with ultraviolet rays.

The amount of the ionic polymer added when the ionic polymer is added to another resin is not particularly limited, but is preferably 1 to 30% by weight, preferably 2 to 20% by weight, based on 1 part by weight of the resin. %, More preferably 5-10% by weight.

Next, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In the examples, ^{1 1} H-NMR was measured at 400 MHz using AV400 manufactured by Bruker Biospin Co., Ltd. and deuterated chloroform or heavy DMSO as a solvent. Further, in the examples, the bis (trifluoromethanesulfonyl) imide anion is abbreviated ^{as TFSI −} , and the bis (fluorosulfonyl) imide anion ^{is abbreviated as FSI −.}

Synthesis example 1
Mix 53.98 g (0.30 mol) of 76.43 wt% choline chloride aqueous solution, 111.00 g (0.29 mol) of 74.90 wt% bis (trifluoromethanesulfonyl) imide lithium aqueous solution and 110.01 g of ion-exchanged water. The resulting mixture was reacted at room temperature for 2 hours. After completion of the reaction, the organic layer was separated from the reaction mixture separated into the organic layer and the aqueous layer, and the obtained organic layer was washed twice with 113 g of ion-exchanged water. The organic layer after washing with water was concentrated and dried under reduced pressure to obtain 69.28 g of (2-hydroxyethyl) trimethylammonium-bis (trifluoromethanesulfonyl) imide (yield 61.00%). ^{The 1} H-NMR data of (2-hydroxyethyl) trimethylammonium = bis (trifluoromethanesulfonyl) imide is shown below.

^{1 1} H-NMR (CDCl ₃ ): δ (ppm) = 4.04 (br, 2H, OCH ₂ ), 3.46 (br, 3H, N ⁺ CH ₂ , OH), 3.18 (s, 9H, N ⁺ (CH ₃ ) ₃ ).

Synthesis example 2
104.43 g (1.32 mol) of pyridine, 197.49 g (1.58 mol) of 2-bromoethanol, and 453.33 g of acetonitrile were mixed and reacted at 80 ° C. for 24 hours. After completion of the reaction, the mixture was cooled to room temperature, the solid precipitated in the reaction mixture was filtered, and the obtained solid was washed twice with 219.56 g of acetonitrile. The solid after washing with acetonitrile was dried under reduced pressure to obtain 220.28 g of 1- (2-hydroxyethyl) pyridinium bromide (yield 81.80%). ^{The 1} H-NMR data of 1- (2-hydroxyethyl) pyridinium bromide is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) = 8.05 (d, 2H, Py-H), 7.63 (t, 1H, Py-H), 7.16 (t, 2H, Py-H), 4.23 (br, 1H, OH), 3.70 (t, 2H, OCH ₂ ), 2.86 (br, 2H, N ⁺ CH ₂ ).

Synthesis example 3
14.58 g (71.45 mmol) of 1- (2-hydroxyethyl) pyridinium bromide obtained in Synthesis Example 2, 28.52 g (75.02 mmol) of a 75.5% bis (trifluoromethanesulfonyl) imide lithium aqueous solution and ions. 28.89 g of exchanged water was mixed and reacted at room temperature for 3 hours. After completion of the reaction, the organic layer was separated from the reaction mixture separated into the organic layer and the aqueous layer, and the obtained organic layer was washed 3 times with 29 g of ion-exchanged water. The organic layer after washing with water was concentrated and dried under reduced pressure to obtain 18.88 g of 1- (2-hydroxyethyl) pyridinium-bis (trifluoromethanesulfonyl) imide (yield 65.36%). ^{The 1} H-NMR data of 1- (2-hydroxyethyl) pyridinium = bis (trifluoromethanesulfonyl) imide is shown below.

^{1 1} H-NMR (CDCl ₃ ): δ (ppm) = 8.66 (d, 2H, Py-H), 8.44 (t, 1H, Py-H), 7.93 (t, 2H, Py-) H), 4.57 (t, 2H, OCH ₂ ), 3.94 (br, 2H, N ⁺ CH ₂ ), 3.60 (br, 1H, OH).

Synthesis example 4
37.74 g (20.44 mmol) of 75.60 wt% choline chloride aqueous solution, 45.70 g (20.85 mmol) of bis (fluorosulfonyl) imide potassium and 48.74 g of ion-exchanged water were mixed and reacted at room temperature for 2 hours. I let you. After completion of the reaction, 13.38 g of methyl ethyl ketone and 50.60 g of dichloromethane were added to the reaction solution, and the organic layer was separated from the reaction mixture separated into the organic layer and the aqueous layer, and the obtained organic layer was obtained. It was washed 3 times with 29.05 g of ion-exchanged water. The organic layer after washing with water was concentrated and dehydrated under reduced pressure to obtain 21.20 g of (2-hydroxyethyl) trimethylammonium-bis (fluorosulfonyl) imide (yield 36.49%). ^{The 1} H-NMR data of (2-hydroxyethyl) trimethylammonium = bis (fluorosulfonyl) imide is shown below.

^{1 1} H-NMR (CDCl ₃ ): δ (ppm) = 4.04 (br, 2H, OCH ₂ ), 3.46 (br, 3H, N ⁺ CH ₂ , OH), 3.18 (s, 9H, N ⁺ (CH ₃ ) ₃ ).

Example 1 Synthesis of 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl-trimethylammonium = bis (trifluoromethanesulfonyl) imide

ヘキサメチレンジイソシアナート８．４１ｇ（５０．００ミリモル）、ジラウリン酸ジブチル錫０．０４ｇ（０．０６ミリモル）及び脱水アセトニトリル１２．６２ｇを混合し、５０℃まで昇温させた。合成例１で得た（２−ヒドロキシエチル）トリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド１９．２２ｇ（５０．００ミリモル）と脱水アセトニトリル１９．２２ｇを混合し、５０℃まで昇温した溶液中に２時間かけて滴下して、５０℃で４時間反応させた。反応終了後、反応混合物を減圧濃縮して溶媒を留去した。得られた濃縮残渣をヘキサン１５．２０ｇで２回洗浄した。ヘキサン洗浄後の液体を減圧下で濃縮乾燥し、２−[Ｎ−（６−イソシアナトヘキシル）カルバモイルオキシ]エチル−トリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド（以下ＩＬ１という）２６．２７ｇを得た（収率９５．０８％）。以下に、ＩＬ１の^１Ｈ−ＮＭＲデータを示す。

8.41 g (50.00 mmol) of hexamethylene diisocyanate, 0.04 g (0.06 mmol) of dibutyl tin dilaurate and 12.62 g of dehydrated acetonitrile were mixed and heated to 50 ° C. 19.22 g (50.00 mmol) of (2-hydroxyethyl) trimethylammonium-bis (trifluoromethanesulfonyl) imide obtained in Synthesis Example 1 and 19.22 g of dehydrated acetonitrile were mixed and heated to 50 ° C. in a solution. The mixture was added dropwise over 2 hours and reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The obtained concentrated residue was washed twice with 15.20 g of hexane. The liquid after washing with hexane is concentrated and dried under reduced pressure to obtain 26.27 g of 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl-trimethylammonium-bis (trifluoromethanesulfonyl) imide (hereinafter referred to as IL1). (Yield 95.08%). The ¹ H-NMR data of IL1 is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) = 7.32 (br, 1H, NH), 7.05 (br, 1H, NH), 4.38 (br, 2H, OCH ₂ ), 3.59 (t, 2H, N ⁺ CH ₂ ), 3.34 (m, 2H, OCNCH ₂ ), 3.12 (s, 9H, N ⁺ CH ₃ ), 3.00 (m, 2H, NHCH ₂₎ ), 1.55 (quint, 2H, OCNCCH ₂ CH ₂ ), 1.44 to 1.25 (m, 6H, CH ₂ CH ₂ CH ₂ ).

Example 2 Synthesis of 2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide

４，４’−ジイソシアン酸メチレンジフェニル１１．２７ｇ（４５．０１ミリモル）、ジラウリン酸ジブチル錫０．０４ｇ（０．０６ミリモル）、脱水トルエン１１．３０ｇ及び脱水アセトニトリル５．６３ｇを混合し、５０℃まで昇温させた。合成例１で得た（２−ヒドロキシエチル）トリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド１７．３０ｇ（４５．０１ミリモル）と脱水アセトニトリル１７．３５ｇを混合し、５０℃まで昇温した溶液中に２時間かけて滴下して、５０℃で４時間反応させた。反応終了後、反応混合物を減圧濃縮して溶媒を留去した。得られた濃縮残渣を脱水トルエン１７．１４ｇで２回洗浄した。トルエン洗浄後の液体を減圧下で濃縮乾燥し、２−｛Ｎ−[４−[（４−イソシアナトフェニル）メチル]フェニル]カルバモイルオキシ｝エチルトリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド（以下ＩＬ２という）２６．７９ｇを得た（収率９３．８０％）。以下に、ＩＬ２の^１Ｈ−ＮＭＲデータを示す。

11.27 g (45.01 mmol) of methylenediphenyl 4,4'-diisosocyanate, 0.04 g (0.06 mmol) of dibutyltin dilaurate, 11.30 g of dehydrated toluene and 5.63 g of dehydrated acetonitrile were mixed and mixed at 50 ° C. The temperature was raised to. 17.30 g (45.01 mmol) of (2-hydroxyethyl) trimethylammonium-bis (trifluoromethanesulfonyl) imide obtained in Synthesis Example 1 and 17.35 g of dehydrated acetonitrile were mixed and heated to 50 ° C. in a solution. The mixture was added dropwise over 2 hours and reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The obtained concentrated residue was washed twice with 17.14 g of dehydrated toluene. The liquid after washing with toluene is concentrated and dried under reduced pressure, and 2-{N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide (hereinafter IL2). 26.79 g was obtained (yield 93.80%). The ¹ H-NMR data of IL2 is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) 9.67 (br, 1H, NH), 7.40 (d, 2H, Ar-H), 7.19 to 7.13 (m, 6H) , Ar-H), 4.52 (br, 2H, OCH ₂ ), 3.87, 3.82 (s, 2H, Ar-CH ₂ ), 3.68 (t, 2H, N ⁺ CH ₂ ), 3.16 (s, 9H, N ⁺ CH ₃ ).

Example 3 Synthesis of 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide

１，４−フェニレンジイソシアナート７．２１ｇ（４５．０１ミリモル）、ジラウリン酸ジブチル錫０．０４ｇ（０．０６ミリモル）及び脱水アセトニトリル２１．７３ｇを混合し、５０℃まで昇温させた。合成例１で得た（２−ヒドロキシエチル）トリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド１７．３０ｇ（４５．０１ミリモル）と脱水アセトニトリル１７．３５ｇを混合し、５０℃まで昇温した溶液中に２時間かけて滴下して、５０℃で４時間反応させた。反応終了後、反応混合物を減圧濃縮して溶媒を留去した。得られた濃縮残渣を脱水トルエン１４．７１ｇで２回洗浄した。トルエン洗浄後の液体を減圧下で濃縮乾燥し、２−[Ｎ−（４−イソシアナトフェニル）カルバモイルオキシ]エチルトリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド（以下ＩＬ３という）２２．６０ｇを得た（収率９２．２１％）。以下に、ＩＬ３の^１Ｈ−ＮＭＲデータを示す。

7.21 g (45.01 mmol) of 1,4-phenylenediisocyanate, 0.04 g (0.06 mmol) of dibutyltin dilaurate and 21.73 g of dehydrated acetonitrile were mixed and heated to 50 ° C. 17.30 g (45.01 mmol) of (2-hydroxyethyl) trimethylammonium-bis (trifluoromethanesulfonyl) imide obtained in Synthesis Example 1 and 17.35 g of dehydrated acetonitrile were mixed and heated to 50 ° C. in a solution. The mixture was added dropwise over 2 hours and reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The obtained concentrated residue was washed twice with 14.71 g of dehydrated toluene. The liquid after washing with toluene was concentrated and dried under reduced pressure to obtain 22.60 g of 2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyltrimethylammonium-bis (trifluoromethanesulfonyl) imide (hereinafter referred to as IL3). (Yield 92.21%). The ¹ H-NMR data of IL3 is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) 9.85, 9.66 (br, 1H, NH), 7.49 (d, 2H, Ar-H), 7.41 (d, 1H) , Ar-H), 7.22 (d, 1H, Ar-H), 4.52 (br, 2H, OCH ₂ ), 3.69 (t, 2H, N ⁺ CH ₂ ), 3.16 (s) , 9H, N ⁺ CH ₃ ).

２，４−ジイソシアン酸トリレン５．２３ｇ（４５．０１ミリモル）、ジラウリン酸ジブチル錫０．０４ｇ（０．０６ミリモル）及び脱水アセトニトリル１５．０５ｇを混合し、５０℃まで昇温させた。合成例１で得た（２−ヒドロキシエチル）トリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド１１．５４ｇ（３０．０３ミリモル）と脱水アセトニトリル１１．５４ｇを混合し、５０℃まで昇温した溶液中に２時間かけて滴下して、５０℃で４時間反応させた。反応終了後、反応混合物を減圧濃縮して溶媒を留去した。得られた濃縮残渣を脱水トルエン１０．０６ｇで２回洗浄した。トルエン洗浄後の液体を減圧下で濃縮乾燥し、２−[Ｎ−（３−イソシアナト−４−メチルフェニル）カルバモイルオキシ]エチルトリメチルアンモニウム＝ビス（トリフルオロメタンスルホニル）イミド（以下ＩＬ４という）１５．９８ｇを得た（収率９５．２９％）。以下に、ＩＬ４の^１Ｈ−ＮＭＲデータを示す。 Example 4 Synthesis of 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide

5.23 g (45.01 mmol) of trilene 2,4-diisosocyanate, 0.04 g (0.06 mmol) of dibutyltin dilaurate and 15.05 g of dehydrated acetonitrile were mixed and heated to 50 ° C. 11.54 g (30.03 mmol) of (2-hydroxyethyl) trimethylammonium-bis (trifluoromethanesulfonyl) imide obtained in Synthesis Example 1 and 11.54 g of dehydrated acetonitrile were mixed and heated to 50 ° C. in a solution. The mixture was added dropwise over 2 hours and reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The obtained concentrated residue was washed twice with 10.06 g of dehydrated toluene. The liquid after washing with toluene is concentrated and dried under reduced pressure to 15.98 g of 2- [N- (3-isocyanato-4-methylphenyl) carbamoyloxy] ethyltrimethylammonium = bis (trifluoromethanesulfonyl) imide (hereinafter referred to as IL4). Was obtained (yield 95.29%). The ¹ H-NMR data of IL4 is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) 9.80, 8.99 (br, 1H, NH), 7.35 (br, 1H, Ar-H), 7.20 (m, 2H) , Ar-H), 4.52 (br, 2H, OCH ₂ ), 3.68 (br, 2H, N ⁺ CH ₂ ), 3.16 (s, 9H, N ⁺ CH ₃ ), 2.23, 2.16 (s, 3H, Ar-CH ₃ ).

Example 5 Synthesis of 1-{2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl} pyridinium = bis (trifluoromethanesulfonyl) imide

４，４’−ジイソシアン酸メチレンジフェニル１１．２７ｇ（４５．０１ミリモル）、ジラウリン酸ジブチル錫０．０４ｇ（０．０６ミリモル）、脱水トルエン１２．７２ｇ及び脱水アセトニトリル６．７１ｇを混合し、５０℃まで昇温させた。合成例３で得た１−（２−ヒドロキシエチル）ピリジニウム＝ビス（トリフルオロメタンスルホニル）イミド１８．２０ｇ（４５．０１ミリモル）と脱水アセトニトリル１８．２６ｇを混合し、５０℃まで昇温した溶液中に２時間かけて滴下して、５０℃で４時間反応させた。反応終了後、反応混合物を減圧濃縮して溶媒を留去した。得られた濃縮残渣を脱水トルエン１７．６８ｇで３回洗浄した。トルエン洗浄後の液体を減圧下で濃縮乾燥し、１−｛２−｛Ｎ−[４−[（４−イソシアナトフェニル）メチル]フェニル]カルバモイルオキシ｝エチル｝ピリジニウム＝ビス（トリフルオロメタンスルホニル）イミド（以下ＩＬ５という）２７．０４ｇを得た（収率９１．７９％）。以下に、ＩＬ５の^１Ｈ−ＮＭＲデータを示す。

11.27 g (45.01 mmol) of methylenediphenyl 4,4'-diisosocyanate, 0.04 g (0.06 mmol) of dibutyltin dilaurate, 12.72 g of dehydrated toluene and 6.71 g of dehydrated acetonitrile were mixed and 50 ° C. The temperature was raised to. 18.20 g (45.01 mmol) of 1- (2-hydroxyethyl) pyridinium = bis (trifluoromethanesulfonyl) imide obtained in Synthesis Example 3 and 18.26 g of dehydrated acetonitrile were mixed and heated to 50 ° C. in a solution. Was added dropwise over 2 hours and reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The obtained concentrated residue was washed 3 times with 17.68 g of dehydrated toluene. The liquid after washing with toluene is concentrated and dried under reduced pressure, and 1-{2- {N- [4-[(4-isocyanatophenyl) methyl] phenyl] carbamoyloxy} ethyl} pyridinium = bis (trifluoromethanesulfonyl) imide 27.04 g (hereinafter referred to as IL5) was obtained (yield 91.79%). The ¹ H-NMR data of IL5 is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) 9.66 (br, 1H, NH), 9.15 (d, 2H, Py-H), 8.62 (t, 1H, Py-H) ), 8.18 (t, 2H, Py-H), 7.40 (br, 2H, Ar-H), 7.19 to 7.10 (m, 6H, Ar-H), 4.99 (br) , 2H, OCH ₂ ), 4.67 (br, 2H, N ⁺ CH ₂ ), 3.84, 3.80 (s, 2H, Ar-CH ₂ ).

Example 6 Synthesis of 1- {2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl} pyridinium = bis (trifluoromethanesulfonyl) imide

１，４−フェニレンジイソシアナート７．２１ｇ（４５．０１ミリモル）、ジラウリン酸ジブチル錫０．０４ｇ（０．０６ミリモル）及び脱水アセトニトリル２１．２２ｇを混合し、５０℃まで昇温させた。合成例３で得た１−（２−ヒドロキシエチル）ピリジニウム＝ビス（トリフルオロメタンスルホニル）イミド１８．２０ｇ（４５．０１ミリモル）と脱水アセトニトリル１８．４２ｇを混合し、５０℃まで昇温した溶液中に２時間かけて滴下して、５０℃で４時間反応させた。反応終了後、反応混合物を減圧濃縮して溶媒を留去した。得られた濃縮残渣を脱水トルエン１５．２４ｇで３回洗浄した。トルエン洗浄後の液体を減圧下で濃縮乾燥し、１−｛２−[Ｎ−（４−イソシアナトフェニル）カルバモイルオキシ]エチル｝ピリジニウム＝ビス（トリフルオロメタンスルホニル）イミド（以下ＩＬ６という）２３．７６ｇを得た（収率９３．５４％）。以下に、ＩＬ６の^１Ｈ−ＮＭＲデータを示す。

7.21 g (45.01 mmol) of 1,4-phenylenediisocyanate, 0.04 g (0.06 mmol) of dibutyltin dilaurate and 21.22 g of dehydrated acetonitrile were mixed and heated to 50 ° C. 18.20 g (45.01 mmol) of 1- (2-hydroxyethyl) pyridinium = bis (trifluoromethanesulfonyl) imide obtained in Synthesis Example 3 and 18.42 g of dehydrated acetonitrile were mixed and heated to 50 ° C. in a solution. Was added dropwise over 2 hours and reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The obtained concentrated residue was washed 3 times with 15.24 g of dehydrated toluene. The liquid after washing with toluene is concentrated and dried under reduced pressure to obtain 23.76 g of 1- {2- [N- (4-isocyanatophenyl) carbamoyloxy] ethyl} pyridinium = bis (trifluoromethanesulfonyl) imide (hereinafter referred to as IL6). Was obtained (yield 93.54%). The ¹ H-NMR data of IL6 is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) 9.81, 9.60 (br, 1H, NH), 9.13 (d, 2H, Py-H), 8.66 (t, 1H) , Py-H), 8.21 (t, 2H, Py-H), 7.37 (br, 2H, Ar-H), 7.29 (br, 1H, Ar-H), 7.19 (d) , 1H, Ar-H), 4.96 (br, 2H, OCH ₂ ), 4.64 (m, 2H, N ⁺ CH ₂ ).

Example 7 Synthesis of 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl-trimethylammonium = bis (fluorosulfonyl) imide

ヘキサメチレンジイソシアナート１０．１０ｇ（６０．００ミリモル）、ジラウリン酸ジブチル錫０．０４ｇ（０．０６ミリモル）及び脱水アセトニトリル１５．１４ｇを混合し、５０℃まで昇温させた。合成例４で得た（２−ヒドロキシエチル）トリメチルアンモニウム＝ビス（フルオロスルホニル）イミド１７．０６ｇ（６０．００ミリモル）と脱水アセトニトリル１７．０６ｇを混合し、５０℃まで昇温した溶液中に２時間かけて滴下して、５０℃で４時間反応させた。反応終了後、反応混合物を減圧濃縮して溶媒を留去した。得られた濃縮残渣をヘキサン１３．５８ｇで２回洗浄した。ヘキサン洗浄後の液体を減圧下で濃縮乾燥し、２−[Ｎ−（６−イソシアナトヘキシル）カルバモイルオキシ]エチル−トリメチルアンモニウム＝ビス（フルオロスルホニル）イミド（以下ＩＬ７という）２５．７５ｇを得た（収率９４．８４％）。以下に、ＩＬ７の^１Ｈ−ＮＭＲデータを示す。

10.10 g (60.00 mmol) of hexamethylene diisocyanate, 0.04 g (0.06 mmol) of dibutyl tin dilaurate and 15.14 g of dehydrated acetonitrile were mixed and heated to 50 ° C. 17.06 g (60.00 mmol) of (2-hydroxyethyl) trimethylammonium-bis (fluorosulfonyl) imide obtained in Synthesis Example 4 and 17.06 g of dehydrated acetonitrile were mixed and 2 in a solution heated to 50 ° C. It was added dropwise over time and reacted at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and the solvent was distilled off. The obtained concentrated residue was washed twice with 13.58 g of hexane. The liquid after washing with hexane was concentrated and dried under reduced pressure to obtain 25.75 g of 2- [N- (6-isocyanatohexyl) carbamoyloxy] ethyl-trimethylammonium = bis (fluorosulfonyl) imide (hereinafter referred to as IL7). (Yield 94.84%). The ¹ H-NMR data of IL7 is shown below.

^{1 1} H-NMR (DMSO-d ₆ ): δ (ppm) = 7.31 (br, 1H, NH), 7.05 (br, 1H, NH), 4.38 (br, 2H, OCH ₂ ), 3.59 (t, 2H, N ⁺ CH ₂ ), 3.34 (m, 2H, OCNCH ₂ ), 3.11 (s, 9H, N ⁺ CH ₃ ), 2.99 (m, 2H, NHCH ₂₎ ), 1.54 (quint, 2H, OCNCCH ₂ CH ₂ ), 1.43 to 1.25 (m, 6H, CH ₂ CH ₂ CH ₂ )

Manufacturing example 1
Ethyl acrylate (hereinafter referred to as EA) 9.48 g, 2-hydroxyethyl acrylate (hereinafter referred to as HEA) 0.5 g, acrylic acid (hereinafter referred to as AA) 0.02 g, 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) 0.2 g and 18.6 g of ethyl acetate were mixed, purged with nitrogen for 3 minutes, and polymerized at 60 ° C. for 22 hours under a nitrogen atmosphere. The obtained reaction mixture was diluted with ethyl acetate to obtain a 25 wt% ethyl acetate solution of an acrylic resin composition (hereinafter referred to as P (EA-HEA-AA)).

Example 8
To a 25 wt% ethyl acetate solution of P (EA-HEA-AA) produced in Production Example 1, 0.5 g of IL1 obtained in Example 1 and 0.02 g of dibutyltin dilaurate were added, and purged with nitrogen for 3 minutes. Then, the reaction was carried out at 50 ° C. for 6 hours in a nitrogen atmosphere. The obtained reaction mixture was diluted with ethyl acetate to obtain a 20 wt% ethyl acetate solution of an ionic polymer (hereinafter referred to as P (EA-HEA (IL1) -AA)).

Example 9
In Example 8, a 20 wt% ethyl acetate solution of an ionic polymer (hereinafter referred to as P (hereinafter referred to as P (EA-HEA (IL2) -AA))) was obtained in the same manner as in Example 8 except that IL2 was used instead of IL1. rice field.

Example 10
In Example 8, a 20 wt% ethyl acetate solution of an ionic polymer (hereinafter referred to as P (hereinafter referred to as P (EA-HEA (IL3) -AA))) was obtained in the same manner as in Example 8 except that IL3 was used instead of IL1. rice field.

Example 11
In Example 8, a 20 wt% ethyl acetate solution of an ionic polymer (hereinafter referred to as P (hereinafter referred to as P (EA-HEA (IL4) -AA))) was obtained in the same manner as in Example 8 except that IL4 was used instead of IL1. rice field.

Example 12
In Example 8, a 20 wt% ethyl acetate solution of an ionic polymer (hereinafter referred to as P (hereinafter referred to as P (EA-HEA (IL5) -AA))) was obtained in the same manner as in Example 8 except that IL5 was used instead of IL1. rice field.

Example 13
In Example 8, a 20 wt% ethyl acetate solution of an ionic polymer (hereinafter referred to as P (hereinafter referred to as P (EA-HEA (IL6) -AA))) was obtained in the same manner as in Example 8 except that IL6 was used instead of IL1. rice field.

Evaluation example 1
(Creation of evaluation sheet)
The P (EA-HEA (IL1) -AA) obtained in Example 8 was obtained on a polyethylene terephthalate (PET) film (thickness 100 μm) using a bar coater so that the thickness after drying was about 25.6 μm. After applying a 20 wt% ethyl acetate solution, the film was dried at 80 ° C. for 5 minutes to prepare an evaluation sheet.
(Measurement of surface resistivity)
The obtained evaluation sheet was left to stand for 3 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 50%, and then using a Mitsubishi Chemical Corporation High Lester UP (MCP-HT450), the temperature was 23 ± 3 ° C. and the relative humidity was 45. The surface resistance (Ω / □) of the evaluation sheet was measured under the condition of ± 5% with a probe URS, a measurement voltage of 500 V, and a sampling time of 60 seconds. Then, the evaluation sheet was immersed in hot water at 60 ° C. for 9 hours and 18 hours, dried, and the surface resistivity was measured by the same method as described above. The results are shown in Table 1.

Evaluation example 2
An evaluation sheet was prepared in the same manner as in Evaluation Example 1 except that a 20 wt% ethyl acetate solution of P (EA-HEA (IL2) -AA) obtained in Example 9 was used for the acrylic resin composition. The surface resistivity was measured. The results are shown in Table 1.

Evaluation example 3
An evaluation sheet was prepared in the same manner as in Evaluation Example 1 except that a 20 wt% ethyl acetate solution of P (EA-HEA (IL3) -AA) obtained in Example 10 was used for the acrylic resin composition. The surface resistivity was measured. The results are shown in Table 1.

Evaluation example 4
An evaluation sheet was prepared in the same manner as in Evaluation Example 1 except that a 20 wt% ethyl acetate solution of P (EA-HEA (IL4) -AA) obtained in Example 11 was used for the acrylic resin composition. The surface resistivity was measured. The results are shown in Table 1.

Evaluation example 5
An evaluation sheet was prepared in the same manner as in Evaluation Example 1 except that a 20 wt% ethyl acetate solution of P (EA-HEA (IL5) -AA) obtained in Example 12 was used for the acrylic resin composition. The surface resistivity was measured. The results are shown in Table 1.

Evaluation example 6
An evaluation sheet was prepared in the same manner as in Evaluation Example 1 except that a 20 wt% ethyl acetate solution of P (EA-HEA (IL6) -AA) obtained in Example 13 was used for the acrylic resin composition. The surface resistivity was measured. The results are shown in Table 1.

Comparative Example 1
In Evaluation Example 1, a 25 wt% ethyl acetate solution of P (EA-HEA-AA) obtained in Production Example 1 was used instead of the 20 wt% ethyl acetate solution of P (EA-HEA (IL1) -AA). An evaluation sheet was prepared in the same manner as in Evaluation Example 1 except for the above, and the surface resistance thereof was measured. The results are shown in Table 1.

Comparative Example 2
1-Hexyl-4-methylpyridinium = bis (trifluoromethanesulfonyl) imide (hereinafter referred to as ILA) 0 in 8.0 g of a 25 wt% ethyl acetate solution of P (EA-HEA-AA) obtained in Production Example 1. .10 g and 2.4 g of ethyl acetate were added to obtain a 20 wt% ethyl acetate solution of an acrylic resin composition (hereinafter referred to as P (EA-HEA-AA) + ILA).
Evaluation Example 1 except that a 20 wt% ethyl acetate solution of P (EA-HEA-AA) + ILA was used instead of the 20 wt% ethyl acetate solution of P (EA-HEA (IL1) -AA). An evaluation sheet was prepared in the same manner as in No. 1, and its surface resistance was measured. The results are shown in Table 1.

Claims (12)

Onium salt represented by the formula (1).
Equation (1):

[In the formula, L is represented by an alkylene group which may have a substituent or an arylene group which may have a substituent, A ⁻ is an anion having a fluorine atom, and B ⁺ is represented by the formula (2). Ammonium cation, pyridinium cation represented by formula (3), imidazolium cation represented by formula (4) or phosphonium cation represented by formula (5) , D represents O, NH or S.
Equation (2):

(In the formula, R ^{1 to} R ³ represent an alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other at the terminal to form a piperidine ring or a pyrrolidine ring. A is 1 to 20. Is an integer of.)
Equation (3):

(In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. B is an integer of 1 to 20.)
Equation (4):

(In the formula, R ⁵ represents an alkyl group having 1 to 20 carbon atoms. C is an integer of 1 to 20.)
Equation (5):

(In the formula, R ^{6 to} R ⁸ represent an alkyl group having 1 to 20 carbon atoms. D is an integer of 1 to 20.)] The onium salt according to claim 1 , wherein the anion having a fluorine atom is a trifluoromethanesulfonic acid anion, a bis (trifluoromethanesulfonyl) imide anion, a bis (fluorosulfonyl) imide anion, a tetrafluoroborate anion, or a hexafluorophosphate anion. Equation (6):
^{HD-B + X - (6} )
(In the formula, B and D are the same as above ^{. X −} represents a halogen anion.)
Halide salt and formula (7):
M ⁺ A ^- (7)
(In the formula, M ⁺ represents a hydrogen ion or an alkali metal ion ^{. A −} is the same as described above.)
By the anion exchange reaction with the alkali metal compound represented by, the formula (8):
^{HD-B + A - (8} )
(Wherein, D, ^{B +} or A ^- is as defined above.)
The onium salt represented by is synthesized, and further formula (9):
OCN-L-NCO (9)
(In the formula, L is the same as above.)
The method for producing an onium salt according to claim 1 or 2, wherein the onium salt is reacted with the diisocyanate represented by. An ionic polymer having a structural unit represented by the following formula (10).
Equation (10):

[In the formula, L is an alkylene group which may have a substituent or an arylene group which may have a substituent , D is O, NH or S , and B ⁺ is ammonium represented by the formula (2). A cation, a pyridinium cation represented by the formula (3), an imidazolium cation represented by the formula (4) or a phosphonium cation represented by the formula (5), and A ⁻ represent an anion having a fluorine atom . R ^{9 to} R ¹¹ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹² represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. x and n are integers of 1 or more, and y and z are integers of 0 or 1 or more. E is a bond represented by the following formula (11) or formula (12).
Equation (2):

(In the formula, R ^{1 to} R ³ represent an alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² may be bonded to each other at the terminal to form a piperidine ring or a pyrrolidine ring. A is 1 to 20. Is an integer of.)
Equation (3):

(In the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. B is an integer of 1 to 20.)
Equation (4):

(In the formula, R ⁵ represents an alkyl group having 1 to 20 carbon atoms. C is an integer of 1 to 20.)
Equation (5):

(In the formula, R ^{6 to} R ⁸ represent an alkyl group having 1 to 20 carbon atoms. D is an integer of 1 to 20.)]
Equation (11):

Equation (12):

(In the formula, G is an alkylene group having 1 to 20 carbon atoms which may have a substituent.)) The ionic polymer according to claim 4 , wherein y and z are integers of 1 or more. A method for producing an ionic polymer in which an acrylic polymer having a hydroxyl group is reacted with at least one onium salt according to claim 1 or 2. 6. acrylic polymer is a polymer obtained from an acrylic monomer composition comprising at least one of the hydroxyalkyl acrylate compounds or acrylic acid compound represented by the formula (14) represented by the formula (13) with the hydroxyl group The method for producing an ionic polymer according to.
Equation (13):

(In the formula, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent , and R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
Equation (14):

(In the formula, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) The ionicity according to claim 6 , wherein the acrylic polymer having a hydroxyl group is a polymer obtained from an acrylic monomer composition containing a hydroxyalkyl acrylate compound represented by the formula (13) and an acrylic acid compound represented by the formula (14). Method for producing polymer.
Equation (13):

(In the formula, G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R ¹³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
Equation (14):

(In the formula, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) The method for producing an ionic polymer according to claim 7 or 8 , further comprising an alkyl acrylate compound represented by the formula (15) in the acrylic monomer composition.
Equation (15):

(In the formula, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R ¹⁶ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.) Claims 6 to 9 in which 0.1 to 0.3 mol of at least one onium salt according to any one of claims 1 or 2 is reacted with 1 mol of the hydroxyl group in the acrylic polymer having a hydroxyl group. The method for producing an ionic polymer according to any one of. An antistatic agent comprising the ionic polymer according to claim 4 or 5. A resin composition containing the antistatic agent according to claim 11 and another resin.