JP2013087259A - Method for producing water-insoluble ionic vinyl monomer and antistatic agent and antistatic composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-purity ionic vinyl monomer that has good compatibility with a resin and an organic solvent and does not contain a metal ion, an organic solvent and water; and an antistatic agent and an antistatic resin composition comprising the monomer.SOLUTION: The ionic vinyl monomer is synthesized with high purity and a high yield, which is represented by general formula (1), wherein Rrepresents a hydrogen atom or a methyl group; Rand Reach independently represents a 1-3C alkyl group, and may be the same or different from each other; Rrepresents a 1-3C alkyl group, a 1-3C alkenyl group, or a benzyl group; Y represents an oxygen atom or NH-; Z represents a 1-3C alkylene group; and Rfand Rfmay be the same or different from each other and each represents a 1-4C perfluoroalkyl group or a fluoro group with the carbon number of 0. A polymer and the like comprising the ionic vinyl monomer are used as antistatic active ingredients.

Description

The present invention relates to a metal ion-free high-quality water-insoluble ionic vinyl monomer that does not contain an organic solvent and water, a method for producing the same, an antistatic agent comprising the monomer, and an antistatic resin containing the antistatic agent Relates to the composition.

Since quaternary ammonium salts have excellent antistatic performance, they have been conventionally known as antistatic agents for resins (Patent Documents 1 and 2). In particular, in recent years, many polymer-type quaternary ammonium salts that are difficult to bleed out on the resin surface and can maintain the antistatic effect continuously have been reported (Patent Document 3).

Among them, it is known to use acrylate-based and acrylamide-based quaternary cationic vinyl monomers as base monomers for polymer antistatic compositions. However, since many quaternary cationic vinyl monomers are solid at room temperature and have high hygroscopicity, they are usually distributed in the form of an aqueous solution for manufacturing reasons. For example, methyl chloride is added as a quaternizing agent to N, N-dimethylaminopropylacrylamide, which is an unsaturated tertiary amine, and a quaternization reaction is performed in the presence of a mixed solvent composed of water and an aprotic organic solvent. There is a method (Patent Document 4), a method of performing quaternization reaction of N, N-dimethylaminoethyl acrylate and benzyl chloride in acetone, and then adding water and removing acetone under reduced pressure (Patent Document 5). . Of course, since the quaternary cationic vinyl monomer obtained by this method is usually an aqueous solution type, when it is applied to a substrate in the monomer state and cured with active energy rays or the like, the drying property at the time of coating is used. In addition, since the quaternary cationic vinyl monomer has high polarity, it has poor compatibility with general-purpose resins, polyfunctional acrylic monomers, oligomers, organic solvents, etc. There was a problem that it was not possible. Even if the quaternary cationic vinyl monomer is purified to a high purity and dissolved in a polar organic solvent, these monomers themselves have high hydrophilicity. The solubility in other components is low, and it is condensed in the resin or deposited from the resin, and a continuous antistatic film cannot be formed, and the target antistatic performance may not be achieved.

Accordingly, various attempts have been made to improve the compatibility with resins and organic solvents. For example, a method in which an acrylate-based quaternary cationic vinyl monomer is copolymerized with another polymerizable vinyl monomer has been reported (Patent Documents 6 and 7). However, in these methods, since the content of the quaternary cationic vinyl monomer in the antistatic composition is lowered, it is necessary to add a large amount of this copolymer in order to obtain the target antistatic performance. As a result, various properties of the resin are deteriorated, and the price of the resin composition is increased.

On the other hand, for the purpose of improving the compatibility of the quaternary cationic vinyl monomer itself, for example, ionic vinyl monomers having anions such as bis (trifluoromethanesulfonyl) imide have been proposed (Patent Documents 8, 9, 10, 11). ).

These proposed ionic vinyl monomers are synthesized by a known production method in which a tertiary amine is quaternized with an alkyl halide or dialkylsulfonic acid and then an anion exchange reaction is performed using a salt having the target anion. For example, in Patent Document 8, after an anion exchange reaction under heating at 60 ° C. in an aqueous solvent, the obtained ionic vinyl monomer is purified by dehydration under reduced pressure under heating at 70 ° C. to obtain the desired ionic properties. Acquired vinyl monomer.

However, since the ionic vinyl monomer has an unsaturated group, it may be polymerized when subjected to a reaction at a high temperature of 60 to 70 ° C. and distillation for a long time, and the obtained monomer has low purity including the polymer. It will be a thing. In this patent document, there is no description about the purity of the obtained monomer.

Patent Documents 9 and 10 are also obtained by separating an ionic vinyl monomer phase separated into two layers from water after an anion exchange reaction in an aqueous solvent, as in Patent Document 8.

However, since the target ionic vinyl monomer is slightly soluble in water (for example, the solubility of acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide described in Patent Document 8 in water is 1.3 (g / 100 g). Water)), repeated washing with water to remove unreacted raw materials and by-products results in a decrease in yield. Moreover, since the obtained ionic vinyl monomer is usually a high-viscosity liquid, there is a problem of recovery loss due to apparatus adhesion. Further, these patent documents do not describe any yield or purity of the obtained ionic vinyl monomer.

Patent Document 11 proposes an ionic vinyl monomer that does not contain metal ions as a material applied to electronic products and electronic components. However, the proposed ionic vinyl monomer is also synthesized by the above-described known method, that is, a salt exchange reaction using a quaternary cationic vinyl monomer as a raw material and a salt as an anion in an aqueous solution. In this method, the metal salt which is a by-product after the raw material and the salt exchange remains, and mixing into the product of metal ions cannot be avoided. Even if a minute amount of metal ions remain, carbon dioxide in the air is easily absorbed, corrosion to the metal is promoted, and there are cases where it cannot be used as an electronic material, so the remaining amount must be extremely reduced. However, the patent document does not describe a specific purification method of the ionic vinyl monomer, and further does not describe a method for reducing metal ions or the contents of metals and metal ions in the target product.

In addition, a purification method in which a general-purpose ionic liquid that is hardly soluble in water is extracted and separated with a chlorine-based organic solvent that separates into two layers with water such as dichloromethane has been reported (Patent Documents 12, 13, and 14). However, it is theoretically impossible to completely volatilize and remove volatile components from a non-volatile ionic liquid simply by concentrating the organic solvent and water under reduced pressure. In particular, in the case of a chlorinated solvent such as dichloromethane, there are concerns about an increase in environmental burden due to residual chlorine, corrosiveness to metals, etc. Especially when it is used as an electronic material, it may cause a malfunction of electronic products and cause failure. there is a possibility.

JP 2008-231240 A JP 2008-13636 A JP 2008-231196 A Japanese Patent Laid-Open No. 63-201115 JP 07-267906 A Japanese Patent Laid-Open No. 07-150130 JP 2007-51241 A JP 2007-9042 A WO 2004-027789 JP 2005-255843 A JP 2009-179671 A JP 2006-210259 A JP 2008-156597 A JP 2010-127772 A

As described above, a high-purity, high-yield, high-purity ionic vinyl monomer composed of an ammonium cation and a bis (perfluoroalkanesulfonyl) imide anion, free of metal ions and containing no organic solvent and water, A method for industrial production is not conventionally known. In addition, it has excellent compatibility with general-purpose acrylic monomers, organic solvents and resins, is water-insoluble, has good moisture resistance, can be applied to UV curing, and can continue to have an antistatic effect for a long time after curing. However, an ionic vinyl monomer for an antistatic agent that is preferably used, an antistatic agent comprising the monomer, and an antistatic composition have not yet been easily obtained.

The first object of the present invention is to obtain a high-quality water-insoluble ionic vinyl monomer that is free of metal ions and does not contain an organic solvent and water.
The second object of the present invention is to provide an efficient and economical method for producing the ionic vinyl monomer.
The third object of the present invention is to disperse uniformly in a general-purpose acrylic monomer or other antistatic composition comprising the ionic vinyl monomer as a constituent, having an excellent antistatic effect and long-term sustainable moisture resistance and water resistance. An object is to provide an antistatic agent having decomposability and an antistatic composition containing the antistatic agent.

As a result of diligent studies to solve these problems, the present inventor is conducted in a two-phase system in which a water-insoluble organic solvent having a solubility parameter of 7 to 11 (cal / cm ³ ) ^0.5 and water coexist. After an anion exchange reaction between the quaternary ammonium salt monomer and the bis (perfluoroalkanesulfonyl) imide salt, the organic solvent phase is separated, concentrated under reduced pressure, and further dried with an inert gas or dry air, and the organic solvent and By removing water and also by adding an ion adsorbent to the aqueous phase during anion exchange reaction, the ionic vinyl monomer represented by the following general formula (1) can be obtained with high purity and high yield. Further, the present inventors have found that the problems of the antistatic agent and the antistatic composition can be solved by using the ionic vinyl monomer.

（式中、Ｒ_１は水素原子またはメチル基を、Ｒ_２及びＲ_３は各々独立に炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ｒ_４は炭素数１〜３のアルキル基、炭素数１〜３のアルケニル基またはベンジル基を表し、Ｙは酸素原子またはＮＨを表し、Ｚは炭素数１〜３のアルキレン基を表し、Ｘ^- は直鎖状のスルホンイミドアニオン[(Ｒｆ^１ＳＯ₂)(Ｒｆ^２ＳＯ₂)Ｎ]^- （但し、Ｒｆ^１及びＲｆ^２は同じであっても異なっていてもよく、炭素数１〜４のペルフルオロアルキル基または炭素数０のフルオロ基を表す。）、または環状のイミドアニオン[ＣＦ₂(ＣＦ₂ＳＯ₂) ₂ Ｎ]^-を表す。）

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other, and R ₄ has 1 carbon atom) Represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, and X ⁻ represents a linear sulfone. Imido anion [(Rf ¹ SO ₂ ) (Rf ² SO ₂ ) N] ⁻ (where Rf ¹ and Rf ² may be the same or different, and are a C 1-4 perfluoroalkyl group or carbon number Represents a fluoro group of 0), or represents a cyclic imide anion [CF ₂ (CF ₂ SO ₂ ) ₂ N] ⁻ .)

（式中、Ｒ_１は水素原子またはメチル基を、Ｒ_２及びＲ_３は各々独立に炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ｒ_４は炭素数１〜３のアルキル基、炭素数１〜３のアルケニル基またはベンジル基を表し、Ｙは酸素原子またはＮＨを表し、Ｚは炭素数１〜３のアルキレン基を表し、Ｘ^- は直鎖状のスルホンイミドアニオン[(Ｒｆ^１ＳＯ₂)(Ｒｆ^２ＳＯ₂)Ｎ]^- （但し、Ｒｆ^１及びＲｆ^２は同じであっても異なっていてもよく、炭素数１〜４のペルフルオロアルキル基または炭素数０のフルオロ基を表す。）、または環状のイミドアニオン[ＣＦ₂(ＣＦ₂ＳＯ₂) ₂ Ｎ]^-を表す。）
で表される金属イオンフリー（金属イオン含量は０．１ｐｐｍ以下）、且つ有機溶媒及び水の含有量は１００ｐｐｍ未満且つ純度９９％以上である、イオン性ビニルモノマー
２）イオン性ビニルモノマーが、一般式（２）

（式中、Ｍ^＋はカチオンを表し、Ｘ^- は直鎖状のスルホンイミドアニオン[(Ｒｆ^１ＳＯ₂)(Ｒｆ^２ＳＯ₂)Ｎ]^- （但し、Ｒｆ^１及びＲｆ^２は同じであっても異なっていてもよく、炭素数１〜４のペルフルオロアルキル基または炭素数０のフルオロ基を表す。）、または環状のイミドアニオン[ＣＦ₂(ＣＦ₂ＳＯ₂) ₂ Ｎ]^-を表す。）で表されるビス（ペルフルオロアルカンスルホニル）イミド塩と、一般式（３）

（式中、Ｒ_１は水素原子又はメチル基を、Ｒ_２及びＲ_３は各々独立に炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ｒ_４は炭素数１〜３のアルキル基、炭素数１〜３のアルケニル基又はベンジル基を表し、Ｙは酸素原子又はＮＨを表し、Ｚは炭素数１〜３のアルキレン基を表し、Ｑ^-はアニオンを表す。）で表される４級カチオン性ビニルモノマーの、非水溶性有機溶媒及び水が共存する二相系で行われるイオン交換反応により合成されることを特徴とする前記１）記載のイオン性ビニルモノマーの製造方法
３）前記非水溶性有機溶媒は、溶解度パラメーターが７〜１１ (cal/cm³)^0.5を有する非塩素系有機溶媒から選ばれる１種又は２種以上である前記２）記載の製造方法
４）前記非水溶性有機溶媒が、酢酸エステル類又はケトン類である前記２）乃至３）記載の製造方法
５）前記イオン交換反応中にさらに水相にイオン吸着剤を添加することを特徴とする前記２）乃至４）記載のイオン性ビニルモノマーの製造方法
６）前記イオン吸着剤が水溶性金属イオン吸着剤から選ばれる1種又は２種以上である前記２）乃至５）記載のイオン性ビニルモノマーの製造方法
７）前記水溶性イオン吸着剤が水溶性ポリマーであることを特徴とする前記２）乃至５）記載のイオン性ビニルモノマーの製造方法
８）前記２）乃至７）の方法により製造されたイオン性ビニルモノマーをラジカル重合させることにより得られる金属イオンフリー（金属イオン含量は０．１ｐｐｍ以下）のイオン性ホモオリゴマー又はホモポリマー
９）前記２）乃至７）の方法により製造されたイオン性ビニルモノマーと他の共重合可能のビニル系単量体との共重合で得られる金属イオンフリー（金属イオン含量は０．１ｐｐｍ以下）のイオン性コオリゴマー又はコポリマー
１０）前記２）乃至７）の方法により製造されたイオン性ビニルモノマー及び／又は請求項８）又は９）のオリゴマー若しくはポリマーからなる金属イオンフリー（金属イオン含量は０．１ｐｐｍ以下）の帯電防止剤
１１）前記１０）記載の帯電防止剤又は該帯電防止剤を含有する帯電防止性樹脂組成物であって、前記１）の、又は前記２）乃至前記７）の方法により製造されたイオン性ビニルモノマーを構成単位として０．１〜９０重量％含有するもの
１２）前記１０）記載の帯電防止剤又は１１）記載の帯電防止剤を含有する帯電防止性樹脂組成物であって、さらに多官能（メタ）アクリレート及び／又は多官能（メタ）アクリルアミドを含有する帯電防止組成物
１３）基材上に前記１０）〜１２）いずれか一項に記載の帯電防止剤又は帯電防止組成物を塗装した後、活性エネルギー線又は熱により硬化して形成されることを特徴とする帯電防止膜
１４）少なくとも片面に前記１３）記載の帯電防止膜を有することを特徴とする帯電防止フィルム、シート
を提供するものである。
That is, the present invention
1) General formula (1)

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other, and R ₄ has 1 carbon atom) Represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, and X ⁻ represents a linear sulfone. Imido anion [(Rf ¹ SO ₂ ) (Rf ² SO ₂ ) N] ⁻ (where Rf ¹ and Rf ² may be the same or different, and are a C 1-4 perfluoroalkyl group or carbon number Represents a fluoro group of 0), or represents a cyclic imide anion [CF ₂ (CF ₂ SO ₂ ) ₂ N] ⁻ .)
The metal ion-free (metal ion content is 0.1 ppm or less) and the organic solvent and water content is less than 100 ppm and the purity is 99% or more. 2) The ionic vinyl monomer is generally Formula (2)

(Wherein M ⁺ represents a cation and X ⁻ represents a linear sulfonimide anion [(Rf ¹ SO ₂ ) (Rf ² SO ₂ ) N] ⁻ (where Rf ¹ and Rf ² are the same) And may be different, and represents a perfluoroalkyl group having 1 to 4 carbon atoms or a fluoro group having 0 carbon atoms), or a cyclic imide anion [CF ₂ (CF ₂ SO ₂ ) ₂ N] ⁻ .) A bis (perfluoroalkanesulfonyl) imide salt represented by the general formula (3)

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group having 1 to 3 carbon atoms, and may be the same as or different from each other, and R ₄ represents 1 carbon atom) An alkyl group having ˜3, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, and Q ⁻ represents an anion.) The ionic vinyl monomer according to 1) above, which is synthesized by an ion exchange reaction performed in a two-phase system in which a water-insoluble organic solvent and water coexist Production method
3) The production method 4) according to 2), wherein the water-insoluble organic solvent is one or more selected from non-chlorine organic solvents having a solubility parameter of 7 to 11 (cal / cm ³ ) ^0.5. The production method according to 2) to 3) above, wherein the water-insoluble organic solvent is an acetate ester or a ketone. 5) An ion adsorbent is further added to the aqueous phase during the ion exchange reaction. Production method of ionic vinyl monomer according to 2) to 4) 6) Ionic vinyl monomer according to 2) to 5), wherein the ion adsorbent is one or more selected from water-soluble metal ion adsorbents. 7) The method for producing an ionic vinyl monomer according to 2) to 5) above, wherein the water-soluble ion adsorbent is a water-soluble polymer. 8) It is produced by the method according to 2) to 7). Ionic Metal ion free (metal ion content is 0.1 ppm or less) ionic homooligomers or homopolymers obtained by radical polymerization of nyl monomers 9) Ionic vinyl monomers produced by the above methods 2) to 7) and others A metal ion-free (metal ion content of 0.1 ppm or less) ionic co-oligomer or copolymer obtained by copolymerization with a copolymerizable vinyl monomer 10) prepared by the above methods 2) to 7) Metal ion-free (metal ion content is 0.1 ppm or less) antistatic agent comprising the ionic vinyl monomer and / or oligomer or polymer of claim 8) or 9) An antistatic resin composition containing an antistatic agent, comprising the above 1) or 2) to 7) An antistatic resin composition containing 0.1 to 90% by weight of an ionic vinyl monomer produced by the method as a constituent unit 12) The antistatic agent described in 10) or the antistatic agent described in 11) The antistatic composition according to any one of 10) to 12) above, wherein the antistatic composition further contains a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide. An antistatic film formed by coating with an antistatic composition and then cured by active energy rays or heat. 14) Charge comprising the antistatic film described in 13) above on at least one side. A prevention film and sheet are provided.

According to the method of the present invention, a high-purity water-insoluble ionic vinyl monomer that is free of metal ions and does not contain an organic solvent and water can be easily produced in a high yield. In addition, the ionic vinyl monomer is water-insoluble, and the antistatic agent and antistatic composition containing the ionic vinyl monomer are transparent and not colored, and are soluble and compatible with general-purpose acrylic monomers and organic solvents. Since it is excellent, it can be uniformly dispersed in other antistatic compositions, has good moisture resistance and hydrolysis resistance, has an excellent antistatic effect and can last for a long time. An antistatic agent, an antistatic resin composition containing the antistatic agent, an antistatic layer, an antistatic film or an antistatic film, and a sheet can be provided.

Hereinafter, the present invention will be described in detail.
The ionic vinyl monomer of the present invention is any one of an ionic (meth) acrylamide monomer represented by the general formula (1), an ionic (meth) acrylate monomer, and an oligomer or polymer composed of these monomers. It consists of one or more.

In the general formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same or different, ₄ represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, Rf ¹ and Rf ² may be the same or different, and represents a perfluoroalkyl group having 1 to 4 carbon atoms or a fluoro group having 0 carbon atoms.

Specific examples of the cation of the ionic vinyl monomer represented by the general formula (1) include acryloylaminomethyltrimethylammonium, acryloylaminomethyltriethylammonium, acryloylaminomethyltripropylammonium, acryloylaminoethyltrimethylammonium, and acryloylamino. Propyltrimethylammonium, acryloylaminopropylmethyldiethylammonium, acryloylaminopropylethyldimethylammonium, acryloylaminopropylmethyldipropylammonium, acryloylaminopropyltriethylammonium, acryloylaminopropyltripropylammonium, acryloylaminoethyldimethylbenzylammonium, acryloylaminopropiyl Dimethylbenzylammonium, acryloylaminopropyldiethylbenzylammonium, acryloylaminopropylmethyldibenzylammonium, acryloylaminopropylethyldibenzylammonium, methacryloylaminomethyltrimethylammonium, methacryloylaminomethyltriethylammonium, methacryloylaminomethyltripropylammonium, methacryloylaminoethyltrimethyl Ammonium, methacryloylaminopropyltrimethylammonium, methacryloylaminopropylmethyldiethylammonium, methacryloylaminopropylethyldimethylammonium, methacryloylaminopropylmethyldipropylammonium, methacryloylaminopropyltriethylan Acrylamide 4 such as nium, methacryloylaminopropyltripropylammonium, methacryloylaminoethyldimethylbenzylammonium, methacryloylaminopropyldimethylbenzylammonium, methacryloylaminopropyldiethylbenzylammonium, methacryloylaminopropylmethyldibenzylammonium, methacryloylaminopropylethyldibenzylammonium Quaternary ammonium cation and methacrylamide quaternary ammonium cation, acryloyloxymethyltrimethylammonium, acryloyloxymethyltriethylammonium, acryloyloxymethyltripropylammonium, acryloyloxyethyltrimethylammonium, acryloyloxypropylto Limethylammonium, acryloyloxypropylmethyldiethylammonium, acryloyloxypropylethyldimethylammonium, acryloyloxypropylmethyldipropylammonium, acryloyloxypropyltriethylammonium, acryloyloxypropyltripropylammonium, acryloyloxyethyldimethylbenzylammonium, acryloyloxypropyldimethyl Benzylammonium, acryloyloxypropyldiethylbenzylammonium, acryloyloxypropylmethyldibenzylammonium, acryloyloxypropylethyldibenzylammonium, methacryloyloxymethyltrimethylammonium, methacryloyloxymethyltriethylammonium, Tacryloyloxymethyltripropylammonium, methacryloyloxyethyltrimethylammonium, methacryloyloxypropyltrimethylammonium, methacryloyloxypropylmethyldiethylammonium, methacryloyloxypropylethyldimethylammonium, methacryloyloxypropylmethyldipropylammonium, methacryloyloxypropyltriethylammonium, methacryloyloxy Propyltripropylammonium, methacryloyloxyethyldimethylbenzylammonium, methacryloyloxypropyldimethylbenzylammonium, methacryloyloxypropyldiethylbenzylammonium, methacryloyloxypropylmethyldibenzylammonium, Acryloyloxy propyl ethyl dibenzyl ammonium acrylate quaternary ammonium cation and methacrylate quaternary ammonium cation or the like, and the like. In particular, acryloylaminopropyltrimethylammonium, methacryloylaminopropyltrimethylammonium, acryloylaminopropyldimethylbenzylammonium, methacryloylaminopropyldimethylbenzylammonium, acryloyloxyethyltrimethylammonium, particularly preferable in terms of easy availability of inexpensive industrial raw materials, Methacryloyloxyethyltrimethylammonium, acryloyloxyethyldimethylbenzylammonium, and methacryloyloxyethyldimethylbenzylammonium.

Specific examples of the anion of the ionic vinyl monomer represented by the general formula (1) include bis (trifluoromethanesulfonyl) imide, bis (fluorosulfonyl) imide, bis (pentafluoroethanesulfonyl) imide, and bis (hepta). Fluoropropanesulfonyl) imide, bis (nonafluorobutanesulfonyl) imide, [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, and the like.

Specific examples of the ionic vinyl monomer represented by the general formula (1) include acryloylaminomethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminomethyltriethylammonium bis (trifluoromethanesulfonyl) imide, and acryloylaminomethyltripropyl. Ammonium bis (trifluoromethanesulfonyl) imide, acryloylaminoethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropylmethyldiethylammonium bis (trifluoromethanesulfonyl) imide, acryloyl Aminopropylethyldimethylammonium (Trifluoromethanesulfonyl) imide, acryloylaminopropylmethyldipropylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropyltriethylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropyltripropylammonium bis (trifluoromethanesulfonyl) imide, Acryloylaminoethyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropyldiethylbenzylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropylmethyldibenzylan Ni-bis (trifluoromethanesulfonyl) imide, acryloylaminopropylethyldibenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminomethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminomethyltriethylammonium bis (trifluoromethanesulfonyl) imide, methacryloyl Aminomethyltripropylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminoethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropylmethyldiethylammonium Bis (trifluoromethanesulfonyl) imide, methacryloylaminopropylethyldimethylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropylmethyldipropylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropyltriethylammonium bis (trifluoromethanesulfonyl) imide, Methacryloylaminopropyltripropylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminoethyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropyldiethyl Benzylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropylmethyldibenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropylethyldibenzylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminomethyltrimethylammonium bis (fluorosulfonyl) ) Imide, acryloylaminomethyltriethylammonium bis (fluorosulfonyl) imide, acryloylaminomethyltripropylammonium bis (fluorosulfonyl) imide, acryloylaminoethyltrimethylammonium bis (fluorosulfonyl) imide, acryloylaminopropyltrimethylammonium bis (fluorosulfonyl) Imide Acryloylaminopropylmethyldiethylammonium bis (fluorosulfonyl) imide, acryloylaminopropylethyldimethylammonium bis (fluorosulfonyl) imide, acryloylaminopropylmethyldipropylammonium bis (fluorosulfonyl) imide, acryloylaminopropyltriethylammonium bis (fluorosulfonyl) Imide, acryloylaminopropyltripropylammonium bis (fluorosulfonyl) imide, acryloylaminoethyldimethylbenzylammonium bis (fluorosulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis (fluorosulfonyl) imide, acryloylaminopropyldiethylbenzylammonium bis (fluoro) (Rosulfonyl) imide, acryloylaminopropylmethyldibenzylammonium bis (fluorosulfonyl) imide, acryloylaminopropylethyldibenzylammonium bis (fluorosulfonyl) imide, methacryloylaminomethyltrimethylammonium bis (fluorosulfonyl) imide, methacryloylaminomethyltriethylammonium Bis (fluorosulfonyl) imide, methacryloylaminomethyltripropylammonium bis (fluorosulfonyl) imide, methacryloylaminoethyltrimethylammonium bis (fluorosulfonyl) imide, methacryloylaminopropyltrimethylammonium bis (fluorosulfonyl) imide, methacryloylaminopropylmethyldiethylammonium (Fluorosulfonyl) imide, methacryloylaminopropylethyldimethylammonium bis (fluorosulfonyl) imide, methacryloylaminopropylmethyldipropylammonium bis (fluorosulfonyl) imide, methacryloylaminopropyltriethylammonium bis (fluorosulfonyl) imide, methacryloylaminopropyltri Propyl ammonium bis (fluorosulfonyl) imide, methacryloylaminoethyldimethylbenzylammonium bis (fluorosulfonyl) imide, methacryloylaminopropyldimethylbenzylammonium bis (fluorosulfonyl) imide, methacryloylaminopropyldiethylbenzylammonium bis (fluorosulfonyl) imide, methacryloyl Nopropylmethyldibenzylammonium bis (fluorosulfonyl) imide, methacryloylaminopropylethyldibenzylammonium bis (fluorosulfonyl) imide, acryloylaminomethyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminomethyltriethylammonium bis (pentafluoro) Ethanesulfonyl) imide, acryloylaminomethyltripropylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminoethyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminopropyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, acryloylamino Propylmethyldiethyl Ammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminopropylethyldimethylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminopropylmethyldipropylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminopropyltriethylammonium bis (pentafluoro) Ethanesulfonyl) imide, acryloylaminopropyltripropylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminoethyldimethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, Acryloylaminopro Rudiethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminopropylmethyldibenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminopropylethyldibenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminomethyltrimethylammonium Bis (pentafluoroethanesulfonyl) imide, methacryloylaminomethyltriethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminomethyltripropylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminoethyltrimethylammonium bis (pentafluoroethanesulfonyl) Imido, methacrylo Ruaminopropyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminopropylmethyldiethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminopropylethyldimethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminopropylmethyldipropyl Ammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminopropyltriethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminopropyltripropylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminoethyldimethylbenzylammonium bis (pentafluoroethane) Sulfo Nyl) imide, methacryloylaminopropyldimethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminopropyldiethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloylaminopropylmethyldibenzylammonium bis (pentafluoroethanesulfonyl) imide, Methacryloylaminopropylethyldibenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloylaminomethyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminomethyltriethylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminomethyltripropylammonium Screw Tafluoropropanesulfonyl) imide, acryloylaminoethyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropylmethyldiethylammonium bis (heptafluoropropanesulfonyl) imide, Acryloylaminopropylethyldimethylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropylmethyldipropylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropyltriethylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropyltripropyl Ammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminoethyldimethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropyldiethylbenzylammonium bis (heptafluoro) Propanesulfonyl) imide, acryloylaminopropylmethyldibenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminopropylethyldibenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminomethyltrimethylammonium bis (heptafluoropropanesulfonyl) imide , Meta Acryloylaminomethyltriethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminomethyltripropylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminoethyltrimethylammonium bis
(Heptafluoropropanesulfonyl) imide, methacryloylaminopropyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropylmethyldiethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropylethyldimethylammonium bis (heptafluoropropanesulfonyl) Imido, methacryloylaminopropylmethyldipropylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropyltriethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropyltripropylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylamino Ethyldimethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropyldimethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropyldiethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropylmethyldibenzylammonium Bis (heptafluoropropanesulfonyl) imide, methacryloylaminopropylethyldibenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloylaminomethyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminomethyltriethylammonium bis (nonafluorobutanesulfo) ) Imide, acryloylaminomethyltripropylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminoethyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropyl Methyldiethylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropylethyldimethylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropylmethyldipropylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropyltriethylammonium bis ( Nonafluorobutanesulfonyl) imide , Acryloylaminopropyltripropylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminoethyldimethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropyldiethyl Benzylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropylmethyldibenzylammonium bis (nonafluorobutanesulfonyl) imide, acryloylaminopropylethyldibenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminomethyltrimethylammonium bis ( Nonafluorobutanesulfonyl Imido, methacryloylaminomethyltriethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminomethyltripropylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminoethyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropyltrimethylammonium Bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropylmethyldiethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropylethyldimethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropylmethyldipropylammonium bis (nonafluoro) Butanesulfoni ) Imide, methacryloylaminopropyltriethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropyltripropylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminoethyldimethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropyl Dimethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropyldiethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropylmethyldibenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloylaminopropylethyldibenzylammonium Screw (Nonaph Trifluorobutanesulfonyl) imide, acryloylaminomethyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminomethyltriethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminomethyl Tripropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminoethyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropyltrimethylammonium [(trifluoromethanesulfonyl) ( Pentafluoroethanesulfonyl)] imide, acryloyl Aminopropylmethyldiethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropylethyldimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropylmethyldipropylammonium [( Trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropyltriethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropyltripropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) )] Imide, acryloylaminoethyldimethyl Benzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropyldimethylbenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropyldiethylbenzylammonium [(trifluoromethanesulfonyl) (Pentafluoroethanesulfonyl)] imide, acryloylaminopropylmethyldibenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminopropylethyldibenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) ] Imido, methacryloylaminomethyltrimethylan Monium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminomethyltriethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminomethyltripropylammonium [(trifluoromethanesulfonyl) (penta Fluoroethanesulfonyl)] imide, methacryloylaminoethyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminopropyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminopropyl Methyl diethylammonium [(trifluoromethyl Sulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminopropylethyldimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminopropylmethyldipropylammonium [(trifluoromethanesulfonyl) (pentafluoroethane Sulfonyl)] imide, methacryloylaminopropyltriethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminopropyltripropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminoethyldimethyl Benzyl ammonium [(trifluoromethanesulfo ) (Pentafluoroethanesulfonyl)] imide, methacryloylaminopropyldimethylbenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminopropyldiethylbenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) ] Imide, methacryloylaminopropylmethyldibenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloylaminopropylethyldibenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloylaminomethyl Trimethylammonium cyclo-hexafluoropropane-1, 3-bis (sulfonyl) imide, acryloylaminomethyltriethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminomethyltripropylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide , Acryloylaminoethyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropylmethyldiethylammoniumcyclo -Hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropylethyldimethylammonium cyclo-hexa Fluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropylmethyldipropylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropyltriethylammonium cyclo-hexafluoropropane-1,3- Bis (sulfonyl) imide, acryloylaminopropyltripropylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminoethyldimethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, Acryloylaminopropyldimethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropyl Ethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropylmethyldibenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloylaminopropylethyldibenzylammonium cyclo -Hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminomethyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminomethyltriethylammonium cyclo-hexafluoropropane-1,3 -Bis (sulfonyl) imide, methacryloylaminomethyltripropylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) ) Imide, methacryloylaminoethyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminopropyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide,
Tacryloylaminopropylmethyldiethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminopropylethyldimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminopropylmethyldi Propylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminopropyltriethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminopropyltripropylammonium cyclo-hexafluoropropane -1,3-bis (sulfonyl) imide, methacryloylaminoethyldimethylbenzylammonium cyclohexafur Lopropane-1,3-bis (sulfonyl) imide, methacryloylaminopropyldimethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminopropyldiethylbenzylammonium cyclo-hexafluoropropane-1,3- Bis (sulfonyl) imide, methacryloylaminopropylmethyldibenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloylaminopropylethyldibenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) Ionic (meth) acrylamide monomers such as imide and acryloyloxymethyltrimethylammonium bis (trifluoromethanesulfonyl) Imido, acryloyloxymethyltriethylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxymethyltripropylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxypropyltrimethylammonium bis (trifluoro) (Romethanesulfonyl) imide, acryloyloxypropylmethyldiethylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxypropylethyldimethylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxypropylmethyldipropylammonium bis (trifluoromethanesulfonyl) imide, Liloyloxypropyltriethylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxypropyltripropylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxyethyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxypropyldimethylbenzylammonium bis ( Trifluoromethanesulfonyl) imide, acryloyloxypropyldiethylbenzylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxypropylmethyldibenzylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxypropylethyldibenzylammonium bis (trifluoromethanesulfonyl) imi , Methacryloyloxymethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxymethyltriethylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxymethyltripropylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxyethyltrimethylammonium bis (trifluoromethane) Sulfonyl) imide, methacryloyloxypropyltrimethylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxypropylmethyldiethylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxypropylethyldimethylammonium bis (trifluoromethanesulfonyl) imide, Acryloyloxypropylmethyldipropylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxypropyltriethylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxypropyltripropylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxyethyldimethylbenzylammonium bis (Trifluoromethanesulfonyl) imide, methacryloyloxypropyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxypropyldiethylbenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxypropylmethyldibenzylammonium bis (trifluoromethanes) Sulfonyl) imide, methacryloyloxypropylethyldibenzylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxymethyltrimethylammonium bis (fluorosulfonyl) imide, acryloyloxymethyltriethylammonium bis (fluorosulfonyl) imide, acryloyloxymethyltripropylammonium bis (Fluorosulfonyl) imide, acryloyloxyethyltrimethylammonium bis (fluorosulfonyl) imide, acryloyloxypropyltrimethylammonium bis (fluorosulfonyl) imide, acryloyloxypropylmethyldiethylammonium bis (fluorosulfonyl) imide, acryloyloxypropylethyldimethylammonium bis ( Fluorosulfonyl) imide, acryloyloxypropylmethyldipropylammonium bis (fluorosulfonyl) imide, acryloyloxypropyltriethylammonium bis (fluorosulfonyl) imide, acryloyloxypropyltripropylammonium bis (fluorosulfonyl) imide, acryloyloxyethyldimethylbenzyl Ammonium bis (fluorosulfonyl) imide, acryloyloxypropyldimethylbenzylammonium bis (fluorosulfonyl) imide, acryloyloxypropyldiethylbenzylammonium bis (fluorosulfonyl) imide, acryloyloxypropylmethyldibenzylammonium bis (fluorosulfonyl) imide, acryloyloxy Propylethyldi Benzylammonium bis (fluorosulfonyl) imide, methacryloyloxymethyltrimethylammonium bis (fluorosulfonyl) imide, methacryloyloxymethyltriethylammonium bis (fluorosulfonyl) imide, methacryloyloxymethyltripropylammonium bis (fluorosulfonyl) imide, methacryloyloxyethyl Trimethylammonium bis (fluorosulfonyl) imide, methacryloyloxypropyltrimethylammonium bis (fluorosulfonyl) imide, methacryloyloxypropylmethyldiethylammonium bis (fluorosulfonyl) imide, methacryloyloxypropylethyldimethylammonium bis (fluorosulfonyl) imide, methacryloyloxypro Pyrmethyldipropylammonium bis (fluorosulfonyl) imide, methacryloyloxypropyltriethylammonium bis (fluorosulfonyl) imide, methacryloyloxypropyltripropylammonium bis (fluorosulfonyl) imide, methacryloyloxyethyldimethylbenzylammonium bis (fluorosulfonyl) imide, Methacryloyloxypropyldimethylbenzylammonium bis (fluorosulfonyl) imide, methacryloyloxypropyldiethylbenzylammonium bis (fluorosulfonyl) imide, methacryloyloxypropylmethyldibenzylammonium bis (fluorosulfonyl) imide, methacryloyloxypropylethyldibenzylammonium bis (fluoros) Phonyl) imide, acryloyloxymethyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxymethyltriethylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxymethyltripropylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxyethyl Trimethylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropylmethyldiethylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropylethyldimethylammonium bis (pentafluoro) Ethanesulfoni ) Imide, acryloyloxypropylmethyldipropylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropyltriethylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropyltripropylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxy Ethyldimethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropyldimethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropyldiethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxypropylmethyldibenzylammonium Bis (Pentafu Fluoroethanesulfonyl) imide, acryloyloxypropylethyldibenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxymethyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxymethyltriethylammonium bis (pentafluoroethanesulfonyl) imide , Methacryloyloxymethyltripropylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxyethyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropylmethyldiethylammonium Screw( N-fluorofluorosulfonylsulfonyl) imide, methacryloyloxypropylethyldimethylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropylmethyldipropylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropyltriethylammonium bis (pentafluoroethanesulfonyl) Imido, methacryloyloxypropyltripropylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxyethyldimethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropyldimethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropyl Ethylbenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropylmethyldibenzylammonium bis (pentafluoroethanesulfonyl) imide, methacryloyloxypropylethyldibenzylammonium bis (pentafluoroethanesulfonyl) imide, acryloyloxymethyltrimethylammonium bis (Heptafluoropropanesulfonyl) imide, acryloyloxymethyltriethylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxymethyltripropylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxyethyltrimethylammonium bis (heptafluoropropanesulfonyl) imide , Acryloyl Oxypropyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropylmethyldiethylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropylethyldimethylammonium bis (
Heptafluoropropanesulfonyl) imide, acryloyloxypropylmethyldipropylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropyltriethylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropyltripropylammonium bis (heptafluoropropanesulfonyl) Imido, acryloyloxyethyldimethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropyldimethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropyldiethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropiyl Methyldibenzylammonium bis (heptafluoropropanesulfonyl) imide, acryloyloxypropylethyldibenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxymethyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxymethyltriethylammonium bis ( Heptafluoropropanesulfonyl) imide, methacryloyloxymethyltripropylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxyethyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropyltrimethylammonium bis (heptafluoropropanesulfonyl) imide, Me Acryloyloxypropylmethyldiethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropylethyldimethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropylmethyldipropylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropyl Triethylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropyltripropylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxyethyldimethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropyldimethylbenzylammonium bis ( Heptafluoropropanesulfonyl) imide, methacryloyloxypropyldiethylbenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropylmethyldibenzylammonium bis (heptafluoropropanesulfonyl) imide, methacryloyloxypropylethyldibenzylammonium bis (heptafluoropropane) Sulfonyl) imide, acryloyloxymethyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxymethyltriethylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxymethyltripropylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxyethyl Trimethylammo Umbis (nonafluorobutanesulfonyl) imide, acryloyloxypropyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxypropylmethyldiethylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxypropylethyldimethylammonium bis (nonafluorobutanesulfonyl) ) Imide, acryloyloxypropylmethyldipropylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxypropyltriethylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxypropyltripropylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxy Ethyl dimethyl benzylammoni Mubis (nonafluorobutanesulfonyl) imide, acryloyloxypropyldimethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxypropyldiethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxypropylmethyldibenzylammonium bis (nonafluoro) Butanesulfonyl) imide, acryloyloxypropylethyldibenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxymethyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxymethyltriethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyl Oxymethyltripropylammo Ni-bis (nonafluorobutanesulfonyl) imide, methacryloyloxyethyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropyltrimethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropylmethyldiethylammonium bis (nonafluorobutanesulfonyl) Imido, methacryloyloxypropylethyldimethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropylmethyldipropylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropyltriethylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropyl Tripropyl Ammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxyethyldimethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropyldimethylbenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropyldiethylbenzylammonium bis (nonafluoro) Butanesulfonyl) imide, methacryloyloxypropylmethyldibenzylammonium bis (nonafluorobutanesulfonyl) imide, methacryloyloxypropylethyldibenzylammonium bis (nonafluorobutanesulfonyl) imide, acryloyloxymethyltrimethylammonium [(trifluoromethanesulfonyl) (penta Fluoroethanesulfonyl ], Acryloyloxymethyltriethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxymethyltripropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxyethyltrimethylammonium [ (Trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxypropyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxypropylmethyldiethylammonium [(trifluoromethanesulfonyl) (pentafluoroethane Sulfonyl)] imide, acryloyloxypropyl Ethyldimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxypropylmethyldipropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxypropyltriethylammonium [(trifluoromethanesulfonyl) ) (Pentafluoroethanesulfonyl)] imide, acryloyloxypropyltripropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxyethyldimethylbenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] Imido, acryloyloxypropyldimethylbenzylamine Nitro [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxypropyldiethylbenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxypropylmethyldibenzylammonium [(trifluoromethanesulfonyl) (Pentafluoroethanesulfonyl)] imide, acryloyloxypropylethyldibenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxymethyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide , Methacryloyloxymethyltriethylammonium [(Trif Oromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxymethyltripropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxyethyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) )] Imide, methacryloyloxypropyltrimethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxypropylmethyldiethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxypropylethyldimethyl Ammonium [(trifluoromethanesulfonyl ) (Pentafluoroethanesulfonyl)] imide, methacryloyloxypropylmethyldipropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxypropyltriethylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] Imido, methacryloyloxypropyltripropylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxyethyldimethylbenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxypropyldimethylbenzylammonium [(Trifluoromethanesulfonyl) (Pen Fluoroethanesulfonyl)] imide, methacryloyloxypropyldiethylbenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, methacryloyloxypropylmethyldibenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, Methacryloyloxypropylethyldibenzylammonium [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl)] imide, acryloyloxymethyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxymethyltriethylammonium cyclo- Hexafluoropropane-1,3-bis (sulfonyl) imide, a Liloyloxymethyltripropylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxyethyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxypropyltrimethylammoniumcyclo -Hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxypropylmethyldiethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxypropylethyldimethylammonium cyclo-hexafluoropropane-1 , 3-Bis (sulfonyl) imide, acryloyloxypropylmethyldipropylammonium cyclo-hexafluoropropane-1,3- Bis (sulfonyl) imide, acryloyloxypropyltriethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxypropyltripropylammonium cyclo-hexafluoropropane-1,3-bis (sulfo)
Nyl) imide, acryloyloxyethyldimethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxypropyldimethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxy Propyldiethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxypropylmethyldibenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, acryloyloxypropylethyldibenzylammonium Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxymethyltrimethylammonium cyclo Hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxymethyltriethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxymethyltripropylammonium cyclo-hexafluoropropane-1,3 -Bis (sulfonyl) imide, methacryloyloxyethyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxypropyltrimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyl Oxypropylmethyldiethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxypropi Ethyldimethylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxypropylmethyldipropylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxypropyltriethylammonium cyclo-hexa Fluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxypropyltripropylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxyethyldimethylbenzylammonium cyclo-hexafluoropropane-1,3 -Bis (sulfonyl) imide, methacryloyloxypropyldimethylbenzylammonium cyclo-hexafluoropropane-1,3-bi Sus (sulfonyl) imide, methacryloyloxypropyldiethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide, methacryloyloxypropylmethyldibenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide And ionic (meth) acrylate monomers such as methacryloyloxypropylethyldibenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide.

In view of easy availability of inexpensive industrial raw materials, acryloylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imide, methacryloylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloylaminopropyldimethylbenzylammonium bis are particularly preferable. (Trifluoromethanesulfonyl) imide, acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide, acryloyloxyethyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide, methacryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide.

（式中、Ｍ^＋はカチオンを表し、Ｘ^- は直鎖状のスルホンイミドアニオン[(Ｒｆ^１ＳＯ₂)(Ｒｆ^２ＳＯ₂)Ｎ]^- （但し、Ｒｆ^１及びＲｆ^２は同じであっても異なっていてもよく、炭素数１〜４のペルフルオロアルキル基または炭素数０のフルオロ基を表す。）、または環状のイミドアニオン[ＣＦ₂(ＣＦ₂ＳＯ₂) ₂ Ｎ]^-を表す。）で表されるビス（ペルフルオロアルカンスルホニル）イミド塩と、一般式（３）

（式中、Ｒ_１は水素原子又はメチル基を、Ｒ_２及びＲ_３は各々独立に炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ｒ_４は炭素数１〜３のアルキル基、炭素数１〜３のアルケニル基又はベンジル基を表し、Ｙは酸素原子又はＮＨを表し、Ｚは炭素数１〜３のアルキレン基を表し、Ｑ^-はアニオンを表す。）で表される４級カチオン性ビニルモノマーを、非水溶性有機溶媒及び水が共存する二相系溶媒下でイオン交換反応する工程、（ｂ）さらに水相にイオン吸着剤を添加する工程、（ｃ）イオン交換反応により生成した一般式（１）で表されるイオン性ビニルモノマーを含有する非水溶性有機溶媒相と水相を二相分離させて水相を除去する工程、（ｄ）非水溶性有機溶媒相を減圧下の濃縮後、乾燥不活性ガス乃至乾燥空気のバブリングをさらに行う工程、からなり、金属イオンフリー、且つ有機溶媒及び水の含有量の少ない、一般式（１）で表される高純度の非水溶性イオン性ビニルモノマーを高収率で製造することができる。 The production method of the present invention comprises (a) the general formula (2)

(Wherein M ⁺ represents a cation and X ⁻ represents a linear sulfonimide anion [(Rf ¹ SO ₂ ) (Rf ² SO ₂ ) N] ⁻ (where Rf ¹ and Rf ² are the same) And may be different, and represents a perfluoroalkyl group having 1 to 4 carbon atoms or a fluoro group having 0 carbon atoms), or a cyclic imide anion [CF ₂ (CF ₂ SO ₂ ) ₂ N] ⁻ .) A bis (perfluoroalkanesulfonyl) imide salt represented by the general formula (3)

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group having 1 to 3 carbon atoms, and may be the same as or different from each other, and R ₄ represents 1 carbon atom) An alkyl group having ˜3, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, and Q ⁻ represents an anion.) A step of ion-exchange reaction of a quaternary cationic vinyl monomer represented by the formula (2) in a two-phase solvent in which a water-insoluble organic solvent and water coexist, (b) a step of adding an ion adsorbent to the aqueous phase; c) a step of removing the aqueous phase by separating the water-insoluble organic solvent phase containing the ionic vinyl monomer represented by the general formula (1) represented by the general formula (1) and the aqueous phase into two phases, (d) After concentrating the water-soluble organic solvent phase under reduced pressure, dry inert gas or The method further comprises a step of bubbling dry air, and has a high yield of a high-purity water-insoluble ionic vinyl monomer represented by the general formula (1), which is free of metal ions and has a small content of organic solvent and water. Can be manufactured.

The bis (perfluoroalkanesulfonyl) imide salt represented by the general formula (2), which is the starting material in the step (a) of the present invention, specifically includes bis (trifluoromethanesulfonyl) imide lithium salt, bis (trifluoromethane) Sulfonyl) imide potassium salt, bis (trifluoromethanesulfonyl) imide sodium salt, bis (trifluoromethanesulfonyl) imide ammonium salt, bis (fluorosulfonyl) imide potassium salt, bis (fluorosulfonyl) imide sodium salt, bis (fluorosulfonyl) imide Ammonium salt, bis (hexafluoroethanesulfonyl) imide lithium salt, bis (hexafluoroethanesulfonyl) imide potassium salt, bis (hexafluoroethanesulfonyl) imide sodium salt, bis (heptaf) Oro propane sulfonyl) imide lithium salt, bis (nonafluorobutanesulfonyl) imide lithium salt, [(trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) imide potassium salt and the like.

The quaternary cationic vinyl monomer represented by the general formula (3), which is another starting material of the present invention, is a quaternary cationic (meth) acrylamide monomer and a quaternary cationic (meth) acrylate monomer.

In the general formula (3), R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same or different, ₄ represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, and Q ⁻ represents Halogen ions such as Cl ⁻ , Br ⁻ and I ⁻ or OH ⁻ , CH ₃ COO ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , HSO ₄ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO _{3 ^{-, CH 3 C 6 H 6}} SO 3 -, C 4 F 9 SO 3 -, represents an inorganic anion or an organic acid anion and the like.

（式中、Ｒ_１は水素原子又はメチル基を、Ｒ_２及びＲ_３は各々独立に炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ｒ_４は炭素数１〜３のアルキル基、炭素数１〜３のアルケニル基又はベンジル基を表し、Ｙは酸素原子又はＮＨを表し、Ｚは炭素数１〜３のアルキレン基を表す）で表されるＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリルアミド及び／又はＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレートに４級化剤としてのハロゲン化アルキル又はハロゲン化ベンジル、ジアルキル硫酸、炭酸ジアルキルあるいはアルキルトルエンスルフォネート、ベンゼンスルフォネート、ｐ−トルエンスルフォネートを水又は有機溶媒中で４級化反応させ、ジアルキルアミノアルキル（メタ）アクリルアミド４級塩及び／又はＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート４級塩を得ることができる。さらに、必要に応じ４級アンモニウム水酸化物を経由して無機酸や有機酸で中和処理することによりアニオンを変化させ、種々のジアルキルアミノアルキル（メタ）アクリルアミド４級塩及び／又はＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート４級塩を得ることができる。 The quaternary cationic vinyl monomer can be produced using a known method. For example, the following general formula (4)

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group having 1 to 3 carbon atoms, and may be the same as or different from each other, and R ₄ represents 1 carbon atom) Represents an alkyl group having 3 to 3, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, and Z represents an alkylene group having 1 to 3 carbon atoms). Dialkylaminoalkyl (meth) acrylamide and / or N, N-dialkylaminoalkyl (meth) acrylate, alkyl halide or benzyl halide as a quaternizing agent, dialkyl sulfate, dialkyl carbonate or alkyl toluenesulfonate, benzene sulfate Dialkylaminoalkyl (meth) acrylamide 4 is obtained by quaternizing phonate or p-toluenesulfonate in water or an organic solvent. A quaternary salt and / or an N, N-dialkylaminoalkyl (meth) acrylate quaternary salt can be obtained. Further, if necessary, the anion is changed by neutralizing with an inorganic acid or an organic acid via a quaternary ammonium hydroxide, and various dialkylaminoalkyl (meth) acrylamide quaternary salts and / or N, N -A dialkylaminoalkyl (meth) acrylate quaternary salt can be obtained.

Examples of the N, N-dialkylaminoalkyl (meth) acrylamide include N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth). Acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-methylethylaminoethyl (meth) acrylamide, N, N-methylpropylaminoethyl (meth) acrylamide, N, N-methylethylaminopropyl (meth) Examples include acrylamide, N, N-methylpropylaminopropyl (meth) acrylamide, and N, N-dipropylaminopropyl (meth) acrylamide.

Examples of the N, N-dialkylaminoalkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth). Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-methylethylaminoethyl (meth) acrylate, N, N-methylpropylaminoethyl (meth) acrylate, N, N-methylethylaminopropyl (meth) Examples thereof include acrylate, N, N-methylpropylaminopropyl (meth) acrylate, N, N-dipropylaminopropyl (meth) acrylate, and the like.

In addition, when a water-soluble quaternary cationic vinyl monomer is directly used as a raw material, an aqueous methyl chloride quaternary salt solution of N, N-dimethylaminopropylacrylamide (“DMAPAA-Q” manufactured by Kojin Co., Ltd.) and N, N -Methyl chloride quaternary salt aqueous solution of dimethylaminoethyl acrylate (“DMAEA-Q” manufactured by Kojin Co., Ltd.), benzyl chloride quaternary salt aqueous solution of N, N-dimethylaminoethyl acrylate (“DMAEA manufactured by Kojin Co., Ltd.) -BQ ") is particularly preferable from the viewpoint of availability as an inexpensive industrial product raw material.

The amount of the quaternary cationic vinyl monomer represented by the general formula (3) is usually 0.5 mol or more with respect to 1 mol of the bis (perfluoroalkanesulfonyl) imide salt represented by the general formula (2). Yes, preferably 0.8 to 1.5 mol, more preferably 0.9 to 1.1 mol. If the amount used is less than 0.5 mol or more than 1.5 mol, one of the raw materials remains excessively, so that purification after the reaction becomes difficult and the yield of the target product is lowered, which is not preferable. . It is also economically disadvantageous.

As the reaction solvent, a two-phase system in which a water-insoluble organic solvent and water coexist is used. The ratio (volume ratio) between the water-insoluble organic solvent and water is not particularly limited, but is usually in the range of (10/1) to (1/10), and (5/1) to (1/5). It is preferable that it is the range of these.

The amount of the water-insoluble organic solvent is not particularly limited, but a range in which the concentration of the ionic vinyl monomer of the present invention is 1 to 90% by weight is preferable. A range of 5 to 70% by weight is particularly preferable. If the amount is less than 1% by weight, it is difficult to efficiently recover the product to the organic phase. If the amount exceeds 90% by weight, the viscosity of the organic phase after the reaction is increased, and separation and removal of by-products are prevented. It becomes difficult.

The “water-insoluble organic solvent” in the present invention is an organic solvent that does not completely dissolve in water but can be separated at least partially from water to form a two-phase system, and has a solubility parameter (SP value). ) Is 7 to 11 (cal / cm ³ ) ^0.5 , more preferably a non-chlorine organic solvent having an SP value of 8 to 9. When the SP value is in the range of 7 to 11, the ionic vinyl monomer of the present invention is soluble, the by-product metal salt is insoluble, the by-product is easily dissolved in the aqueous phase, and the anion exchange reaction is accelerated. The target ionic vinyl monomer can be obtained in high yield. The solubility parameter of the present invention is a value indicated by pages IV-337 to IV-359 of H. Burrell's Polymer Handbook, 2nd edition (edited by J. Brandrup and EHImmergut) Wiley Interscience, New York, (1975). is there. If the solubility parameter is less than 7, both the raw quaternary cationic vinyl monomer and the produced ionic vinyl monomer are insoluble, and the anion exchange reaction cannot be performed efficiently. On the other hand, if it exceeds 11, it becomes a homogeneous reaction solution that dissolves the quaternary cationic vinyl monomer, the produced ionic vinyl monomer, and the anion-exchanged metal salt, and only the desired ionic vinyl monomer is isolated with high purity. It becomes difficult.

Examples of such a water-insoluble organic solvent include acetate-based organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, and methyl isopropyl ketone. And ketone-based organic solvents. Among these, butyl acetate and methyl isobutyl ketone are preferable because inexpensive industrial products are easily obtained, safety is high, and handling is easy. These solvents can be used alone or in combination of two or more.

The reaction temperature is usually 10 ° C. or higher, preferably 15 to 60 ° C., particularly preferably 20 to 40 ° C. When reaction temperature is less than 10 degreeC, reaction rate becomes slow and the required reaction time to complete becomes long. On the other hand, if it exceeds 60 ° C., the quaternary cationic vinyl monomer as a raw material and the ionic vinyl monomer as a product may be polymerized.

The ion adsorbent in the step (b) of the present invention is dissolved in the aqueous phase during the ion exchange reaction (a) performed in a two-phase system in which a water-insoluble organic solvent and water coexist, It adsorbs ions such as lithium ions (Li ⁺ ) and potassium ions (K ⁺ ) derived from by-products, and a water-soluble metal ion adsorbent can be used.

A water-soluble polymer can be used as the water-soluble metal ion adsorbent. Here, the water-soluble polymer refers to a polymer having a dissolution amount of 1 g or more when dissolved in 100 g of water at 25 ° C., and preferably 10 g or more. When the dissolution amount is less than 1 g, the concentration of the aqueous polymer solution may be too thin to sufficiently adsorb water-soluble metal ions.

Examples of such water-soluble polymers include acrylic acid water-soluble polymers having a carboxyl group in the side chain, such as homopolymers of acrylic acid and / or copolymers with other vinyl monomers, and N-substituted acrylamides. An acrylamide-based water-soluble polymer having an N-substituted amide group in the side chain, such as a homopolymer and a copolymer with other vinyl monomers. Among these, acrylic acid, N-vinylpyrrolidone, N, N-dimethylacrylamide, and acryloylmorpholine are preferable as raw material monomers because inexpensive industrial products are easily available and can be easily polymerized. These water-soluble polymers can be used alone or in combination of two or more.

Acrylic acid-based water-soluble polymers dissociate carboxyl groups in the side chain in aqueous solution, and the generated anions adsorb and fix metal ions in the aqueous phase, resulting in transfer to the organic phase where ionic vinyl monomers are present. Is suppressed, and a metal ion-free ionic vinyl monomer can be obtained. On the other hand, a water-soluble polymer containing acryloylmorpholine, N, N-dimethylacrylamide, and vinylpyrrolidone as a structural unit easily forms a complex structure with Lewis acidic metal ions such as lithium ions. It is valid.

The weight average molecular weight of the water-soluble polymer is not particularly limited in terms of polyethylene oxide, but is usually 1,000 to 20,000,000, preferably 10,000 to 5,000,000, more preferably 100,000 to 2,000,000. When the molecular weight of the water-soluble polymer is 1,000 or less, the polymer itself may be dissolved in the organic phase, which is not preferable. On the other hand, when the molecular weight exceeds 20,000,000, the solution viscosity of the aqueous phase is remarkably improved, and operations such as extraction and separation become difficult, which is not preferable.

The amount of the water-soluble polymer used as the metal ion adsorbent is usually 0.001 to 0.05 mol, preferably 0.005 to 0.02 mol, relative to 1 mol of the ionic vinyl monomer. When the amount of the water-soluble polymer used is less than 0.001 mol, metal ions may not be completely adsorbed. When the amount exceeds 0.05 mol, the viscosity of the aqueous solution becomes high in the high-molecular-weight aqueous polymer, The time required for the two-phase separation from the organic phase may be long.

In the step (c) of the present invention, the reaction solution is allowed to stand to separate into a water-insoluble organic solvent phase and an aqueous phase, and then the aqueous phase is removed from the system. The obtained water-insoluble organic solvent phase preferably further has a step of washing with water. Specifically, water is further added to the water-insoluble organic solvent phase, followed by stirring and standing separation to dissolve and remove by-product salts, water-soluble unreacted components and the like in the water phase. The ion adsorbent used in step (b) may be further added to the water used at this time. The type of ion adsorbent may be the same as or different from that used in the step (b).

In the step (d) of the present invention, the water-insoluble organic solvent phase is concentrated under reduced pressure, further dry inert gas or air is bubbled to remove the remaining organic solvent and water, The intended ionic vinyl monomer of the general formula (1) can be obtained.

The concentration temperature and bubbling temperature are usually 10 ° C. or higher, preferably 15 to 60 ° C., particularly preferably 20 to 50 ° C. If the operating temperature is less than 10 ° C., the time required to remove the residual solvent and water becomes longer. On the other hand, when it exceeds 60 degreeC, the ionic vinyl monomer of this invention may superpose | polymerize.

Since the ionic vinyl monomer of the present invention has a high viscosity and no vapor pressure, about 1 to 10% of an organic solvent remains in a normal concentration, and a high-purity product cannot be obtained. In addition, since the ionic vinyl monomer of the present invention has an unsaturated group, it may be polymerized when distilled for a long time to remove the organic solvent. Therefore, the present inventors pay attention to the characteristic that mist of a volatile organic solvent is generated by bubbling of an inert gas or air and is entrained in an air flow of the inert gas or air. We proposed that residual organic solvent and water be removed to 100 ppm or less by bubbling, and resulted in obtaining a high purity ionic vinyl monomer having a purity of 99% or more in a simple and economical manner with a high yield. That is, the organic solvent is evaporated, removed and recovered while bubbling dry inert gas or dry air above the melting point of the ionic vinyl monomer.

When the residual solvent after completion of the reaction is 10% or more, it is preferable because a bubbling treatment of a dry inert gas or dry air is more efficient after removal to a concentration lower than 10% by concentration under reduced pressure.

The dry inert gas group consisting of dry rare gas such as dry nitrogen, dry helium, dry neon, dry argon, dry krypton, dry xenon and dry radon as the dry inert gas, which does not react with the ionic vinyl monomer of the present invention or At least one selected from dry air can be used. Among these, dry air and dry nitrogen are particularly preferable in terms of easy availability of inexpensive industrial raw materials. These dry inert gases can be used alone or in combination of two or more.

Since the ionic vinyl monomer of the present invention is non-volatile, the gas flow rate during the dry inert gas or dry air bubbling treatment need not be particularly limited. Although it varies depending on the type and amount of the remaining organic solvent, a range of 1 mL / min to 100 L / min is preferable. Further, a range of 10 mL / min to 10 L / min is particularly preferable. If it is less than 1 mL / min, the organic solvent removal rate will be remarkably slow. If it exceeds 100 L / min, it becomes uneconomical, and if there is a large amount of residual organic solvent, the amount of mist generated is large, and problems such as troubles due to bumping may occur.

Since the ionic vinyl monomer of the present invention has high polymerizability, it is preferable to carry out the distillation under reduced pressure after completion of the reaction, and the recovery and removal of the organic solvent by dry inert gas or dry air bubbling in the presence of a polymerization inhibitor. .

A well-known thing can be used as a polymerization inhibitor. For example, hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,6-di-tert-butylparahydroquinone, 2,5-di-tert-butylhydroquinone, 2,4-dimethyl-6-tertbutylphenol, hydroquinone monomethyl ether, etc. Phenol compounds, N-isopropyl-N′-phenyl-para-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-para-phenylenediamine, N- (1-methylheptyl) -N ′ -Phenyl-para-phenylenediamine, N, N'-diphenyl-para-phenylenediamine, paraphenylenediamines such as N, N'-di-2-naphthyl-para-phenylenediamine, and amine compounds such as thiodiphenylamine; , 2,6,6-Tetramethylpipe Examples include piperidine 1-oxyl free radical compounds such as gin-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 oxyl, acetamidotetramethylpiperidine-1-oxyl, and the like. it can. These polymerization inhibitors may be used alone or in combination of two or more.

The addition amount of a polymerization inhibitor is 1-10000 ppm with respect to the ionic vinyl monomer of this invention, Preferably it is 5-5000 ppm.

By the above method, an ionic vinyl monomer having a purity of 99% or more can be obtained. Further, if necessary, the residual metal ions may be reduced by reverse osmosis membrane treatment, ion exchange resin treatment, chelate resin treatment, or purification means such as column chromatography.

When the ionic vinyl monomer of the present invention is liquid at room temperature, it can be used as an antistatic agent with high purity. Further, when it is liquid or solid at room temperature, it can be dissolved in an organic solvent or a vinyl monomer that is liquid at room temperature, and used in a solution state. When diluted with an organic solvent, it may be the same as or different from the reaction solvent, and the solubility parameter (SP value) is ^preferably in the range of 7 to 15 (cal / cm ³ ) ^0.5 .

The ionic vinyl monomer of the present invention and / or the oligomer and / or polymer containing the monomer as a constituent component, when applied to a molded article such as plastic and then dried, can be used alone or with antistatic properties. The effects of coating properties, scratch resistance and high hardness can be sufficiently exhibited. In addition, polyfunctional (meth) acrylates or polyfunctional (meth) acrylamides having two or more ethylene groups are added within a range that does not impair the original antistatic properties, moisture resistance, hydrolysis resistance, etc. of the present invention. Furthermore, by utilizing the excellent compatibility between the ionic vinyl monomer and the polyfunctional (meth) acrylate or polyfunctional (meth) acrylamide, a uniform cross-linkable film can be formed on the substrate surface, and further film forming properties And the performance of the coating film such as scratch resistance can be improved.

Such polyfunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Erythritol tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, tripropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ditetraethylene glycol di (meth) acrylate DOO, epoxy (meth) acrylate, monomers and oligomers such as urethane (meth) acrylate.

As a commercial item of such a polyfunctional (meth) acrylate, for example, Aronix M-400, M-450, M-305, M-309, M-310, M-315, M-320, TO-1200, TO-1231, TO-595, TO-756 (above, manufactured by Toagosei Co., Ltd.), KAYARD D-310, D-330, DPHA, DPHA-2C (above, manufactured by Nippon Kayaku Co., Ltd.), Nikalac MX-302 (Sanwa Chemical) Etc.).

Examples of the polyfunctional (meth) acrylamide include monomers such as methylene bisacrylamide, methylene bismethacrylamide, ethylene bisacrylamide, ethylene bismethacrylamide, and diallyl acrylamide, and oligomers such as urethane acrylamide (Japanese Patent Laid-Open No. 2002-37849). .

These polyfunctional (meth) acrylates and polyfunctional (meth) acrylamides may be used alone or in combination of a plurality of polyfunctional monomers and oligomers. Moreover, when using such a polyfunctional monomer and oligomer, it is preferable to make it contain 0.001 to 25000 weight% with respect to the ionic vinyl monomer structural unit of this invention, and to make it contain 50 to 20000 weight%. Particularly preferred. If the content is less than 0.1% by weight, the effect of addition is not recognized. If the content exceeds 25000% by weight, the crosslinking rate increases, so that the hardness and scratch resistance of the coating film are improved, but the elasticity is lost. Easily break.

The ionic vinyl monomer of the present invention can obtain an oligomer or / and polymer by homopolymerization in the presence of a radical initiator. Furthermore, when various properties of the antistatic composition and the antistatic layer, for example, to adjust the cured product properties to be hard or soft, other polymerizable compounds may be mixed and copolymerized. , Alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, unsaturated nitrile monomer, unsaturated carboxylic acid, amide group-containing monomer, methylol group-containing monomer, alkoxymethyl group-containing monomer, epoxy group-containing monomer, multifunctional monomer, Examples thereof include radical polymerization compounds having a reactive double bond in the molecular chain such as vinyl ester and olefin.

Examples of alkyl (meth) acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate Isopropyl acrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and the like.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, monoalkyl itaconate and the like.

Such a polymerizable compound is not limited to one type, and a plurality of types may be used in combination.

The ionic vinyl monomer of the present invention can be made into a polymer or copolymer by a known method with a polymerizable compound. As the polymerization method, for example, methods such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like can be used.

Examples of radical polymerization initiators include azo compound catalysts such as azobisisobutyronitrile and azobisvaleronitrile, peroxide catalysts such as benzoyl peroxide and hydrogen peroxide, peroxides such as ammonium persulfate and sodium persulfate. A sulfate-based catalyst or the like can be used. The usage-amount of a polymerization initiator is 0.05 to 10 weight% with respect to 100 weight% of polymerizable monomers, Preferably it is 0.2 to 3 weight%.

Since the content of the ionic vinyl monomer of the present invention depends on the polyfunctional (meth) acrylate used, the viscosity of the polyfunctional (meth) acrylamide, the blending amount of other polymerizable compounds, and the physical properties required for the resin composition, Although not particularly limited, the solid content ratio in the antistatic composition is 0.1 to 90% by weight, preferably 1 to 60% by weight. When the content of the ionic vinyl monomer is 0.1% by weight or less, the antistatic performance is insufficient, and when it exceeds 90% by weight, the transparency is inferior.

Antistatic agent containing ionic vinyl monomer of the present invention and / or oligomer or polymer containing monomer as constituent, and further containing polyfunctional (meth) acrylate and / or polyfunctional (meth) acrylamide in the antistatic agent Since the antistatic composition is coated on a substrate and cured, it is preferable to contain a reactive diluent or an organic solvent in order to adjust the viscosity to be applicable.

The reactive diluent is not particularly limited as long as it is a low-viscosity vinyl monomer having a viscosity at 25 ° C. of 500 mPa · s or less, but it requires fast curing, low odor, high flash point, and high coating film hardness. From the viewpoint, hydroxyethyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, acryloylmorpholine and the like are preferable.

The organic solvent is preferably one that can dissolve the ionic vinyl monomer of the present invention, oligomers and polymers containing the monomer as constituents. In particular, an organic solvent having a solubility parameter of 7 to 15 (cal / cm ³ ) ^0.5 is preferable for the ionic vinyl monomer and the oligomer and polymer obtained by homopolymerization.

Since the antistatic composition containing the ionic vinyl monomer of the present invention as a constituent component can be cured by active energy rays or heat, it is applied to a molded article such as plastic, dried, and cured to prevent the antistatic composition. It can be used as a conductive hard coat resin composition.

The active energy ray of the present invention is defined as an energy ray capable of decomposing a compound (photopolymerization initiator) that generates active species to generate active species. Examples of such active energy rays include light energy rays such as visible light, ultraviolet rays (UV), infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays because it has a certain energy level, has a high curing rate, is relatively inexpensive, and is compact.

When photocuring the ionic vinyl monomer of the present invention, a photoinitiator is added. The photoinitiator is not particularly necessary when an electron beam is used as the active energy ray, but is necessary when ultraviolet rays are used. The photoinitiator may be appropriately selected from ordinary ones such as acetophenone, benzoin, benzophenone, and thioxanthone. Among the photoinitiators, commercially available photoinitiators are manufactured by Ciba Specialty Chemicals, Inc., trade names Darocure 1116, Darocure 1173, IRGACURE 184, IRGACURE 369, IRGACURE 500, IRGACURE 651, IRGACURE 754, IRGACURE 819, IRGACURE 129, IRGACURE 1800, IRGACURE IRGACURE TPO, manufactured by UCB, trade name Ubekrill P36, etc. can be used.

In addition to pigments, dyes, surfactants, antiblocking agents, binders, crosslinking agents, antioxidants, UV absorbers and the like as long as they do not impair the antistatic properties and compatibility properties of the ionic vinyl monomer of the present invention. These optional components may be used in combination.

In the preparation of the antistatic composition of the present invention, the order of addition of these composition components includes an ionic vinyl monomer and / or an oligomer or polymer containing the monomer as a constituent, a reactive diluent and / or an organic solvent, It is preferable to carry out in order of polyfunctional (meth) acrylate or / and polyfunctional (meth) acrylamide, a photopolymerization initiator, and other additives.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.

In the following examples and comparative examples, the characteristics of the antistatic composition were evaluated by the following methods.
(1) Method for quantifying ionic vinyl monomer Using a potentiometric automatic titrator (device name: AT-610, manufactured by Kyoto Electronics Industry Co., Ltd.), a sodium tetraphenylborate solution having a concentration of 0.02 mol / L (manufactured by Kanto Chemical Co., Inc.) ) To obtain the quaternary ammonium salt concentration from the titration amount.
(2) Molecular weight measurement method of aqueous solution polymer The weight average molecular weight is obtained by converting the result of analysis by gel permeation chromatography (GPC) using a calibration curve prepared using polyethylene oxide as a standard sample. Here, the measurement conditions of GPC are as follows.
GPC: LC-10A manufactured by Shimadzu Corporation
Column: Ultrahydrogel Liner (7.8 mm x 300 mm) manufactured by Waters
Detector: differential refractometer RID-10A
Eluent: 0.5 mol / L Sodium nitrate aqueous solution Flow rate: 0.5 mL / min Temperature: 30 ° C
Sample concentration: 0.1%
Sample injection volume: 20 μL
(3) Production of Antistatic Film A polyethylene terephthalate (PET) film having a thickness of 100 μm was stuck on a glass plate (length 200 × width 200 × thickness 5 mm) and fixed on a horizontal surface so as not to move. An antistatic hard coat agent is dropped in the form of a strip on the end of the PET film, and both ends are pressed with a bar coater (RDS60) so that a uniform force is applied to the entire film. The same speed (5 cm / sec) without rotation Then, the paint was pulled to the near side, and the solvent was removed at 80 ° C. for 3 minutes with a hot air dryer to obtain a coating film. The adhesion state of the coating film was visually observed to evaluate the film formability and stickiness.
Formability of coating film A: Uniform coating film without repelling;
○: There is very little repellency, but the coating film is almost uniform;
Δ: There is some repelling, but the coating film is almost uniform as a whole;
X: A lot of repelling and a non-uniform coating film.
Stickiness ◎: No stickiness at all;
○: Slightly sticky;
Δ: Slight stickiness;
X: There is clear stickiness.
(4) Ultraviolet curing An antistatic hard coat film was obtained by curing with irradiation of ultraviolet rays with the coated surface facing upward. The ultraviolet curing condition is such that an ultraviolet irradiation device (Oak Seisakusho Model OHD320M) equipped with a high pressure mercury lamp with an output of 300 W and an output of 50 W / cm per unit is used, and the ultraviolet energy is 10 mJ / cm ² per ^second. The distance between the sample plate and the lamp was adjusted. The irradiation time required until the surface of the coating film was not sticky was measured as the curing time. After curing, the transparency of the coating film on each PET film was visually observed, and the surface resistivity measurement, scratch resistance test, moisture resistance test, and pencil hardness test were performed by the following methods.
Transparency of coating after curing ◎: Transparent and smooth surface;
○: Transparent but uneven
Δ: Slight cloudiness or unevenness;
X: Extremely cloudy or uneven (5) Surface resistivity measurement Using a template (length 110 x width 110 mm), the antistatic hard coat film is cut with a cutter knife and adjusted to a temperature of 25 ° C and a relative humidity of 60% The sample was placed in a thermostatic chamber and allowed to stand for 24 hours to obtain a sample for measuring surface resistivity. Based on JIS K 6911, the measurement was performed using a digital electrometer (R8252 type: manufactured by ADC Corporation).
(6) Scratch resistance test Using steel wool of # 0000, the steel wool was reciprocated 10 times on the antistatic hard coat film while applying a load of 200 g / cm ² to evaluate the presence or absence of scratches.
Scratch resistance evaluation A: Almost no film peeling or scratches are observed;
○: slight thin scratches are observed on the membrane;
Δ: A streak is found on the entire surface of the membrane;
X: Peeling of the film occurs.
(7) Moisture resistance test The antistatic hard coat film was stored in a constant temperature bath at 40 ° C. and 90% RH for 3 days, and the change in the appearance of the film was visually evaluated.
A: No change in appearance;
○: A level in which a slight change in appearance such as whitening is observed but is not a problem;
Δ: Slight change in appearance such as whitening is observed;
×: Appearance change such as whitening is remarkably recognized;
(8) Pencil Hardness Test A pencil hardness test was performed on the antistatic hard coat film based on JIS K 5400.

<Synthesis of water-soluble polymer aqueous solution>
Polymer aqueous solution production example 1
A 1 L reaction vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was charged with 250 g of deionized water and 45 g of acryloylmorpholine (ACMO), and the pH was adjusted to 6.5 with dilute sulfuric acid. To remove oxygen in the reaction system. The temperature inside the system was 25 ° C., and 2.91 g of 5 wt% ammonium persulfate aqueous solution and 3.65 g of 2 wt% sodium hydrogen sulfite aqueous solution were added as initiators. The mixture was stirred at 25 ° C. for 10 hours while blowing nitrogen gas. Thereafter, 150 g of deionized water was added to obtain an aqueous acryloylmorpholine homopolymer solution having a solid content of 10% by weight and a weight average molecular weight of 730,000.

Polymer aqueous solution production example 2
400 g of deionized water and 45 g of acryloylmorpholine (ACMO) were charged into a 1 L reaction vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, and oxygen in the reaction system was removed through nitrogen gas. The system was adjusted to 50 ° C., and 2.06 g of a 10 wt% aqueous solution of a water-soluble azo initiator VA-044 (manufactured by Wako Pure Chemical Industries) was added. While blowing nitrogen gas, the mixture was stirred at 50 ° C. for 10 hours to obtain an aqueous solution of acryloylmorpholine homopolymer having a solid content of 10% and a weight average molecular weight of 220,000.

Synthesis examples and comparative synthesis examples which are production examples of ionic vinyl monomers are shown below.
Synthesis example 1
In a 1 L three-necked flask, 105.7 g of lithium bis (trifluoromethanesulfonyl) imide was dissolved in 200 g of ion-exchanged water to prepare an aqueous solution of lithium bis (trifluoromethanesulfonyl) imide. To this aqueous solution, 90 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) was added, followed by 100 g of butyl acetate, and acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd., weight) as an ion adsorbent. An aqueous polymer solution in which 0.2 g (average molecular weight 250,000) was dissolved in 10 g of water was added and stirred for 2 hours. After that, among the separated two layers, the organic phase (ionic vinyl monomer butyl acetate solution) was separated. 100 g of ion-exchanged water was added to the separated organic phase and washed. After this washing operation was further performed twice, 0.3 g of hydroquinone monomethyl ether was added to the organic phase, followed by concentration under reduced pressure at 40 ° C. and 5 torr. The gas chromatograph confirmed 1.6% of butyl acetate. Subsequently, bubbling with dry air (flow rate: 500 mL / min) at 40 ° C. for 4 hours under normal pressure to clear the target product acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSIQ). As a liquid, 159.8 g was obtained. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 83 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 99.2%. In elemental analysis, measured values (C: 27.55%, H: 3.31%, N: 6.45%) are theoretical values (C: 27.40%, H: 3.68%, N: 6. 39%). Lithium ions were quantified by dielectric coupled plasma emission analysis (ICP) and were not detected (0.1 ppm or less). Further, the solubility of the target product DMAEA-TFSIQ in water was 1.3 g / 100 g of water at 25 ° C.

Synthesis example 2
In Synthesis Example 1, 100 g of methyl isobutyl ketone was used instead of butyl acetate, and the reaction was performed in the same manner as in Synthesis Example 1, and the target product acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSIQ) was colorless and transparent. As a liquid, 157.8 g was obtained. By gas chromatograph, methyl isobutyl ketone was not detected (100 ppm or less). From the moisture measurement, the moisture content was 92 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 98.0%. In elemental analysis, measured values (C: 27.30%, H: 3.35%, N: 6.18%) are theoretical values (C: 27.40%, H: 3.68%, N: 6. 39%). Lithium ions were quantified by dielectric coupling type plasma emission analysis (ICP) and were not detected (0.1 ppm or less).

Synthesis example 3
In Synthesis Example 1, 117.6 g of potassium bis (trifluoromethanesulfonyl) imide was used instead of lithium bis (trifluoromethanesulfonyl) imide, and the polymer aqueous solution production example 1 was prepared instead of acrylic acid polymer as an ion adsorbent. The reaction was carried out in the same manner as in Synthesis Example 1 using 3 g of an acryloylmorpholine polymer aqueous solution to obtain 158.1 g of the desired product acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSIQ) as a colorless transparent liquid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 88 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.8%. The yield was 98.0%. In elemental analysis, measured values (C: 27.46%, H: 3.71%, N: 6.24%) are theoretical values (C: 27.40%, H: 3.68%, N: 6. 39%). Potassium ions were quantified by inductively coupled plasma optical emission spectrometry (ICP) and were not detected (0.1 ppm or less).

Synthesis example 4
In a 500 mL three-necked flask, 67.3 g of potassium bis (fluorosulfonyl) imide was dissolved in 67 g of ion-exchanged water to prepare an aqueous potassium bis (fluorosulfonyl) imide solution. To this aqueous solution, 75 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) was added, followed by 34 g of butyl acetate and stirred for 1 hour. Subsequently, 1 g of an acryloylmorpholine polymer aqueous solution produced in Polymer aqueous solution production example 2 was added as an ion adsorbent, and the mixture was further stirred for 1 hour. Thereafter, of the separated two layers, the organic phase was separated. 30 g of ion-exchanged water was added to the separated organic phase and washed. After this washing operation was further performed twice, 0.02 g of 2,2,6,6-tetramethylpiperidine-1oxyl was added to the organic phase and concentrated under reduced pressure at 40 ° C. and 5 torr. Gas chromatograph confirmed 1.5% of butyl acetate. Subsequently, bubbling with dry air (flow rate: 500 mL / min) is performed at 40 ° C. for 4 hours under normal pressure, and the target product acryloyloxyethyltrimethylammonium bis (fluorosulfonyl) imide (DMAEA-FSIQ) is a clear liquid. As a result, 101.2 g was obtained. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 85 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.8%. The yield was 97.6%. In elemental analysis, measured values (C: 28.26%, H: 4.38%, N: 8.13%) are theoretical values (C: 28.40%, H: 4.77%, N: 8.28). %). Potassium ions were quantified by dielectric coupled plasma emission analysis (ICP) and were not detected (0.1 ppm or less). The solubility of the target product DMAEA-FSIQ in water was 1.9 g / 100 g of water at 25 ° C.

Synthesis example 5
In a 200 mL three-necked flask, 15.8 g of lithium bis (pentafluoroethanesulfonyl) imide was dissolved in 30 g of ion-exchanged water to prepare an aqueous solution of lithium bis (pentafluoroethanesulfonyl) imide. To this aqueous solution, 10 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) was added, and then 15 g of butyl acetate was added and stirred for 1 hour. Subsequently, an aqueous polymer solution in which 0.02 g of an acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 250,000) was dissolved in 1 g of water was added as an ion adsorbent, and further stirred for 1 hour. Thereafter, of the separated two layers, the organic phase was separated. The separated organic phase was washed with 15 g of ion-exchanged water. After this washing operation was further performed twice, the organic phase was concentrated under reduced pressure at 40 ° C. and 5 torr. The gas chromatograph confirmed 1.7% of butyl acetate. Subsequently, bubbling with dry nitrogen (flow rate: 500 mL / min) at 100 ° C. for 4 hours under normal pressure, followed by cooling to room temperature, the target product acryloyloxyethyltrimethylammonium bis (pentafluoroethanesulfonyl) imide 21.4 g of (DMAEA-PFSIQ) was obtained as white crystals. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 88 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.8%. The yield was 97.2%. In elemental analysis, measured values (C: 26.61%, H: 3.19%, N: 5.32%) are theoretical values (C: 26.77%, H: 3.00%, N: 5.20). %). Lithium ions were quantified by dielectric coupled plasma emission analysis (ICP) and were not detected (0.1 ppm or less). The solubility of the target product DMAEA-PFSIQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis Example 6
In Synthesis Example 5, 20.6 g of sodium bis (heptafluoropropanesulfonyl) imide was used instead of lithium bis (pentafluoroethanesulfonyl) imide, and the reaction was conducted in the same manner as in Synthesis Example 5 to produce the desired product acryloyloxyethyltrimethylammonium bis. 25.8 g of (heptafluoropropanesulfonyl) imide (DMAEA-HFSIQ) was obtained as white crystals. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 71 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.7%. The yield was 98.8%. In elemental analysis, measured values (C: 26.82%, H: 2.61%, N: 4.42%) are theoretical values (C: 26.34%, H: 2.53%, N: 4.39). %). Sodium ions were quantified by inductively coupled plasma optical emission spectrometry (ICP) and were not detected (0.1 ppm or less). The solubility of the target product DMAEA-HFSIQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis example 7
In a 1 L three-necked flask, 104.5 g of lithium bistrifluoromethanesulfonyl) imide was dissolved in 200 g of ion-exchanged water to prepare an aqueous lithium bis (trifluoromethanesulfonyl) imide solution. To this aqueous solution, 100 g of a 75% aqueous solution of acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: DMAPAA-Q) was added, and subsequently 100 g of butyl acetate was added and stirred for 1 hour. Subsequently, an aqueous polymer solution in which 0.2 g of an acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 250,000) was dissolved in 10 g of water was added as an ion adsorbent, and further stirred for 1 hour. Thereafter, of the separated two layers, the organic phase was separated. 100 g of ion-exchanged water was added to the separated organic phase and washed. After this washing operation was further performed twice, the organic phase was concentrated under reduced pressure at 40 ° C. and 5 torr. The gas chromatograph confirmed butyl acetate 2.2%. Subsequently, bubbling with dry air (flow rate 500 mL / min) at 40 ° C. for 4 hours under normal pressure to clear the target product acryloylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAPAA-TFSIQ) As a liquid, 162.7 g was obtained. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 76 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 99.2%. In elemental analysis, measured values (C: 29.13%, H: 4.21%, N: 9.53%) are theoretical values (C: 29.27%, H: 4.24%, N: 9. 31%). Lithium ions and calcium ions were quantified by inductively coupled plasma emission spectrometry (ICP) and were not detected (0.1 ppm or less). The solubility of the desired product DMAPAA-TFSIQ in water was 3.0 g / 100 g water at 25 ° C.

Synthesis Example 8
In a 500 mL three-necked flask, 79.8 g of potassium bis (fluorosulfonyl) imide was dissolved in 80 g of ion-exchanged water to prepare an aqueous potassium bis (fluorosulfonyl) imide solution. To this aqueous solution was added 100 g of a 75% aqueous solution of acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: DMAPAA-Q), followed by 40 g of methyl isobutyl ketone, and further an acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd.) as an ion adsorbent. A polymer aqueous solution in which 0.13 g of a weight average molecular weight of 250,000) was dissolved in 10 g of water was added, and the mixture was further stirred for 1 hour. Thereafter, of the separated two layers, the organic phase was separated. 40 g of ion-exchanged water was added to the separated organic phase and washed. After this washing operation was further performed twice, the organic phase was concentrated under reduced pressure at 40 ° C. and 5 torr. A gas chromatograph confirmed 1.8% butyl acetate. Subsequently, bubbling with dry air (flow rate: 500 mL / min) at 40 ° C. for 4 hours under normal pressure, and the target product acryloylaminopropyltrimethylammonium bis (fluorosulfonyl) imide (DMAPAA-FSIQ) is a clear liquid. As a result, 123.3 g was obtained. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 76 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.8%. The yield was 96.5%. In the elemental analysis, measured values (C: 30.63%, H: 5.31%, N: 12.08%) are theoretical values (C: 30.76%, H: 5.45%, N: 11.96). %). Chlorine ions were quantified by ion chromatography and found to be 1 ppm or less. In addition, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by dielectric coupled plasma emission analysis (ICP), and the respective contents were 0.1 ppm or less. It was not detected (0.1 ppm or less). Further, the solubility of the desired product DMAPAA-FSIQ in water was 7.5 g / 100 g of water at 25 ° C.

Synthesis Example 9
In Synthesis Example 5, instead of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q), 10 g of 75% aqueous solution of acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: DMAPAA-Q) was used. 5 to obtain 19.3 g of the desired product acryloylaminopropyltrimethylammonium bis (pentafluoroethanesulfonyl) imide (DMAPAA-PFSIQ) as a transparent liquid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 79 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.7%. The yield was 96.2%. In the elemental analysis, the actual measured values (C: 28.10%, H: 3.38%, N: 7.42%) are the theoretical values (C: 28.32%, H: 3.47%, N: 7.62). %). Lithium ions were quantified by dielectric coupled plasma emission analysis (ICP) and were not detected (0.1 ppm or less). The solubility of the target product DMAPAA-PFSIQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis Example 10
In Synthesis Example 9, 22.5 g of potassium bis (nonafluorobutanesulfonyl) imide was used instead of lithium bis (pentafluoroethanesulfonyl) imide, and the reaction was performed in the same manner as in Synthesis Example 10 to obtain the desired product acryloylaminopropyltrimethylammonium bis. 26.1 g of (nonafluorobutanesulfonyl) imide (DMAPAA-NFSIQ) was obtained as a white solid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 88 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 95.6%. In elemental analysis, measured values (C: 27.20%, H: 2.37%, N: 5.61%) are theoretical values (C: 27.17%, H: 2.55%, N: 5.59). %). Potassium ions were quantified by inductively coupled plasma optical emission spectrometry (ICP) and were not detected (0.1 ppm or less). Further, the solubility of the desired product DMAPAA-NFSIQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis Example 11
Under a nitrogen atmosphere, 100 g of N, N-dimethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd .: DMAEMA) and 132 g of water are added to a 1 L autoclave glass container, and the internal temperature is adjusted to 30 ° C. or lower, and chlorinated while stirring. Methyl was injected to perform a quaternization reaction. When the residual free amine (residual DMAEMA) in the reaction solution became 0.2% or less, excess methyl chloride in the reaction solution was distilled off under reduced pressure, and an aqueous solution containing 50% methacryloyloxyethyltrimethylammonium chloride (DMAEMA-Q). 262 g (yield 99.1%) was obtained.
Subsequently, 69.3 g of lithium bis (trifluoromethanesulfonyl) imide was dissolved in 70 g of ion-exchanged water in a 500 mL three-necked flask to prepare an aqueous solution of lithium bis (trifluoromethanesulfonyl) imide. To this aqueous solution, 100 g of DMAEMA-Q 50% aqueous solution was added, followed by 60 g of butyl acetate and stirred for 1 hour. Subsequently, an aqueous polymer solution in which 0.11 g of an acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 250,000) was dissolved in 10 g of water was added as an ion adsorbent, and further stirred for 1 hour. Thereafter, of the separated two layers, the organic phase was separated. 60 g of ion-exchanged water was added to the separated organic phase and washed. After performing this washing operation two more times, 0.2 g of hydroquinone monomethyl ether and 0.02 g of 2,2,6,6-tetramethylpiperidine-1 oxyl were added to the organic phase and concentrated under reduced pressure at 40 ° C. and 5 torr. . The gas chromatograph confirmed 1.7% of butyl acetate. Subsequently, bubbling with dry air (flow rate: 500 mL / min) at 40 ° C. for 4 hours under normal pressure to clear the target product, methacryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEMA-TFSIQ). 108.1 g was obtained as a liquid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 82 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.8%. The yield was 99.1%. In elemental analysis, measured values (C: 30.63%, H: 5.31%, N: 12.08%) are theoretical values (C: 29.20%, H: 4.01%, N: 6.19). %). Lithium ions were quantified by dielectric coupled plasma emission analysis (ICP) and were not detected (0.1 ppm or less). Further, the solubility of the target product DMAEMA-TFSIQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis Example 12
In a 1 L three-necked flask, 72.0 g of lithium bis (trifluoromethanesulfonyl) imide was dissolved in 270 g of ion-exchanged water to prepare an aqueous lithium bis (trifluoromethanesulfonyl) imide solution. To this aqueous solution, 90 g of a 75% aqueous solution of acryloyloxyethyldimethylbenzylammonium chloride (manufactured by Kojin: DMAEA-BQ) was added, and subsequently 130 g of butyl acetate was added and stirred for 1 hour. Subsequently, an aqueous polymer solution in which 0.13 g of an acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 250,000) was dissolved in 10 g of water was added as an ion adsorbent, and further stirred for 1 hour. Thereafter, of the separated two layers, the organic phase was separated. 180 g of ion-exchanged water was added to the separated organic phase and washed. After this washing operation was further performed twice, 0.1 g of thiodiphenylamine was added to the organic phase, followed by concentration under reduced pressure at 40 ° C. and 5 torr. The gas chromatograph confirmed 1.7% of butyl acetate. Subsequently, bubbling with dry air (flow rate: 500 mL / min) at 40 ° C. for 4 hours under normal pressure, the target product acryloyloxyethyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSIBQ) was added. 126.6 g was obtained as a clear liquid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 79 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 98.3%. In elemental analysis, measured values (C: 37.12%, H: 3.89%, N: 5.25%) are theoretical values (C: 37.35%, H: 3.92%, N: 5. 44%). Lithium ions were quantified by dielectric coupled plasma emission analysis (ICP) and were not detected (0.1 ppm or less). The solubility of the target product DMAEA-TFSIBQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis Example 13
In Synthesis Example 12, 130 g of methyl isobutyl ketone was used instead of butyl acetate, and the reaction was performed in the same manner as in Synthesis Example 12 to convert acryloyloxyethyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSIBQ) as a colorless transparent liquid. 125.8 g was obtained. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 83 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 97.6%. In elemental analysis, measured values (C: 37.31%, H: 3.99%, N: 5.28%) are theoretical values (C: 37.35%, H: 3.92%, N: 5. 44%). Potassium ions were quantified by inductively coupled plasma optical emission spectrometry (ICP) and were not detected (0.1 ppm or less).

Synthesis Example 14
In Synthesis Example 12, 55.0 g of potassium bis (fluorosulfonyl) imide was used instead of lithium bis (trifluoromethanesulfonyl) imide, and the reaction was performed in the same manner as in Synthesis Example 12 to obtain the target product acryloyloxyethyldimethylbenzylammonium bis (fluoro 101.2 g of sulfonyl) imide (DMAEA-FSIBQ) was obtained as a transparent liquid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 80 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.8%. The yield was 97.4%. In the elemental analysis, measured values (C: 40.31%, H: 4.92%, N: 6.65%) are theoretical values (C: 40.57%, H: 4.86%, N: 6.76). %). Potassium ions were quantified by inductively coupled plasma optical emission spectrometry (ICP) and were not detected (0.1 ppm or less). The solubility of the target product DMAEA-FSIBQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis Example 15
In Synthesis Example 12, instead of lithium bis (trifluoromethanesulfonyl) imide, 82.3 g of potassium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide was reacted in the same manner as in Synthesis Example 12, and the desired product 127.7 g of acryloyloxyethyldimethylbenzylammonium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide (DMAEA-CFSIBQ) was obtained as a transparent liquid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 70 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 97.5%. In elemental analysis, measured values (C: 38.28%, H: 3.73%, N: 5.34%) are theoretical values (C: 38.78%, H: 3.83%, N: 5.32). %). Potassium ions were quantified by inductively coupled plasma optical emission spectrometry (ICP) and were not detected (0.1 ppm or less). Further, the solubility of the target product DMAEA-CFSIBQ in water was 0.1 g / 100 g or less at 25 ° C.

Synthesis Example 16
To a 300 mL three-necked flask, 70 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: DMAPAA) and 42.2 g of ion-exchanged water were added, the internal temperature was adjusted to 30 ° C., and 56.7 g of benzyl chloride was added while stirring. The solution was added dropwise and subjected to a quaternization reaction at a reaction temperature of 30 ° C. to 35 ° C. for 5 hours to obtain 168.2 g of a 75% aqueous solution of acryloylaminopropyldimethylbenzylammonium chloride (DMAPAA-BQ) (yield 99.6%). .
Subsequently, 68.7 g of lithium bis (trifluoromethanesulfonyl) imide was dissolved in 120 g of ion-exchanged water in a 1 L three-necked flask to prepare a lithium bis (trifluoromethanesulfonyl) imide aqueous solution. To this aqueous solution, 90 g of a DMAPAA-BQ 75% aqueous solution was added, followed by 60 g of butyl acetate, and further 3 g of the acryloylmorpholine polymer aqueous solution produced in Polymer aqueous solution production example 1 was added as an ion adsorbent and stirred for 2 hours. Thereafter, of the separated two layers, the organic phase was separated. 60 g of ion-exchanged water was added to the separated organic phase and washed. After this washing operation was further performed twice, the organic phase was concentrated under reduced pressure at 40 ° C. and 5 torr. The gas chromatograph confirmed 1.7% of butyl acetate. Subsequently, bubbling with dry air (flow rate 500 mL / min) at 40 ° C. for 4 hours under normal pressure, and the target product acryloylaminopropyldimethylbenzylammonium bis (trifluoromethanesulfonyl) imide (DMAPAA-TFSIBQ) As a clear liquid, 123.3 g was obtained. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 69 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.9%. The yield was 97.8%. In elemental analysis, measured values (C: 38.91%, H: 4.27%, N: 7.89%) are theoretical values (C: 38.71%, H: 4.39%, N: 7. 97%). Lithium ions were quantified by dielectric coupled plasma emission analysis (ICP) and were not detected (0.1 ppm or less). Further, the solubility of the target product DMAPAA-TFSIBQ in water was 0.1 g / 100 g or less at 25 ° C.

Comparative Synthesis Example 1
In a 500 mL three-necked flask, 117.6 g of potassium bis (trifluoromethanesulfonyl) imide was dissolved in 73.5 g of ion-exchanged water to prepare a potassium bis (trifluoromethanesulfonyl) imide aqueous solution. To this aqueous solution, 90 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) was added and stirred for 2 hours. Thereafter, the organic phase (ionic vinyl monomer phase) was separated from the separated two layers. 100 g of ion-exchanged water was added to the separated organic phase and washed. This washing operation was further performed twice, and then concentrated under reduced pressure at 70 ° C. and 5 torr. After 1 hour, the viscosity of the concentrated liquid increased, and the spinnability by polymerization was confirmed. Furthermore, the water content was 6000 ppm by moisture measurement, and the potassium ion was quantified by dielectric bond type plasma emission analysis (ICP) to be 18000 ppm).

Comparative Synthesis Example 2
In a 1 L three-necked flask, 105.7 g of lithium bis (trifluoromethanesulfonyl) imide was dissolved in 450 g of ion-exchanged water to prepare a lithium bis (trifluoromethanesulfonyl) imide aqueous solution. To this aqueous solution, 90 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) was added and stirred for 2 hours. Thereafter, the organic phase (ionic vinyl monomer phase) was separated from the separated two layers. 100 g of ion-exchanged water was added to the separated organic phase and washed. After performing this washing operation twice more, 0.3 g of hydroquinone monomethyl ether was added to the organic phase, and the mixture was concentrated under reduced pressure at 40 ° C. and 5 torr. The target product acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide 108.5g of (DMAEA-TFSIQ) was obtained as a transparent liquid. From the moisture measurement, the moisture content was 3300 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 98.8%. The yield was 67.1%. Lithium ions were quantified by dielectric coupled plasma emission analysis (ICP), and the lithium ions were 1050 ppm.

Comparative Synthesis Example 3
In Synthesis Example 1, an aqueous solution of an acrylic acid polymer as a metal ion adsorbent was not added to the aqueous phase, but reacted in the same manner as in Synthesis Example 1 to obtain 158.6 g of the ionic vinyl monomer DMAEA-TFSIQ as a transparent liquid. By gas chromatograph, butyl acetate was not detected (100 ppm or less). From the moisture measurement, the moisture content was 72 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 99.8%. The yield was 98.4%. Furthermore, lithium ion was quantified by dielectric coupling type plasma emission analysis (ICP), and was 1100 ppm).

Comparative Synthesis Example 4
In a 1 L three-necked flask, 142.7 g of lithium bis (trifluoromethanesulfonyl) imide was dissolved in 360 g of ion-exchanged water to prepare an aqueous solution of lithium bis (trifluoromethanesulfonyl) imide. To this aqueous solution, 90 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) was added, and then 140 g of dichloromethane was added and stirred for 2 hours. Thereafter, 220 g of dichloromethane was added, and the dichloromethane phase and the aqueous phase were separated. 180 g of ion-exchanged water was added to the separated organic phase (ionic vinyl monomer phase) and washed. After this washing operation was further performed twice, the obtained organic phase was concentrated under reduced pressure at 60 torr and 35 ° C., and the target product acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSIQ) was obtained. 127.3 was obtained as a clear liquid. According to the gas chromatograph, dichloromethane was 2.8%. From the moisture measurement, the moisture content was 1900 ppm. When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 96.1%. The yield was 76.0%. Lithium ion was 140 ppm by inductively coupled plasma optical emission spectrometry (ICP).

Comparative Synthesis Example 5
Under a nitrogen atmosphere, 200 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) and 270 g of methanol are added to a 1 L autoclave glass container, the internal temperature is adjusted to 30 ° C. or less, and methyl chloride is injected while stirring. A quaternization reaction was carried out.
When the residual free amine (residual DMAEA) in the reaction solution became 0.3% or less, excess methyl chloride in the reaction solution was distilled off under reduced pressure, and methanol containing acryloyloxyethyltrimethylammonium chloride (DMAEA-Q) 50%. 532 g (yield 98.3%) of liquid was obtained.
Subsequently, 117.4 g of potassium bis (trifluoromethanesulfonyl) imide and 350 g of methanol were added to a 500 mL three-necked flask, and while stirring the solution, 142 g of the DMAEA-Q 50% -containing methanol solution synthesized above was added at 25 ° C. Was added dropwise over 1 hour, and a white crystalline solid was precipitated at the same time. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours. The crystals were filtered and washed with methanol, 0.03 g of 2,2,6,6-tetramethylpiperidine-1oxyl was added, and the mixture was added at 40 ° C., 5 torr. And concentrated under reduced pressure. The gas chromatograph confirmed methanol 4.3%. Subsequently, bubbling with dry air (flow rate: 500 mL / min) was performed at 40 ° C. for 4 hours to obtain 163.2 g of acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide (DMAEA-TFSIQ) as a target product. It was. The resulting liquid was suspended. By gas chromatography, methanol was not detected (100 ppm or less). From the moisture measurement, the moisture content was 90 ppm. When the quaternary ammonium salt concentration (purity of the target product) was determined by potentiometric titration, it was 84.2%. The yield was 85.5%. According to dielectric coupling type plasma emission analysis (ICP), potassium ion was 14000 ppm.

As can be seen from the results of Synthesis Examples 1 to 16, according to the synthesis method of the present invention, troubles such as polymerization do not occur, and the target metal ion-free and high purity organic solvent and water are completely removed. An ionic vinyl monomer can be obtained in high yield.

On the other hand, from the results of Comparative Synthesis Examples 1 to 5, after the anion exchange reaction in an aqueous solvent, the ionic vinyl monomer phase separated in two layers was separated and concentrated under reduced pressure. Since the ionic vinyl monomer has an unsaturated group, there is a problem of polymerization trouble. In addition, since the ionic vinyl monomer of the present invention is usually a high-viscosity liquid or solid, when it is taken out from the aqueous solvent, the yield is significantly reduced due to a recovery loss.

Furthermore, when an anion exchange reaction is carried out in a water-soluble organic solvent, both the target ionic vinyl monomer and the metal salt produced as a by-product are dissolved in the water-soluble organic solvent. In the case where a water-soluble polymer is not used as the metal ion adsorbent in the aqueous phase, the residual amount of metal ions is as high as several tens to several thousand ppm, which is a problem.

Examples and comparative examples in which an antistatic agent using the ionic vinyl monomer obtained by the production method of the present invention as a composition are shown below.

Example A-1
Preparation of Antistatic Hard Coating Agent After dissolving 23 parts by weight of acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide synthesized in Synthesis Example 1 in 120 parts by weight of methyl ethyl ketone, pentaerythritol triacrylate (Kyoeisha Chemical Co., Ltd.) Manufactured by: Light acrylate PE-3A) 35 parts by weight, as a photoinitiator, 3 parts by weight of Ciba Specialty Chemicals, trade name Darocur 1173 are added and mixed uniformly to obtain an antistatic hard coat agent which can be cured by ultraviolet rays. It was. Thereafter, the obtained hard coat agent was applied to a PET film having a thickness of 100 μm and subjected to ultraviolet curing to produce an antistatic hard coat.

Examples A-2 to 12, Comparative Examples A-13 to 21
An antistatic hard coat was prepared and evaluated in the same manner as in Example A-1, except that the compositions shown in Tables 1 and 2 were used.

Example B-1
<Synthesis of homopolymer solution of ionic vinyl monomer>
In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, 20 parts by weight of acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide synthesized in Synthesis Example 1 and 0.2 weight of azoisobutyronitrile (AIBN) Parts were mixed and dissolved in 120 parts by weight of methanol (MeOH), and polymerized at 60 ° C. for 8 hours under a nitrogen stream to obtain a homopolymer solution (a) of an ionic vinyl monomer.
<Preparation of antistatic hard coat containing homopolymer of ionic vinyl monomer>
10 parts by weight of a homopolymer solution of an ionic vinyl monomer (a), 50 parts by weight of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-3A) and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE) -6A) 50 parts by weight, and 3 parts by weight of Darocur 1173 manufactured by Ciba Specialty Chemicals as a photoinitiator were mixed and dissolved in 120 parts by weight of a mixed solvent of IPA and methyl ethyl ketone (MEK) in a 1: 1 weight ratio. Thus, an antistatic hard coat agent containing a quaternary salt polymer which can be cured by ultraviolet rays was obtained. Thereafter, the obtained hard coat agent was applied to a PET film having a thickness of 100 μm and subjected to ultraviolet curing to produce an antistatic hard coat.

Example B-2
<Synthesis of copolymer solution of ionic vinyl monomer>
In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, 10 parts by weight of acryloyloxyethyltrimethylammonium bis (trifluoromethanesulfonyl) imide synthesized in Synthesis Example 1 and 10 parts by weight of 2-ethylhexyl acrylate (2-EHA) And 0.2 part by weight of AIBN were mixed and dissolved in 120 parts by weight of IPA and polymerized at 70 ° C. for 8 hours under a nitrogen stream to obtain a copolymer solution of an ionic vinyl monomer.
Table 3 shows the mixing ratio of the monomers in the synthesis of the copolymer solution.

Examples B-2 to 6, Comparative Examples B-7 to 8
An antistatic hard coat was prepared and evaluated in the same manner as in Example B-1, except that the composition shown in Table 4 was changed.

From the results of evaluation of UV curability and antistatic property of the coating film of Examples and Comparative Examples, since the conventional quaternary cationic vinyl monomer has chlorine ions as anions, the coating film obtained therefrom is sticky and has poor transparency. It was also found that a uniform coating film could not be obtained due to these causes, the scratch resistance and hardness were lowered, and the antistatic effect was low. Furthermore, when the water content in the ionic vinyl monomer is high, the compatibility with the antistatic composition deteriorates, and a uniform coating film cannot be obtained. Therefore, the obtained antistatic film has poor moisture resistance and causes problems such as whitening of the surface of the coating film.
The ionic vinyl monomer of the present invention is free of metal ions, does not contain an organic solvent and water, has high compatibility with organic solvents and various vinyl monomers, is particularly non-water-soluble, and is a non-polar component in the antistatic composition Therefore, it is possible to obtain a uniform and transparent anti-static coating film which is not colored. The production method of the present invention is simple, and the desired ionic vinyl monomer can be obtained with high purity and high yield. Furthermore, the resulting high-quality ionic vinyl monomer requires less energy for UV curing, has good transparency, is not colored, has high scratch resistance, high hardness, and high hydrolysis resistance, and has excellent charging properties. Preventive effect is obtained.

As described above, the ionic vinyl monomer of the present invention can be produced with high purity and high yield at a sufficient rate even at ordinary temperature and normal pressure. In addition, it is free of metal ions and does not contain organic solvents and water, so it has low environmental impact, is applicable to electronic materials, and has good compatibility with antistatic compositions such as other polyfunctional monomers and organic solvents. It is. An antistatic film formed using an antistatic composition comprising these ionic vinyl monomers has antistatic properties, transparency, scratch resistance, high hardness, difficulty in coloration, and further resistance to moisture and hydrolysis. Excellent. The antistatic layer comprising the ionic vinyl monomer of the present invention is used by adding in advance to a resin such as an ultraviolet curable resin composition, a hard coat resin composition, an ink receiving layer composition, an adhesive composition, etc. Can be suitably used.

Claims (14)

General formula (1)

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other, and R ₄ has 1 carbon atom) Represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, and X ⁻ represents a linear sulfone. Imido anion [(Rf ¹ SO ₂ ) (Rf ² SO ₂ ) N] ⁻ (where Rf ¹ and Rf ² may be the same or different, and are a C 1-4 perfluoroalkyl group or carbon number Represents a fluoro group of 0), or represents a cyclic imide anion [CF ₂ (CF ₂ SO ₂ ) ₂ N] ⁻ .)
An ionic vinyl monomer that is free of metal ions (the metal ion content is 0.1 ppm or less), the organic solvent and water content is less than 100 ppm, and the purity is 99% or more. The ionic vinyl monomer has the general formula (2)

(Wherein M ⁺ represents a cation and X ⁻ represents a linear sulfonimide anion [(Rf ¹ SO ₂ ) (Rf ² SO ₂ ) N] ⁻ (where Rf ¹ and Rf ² are the same) And may be different, and represents a perfluoroalkyl group having 1 to 4 carbon atoms or a fluoro group having 0 carbon atoms), or a cyclic imide anion [CF ₂ (CF ₂ SO ₂ ) ₂ N] ⁻ .) A bis (perfluoroalkanesulfonyl) imide salt represented by the general formula (3)

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represents an alkyl group having 1 to 3 carbon atoms, and may be the same as or different from each other, and R ₄ represents 1 carbon atom) An alkyl group having ˜3, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or NH, Z represents an alkylene group having 1 to 3 carbon atoms, and Q ⁻ represents an anion.) The ionic vinyl monomer according to 1) above, which is synthesized by an ion exchange reaction performed in a two-phase system in which a water-insoluble organic solvent and water coexist Production method. The method according to claim 2, wherein the water-insoluble organic solvent is one or more selected from non-chlorine organic solvents having a solubility parameter of 7 to 11 (cal / cm ³ ) ^0.5 . The method according to claim 2 or 3, wherein the water-insoluble organic solvent is an acetate ester or a ketone. 5. The method for producing an ionic vinyl monomer according to claim 2, wherein an ion adsorbent is further added to the aqueous phase during the ion exchange reaction. 5. The method for producing an ionic vinyl monomer according to claim 2, wherein the ion adsorbent is one or more selected from water-soluble metal ion adsorbents. 7. The method for producing an ionic vinyl monomer according to claim 2, wherein the water-soluble ion adsorbent is a water-soluble polymer. A metal ion-free (metal ion content of 0.1 ppm or less) ionic homooligomer or homopolymer obtained by radical polymerization of an ionic vinyl monomer produced by the method according to claim 2. Metal ion-free (metal ion content is 0.1 ppm or less) ionicity obtained by copolymerization of the ionic vinyl monomer produced by the method of claims 2 to 7 and other copolymerizable vinyl monomers Co-oligomer or copolymer. A metal ion-free (metal ion content of 0.1 ppm or less) antistatic agent comprising the ionic vinyl monomer produced by the method of claims 2 to 7 and / or the oligomer or polymer of claim 8 or 9. The antistatic agent according to claim 10 or an antistatic resin composition containing the antistatic agent, wherein the ionic vinyl monomer produced by the method according to claim 1 or 2 to 7 is used as a constituent unit. Containing 0.1 to 90% by weight. An antistatic resin composition comprising the antistatic agent according to claim 10 or the antistatic agent according to 11, further comprising a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide. object. An antistatic film formed by coating an antistatic agent or an antistatic composition according to any one of claims 10 to 12 on a base material, and then curing the material by active energy rays or heat. An antistatic film or sheet comprising the antistatic film according to claim 13 on at least one side.