JP2011140455A - Method for producing ionic vinyl monomer and antistatic agent and antistatic composition comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an efficient and economical highly pure ionic vinyl monomer. <P>SOLUTION: The method for synthesizing the ionic vinyl monomer represented by formula (1) (wherein, R<SB>1</SB>is H or methyl; R<SB>2</SB>and R<SB>3</SB>are each independently identically or differently 1 to 3C alkyl; R<SB>4</SB>is 1 to 3C alkyl, 1 to 3C alkenyl or benzyl; Y is O or -NH-; Z is 1 to 3C alkylene) is characterized by subjecting a quaternary cationic vinyl monomer and a thiocyanate to an ion exchange reaction in an organic solvent having a solubility parameter of 8 to 16 (cal/cm<SP>3</SP>)<SP>0.5</SP>, precipitating and separating byproducts, and then subjecting the material to a thin film evaporation treatment to recover the organic solvent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for producing an ionic vinyl monomer that is liquid at room temperature, an antistatic agent comprising the monomer, and an antistatic resin composition containing the antistatic agent.

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).

It is common to use acrylate-based and acrylamide-based cationic quaternary ammonium salts as base monomers for polymer antistatic compositions. However, many polymerizable ammonium salts are solid at room temperature, have high polarity, high hygroscopicity, and are normally distributed in the form of an aqueous solution for manufacturing reasons. For example, methyl chloride as a quaternizing agent is added to unsaturated tertiary amine N, N-dimethylaminopropylacrylamide, and quaternization reaction is performed in the presence of a mixed solvent composed of water and an aprotic organic solvent. The method is often used (Patent Document 4). Of course, since the cationic quaternary ammonium salt monomer obtained by this method is usually an aqueous solution type, the drying property at the time of coating is poor, and it is also possible to use general-purpose resins, polyfunctional acrylic monomers, oligomers, organic solvents, etc. There is a problem in that the compatibility is poor, it cannot be uniformly dispersed, and effective antistatic properties cannot be exhibited. Even if the quaternary ammonium salt monomer is purified to a high purity and dissolved in a polar organic solvent, these monomers themselves have high hydrophilicity and are solid at room temperature. In some cases, the solubility in other components in the resin is low, and it is condensed in the resin or deposited from the resin, so that 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 of copolymerizing and using an acrylate quaternary ammonium monomer and another polymerizable vinyl monomer has been reported (Patent Documents 5 and 6). But with these methods,
Since the content of the cationic vinyl monomer in the antistatic composition decreases, 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 However, there is a problem that the price of the resin composition increases.

For the purpose of improving the compatibility of the quaternary ammonium salt monomer itself, for example, Patent Document 7,
Nos. 8 and 9 propose polymerizable compounds having weakly coordinating anions. However, these proposed anions such as bis (trifluoromethanesulfonyl) imide are organic fluorine compounds containing 4 to 6 fluorine atoms per molecule and are extremely difficult to decompose in the natural environment. As a substance, reduction of the amount used and complete abolition are required as environmental measures.

On the other hand, ammonium salts using thiocyanate ions as anions have been proposed in order to provide transparency and solubility in resins and solvents (Patent Documents 10, 11, and 12). However, all of these proposed ammonium thiocyanates are synthesized by a known metal salt reaction method using ammonium chloride salt or bromide salt as a raw material. That is, it is a method in which an anion exchange reaction between a quaternary ammonium chloride or bromide salt and a thiocyanic acid metal salt is carried out in an aqueous solution, and the target product is extracted and separated with an organic solvent such as ethyl acetate. As known, it is essential that the target product is hardly soluble in water and soluble or easily soluble in an organic solvent as a precondition that can be extracted from an aqueous solution into an organic solvent, but reported in Patent Documents 11 and 12. Some acrylate-based or acrylamide-based ammonium cations are water-soluble, and acrylate-based or acrylamide-based ammonium thiocyanate quaternary salts composed of their water-soluble thiocyanate anions, that is, the ionic vinyl monomer of the present invention, Of course, it is water-soluble. Moreover, the ionic vinyl monomer can be mixed with water in any proportion, and the solubility in ethyl acetate is less than 5%. Therefore, it has been clearly difficult to efficiently produce and separate the ionic vinyl monomer of the present invention by a known extraction separation method.

JP 2008-231240 A JP 2008-13636 A JP 2008-231196 A Japanese Patent Laid-Open No. 63-201115 JP 2007-332181 A JP 2000-129245 A JP 2007-9042 A JP 2005-255843 A JP 2006-45425 A JP 2009-13295 A JP 2009-197074 A JP 2009-179671 A

As described above, a method for industrially producing an ionic vinyl monomer, which is a colorless transparent liquid at room temperature, composed of an ammonium cation and a thiocyanate anion, has not been known so far. . In addition, it has good compatibility with general-purpose acrylic monomers, has excellent hydrolysis resistance, can be applied to UV curing, and can maintain an antistatic effect for a long time after curing.
An inexpensive ionic vinyl monomer that is liquid at room temperature, an antistatic agent comprising the monomer, and an antistatic composition for an antistatic agent have not yet been easily obtained.

A first object of the present invention is to provide an efficient and economical method for producing a high purity quaternary ammonium salt ionic vinyl monomer that is liquid at room temperature. The second object of the present invention is that it can be uniformly dispersed in a general-purpose acrylic monomer or other antistatic agent composition comprising the quaternary ammonium salt ionic vinyl monomer as a constituent, has an excellent antistatic effect and can be sustained for a long time. It is to provide an antistatic agent having excellent hydrolysis resistance and an antistatic composition containing the antistatic agent.

As a result of intensive studies to solve these problems, the present inventor has found that the anion of a quaternary cationic vinyl monomer and thiocyanate in an organic solvent having a solubility parameter of 8 to 16 (cal / cm ³ ) ^0.5. After performing the exchange reaction, the by-product salt precipitated from the organic solvent is separated, and the organic solvent is recovered by a thin film evaporator to obtain the ionic vinyl monomer represented by the following general formula (1) with high purity and high yield. The present inventors have found a method that can be obtained at a high rate, and further 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す。）有機溶媒中で、一般式（２）で表され
る４級カチオン性ビニルモノマー

（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^-はアニオンを表す。）と一般式（
３）、

（式中、Ｍ^ｎ＋はカチオンを表す。）で表されるチオシアン酸塩とのイオン交換反応により合成されることを特徴とする製造方法、
２）溶解度パラメーターが８〜１６(cal/cm³)^0.5である有機溶媒からなる群から選択された１種または２種以上の有機溶媒中で前記１）記載のイオン性ビニルモノマーの製造方法、
３）４級カチオン性ビニルモノマーとチオシアン酸塩を有機溶媒に溶解、イオン交換反応を行い、副生成物であるＭ^ｎ＋（Ｘ^-）_ｎ塩が有機溶媒から析出、分離することを特徴とする前記１）と２）記載のイオン性ビニルモノマー製造方法、
４）副生成物分離後、有機溶媒を薄膜蒸発処理で回収することを特徴とする前記１乃至請求３）記載のイオン性ビニルモノマー製造方法、
５）前記１）乃至４）記載の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イオン性ホモオリゴマーとホモポリマー、
６）前記１）乃至４）記載のイオン性ビニルモノマーと他の共重合可能なビニル系単量体
との共重合で得られるイオン性コオリゴマーとコポリマー、
７）前記１）乃至６）記載のイオン性ビニルモノマー及び／又はオリゴマー若しくはポリ
マーからなる帯電防止剤、
８）前記７）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組成物であって、請
求項１記載の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
、９）前記７）記載の帯電防止剤を含有する帯電防止組成物であって、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、
１０）基材上に前記７〜９）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布
した後、活性エネルギー線又は熱により重合して形成されることを特徴とする帯電防止層
、
１１）少なくとも片面に前記７）記載の帯電防止層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, in the present invention, 1) an ionic vinyl monomer which is a compound represented by the 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 3 to 3 carbon atoms, 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.) A quaternary cationic vinyl monomer represented by the general formula (2)

(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 of ˜3, an alkenyl group of 1 to 3 carbon atoms or a benzyl group, Y is an oxygen atom or —NH—
Z represents an alkylene group having 1 to 3 carbon atoms, and X ⁻ represents an anion. ) And general formula (
3),

(Wherein, M ^{n +} represents a cation), which is synthesized by an ion exchange reaction with thiocyanate,
2) A method for producing an ionic vinyl monomer as described in 1) above, in one or more organic solvents selected from the group consisting of organic solvents having a solubility parameter of 8 to 16 (cal / cm ³ ) ^0.5 ,
3) A quaternary cationic vinyl monomer and thiocyanate are dissolved in an organic solvent and subjected to an ion exchange reaction, and a by-product M ^{n +} (X ⁻ ) _n salt is precipitated and separated from the organic solvent. The ionic vinyl monomer production method according to 1) and 2) above,
4) The method for producing an ionic vinyl monomer according to 1 to 3) above, wherein the organic solvent is recovered by thin film evaporation after separation of the by-product,
5) Ionic homooligomers and homopolymers obtained by radical polymerization of the ionic vinyl monomers described in 1) to 4) above,
6) An ionic co-oligomer and copolymer obtained by copolymerization of the ionic vinyl monomer described in 1) to 4) above with another copolymerizable vinyl monomer,
7) An antistatic agent comprising the ionic vinyl monomer and / or oligomer or polymer according to 1) to 6) above,
8) The antistatic agent according to 7) or an antistatic composition containing the antistatic agent, wherein the ionic vinyl monomer according to claim 1 is contained as a constituent unit in an amount of 0.1 to 90% by weight, 9) An antistatic composition containing the antistatic agent described in 7) above, further comprising a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide,
10) Antistatic, characterized by being formed by applying an antistatic agent or an antistatic composition according to any one of 7 to 9) on a substrate and then polymerizing with active energy rays or heat. layer,
11) Provided is an antistatic film or sheet having the antistatic layer described in 7) on at least one surface.

According to the method of the present invention, a high-purity ionic vinyl monomer that is a colorless transparent liquid at room temperature can be easily produced in a high yield. In addition, the antistatic agent and the antistatic agent composition comprising the ionic vinyl monomer as a constituent have hydrolysis resistance, are transparent and not colored, and are soluble and compatible with general-purpose acrylic monomers and organic solvents. Therefore, it can be uniformly dispersed in other antistatic agent compositions, has an excellent antistatic effect and can last for a long time. An antistatic agent, an antistatic 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 formula of 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, and R ₄ has 1 to 3 carbon atoms
An alkyl group, 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.

As the ionic vinyl monomer of the present invention, specifically, acryloylaminomethyltrimethylammonium thiocyanate, acryloylaminomethyltriethylammonium thiocyanate, acryloylaminomethyltripropylammonium thiocyanate, acryloylaminoethyltrimethylammonium thiocyanate Acryloylaminopropyltrimethylammonium thiocyanate, acryloylaminopropylmethyldiethylammonium thiocyanate, acryloylaminopropylethyldimethylammonium thiocyanate, acryloylaminopropylmethyldipropylammonium thiocyanate, acryloylaminopropyltriethylammonium thiocyanate, Acryloylaminopropyltrip Pyrammonium thiocyanate, acryloylaminoethyldimethylbenzylammonium thiocyanate, acryloylaminopropyldimethylbenzylammonium thiocyanate, acryloylaminopropyldiethylbenzylammonium thiocyanate, acryloylaminopropylmethyldibenzylammonium thiocyanate, acryloylaminopropyl Ethyl dibenzylammonium thiocyanate, methacryloylaminomethyltrimethylammonium thiocyanate, methacryloylaminomethyltriethylammonium thiocyanate, methacryloylaminomethyltripropylammonium thiocyanate, methacryloylaminoethyltrimethylammonium thiocyanate, methacryloylaminopropionate Trimethylammonium thiocyanate, methacryloylaminopropylmethyldiethylammonium thiocyanate, methacryloylaminopropylethyldimethylammonium thiocyanate, methacryloylaminopropylmethyldipropylammonium thiocyanate, methacryloylaminopropyltriethylammonium thiocyanate, methacryloylaminopropyltri Propylammonium thiocyanate, methacryloylaminoethyldimethylbenzylammonium thiocyanate, methacryloylaminopropyldimethylbenzylammonium thiocyanate, methacryloylaminopropyldiethylbenzylammonium thiocyanate, methacryloylaminopropylmethyldibenzylammonium thiocyanate And (meth) acrylamide ammonium alkyl thiocyanate quaternary cationic monomers such as methacryloylaminopropylethyldibenzylammonium thiocyanate, or acryloyloxymethyltrimethylammonium thiocyanate, acryloyloxymethyltriethylammonium thiocyanate Narate, acryloyloxymethyltripropylammonium thiocyanate, acryloyloxyethyltrimethylammonium thiocyanate, acryloyloxypropyltrimethylammonium thiocyanate, acryloyloxypropylmethyldiethylammonium thiocyanate, acryloyloxypropylethyldimethylammonium thiocyanate, Acryloyloxypropylmethyldi Ropylammonium thiocyanate, acryloyloxypropyltriethylammonium thiocyanate, acryloyloxypropyltripropylammonium thiocyanate, acryloyloxyethyldimethylbenzylammonium thiocyanate, acryloyloxypropyldimethylbenzylammonium thiocyanate, acryloyloxypropyldiethyl Benzylammonium thiocyanate,
Acryloyloxypropylmethyldibenzylammonium thiocyanate, acryloyloxypropylethyldibenzylammonium thiocyanate, methacryloyloxymethyltrimethylammonium thiocyanate, methacryloyloxymethyltriethylammonium thiocyanate, methacryloyloxymethyltripropylammonium thiocyanate, Methacryloyloxyethyltrimethylammonium thiocyanate, methacryloyloxypropyltrimethylammonium thiocyanate, methacryloyloxypropylmethyldiethylammonium thiocyanate, methacryloyloxypropylethyldimethylammonium thiocyanate, methacryloyloxypropylmethyldipropylammonium thiocyanate Inert, methacryloyloxypropyl triethylammonium thiocyanate, methacryloyloxypropyl tripropylammonium thiocyanate, methacryloyloxyethyl dimethylbenzyl ammonium thiocyanate,
(Meth) acrylate ammonium alkylthio such as methacryloyloxypropyldimethylbenzylammonium thiocyanate, methacryloyloxypropyldiethylbenzylammonium thiocyanate, methacryloyloxypropylmethyldibenzylammonium thiocyanate, methacryloyloxypropylethyldibenzylammonium thiocyanate And cyanate quaternary cationic monomers. Among them, acryloylaminopropyltrimethylammonium thiocyanate, methacryloylaminopropyltrimethylammonium thiocyanate, acryloyloxyethyltrimethylammonium thiocyanate, methacryloyloxyethyltrimethylammonium ammonium are particularly easy to obtain inexpensive industrial raw materials. Thiocyanate is preferred.

The quaternary cationic vinyl monomer represented by the general formula (2) which is the starting material of the present invention is a quaternary cationic (meth) acrylamide monomer and a quaternary cationic (meth) acrylate monomer.

In the general formula (2), 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 has 1 to 3 carbon atoms
An alkyl group, 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, X ⁻ represents Cl ⁻ , Br ^−. , I ^{− and the} like halogen ions 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
^{-, (CF 3 SO 2)}} 2 N - represents the, inorganic acid anion or an organic acid anion.

（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、）で表されるＮ，Ｎ−ジアルキルアミノ
アルキル（メタ）アクリルアミド又は／及び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またはジアルキル硫酸、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または有機溶媒中で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級塩又は／及び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級塩又は／及び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)

(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 3 to 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 N represented by , N-dialkylaminoalkyl (meth) acrylamide or / and N, N-dialkylaminoalkyl (meth)
Alkyl halide or dialkyl sulfuric acid as quaternizing agent, dialkyl carbonate or alkyltoluene sulfonate, benzene sulfonate, p-toluene sulfonate is quaternized in water or organic solvent to acrylate, and dialkylamino Alkyl (meth) acrylamide quaternary salts and / or N, N-dialkylaminoalkyl (meth) acrylate quaternary salts 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, N, N-dimethylaminopropyl (meth) acrylamide, N, N
-Diethylaminopropyl (meth) acrylamide, N, N-methylethylaminoethyl (meth) acrylamide, N, N-methylpropylaminoethyl (meth) acrylamide, N, N-methylethylaminopropyl (meth) acrylamide, N, N -Methylpropylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth)
Examples include acrylamide.

Examples of the N, N-dialkylaminoalkyl (meth) acrylate include N, N
-Dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth)
Acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-methylethylaminoethyl (meth) acrylate, N, N-methylpropylaminoethyl (meth) acrylate N, N-methylethylaminopropyl (meth) 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 used as a raw material, a methyl chloride salt aqueous solution of N, N-dimethylaminopropylacrylamide (manufactured by Kojin Co., Ltd., “DMA
PAA-Q ") and a methyl chloride salt aqueous solution of N, N-dimethylaminoethyl acrylate (" DMAEA-Q "manufactured by Kojin Co., Ltd.) are particularly preferred from the viewpoint of availability as an inexpensive industrial raw material.

Another starting material of the present invention is thiocyanic acid or thiocyanate represented by the general formula (3). Specific examples of thiocyanate include monovalent and polyvalent thiocyanate such as sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, ammonium thiocyanate, zinc thiocyanate, calcium thiocyanate, barium thiocyanate, and aluminum thiocyanate. Salt.

As the organic solvent for the reaction, the solubility parameter (SP value) ranges from 8 to 16 (cal / cm ³ ) ^0.5.
More preferably, it is 9-15. In the range of 8 to 16, the quaternary cationic vinyl monomer and thiocyanic acid or thiocyanate as raw materials of the present invention are soluble, the product ionic vinyl monomer is soluble, and the by-product is insoluble. Slightly soluble (3 per 100 g solvent)
g), an anion exchange reaction is promoted by precipitation of by-products, and an ionic vinyl monomer can be obtained in a high yield. The solubility parameter of the present invention is H. Burrell's Polymer Handbook, 2nd edition (edited by J. Brandrup and EHImmergut) Wiley Intersc.
This is the value indicated by pages IV-337 to IV-359 of ience, New York, (1975).

Examples of such an organic solvent include methanol, ethanol, 1-propanol, 2
-Propanol, 1-butanol, 2-butanol, tert-butanol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, toluene, xylene, ethylene glycol, propylene glycol, glycerin, ethylene Examples include glycol monomethyl ether and propylene glycol monomethyl ether. Among these, methanol, isopropanol, and propylene glycol monomethyl ether 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 amount of the organic solvent is not particularly limited, but the concentration of the target ionic vinyl monomer is 1
A range of ˜90% is preferable. A range of 5 to 70 is particularly preferable. If it is less than 1%, it is difficult to precipitate the by-product efficiently. If it exceeds 90%, the viscosity of the reaction solution after the reaction becomes high, and separation and removal of the precipitated by-product becomes difficult.

The reaction temperature when synthesizing the ionic vinyl monomer of the present invention is usually 10 ° C. or higher, 15 to 15 ° C.
60 degreeC is preferable and 20-40 degreeC is especially preferable. 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 method for separating and removing the by-product precipitated from the organic solvent is not particularly limited, and may be performed by a known solid-liquid separation method such as precipitation separation, filtration separation, or centrifugal separation. Moreover, in order to remove a by-product economically and efficiently, filtration by a filter and centrifugation by a centrifuge are preferable.

After removing the by-products, the ionic vinyl monomer of the present invention can be obtained with high purity and high yield by recovering the organic solvent using a thin film evaporator. Since the ionic vinyl monomer of the present invention has a high viscosity and no vapor pressure, there is a problem that about 10% of an organic solvent remains in ordinary distillation, and a high-purity product cannot be obtained. Therefore, the present inventors paid attention to the characteristics of the thin film evaporator having a large heat transfer area and heat transfer coefficient, and proposed that the ionic vinyl monomer of the present invention, which is a liquid at room temperature, is processed by the thin film evaporator. As a result, a high-purity product having a purity of 99% or more was obtained. That is, it is a method in which a mixture of an organic solvent and an ionic vinyl monomer is charged into a thin film evaporator, and the organic solvent is evaporated and recovered while forming and flowing a thin film under reduced pressure.

Although the reduced-pressure vacuum degree of thin film evaporation processing changes with the kind of organic solvents to collect | recover, what is necessary is just to perform by the vacuum degree which can liquefy an organic solvent with a cooling trap. The temperature of the thin film evaporation treatment is preferably 20 to 100 ° C, particularly preferably 40 to 60 ° C. If the treatment temperature is less than 20 ° C., the viscosity of the ionic vinyl monomer is high and the organic solvent may not be completely removed, and if it is 100 ° C. or more, the ionic vinyl monomer may be polymerized. is there.

By the above method, 99% or more of high purity ionic vinyl monomer 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.

The ionic vinyl monomer of the present invention is liquid at room temperature and can be used as an antistatic agent while maintaining high purity. Further, it can be dissolved in water or an organic solvent and used in a solution state. When diluted with an organic solvent, the solubility parameter (SP value) is ^preferably in the range of 8 to 16 (cal / cm ³ ) ^0.5 as with the reaction solvent.

The ionic vinyl monomer of the present invention and / or the oligomer or / and 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) acrylate or polyfunctional (meth) acrylamide having two or more ethylene groups is added within a range that does not impair the original antistatic properties and hydrolysis resistance of the present invention, and ions are added. A uniform crosslinkable film can be formed on the surface of the substrate using the excellent compatibility between the functional vinyl monomer and polyfunctional (meth) acrylate or polyfunctional (meth) acrylamide. The performance of the coating film such as the property can be improved.

As such polyfunctional (meth) acrylate, pentaerythritol tetra (meth)
Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate,
Dipentaerythritol 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, epoxy (meth) acrylate, urethane (meth) acrylate And other monomers and oligomers.

As a commercial item of such a polyfunctional (meth) acrylate, for example, Aronix M-4
00, M-450, M-305, M-309, M-310, M-315, M-320, T
O-1200, TO-1231, TO-595, TO-756 (above, manufactured by Toagosei), K
AYARD D-310, D-330, DPHA, DPHA-2C (above, Nippon Kayaku)
Nicalac MX-302 (manufactured by Sanwa Chemical Co., Ltd.) and the like.

Polyfunctional (meth) acrylamides include monomers such as methylene bisacrylamide, methylene bismethacrylamide, ethylene bisacrylamide, ethylene bismethacrylamide, and diallyl acrylamide, and urethane acrylamide (Japanese Patent Laid-Open No. 2002-3).
7849).

These polyfunctional (meth) acrylates and polyfunctional (meth) acrylamides are one kind,
A plurality of polyfunctional monomers and oligomers may be used in combination. Moreover, when using such a polyfunctional monomer and an oligomer, it is preferable to make it contain 0.001-25000weight% with respect to the ionic vinyl monomer structural unit of this invention, Moreover, 50-20000
It is particularly preferable to contain the composition by weight. 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,
Examples thereof include radical polymerization compounds having a reactive double bond in the molecular chain, such as an epoxy group-containing monomer, a polyfunctional monomer, a vinyl ester, and an 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).
An acrylate etc. are mentioned.

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. Examples of the polymerization method include emulsion polymerization, solution polymerization, suspension polymerization,
A method such as bulk polymerization 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.
-90 wt%, preferably 1-60 wt%. 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 preferred.

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, the solubility parameter is 9 to 12 (cal / cm ³ ) ^{0.5 for the} ionic vinyl monomer and the oligomer and polymer obtained by homopolymerization.
The organic solvent is preferable.

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 and dried.
By curing, it can be used as an antistatic 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, Daro.
cure 1173, IRGACURE 184, IRGACURE 369, IRGACURE 500, IRGACURE 651, IR
GACURE754, IRGACURE819, IRGACURE907, IRGACURE1300, IRGACURE1800
, IRGACURE 1870, IRGACURE 2959, IRGACURE 4265, IRGACURE TPO, manufactured by UCB,
The product name Ubekrill P36 can be used.

As long as the properties such as antistatic properties and compatibility of the ionic vinyl monomer of the present invention are not impaired,
Other optional components such as pigments, dyes, surfactants, antiblocking agents, binders, crosslinking agents, antioxidants and ultraviolet absorbers 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, Multifunctional (meth) acrylate and / or polyfunctional (meth)
It is preferable to carry out in order of 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) Quaternary salt quantification method Using a potentiometric automatic titrator (device name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.), titration was performed with a silver nitrate aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a concentration of 0.1 mol / L. And determine the quaternary ammonium salt concentration from the titer. (2) Application and UV curing 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. P
An antistatic hard coating agent is dropped in a strip shape on the other end of the ET film, and a bar coater (R
In DS12), both ends are pressed so that a uniform force is applied to the whole, and the same speed (5c) is obtained without rotating.
m / sec) and pulled to the front, and the solvent was removed with a hot air dryer at 100 ° C. for 3 minutes 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; B: Repelling is very slight but almost uniform coating film; Δ: Repelling is somewhat uniform but almost uniform as a whole X: A coating film with a lot of repellency and non-uniformity. Stickiness ◎: No stickiness at all; ○: Slightly sticky; Δ: Slightly sticky; ×: Clear stickiness. (3) Ultraviolet irradiation was applied with the UV-cured coating surface facing upward to cure, and an antistatic hard coat film was obtained. UV curing conditions are: output 300W, output 50W / c per unit
UV irradiation device with one high-pressure mercury lamp of m (Oak Seisakusho model OHD320M)
The distance between the sample plate and the lamp was adjusted so that the ultraviolet energy per ^second was 10 mJ / cm ² . 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 surface resistivity measurement, scratch resistance test, and pencil hardness test were performed by the following methods. Transparency of coating after curing ◎: Transparent and smooth surface; ○: Transparent but uneven; △: Slightly cloudy or uneven; x: Extremely cloudy or uneven (4) Surface resistivity measurement type Using a plate (110x110mm),
The antistatic hard coat film was cut with a cutter knife, placed in a thermostatic chamber adjusted to a temperature of 25 ° C. and a relative humidity of 60%, and allowed to stand for 24 hours to obtain a sample for measuring surface resistivity. JIS 691
1 was measured using HIGH RESISTANFE METER 4329A manufactured by Yokogawa HEWLETT-PACKARD. (5) Scratch resistance test Using steel wool of # 0000 steel wool,
The sample 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. Abrasion resistance evaluation A: Almost no film peeling or scratches are observed;
○: Slight thin scratches are observed on the film; Δ: Streaky scratches are observed on the entire surface of the film; ×: Delamination of the film occurs. (6) Pencil hardness test An antistatic hard coat agent is dropped onto a glass plate (length 200 × width 200 × thickness 5 mm) in a strip shape, and a uniform force is applied to the whole with a bar coater (RDS12). Then, the both ends were pressed and applied to the front at the same speed (5 cm / sec) without rotating, and the solvent was removed with a hot air dryer at 100 ° C. for 3 minutes. The coated surface of the obtained coating film was turned upward to be cured by irradiation with ultraviolet rays to obtain a sample for measuring pencil hardness. JI
Based on SK 5400, a pencil hardness test was performed.

Synthesis examples and comparative synthesis examples which are production examples of ionic vinyl monomers are shown below.

<Synthesis of ionic vinyl monomer>
Synthesis example 1
Under a nitrogen atmosphere, 100 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: DMAPAA) and 529 g of isopropanol (IPA) are added to a 1 L autoclave glass container, the internal temperature is adjusted to 30 ° C. or lower, and methyl chloride is stirred. And a quaternization reaction was carried out. When the residual free amine (residual DMAPAA) in the reaction solution became 0.2% or less, excess methyl chloride in the reaction solution was distilled off under reduced pressure, and IPA containing 20% acryloylaminopropyltrimethylammonium chloride (DMAPAA-Q). 640 g (yield 96.7%) of a liquid was obtained. Subsequently, 20 g of sodium thiocyanate and 460 g of IPA were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 252 g of the DMAPAA-Q 20% -containing IPA solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with IPA. Then, IPA in the filtrate was recovered by a thin film evaporator at 50 ° C. under a reduced pressure of 26 hPa to obtain the desired ionicity. 54 g of vinyl monomer, acryloylaminopropyltrimethylammonium thiocyanate, was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 96.5%. In elemental analysis, measured values (C: 52.32%, H: 8.28%, N: 18.33%) are theoretical values (C: 52.37%, H: 8.35%, N: 18. 32%).

Synthesis example 2
In Synthesis Example 1, 23.8 g of potassium thiocyanate was used instead of sodium thiocyanate and reacted in the same manner as in Synthesis Example 1 to obtain 53 g of the desired product acryloylaminopropyltrimethylammonium thiocyanate as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield is 9
It was 5.1%. In elemental analysis, measured values (C: 52.18%, H: 8.37%, N: 1
8.21%) agreed with the theoretical values (C: 52.37%, H: 8.35%, N: 18.32%).

Synthesis example 3
In Synthesis Example 1, ammonium thiocyanate 18.7 instead of sodium thiocyanate
was used in the same manner as in Synthesis Example 1 to obtain 52 g of the desired product acryloylaminopropyltrimethylammonium thiocyanate as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 93.7%. In elemental analysis, measured values (C: 52.31%, H: 8.26%, N
: 18.15%) agreed with the theoretical values (C: 52.37%, H: 8.35%, N: 18.32%).

Synthesis example 4
In Synthesis Example 1, 20 g of calcium thiocyanate was used in place of sodium thiocyanate and reacted in the same manner as in Synthesis Example 1 to obtain 54 g of the target product acryloylaminopropyltrimethylammonium thiocyanate as a colorless transparent liquid. 4th by potentiometric titration
When the concentration of the quaternary ammonium salt was determined, the purity of the target product was 100%. Also,
The yield was 95.9%. In elemental analysis, measured values (C: 52.23%, H: 8.33%)
, N: 18.04%) are theoretical values (C: 52.37%, H: 8.35%, N: 18.32%)
).

Synthesis example 5
Under a nitrogen atmosphere, 300 g of DMAPAA and 214 g of methanol were added to a 1 L autoclave glass container, the internal temperature was adjusted to 30 ° C. or lower, and methyl chloride was injected while stirring to carry out a quaternization reaction. When the residual free amine (residual DMAPAA) in the reaction solution became 0.2% or less, excess methyl chloride in the reaction solution was distilled off under reduced pressure, and methanol containing 65% acryloylaminopropyltrimethylammonium chloride (DMAPAA-Q) Liquid 5
90 g (yield 96.6%) was obtained. Subsequently, 30 g of sodium thiocyanate and 600 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 116 g of methanol solution containing DMAPAA-Q 65% synthesized above was added in 2 g.
The mixture was added dropwise at 5 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with methanol. Then, methanol in the filtrate was recovered by a thin film evaporator at 50 ° C. under reduced pressure of 100 hPa (= 75 torr). 80 g of the desired ionic vinyl monomer, acryloylaminopropyltrimethylammonium thiocyanate, was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 95.3%. In elemental analysis, measured values (C: 51.97%, H: 8.14%, N: 18.11%)
Agreed with the theoretical values (C: 52.37%, H: 8.35%, N: 18.32%).

Synthesis Example 6
Under a nitrogen atmosphere, DMAPAA 100 g, IPA26 in a 1 L three-necked flask
7 g was added, the internal temperature was adjusted to 25 ° C., and methyl p-toluenesulfonate 118. with stirring.
8g was dripped and quaternization reaction was implemented. Residual free amine in the reaction solution (residual DMAPAA)
Was confirmed to be 0.3% or less, and 473 g of an IPA solution containing 45% acryloylaminopropyltrimethylammonium p-toluenesulfonate (DMAPAA-TSMQ)
(Yield 97.2%) was obtained. Subsequently, 20 g of sodium thiocyanate and 460 g of IPA were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 185.8 g of the IPPA solution containing DMAPAA-TSMQ 45% 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 dropping, 25 more
After stirring for 2 hours at ° C, the crystals were filtered and washed with IPA, and then the IPA in the filtrate was 26 hP.
It was recovered by a thin film evaporator at 50 ° C. under reduced pressure of a to obtain 54 g of the objective ionic vinyl monomer, acryloylaminopropyltrimethylammonium thiocyanate as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 96.4%. In elemental analysis, measured values (C:
52.09%, H: 8.22%, N: 18.01%) are theoretical values (C: 52.37%, H:
8.35%, N: 18.32%).

Synthesis example 7
In Synthesis Example 6, 20 g of ammonium thiocyanate instead of sodium thiocyanate
Was used in the same manner as in Synthesis Example 6 to obtain 58 g of the desired product acryloylaminopropyltrimethylammonium thiocyanate as a colorless transparent liquid. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 99.8%. The yield was 97.2%. In elemental analysis, measured values (C: 51.9%, H: 8.21%, N
: 18.13%) agreed with the theoretical values (C: 52.37%, H: 8.35%, N: 18.32%).

Synthesis Example 8
Under a nitrogen atmosphere, 200 g of DMAPAA and methanol 185.
5 g was added, the internal temperature was adjusted to 25 ° C., and methyl p-toluenesulfonate 235.
5g was dripped and quaternization reaction was implemented. Residual free amine in the reaction solution (residual DMAPAA)
Was found to be 0.3% or less, and methanol solution 60 containing 70% acryloylaminopropyltrimethylammonium p-toluenesulfonate (DMAPAA-TSMQ) 60
2 g (yield 97.1%) was obtained. Subsequently, 20 g of sodium thiocyanate and 400 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, methanol solution containing 70% DMAPAA-TSMQ synthesized above 119.
4 g was dripped at 25 degreeC over 1 hour, and the white crystalline solid precipitated at the same time. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with methanol. The methanol in the filtrate was recovered by a thin film evaporator at 50 ° C. under a reduced pressure of 100 hPa, and the desired ionicity 54.2 g of a vinyl monomer, acryloylaminopropyltrimethylammonium thiocyanate, was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 96.8%.
In elemental analysis, measured values (C: 52.31%, H: 8.21%, N: 18.27%) are theoretical values (C: 52.37%, H: 8.35%, N: 18. 32%).

Synthesis Example 9
Under a nitrogen atmosphere, 100 g of DMAPAA and 327.7 g of propylene glycol monomethyl ether (PGME) were added to a 1 L three-necked flask, the internal temperature was adjusted to 25 ° C., and 117.7 g of methyl p-toluenesulfonate was added dropwise with stirring. A quaternization reaction was carried out. After confirming that the residual free amine (residual DMAPAA) in the reaction solution was 0.3% or less, acryloylaminopropyltrimethylammonium p-toluenesulfonate (DMAPA)
541.8 g (yield 98.6%) of PGME solution containing 40% of (A-TSMQ) was obtained. continue,
To a 1 L three-necked flask, 15 g of sodium thiocyanate and 420 g of PGME were added, and a uniform solution was prepared while stirring. DMAPAA synthesized above while stirring the solution
-156.8 g of PGME solution containing 40% TSMQ was added dropwise at 25 ° C over 1 hour, and at the same time, a white crystalline solid was deposited. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with PGME. Then, PGME in the filtrate was recovered by a thin film evaporator at 55 ° C. under reduced pressure of 1.33 hPa. 54.2 g of an ionic vinyl monomer, acryloylaminopropyltrimethylammonium thiocyanate, was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 96.8%. In elemental analysis, measured values (C: 52.22%, H:
8.13%, N: 18.31%) are theoretical values (C: 52.37%, H: 8.35%, N: 1)
8.32%).

Synthesis Example 10
In Synthesis Example 1, N, N-dimethylaminopropylmethacrylamide (manufactured by Degussa: DMAPMA) was used instead of DMAPAA to synthesize an IPA solution containing 15% methacryloylaminopropyltrimethylammonium chloride (DMAPMA-Q). Subsequently, in a 1 L three-necked flask, 15 g of sodium thiocyanate, IPA3
45 g was added and a homogeneous solution was prepared with stirring. While stirring the solution, 269 g of the DMAPMA-Q15% -containing IPA solution synthesized above was added dropwise at 25 ° C. over 1 hour and reacted in the same manner as in Synthesis Example 1 to obtain the desired product methacryloylaminopropyltrimethylammonium thiocyanate. 43.5 g of narate was obtained as a colorless transparent liquid. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 99.8%. The yield was 97.6%. In elemental analysis, measured values (C: 54.12%, H: 8.59%, N:
17.04%) agreed with the theoretical values (C: 54.29%, H: 8.70%, N: 17.27%).

Synthesis Example 11
Under a nitrogen atmosphere, DMAPMA 200 g and methyl ethyl ketone (MEK) 693 g are added to a 2 L three-necked flask, the inner temperature is adjusted to 25 ° C., and 230 g of methyl p-toluenesulfonate is added dropwise with stirring to carry out a quaternization reaction. did. After 2 hours, the precipitated crystals were filtered and dried under reduced pressure. As a result, methacryloylaminopropyltrimethylammonium p-toluenesulfonate (DMAPMA-TSMQ) was formed into white crystals.
7 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 98.3%. Subsequently, 20 g of sodium thiocyanate and 400 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 145 g of a solution of DMAPMA-TSMQ synthesized above in methanol (quaternary salt concentration 60%) was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. did. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with methanol. The methanol in the filtrate was recovered by a thin film evaporator at 50 ° C. under a reduced pressure of 100 hPa, and the desired ionicity 56. A vinyl monomer, methacryloylaminopropyltrimethylammonium thiocyanate, as a colorless transparent liquid
7 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 95.7%. In elemental analysis, measured values (C: 5
4.02%, H: 8.13%, N: 17.19%) are theoretical values ((C: 54.29%, H:
8.70%, N: 17.27%).

Synthesis Example 12
N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) 100 g, isopropanol (IPA) 57 in a 1 L autoclave glass container under a nitrogen atmosphere
8 g was added, the internal temperature was adjusted to 30 ° C. or lower, and methyl chloride was injected while stirring to carry out a quaternization reaction. 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 to obtain IPA containing 20% acryloyloxyethyltrimethylammonium chloride (DMAEA-Q). 703 g of liquid (98.6% yield)
) The amount of acrylic acid, which is a reaction byproduct in the reaction solution, determined by high performance liquid chromatography was 705 ppm. Subsequently, 20 g of sodium thiocyanate and 460 g of IPA were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 236 g of DMAEA-Q 20% -containing IPA solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of dropping, further 25 ° C
After stirring for 2 hours, the crystals were filtered, washed with IPA, and IPA in the filtrate was reduced to 26 hPa.
Of the ionic vinyl monomer, acryloyloxyethyltrimethylammonium thiocyanate as a colorless transparent liquid.
. 3 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 93.4%. In elemental analysis, measured values (C:
49.93%, H: 7.42%, N: 12.39%) are theoretical values (C: 49.98%, H:
7.46%, N: 12.95%).

Synthesis Example 13
Under a nitrogen atmosphere, 130 g of DMAEMA and 360.1 g of methanol were added to a 1 L three-necked flask, the inner temperature was adjusted to 25 ° C., and 166.7 g of methyl p-toluenesulfonate was added dropwise with stirring to perform the quaternization reaction. Carried out. Residual free amine in reaction liquid is 0.3%
It was as follows, and it was confirmed by GC analysis that methyl p-toluenesulfonate was not detected, and acryloyloxyethyltrimethylammonium p-toluenesulfonate (DMA
645 g (yield 98.3%) of methanol solution containing 45% of (EA-TSMQ) was obtained. continue,
To a 1 L three-necked flask, add 25 g of sodium thiocyanate and 500 g of methanol,
A homogeneous solution was prepared with stirring. DMAPA synthesized above while stirring the solution
167.5 g of 45% A-TSMQ-containing methanol solution was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with methanol, and then methanol in the filtrate was reduced to 50 h under 100 hPa.
The polymer was recovered by a thin film evaporator at 0 ° C. to obtain 63.4 g of the objective ionic vinyl monomer, acryloyloxyethyltrimethylammonium thiocyanate as a colorless transparent liquid. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 99.9%.
Met. The yield was 96.0%. In elemental analysis, the measured value (C: 49.51%
, H: 7.29%, N: 12.48%) are theoretical values (C: 49.98%, H: 7.46%,
N: 12.95%).

Synthesis Example 14
In Synthesis Example 1, N, N-dimethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd .: DMAEMA) was used instead of DMAPAA, and an IPA solution containing 20% methacryloyloxyethyltrimethylammonium chloride (DMAEMA-Q) was synthesized. Subsequently, 20 g of sodium thiocyanate and 460 g of IPA were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, the DM synthesized above
254 g of AEMA-Q 20% -containing IPA solution was added dropwise at 25 ° C. over 1 hour and reacted in the same manner as in Synthesis Example 1 to obtain 53.2 g of the desired product methacryloyloxyethyltrimethylammonium thiocyanate as a colorless transparent liquid. It was. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 94.6%. In elemental analysis, measured values (C: 52.12%, H: 7.59%, N: 12.04%
) Agreed with the theoretical values (C: 52.15%, H: 7.88%, N: 12.16%).

Synthesis Example 15
In Synthesis Example 5, a methanol solution containing 50% methacryloyloxyethyltrimethylammonium chloride (DMAEMA-Q) was synthesized using DMAEMA instead of DMAPAA. Subsequently, a 1 L three-necked flask was charged with sodium thiocyanate 20
g and 400 g of methanol were added, and a uniform solution was prepared with stirring. While stirring the solution, 101 g of DMAEMA-Q 50% -containing methanol solution synthesized above was added dropwise at 25 ° C. over 1 hour and reacted in the same manner as in Synthesis Example 5 to obtain the desired product methacryloyloxyethyltrimethylammonium thiocyanate. 54.5 g of nat was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 96.9%. In elemental analysis, measured values (C: 51.98%, H:
7.61%, N: 12.31%) are theoretical values (C: 52.15%, H: 7.88%, N: 1)
2.16%).

Synthesis Example 16
Under a nitrogen atmosphere, DMAL 200 g, IPA1 in a 1 L three-necked flask
83.5 g was added, the internal temperature was adjusted to 25 ° C., and methyl p-toluenesulfonate 2 with stirring.
32.4g was dripped and the quaternization reaction was implemented. The residual free amine in the reaction solution was 0.3% or less, and it was confirmed by GC analysis that methyl p-toluenesulfonate was not detected. Methacryloyloxyethyltrimethylammonium p-toluenesulfonate (DMAE)
600 g (yield 97.7%) of IPA solution containing 70% of MA-TSMQ was obtained. 1L
To the three-necked flask, 20 g of sodium thiocyanate and 460 g of IPA were added, and a uniform solution was prepared with stirring. DMAEMA-TS synthesized above while stirring the solution
120 g of MQA-containing IPA solution was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered.
After that, the IPA in the filtrate was recovered with a thin film evaporator at 50 ° C. under a reduced pressure of 26 hPa, and 54.5 g of the target ionic vinyl monomer, methacryloyloxyethyltrimethylammonium thiocyanate was obtained as a colorless transparent liquid. Obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 99.9%. The yield is 9
It was 6.9%. In elemental analysis, measured values (C: 51.92%, H: 7.23%, N: 1
1.98%) agreed with the theoretical values (C: 52.15%, H: 7.88%, N: 12.16%).

Comparative Synthesis Example 1
In a 1 L three-necked flask, 81.1 g of sodium thiocyanate was dissolved in 165 g of ion-exchanged water to obtain a sodium thiocyanate aqueous solution. To this aqueous solution, acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: DMAPAA-Q) 75
A DMAPAA-Q37% aqueous solution obtained by dissolving 286 g of a% aqueous solution in 300 g of ion-exchanged water was added dropwise at 25 ° C. over 2 hours. The reaction solution was uniformly transparent. Subsequently, ethyl acetate 2
Extraction was performed 3 times with 00 g, and the ethyl acetate layer was concentrated. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, it was not detected, and the target product was not obtained.

Comparative Synthesis Example 2
In a 1 L three-necked flask, 97 g of potassium thiocyanate was added to ion-exchanged water.
This was dissolved in 0 g to obtain a potassium thiocyanate aqueous solution. DMAPAA- obtained by dissolving 286 g of 75% aqueous solution of acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: DMAPAA-Q) in 300 g of ion-exchanged water in this aqueous solution.
A Q37% aqueous solution was added dropwise at 25 ° C. over 2 hours. The reaction solution was uniformly transparent. continue,
Extraction was performed 3 times with 200 g of ethyl acetate, and the ethyl acetate layer was concentrated. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, it was not detected, and the target product was not obtained.

Comparative Synthesis Example 3
In a 1 L three-necked flask, 81.1 g of sodium thiocyanate was dissolved in 1000 g of ion-exchanged water to obtain a sodium thiocyanate aqueous solution. To this aqueous solution, methacryloylaminopropyltrimethylammonium chloride (manufactured by MRC Unitech Co., Ltd .: MA
DMAPMA-Q26% obtained by dissolving 261 g of PTAC) in 1000 g of ion-exchanged water
The aqueous solution was added dropwise at 25 ° C. over 2 hours. The reaction solution was uniformly transparent. Subsequently, extraction was performed 3 times with 200 g of ethyl acetate, and the ethyl acetate layer was concentrated. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, it was not detected, and the target product was not obtained.

Comparative Synthesis Example 4
In a 1 L three-necked flask, 81.1 g of sodium thiocyanate was dissolved in 165 g of ion-exchanged water to obtain a sodium thiocyanate aqueous solution. Two DMAEA-Q 37% aqueous solutions obtained by dissolving 250 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) in 280 g of ion-exchanged water were dissolved in this aqueous solution.
The solution was added dropwise at 5 ° C. over 2 hours. The reaction solution was uniformly transparent. Subsequently, 200 g of ethyl acetate
And the ethyl acetate layer was concentrated. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, it was not detected, and the target product was not obtained.

Comparative Synthesis Example 5
In a 1 L three-necked flask, 97 g of potassium thiocyanate was added to ion-exchanged water.
Dissolved in 00 g, an aqueous potassium thiocyanate solution was obtained. To this aqueous solution, methacryloyloxyethyltrimethylammonium chloride (manufactured by Kyoeisha Chemical Co., Ltd .: DQ-100) 205
25% aqueous solution of DMAPAA-Q obtained by dissolving g in 1000 g of ion-exchanged water.
The solution was added dropwise at 2 ° C. over 2 hours. The reaction solution was uniformly transparent. Subsequently, extraction was performed 3 times with 200 g of ethyl acetate, and the ethyl acetate layer was concentrated. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, it was not detected, and the target product was not obtained.

Comparative Synthesis Example 6
In a 1 L three-necked flask, 20 g of sodium thiocyanate, IPA460
g was added and a homogeneous solution was prepared with stirring. While stirring the solution, acryloylaminopropyltrimethylammonium chloride (DMA) obtained by reacting in the same manner as in Synthesis Example 1 was obtained.
(PAA-Q) 252 g of 20% -containing IPA solution was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with IPA. Then, IPA in the filtrate was evaporated at 50 ° C. under a reduced pressure of 26 hPa.
And concentrated under reduced pressure. When the IPA concentration of the concentrate was measured with a gas chromatograph, 10% by weight remained. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 88.6%. The concentrated solution was yellow.

Comparative Synthesis Example 7
In a 1 L three-necked flask, 20 g of sodium thiocyanate, IPA460
g was added and a homogeneous solution was prepared with stirring. While stirring the solution, an IPA solution containing 70% methacryloyloxyethyltrimethylammonium p-toluenesulfonate (DMAEMA-TSSMQ) obtained by reacting in the same manner as in Synthesis Example 16 was added dropwise at 25 ° C. over 1 hour. At the same time, a white crystalline solid precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with IPA. Then, IPA in the filtrate was concentrated under reduced pressure at 50 ° C. under reduced pressure of 4 hPa. When the IPA concentration of the concentrate was measured by gas chromatography, 9.5% by weight remained. The concentrate was spinnable and polymerized. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 87.1%. The concentrated solution was yellow.

As can be seen from the results of Synthesis Examples 1 to 16, according to the synthesis method of the present invention, the target ionic vinyl monomer could be obtained with high purity and high yield without causing problems such as polymerization.

On the other hand, in Comparative Synthesis Examples 1 to 5 carried out using water as the reaction solvent for the anion exchange reaction, the ionic vinyl monomer is isolated because both the target ionic vinyl monomer and the by-product metal salt are dissolved in water. Is difficult. Further, even if extraction is performed with an organic solvent, a target ionic monomer that is water-soluble in the organic solvent layer cannot be extracted.

In Comparative Synthesis Examples 6 to 7 where the thin film evaporator was not used after the by-product was removed, it was difficult to completely remove the organic solvent, and the concentrated liquid was colored. Even if the degree of vacuum is increased,
Since the concentrate was highly viscous and the target ionic monomer was non-volatile, the organic solvent could not be completely removed, and the ionic vinyl monomer was polymerized.

Examples and comparative examples in which the ionic vinyl monomer obtained by the production method of the present application is used as an antistatic agent are shown below.

Example A-1
Preparation of Antistatic Hard Coating Agent After dissolving 14 parts by weight of acryloylaminopropyltrimethylammonium thiocyanate synthesized in Synthesis Example 1 in 120 parts by weight of IPA, pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE) -3A) 62 parts by weight, 3 parts by weight of a product name Darocure 1173 manufactured by Ciba Specialty Chemicals Co., Ltd. was added as a photoinitiator and mixed uniformly to obtain an antistatic hard coat agent capable of ultraviolet curing. Thereafter, the obtained hard coat agent was applied to a PET film having a thickness of 12 μm and cured with ultraviolet rays to produce an antistatic hard coat.

Examples A-2 to 10 and Comparative Examples A-11 to 18
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>
In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, 20 parts by weight of acryloylaminopropyltrimethylammonium thiocyanate synthesized in Synthesis Example 1 and 0.2 parts by weight of azoisobutyronitrile (AIBN) were added to IPA 60. The mixture was dissolved in parts by weight and polymerized at 70 ° C. for 8 hours under a nitrogen stream to obtain an ionic homopolymer solution (a).
<Preparation of antistatic hard coating agent containing ionic polymer>
To 5 parts by weight of the ionic homopolymer solution (a), pentaerythritol triacrylate (
50 parts by weight of Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-3A) and 50 parts by weight of dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A)
As a photoinitiator, product name Darocure 1173 manufactured by Ciba Specialty Chemicals Co., Ltd.
5 parts by weight of a mixed solvent 120 of 1: 1 weight ratio of IPA and methyl ethyl ketone (MEK)
By mixing and dissolving in parts by weight, an antistatic hard coating agent containing an ultraviolet curable quaternary salt polymer was obtained. Then, the obtained hard coat agent was applied to a 100 μm thick PET film,
Ultraviolet curing was performed to produce an antistatic hard coat.

Example B-2
<Synthesis of copolymer solution>
In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, 10 parts by weight of acryloylaminopropyltrimethylammonium thiocyanate synthesized in Synthesis Example 1, 10 parts by weight of 2-ethylhexyl acrylate (EHA), and 0.2% of AIBN A part was mixed and dissolved in 60 parts by weight of IPA and polymerized at 70 ° C. for 8 hours under a nitrogen stream to obtain an ionic copolymer solution (b).
Table 3 shows the mixing ratio of the monomers in the synthesis of the copolymer solution.

Examples B-2 to 7 and Comparative Examples B-8 to 9
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 commercially available quaternary cationic vinyl monomer has a chlorine ion as an anion, the coating film obtained therefrom is sticky and has poor transparency. Further, it was 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. The ionic vinyl monomer of the present invention is a colorless transparent liquid at room temperature, has high compatibility with polyfunctional monomers and organic solvents, and is particularly compatible with nonpolar components in the antistatic agent composition. A transparent, non-colored antistatic coating was obtained. The high-quality ionic vinyl monomer obtained by the production method of the present invention requires less energy for UV curing, has good transparency, is not colored, has high scratch resistance, high hardness, and high hydrolysis resistance, Excellent antistatic effect was 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, since it has a non-halogen-based anion, it has a low environmental burden and good compatibility with other antistatic compositions such as polyfunctional monomers and organic solvents. An antistatic layer formed using an antistatic composition comprising this ionic vinyl monomer is antistatic, transparent, scratch resistant, high in hardness, hardly colored, and excellent in hydrolysis resistance. The antistatic layer comprising the ionic vinyl monomer of the present invention can be suitably used when it is added in advance to a resin such as an ultraviolet curable resin composition or an adhesive composition.

Claims (11)

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 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. Vinyl monomer in an organic solvent,
General formula (3)

(Wherein, M ^{n +} represents a cation),
General formula (2)

(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) to 3 alkyl group, an alkenyl group or a benzyl group having 1 to 3 carbon atoms, Y represents an oxygen atom or -NH-, Z represents an alkylene group having 1 to 3 carbon atoms, X ^- represents an anion )) Is synthesized by an ion exchange reaction of a quaternary cationic vinyl monomer. The method for producing an ionic vinyl monomer according to claim 1, wherein the solubility parameter is one or more selected from the group consisting of organic solvents having a solubility parameter of 8 to 16 (cal / cm ³ ) ^0.5 . A quaternary cationic vinyl monomer and a thiocyanate are dissolved in an organic solvent and subjected to an ion exchange reaction, whereby a M ^{n +} (X ⁻ ) _n salt as a by-product is precipitated and separated from the organic solvent. 3. A method for producing an ionic vinyl monomer according to 1 and 2. 4. The method for producing an ionic vinyl monomer according to claim 1, wherein the organic solvent is recovered by thin film evaporation after the by-product is separated. An ionic homooligomer and a homopolymer obtained by radical polymerization of the ionic vinyl monomer obtained by the method according to claim 1. An ionic co-oligomer and copolymer obtained by copolymerization of the ionic vinyl monomer obtained by the method of claims 1 to 4 with another copolymerizable vinyl monomer. An ionic vinyl monomer obtained by the method of claims 1 to 4 and / or claim 5 or 6.
An antistatic agent comprising an ionic vinyl oligomer or polymer. The antistatic agent according to claim 7 or an antistatic composition containing the antistatic agent, wherein the ionic vinyl monomer according to claim 1 is contained as a constituent unit in an amount of 0.1 to 90% by weight. An antistatic composition containing the antistatic agent according to claim 7, further comprising a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide. An antistatic layer formed by applying an antistatic agent or an antistatic composition according to any one of claims 7 to 9 on a substrate and then polymerizing with an active energy ray or heat. An antistatic film or sheet comprising the antistatic layer according to claim 7 on at least one side.