JP2013001654A - Method for producing unsaturated quaternary ammonium salt compound, and antistatic agent and antistatic composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chloride ion-free and metal salt-free unsaturated quaternary ammonium salt excellent in compatibility, used suitably for various electrochemical devices, and having a continuously excellent antistatic effect, and to provide an antistatic agent comprising an unsaturated quaternary ammonium salt.SOLUTION: After a tertiary amine compound is reacted with a trifluoromethanesulfonic acid ester in the presence of an organic solvent, the organic solvent is removed by inert gas bubbling, to thereby synthesize at high yield, a high-purity unsaturated quaternary ammonium salt compound represented by general formula (1) (in the formula, Rrepresents a hydrogen atom or a methyl group, Rand Reach independently represent 1-3C alkyl group which may be the same or different, Rrepresents 1-3C alkyl group or aryl group, and Z represents 1-3C alkylene group), and then an antistatic layer is formed by using an oligomer and/or a polymer comprising the compound as an antistatic effective component.

Description

The present invention relates to a method for producing a high-quality unsaturated quaternary ammonium salt compound free of chlorine ions and metal ions, an antistatic agent comprising the unsaturated quaternary ammonium salt compound, and the antistatic agent. The present invention relates to an antistatic resin composition to be contained.

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 known that cationic unsaturated quaternary ammonium salts are used as base monomers for polymeric antistatic compositions. However, since many unsaturated ammonium salts have high hydrophilicity, they are usually distributed in the form of an aqueous solution due to the manufacturing relationship. For example, N, N-dimethylaminoethyl acrylate, which is an unsaturated tertiary amine, is used in the presence of a mixed solvent consisting of water and an aprotic organic solvent, and methyl chloride is added as a quaternizing agent to form a quaternization reaction. (Patent Document 4), N, N-dimethylaminoethyl acrylate and benzyl chloride are subjected to a quaternization reaction in acetone, water is added, and acetone is removed under reduced pressure (Patent Document 5). It is often used. 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, the hydrophilicity of these monomers themselves is high. In some cases, the solubility in the component 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 cannot 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 6 and 7). However, in these methods, since the content of the cationic vinyl monomer in the antistatic composition decreases, in order to obtain the target antistatic performance, it is necessary to add a large amount of this copolymer, As a result, there are problems that various properties of the resin are lowered and the price of the resin composition is increased.

For the purpose of improving the compatibility of the quaternary ammonium salt monomer itself, for example, a polymerizable compound having an anion such as bis (trifluoromethanesulfonyl) imide as a weakly coordinating anion has been proposed (Patent Documents 8 and 9). 10). In order to provide transparency and solubility in resins and solvents, ammonium salts using thiocyanate ions as anions have been proposed (Patent Documents 11, 12, and 13). But,
All of these proposed ammonium salts are synthesized by a metal salt reaction method, which is a known method using an ammonium chloride salt or bromide salt as a raw material. That is, an anion exchange reaction between a quaternary ammonium chloride salt or bromide salt and an alkali metal salt of bis (trifluoromethanesulfonyl) imide or a metal salt of thiocyanic acid is carried out in an aqueous solution, and the target product is converted to ethyl acetate or the like. This is a method of extraction and separation with an organic solvent. In this method, it is unavoidable to mix chlorine or bromine ions as anions and products of alkali metal ions or alkaline earth metal ions such as sodium, potassium, lithium and calcium as cations. Environmental impact due to residual chlorine or bromine ions is high, and there is a concern about corrosiveness to metals. In particular, when used as an electronic material, there is a possibility that the function of electronic products may be reduced and a failure may occur. On the other hand, when the metal ions remain, it becomes easy to absorb carbon dioxide in the air, and similarly, corrosion to the metal is promoted, so that it may not be used as an electronic material.

On the other hand, there was a report of a quaternary ammonium salt monomer in which a trifluoromethanesulfonyl group was introduced as an anion (Patent Documents 14 and 15). In Patent Document 14, aminoethyl methacrylate hydrochloride was used as a raw material, and methacryloyloxyethyltrimethylammonium trifluoromethanesulfonate was synthesized as a constituent monomer of a positive resist composition. In Patent Document 15, N, N-dimethylaminoethyl methacrylate and methyl trifluoromethanesulfonate are used as raw materials and the reaction is carried out in dichloromethane as a solvent to synthesize a constituent monomer of a cross-linked copolymer for contact lenses. However, in these patent documents, there is no description about the antistatic effect of a quaternary ammonium salt monomer, an oligomer containing the monomer as a constituent, or a polymer. Even if an unsaturated quaternary ammonium salt compound having a trifluoromethanesulfonyl group as an anion can be obtained by the synthesis methods described in Patent Documents 14 and 15, since a chlorine-based raw material or solvent is used, Residual chlorine in the quaternary ammonium salt monomer cannot be avoided, and problems such as increased environmental load, corrosiveness to metals, and reduced functionality of electronic products have not been solved.

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 JP 2005-255843 A JP 2006-45425 A JP 2009-13295 A JP 2009-197074 A JP 2009-179671 A JP 2007-93778 A JP 09-20814 A

As described above, a method for industrially producing a high-quality unsaturated quaternary ammonium salt compound which is composed of an ammonium cation and a trifluoromethanesulfonate anion and is free of chloride ions and metal ions and which is high quality. Is not known in the past. Also, it has good compatibility with general-purpose acrylic monomers, organic solvents and resins, is highly polymerizable by active energy rays or heat, has high transparency and high moisture resistance, and is also suitable for various electrochemical devices. An inexpensive anti-static agent having an excellent antistatic effect, free of chloride ions and metal salts, and free of organic solvents, and of a high quality unsaturated quaternary ammonium salt compound, An antistatic agent composed of a quaternary ammonium salt compound and an antistatic resin composition containing the antistatic agent have not yet been easily obtained.

The first object of the present invention is to provide an efficient and economical method for producing a high-quality unsaturated quaternary ammonium salt compound that is free of chlorine ions and metal ions and is highly polymerizable by active energy rays or heat. It is to provide.
The second object of the present invention is to have a good compatibility with general-purpose acrylic monomers, organic solvents and resins containing the unsaturated quaternary ammonium salt compound as a constituent component, and uniformly disperse in other antistatic agent compositions. Antistatic agent with excellent antistatic effect and long-term sustainable high transparency and high moisture resistance, and suitable for use in various electrochemical devices, and antistatic properties containing the antistatic agent It is to provide a composition.

As a result of intensive investigations to solve these problems, the present inventor reacted a tertiary amine compound and trifluoromethanesulfonic acid ester in the presence of an organic solvent, concentrated under reduced pressure, and further removed the remaining organic solvent. By removing by active gas bubbling, general formula (1) (wherein 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, and they are identical to each other). And R ₄ represents an alkyl group having 1 to 3 carbon atoms or an aryl group, and Z represents an alkylene group having 1 to 3 carbon atoms.) Found that to get. Furthermore, the antistatic agent comprised by the oligomer and polymer which consist of the said unsaturated quaternary ammonium salt compound and / or the said unsaturated quaternary ammonium salt compound was discovered. The above problems were solved by forming the antistatic layer by dissolving the antistatic agent in an organic solvent and then coating and fixing the antistatic agent on the base material, thereby achieving the present invention.

（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のアルキル基又はアリール基を表し、Ｚは炭素数１〜３のアルキレン基を表す。）で表される不飽和第４級アンモニウム塩化合物が有機溶媒中で、一般式（２）

（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、Ｚは炭素数１〜３のアルキレン基を表す。）で表される３級アミン化合物と、一般式（３）

（式中、Ｒ_４は炭素数１〜３のアルキル基又はアリール基を表す。）で表されるトリフルオロメタンスルホン酸エステルとの４級化反応により合成されることを特徴とする不飽和第４級アンモニウム塩の製造方法、
２）前記不飽和第４級アンモニウム塩化合物を製造するにあたり、有機溶媒として、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチルからなる非プロトン性有機溶媒群から選ばれた少なくとも１種を用いることを特徴とする、前記１）に記載の不飽和第４級アンモニウム塩化合物の製造方法、
３）前記不飽和第４級アンモニウム塩化合物を製造するにあたり、有機溶媒の除去は不活性ガスバブリングによる行うことを特徴とする前記１）又は前記２）記載の不飽和第４級アンモニウム塩化合物の製造方法、
４）前記不飽和第４級アンモニウム塩化合物を製造するにあたり、不活性ガスとして、乾燥窒素、乾燥空気及び乾燥ヘリウム、乾燥ネオン、乾燥アルゴン、乾燥クリプトン、乾燥キセノンと乾燥ラドンなどの乾燥希ガスからなる、前記不飽和第４級アンモニウム塩化合物と反応しない乾燥不活性ガス群から選ばれた少なくとも１種を用いることを特徴とする、前記１）乃至前期３）に記載の不飽和第４級アンモニウム塩化合物の製造方法、
５）前記１〜４いずれか一項に記載の製造方法で合成される塩素イオンフリー（塩素イオン含量は１ｐｐｍ以下）、金属イオンフリー（各種金属イオン含量は１ｐｐｍ以下）、且つ有機溶剤の含有量は１００ｐｐｍ未満の不飽和第４級アンモニウム塩化合物、
６）前記５）記載の不飽和第４級アンモニウム塩化合物をラジカル重合させることにより得られる塩素イオンフリー（塩素イオン含量は１ｐｐｍ以下）且つ金属イオンフリー（各種金属イオン含量は１ｐｐｍ以下）の４級アンモニウム塩含有オリゴマー又はポリマー、
７）前記５）記載の不飽和第４級アンモニウム塩化合物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塩素イオンフリー（塩素イオン含量は１ｐｐｍ以下）且つ金属イオンフリー（各種金属イオン含量は１ｐｐｍ以下）の４級アンモニウム塩含有コオリゴマー又はコポリマー、
８）前記５）乃至前記７）の不飽和第４級アンモニウム塩化合物及び／又はオリゴマー若しくはポリマーからなる塩素イオンフリー（塩素イオン含量は１ｐｐｍ以下）且つ金属イオンフリー（各種金属イオン含量は１ｐｐｍ以下）の帯電防止剤、
９）前記８）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、前記５）の不飽和第４級アンモニウム塩化合物を構成単位として０．１〜９０重量％含有するもの、
１０）前記８）又は９）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、
１１）基材上に前記８）〜１０）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重合して形成されることを特徴とする帯電防止層、
１２）少なくとも片面に前記１１）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, 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) An unsaturated quaternary ammonium salt compound represented by general formula (2) in an organic solvent.

(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; A tertiary amine compound represented by formula (3):

(Wherein R ₄ represents an alkyl group having 1 to 3 carbon atoms or an aryl group) and is synthesized by a quaternization reaction with a trifluoromethanesulfonic acid ester represented by A method for producing a quaternary ammonium salt,
2) In the production of the unsaturated quaternary ammonium salt compound, the organic solvent is made of acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, methyl acetate, ethyl acetate, propyl acetate, butyl acetate. At least one selected from the group of protic organic solvents, wherein the method for producing an unsaturated quaternary ammonium salt compound according to 1) above,
3) In the production of the unsaturated quaternary ammonium salt compound, the organic solvent is removed by inert gas bubbling. The unsaturated quaternary ammonium salt compound according to 1) or 2) above, Production method,
4) In producing the unsaturated quaternary ammonium salt compound, from inert rare gases such as dry nitrogen, dry air and dry helium, dry neon, dry argon, dry krypton, dry xenon and dry radon. The unsaturated quaternary ammonium according to 1) to 3) above, wherein at least one selected from the group of dry inert gases that do not react with the unsaturated quaternary ammonium salt compound is used. A method for producing a salt compound,
5) Chloride ion-free (chlorine ion content is 1 ppm or less), metal ion-free (various metal ion content is 1 ppm or less), and organic solvent content synthesized by the production method according to any one of 1 to 4 above Is an unsaturated quaternary ammonium salt compound of less than 100 ppm,
6) The quaternary of chloride ion free (chlorine ion content is 1 ppm or less) and metal ion free (various metal ion content is 1 ppm or less) obtained by radical polymerization of the unsaturated quaternary ammonium salt compound described in 5) above. An ammonium salt-containing oligomer or polymer,
7) Chloride ion-free (chlorine ion content is 1 ppm or less) obtained by copolymerization of the unsaturated quaternary ammonium salt compound described in 5) above with other copolymerizable vinyl monomers and metal ion-free ( A quaternary ammonium salt-containing co-oligomer or copolymer having various metal ion contents of 1 ppm or less,
8) Chlorine ion free (chlorine ion content is 1 ppm or less) and metal ion free (various metal ion content is 1 ppm or less) comprising the unsaturated quaternary ammonium salt compound and / or oligomer or polymer of 5) to 7) above Antistatic agent,
9) The antistatic agent according to 8) or an antistatic composition containing the antistatic agent, wherein the unsaturated quaternary ammonium salt compound of 5) is contained in an amount of 0.1 to 90% by weight as a constituent unit. What to do,
10) An antistatic composition containing the antistatic agent described in 8) or 9) above, which further contains a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide,
11) Charging characterized by being formed by coating the base material with the antistatic agent or antistatic composition according to any one of 8) to 10) and then polymerizing with active energy rays or heat. Prevention layer,
12) An antistatic film, a sheet comprising the antistatic layer described in 11) above on at least one surface,
Is to provide.

According to the method of the present invention, it is possible to easily produce a high-quality unsaturated quaternary ammonium salt compound with high yield by chlorine ion-free, metal ion-free, and high polymerizability by active energy rays or heat. . In addition, the antistatic agent and antistatic agent composition comprising the unsaturated quaternary ammonium salt compound as a constituent component have good compatibility with general-purpose monomers, organic solvents and resins, and other antistatic agent compositions. It can be uniformly dispersed, has high transparency and high moisture resistance, and has a continuously excellent antistatic effect, so that it can be suitably used for various electrochemical devices. The 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 antistatic agent of the present invention comprises at least one of an unsaturated quaternary ammonium salt compound represented by the general formula (1) and an oligomer or polymer composed of the unsaturated quaternary ammonium salt compound. Is.

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 represents an alkyl group having 1 to 3 carbon atoms or an aryl group, and Z represents an alkylene group having 1 to 3 carbon atoms.

The unsaturated quaternary ammonium salt compound of the present invention is a (meth) acrylate-based quaternary ammonium salt, specifically, acryloyloxymethyltrimethylammonium trifluoromethanesulfonate, acryloyloxymethyltriethylammonium trifluoromethanesulfonate, Acryloyloxymethyltripropylammonium trifluoromethanesulfonate, acryloyloxyethyltrimethylammonium trifluoromethanesulfonate, acryloyloxypropyltrimethylammonium trifluoromethanesulfonate, acryloyloxypropylmethyldiethylammonium trifluoromethanesulfonate, acryloyloxypropylethyldimethylammonium trifluoromethane Sulfonate, Acryloyloxypropylmethyldipropylammonium trifluoromethanesulfonate, acryloyloxypropyltriethylammonium trifluoromethanesulfonate, acryloyloxypropyltripropylammonium trifluoromethanesulfonate, acryloyloxyethyldimethylbenzylammonium trifluoromethanesulfonate, acryloyloxypropyldimethylbenzyl Ammonium trifluoromethanesulfonate, acryloyloxypropyldiethylbenzylammonium trifluoromethanesulfonate, acryloyloxypropylmethyldibenzylammonium trifluoromethanesulfonate, acryloyloxypropylethyldibenzylammonium trifluoromethanesulfonate Nert, methacryloyloxymethyltrimethylammonium trifluoromethanesulfonate, methacryloyloxymethyltriethylammonium trifluoromethanesulfonate, methacryloyloxymethyltripropylammonium trifluoromethanesulfonate, methacryloyloxyethyltrimethylammonium trifluoromethanesulfonate, methacryloyloxypropyltrimethylammonium trifluoromethane Sulfonate, methacryloyloxypropylmethyldiethylammonium trifluoromethanesulfonate, methacryloyloxypropylethyldimethylammonium trifluoromethanesulfonate, methacryloyloxypropylmethyldipropylammonium trifluoromethanesulfonate Methacryloyloxypropyltriethylammonium trifluoromethanesulfonate, methacryloyloxypropyltripropylammonium trifluoromethanesulfonate, methacryloyloxyethyldimethylbenzylammonium trifluoromethanesulfonate, methacryloyloxypropyldimethylbenzylammonium trifluoromethanesulfonate, methacryloyloxypropyldiethyl (Meth) acrylate-based ammonium alkyl trifluoros such as benzylammonium trifluoromethanesulfonate, methacryloyloxypropylmethyldibenzylammonium trifluoromethanesulfonate, and methacryloyloxypropylethyldibenzylammonium trifluoromethanesulfonate Such as methanesulfonate and the like.

Among these, acryloyloxyethyltrimethylammonium trifluoromethanesulfonate and methacryloyloxyethyltrimethylammonium trifluoromethanesulfonate are particularly preferable because inexpensive industrial raw materials are easily available.

The tertiary amine compound represented by the general formula (2) which is the starting material of the present invention is an N, N-disubstituted amino (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, and Z Represents an alkylene group having 1 to 3 carbon atoms.

Examples of the N, N-disubstituted aminoalkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meta) ) 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.

Another starting material of the present invention is a trifluoromethanesulfonic acid ester represented by the general formula (3). Specifically, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, propyl trifluoromethanesulfonate, isopropyl trifluoromethanesulfonate, thiocyanbutyl, isobutyl trifluoromethanesulfonate, tert-butyl trifluoromethanesulfonate, trifluoromethanesulfone Trifluoromethanesulfonic acid alkyl esters such as pentyl acid, hexyl trifluoromethanesulfonate, heptyl trifluoromethanesulfonate, octyl trifluoromethanesulfonate, nonyl trifluoromethanesulfonate, decyl trifluoromethanesulfonate, trifluoromethane such as cyclohexyl trifluoromethanesulfonate Sulfonic acid cycloaliphatic ester, trifluoromethanesulfonic acid phenol Le, trifluoromethanesulfonic acid benzyl, trifluoromethanesulfonic acid tolyl, trifluoromethanesulfonic acid tolyl, trifluoromethanesulfonic acid aryl esters such as trifluoromethanesulfonic acid xylyl and the like. Of these, methyl trifluoromethanesulfonate and ethyl trifluoromethanesulfonate are particularly preferable in terms of melting point and reactivity.

In the quaternization reaction of the tertiary amine compound and trifluoromethanesulfonic acid ester, the molar ratio of the tertiary amine compound and trifluoromethanesulfonic acid ester is arbitrary, but the use of one of them in excess accelerates the completion of the reaction. Is done. When the purpose is to utilize the polymerization characteristics of the unsaturated quaternary ammonium salt compound of the present invention, it is preferable to use an excess of the polymerizable tertiary amine even if a small amount of the tertiary amine remains. This is preferable because it does not affect the polymerization characteristics and antistatic performance of the quaternary ammonium salt compound. The molar ratio of tertiary amine / trifluoromethanesulfonic acid ester is preferably 0.2 to 5 mol, and more preferably 0.5 to 2 mol.

The quaternization reaction is carried out in the presence of an organic solvent. As an organic solvent to be used, it is soluble in either or both of the tertiary amine compound and trifluoromethanesulfonic acid ester which are the starting materials of the present invention (dissolves 5 g or more in 100 g of solvent), and adversely affects the reaction. If it is a solvent that does not reach, it can be widely used. For example, at least one selected from the group of aprotic organic solvents consisting of acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, methyl acetate, ethyl acetate, propyl acetate, and butyl acetate can be used. Among these, butyl acetate is soluble in the tertiary amine compound and trifluoromethanesulfonic acid ester which are starting materials, but hardly soluble in the unsaturated quaternary ammonium salt compound (dissolves less than 5 g in 100 g solvent). It is most preferable because the residual tertiary amine compound and trifluoromethanesulfonic acid ester can be easily removed from the unsaturated quaternary ammonium salt compound as the target product. These solvents can be used alone or in combination of two or more.

The blending amount of the organic solvent used in the quaternization reaction varies depending on the type, but a range in which the concentration of the starting material trifluoromethanesulfonic acid ester is 1 to 95% is preferable. Furthermore, the range which becomes 5 to 90% is especially preferable. If it is less than 1%, the contact efficiency of the raw material is lowered, and the reaction rate is remarkably slowed. If it exceeds 95%, the reaction cannot be controlled, the selectivity may decrease, and problems such as polymerization troubles due to heat generation may occur.

The reaction temperature when synthesizing the unsaturated quaternary ammonium salt compound of the present invention is usually 10 ° C. or higher, preferably 15 to 130 ° C., particularly preferably 20 to 100 ° 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 130 ° C., the raw material or product polymerizable compound may be polymerized. When the starting material to be used has a low boiling point, a closed reactor such as an autoclave can be used.

Water in the reaction system may cause hydrolysis impurities of trifluoromethanesulfonic acid ester as a by-product, and is preferably as little as possible. Since the moisture to be brought in is mainly derived from the raw materials, it is desirable to remove the moisture using a distillation dehydration or a drying agent before the reaction.

The unsaturated quaternary ammonium salt compound of the present invention is, of course, a chlorine ion-free and metal ion-free high-quality product, and the total of various chlorine ions contained in the raw material is 1 ppm. Hereinafter, the total of various metal ions needs to be 1 ppm or less. Here, the metal ions are monovalent metal ions such as sodium ion, lithium ion and potassium ion, divalent metal ions such as calcium ion and magnesium ion, and polyvalent metal ions such as aluminum ion and iron ion.

After completion of the reaction, depending on the compatibility between the surplus raw material and the unsaturated quaternary ammonium salt compound that is the product of the reaction solvent, it can be easily separated and recovered by distillation, extraction, thin film treatment, and used repeatedly. it can.

Since the unsaturated quaternary ammonium salt compound of the present invention has a high viscosity and no vapor pressure, about 1 to 10% of an organic solvent remains in ordinary distillation, and there is a problem that a high-purity product cannot be obtained. It was. Since the quaternary ammonium salt compound of the present invention has an unsaturated group, there is a risk of polymerization if it is distilled for a long time to remove the organic solvent. Furthermore, when an organic solvent having a high boiling point is used as a reaction solvent, if distillation is performed under high temperature and reduced pressure in order to remove this, the unsaturated quaternary ammonium salt compound of the present invention is further polymerized, resulting in a high Obtaining a purity product becomes difficult. Therefore, the present inventors pay attention to the feature that mist of a volatile organic solvent is generated by bubbling of an inert gas and entrained in the inert gas stream, and the residual organic solvent is reduced to 100 ppm or less by bubbling of the inert gas. It was proposed to remove the quaternary unsaturated quaternary ammonium salt compound 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 an inert gas above the melting point of the unsaturated quaternary ammonium salt compound.

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

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

Since the unsaturated quaternary ammonium salt compound of the present invention is non-volatile, the gas flow rate during the inert gas 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 unsaturated quaternary ammonium salt compound of the present invention has high polymerizability, recovery and removal of the organic solvent by distillation under reduced pressure and inert gas bubbling under normal pressure should be carried out in the presence of a polymerization inhibitor. Is preferred. Known polymerization inhibitors can be used, such as hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl parahydroquinone, 2,5-di-tert-butyl hydroquinone, 2, Phenol compounds such as 4-dimethyl-6-tertbutylphenol and hydroquinone monomethyl ether, N-isopropyl-N′-phenyl-para-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-para-phenylene Such as diamine, N- (1-methylheptyl) -N′-phenyl-para-phenylenediamine, N, N′-diphenyl-para-phenylenediamine, N, N′-di-2-naphthyl-para-phenylenediamine, etc. Paraphenylenediamines, thiodiphenylamine, etc. Piperidine such as amine compounds, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 oxyl, acetamidotetramethylpiperidine-1-oxyl Examples thereof include 1-oxyl free radical compounds. 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 unsaturated quaternary ammonium salt compound of this invention, Preferably it is 5-5000 ppm.

By the above method, an unsaturated quaternary ammonium salt compound 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 unsaturated quaternary ammonium salt compound of the present invention is a 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 water or an organic solvent 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 in the range of 8 to 16 (cal / cm ³ ) ^0.5 .

The unsaturated quaternary ammonium salt compound of the present invention and / or the oligomer or / and polymer containing the unsaturated quaternary ammonium salt compound as a constituent component are used after being applied to a molded article such as plastic. In this case, the effects of antistatic properties, coating properties on plastics, 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, transparency, and high moisture resistance of the present invention. , By utilizing the excellent compatibility between the unsaturated quaternary ammonium salt compound and the polyfunctional (meth) acrylate or polyfunctional (meth) acrylamide, a uniform crosslinkable film can be formed on the surface of the substrate. The performance of the coating film such as film forming property and scratch resistance can be improved.

Examples of such polyfunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 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, 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 contain 0.001 to 25000 weight% with respect to the unsaturated quaternary ammonium salt compound structural unit of this invention, and also 50 to 20000 weight% It is particularly preferable to contain it. 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 unsaturated quaternary ammonium salt compound of the present invention is mixed with other polymerizable compounds to adjust various properties of the antistatic composition and the antistatic layer, for example, hardened or softened properties. Polymerizable compounds include alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, unsaturated nitrile monomers, unsaturated carboxylic acids, amide group-containing monomers, methylol group-containing monomers, alkoxymethyl group-containing monomers. And radical polymerization compounds having a reactive double bond in the molecular chain, such as epoxy group-containing monomers, polyfunctional monomers, vinyl esters, and olefins.

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 unsaturated quaternary ammonium salt compound 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%.

  The content of the unsaturated quaternary ammonium salt compound of the present invention is required for the polyfunctional (meth) acrylate to be used, the viscosity of the polyfunctional (meth) acrylamide, the blending amount of other polymerizable compounds, and the resin composition. Although it is based on physical properties, it is not particularly limited, but is 0.1 to 90% by weight, preferably 1 to 60% by weight in terms of solid content in the antistatic composition. When the content of the unsaturated quaternary ammonium salt compound 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 comprising unsaturated quaternary ammonium salt compound of the present invention and / or oligomer or polymer containing the compound as a constituent, polyfunctional (meth) acrylate or / and polyfunctional (meth) acrylamide as the antistatic agent Since the antistatic composition further containing is coated on a substrate by being cured, it is preferable to contain a reactive diluent or an organic solvent in order to adjust the viscosity to be paintable.

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 unsaturated quaternary ammonium salt compound of the present invention and the oligomer and polymer containing the compound as a constituent component. In particular, an organic solvent having a solubility parameter of 9 to 15 (cal / cm ³ ) ^0.5 is preferable for the unsaturated quaternary ammonium salt compound and the oligomer and polymer obtained by homopolymerization.

  Since the antistatic composition containing the unsaturated quaternary ammonium salt compound 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. 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 the unsaturated quaternary ammonium salt compound of the present invention is photocured, 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.

  As long as the properties such as antistatic properties and compatibility of the unsaturated quaternary ammonium salt compound of the present invention are not impaired, pigments, dyes, surfactants, antiblocking agents, binders, crosslinking agents, antioxidants, UV absorption You may use other arbitrary components, such as an agent, together.

When preparing the antistatic composition of the present invention, the addition order of these composition components is an unsaturated quaternary ammonium salt compound and / or an oligomer or polymer containing the unsaturated quaternary ammonium salt compound as a constituent component. , Reactive diluent and / or organic solvent, polyfunctional (meth) acrylate or / and polyfunctional (meth) acrylamide, photopolymerization initiator, and other additives are preferably used in this order.

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 unsaturated quaternary ammonium salt compound 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 (Kanto) Titration is performed by Chemical Co., Ltd., and the quaternary ammonium salt concentration is determined from the titration amount.
(2) Coating 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.
(3) Ultraviolet curing The coated surface was directed upward and cured by ultraviolet irradiation to obtain an antistatic hard coat film. 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 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
Δ: Slight cloudiness or unevenness;
X: Extremely cloudy or uneven (4) 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, measurement was performed using a HIGH RESISTANFE METER 4329A manufactured by Yokogawa HEWLETT-PACKARD.
(5) 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.
(6) 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;
(7) Pencil Hardness Test A pencil hardness test was performed on the antistatic hard coat film based on JIS K 5400.

Synthesis examples and comparative synthesis examples which are production examples of unsaturated quaternary ammonium salt compounds are shown below.

<Synthesis of unsaturated quaternary ammonium salt compound>
Synthesis example 1
Under a nitrogen atmosphere, 40 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) and 160 g of ethyl acetate were added to a 500 mL three-necked flask, the internal temperature was adjusted to 30 ° C., and trifluoromethanesulfonic acid was stirred. 45.4 g of methyl was added dropwise, and a quaternization reaction was carried out at a reaction temperature of 30 ° C to 35 ° C. After 6 hours, the reaction solution was taken out and concentrated under reduced pressure using an evaporator at 30 ° C. and 90 torr. Gas chromatograph quantitative analysis confirmed that ethyl acetate contained 9.1%. Subsequently, bubbling was performed with dry air at a flow rate of 10 mL / min at 35 ° C. under normal pressure for 4 hours, and 84.1 g of the target product acryloyloxyethyltrimethylammonium trifluoromethanesulfonate was obtained as a transparent liquid at room temperature. Obtained. According to a gas chromatograph, ethyl acetate was not detected (100 ppm or less), DMAEA 1000 ppm, and methyl trifluoromethanesulfonate was not detected (100 ppm or less). Further, the quaternary ammonium salt concentration (purity of the target product) was determined by potentiometric titration and found to be 99.8%. The yield was 99.0%. In elemental analysis, measured values (C: 35.07%, H: 5.11%, N: 4.38%) are theoretical values (C: 35.18%, H: 5.25%, N: 4. 56%). Chlorine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and their contents were 1 ppm or less.

Synthesis example 2
Under a nitrogen atmosphere, 40 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) and 110 g of butyl acetate were added to a 300 mL three-necked flask, the internal temperature was adjusted to 30 ° C., and trifluoromethanesulfonic acid was stirred. 43.7 g of methyl was added dropwise, and a quaternization reaction was carried out at a reaction temperature of 30 ° C to 35 ° C. After 5 hours, the lower quaternary ammonium salt layer separated into two layers was taken out and concentrated under reduced pressure at 40 ° C. and 5 torr. A gas chromatograph confirmed 10.5% butyl acetate. Subsequently, bubbling with dry air (flow rate 20 ml / min) was performed at 45 ° C. and normal pressure for 4 hours to obtain 80.1 g of the target product acryloyloxyethyltrimethylammonium trifluoromethanesulfonate as a transparent liquid at room temperature. It was. By gas chromatography, butyl acetate was not detected (100 ppm or less), DMAEA was not detected (100 ppm or less), and methyl trifluoromethanesulfonate was not detected (100 ppm or less). When the concentration of the quaternary ammonium salt (purity of the target product) was determined by potentiometric titration, it was 100%. The yield was 98.0%. In elemental analysis, measured values (C: 35.22%, H: 5.09%, N: 4.35%) are theoretical values (C: 35.18%, H: 5.25%, N: 4. 56%). Chlorine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and their contents were 1 ppm or less.

Synthesis example 3
Under a nitrogen atmosphere, 40 g of N, N-dimethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd .: DMAEMA) and 110 g of butyl acetate are added to a 300 mL three-necked flask, the internal temperature is adjusted to 30 ° C., and trifluoro is stirred. 38 g of methyl methanemethanesulfonate was added dropwise, and a quaternization reaction was carried out at a reaction temperature of 30 ° C to 35 ° C. After 2 hours, the precipitated crystals were filtered and dried under reduced pressure at 40 ° C. and 5 torr. The gas chromatograph confirmed butyl acetate 1.2%. Subsequently, the mixture was heated to 85 ° C. to melt the crystals, bubbled with dry air (flow rate 50 ml / min) for 3 hours under normal pressure, and the target product, methacryloyloxyethyltrimethylammonium trifluoromethanesulfonate, was cooled to room temperature. In this way, 71.0 g was obtained as white crystals that were smooth. By gas chromatography, butyl acetate was not detected (100 ppm or less), DMAMEA was 200 ppm, and methyl trifluoromethanesulfonate was not detected (100 ppm or less). 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 95.5%. In elemental analysis, measured values (C: 37.29%, H: 5.45%, N: 4.37%) are theoretical values (C: 37.38%, H: 5.65%, N: 4. 36%). Chlorine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and their contents were 1 ppm or less.

Synthesis example 4
Under a nitrogen atmosphere, 40 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) and 120 g of butyl acetate were added to a 300 mL three-necked flask, the internal temperature was adjusted to 30 ° C., and trifluoromethanesulfonic acid was stirred. Ethyl 47.4g was dripped and the quaternization reaction was implemented at reaction temperature 30 degreeC-35 degreeC. After 6 hours, the lower quaternary ammonium salt layer separated into two layers was taken out and concentrated under reduced pressure at 40 ° C. and 5 torr. The residual amount of butyl acetate was confirmed to be 9.7% by quantitative analysis using a gas chromatograph. Subsequently, bubbling was performed with dry air at a flow rate of 10 ml / min at 45 ° C. under normal pressure for 4 hours to obtain 82.8 g of the target product acryloyloxyethyldimethylethylammonium trifluoromethanesulfonate as a transparent liquid at room temperature. . By gas chromatography, butyl acetate was not detected (100 ppm or less), DMAEA was not detected (100 ppm or less), and ethyl trifluoromethanesulfonate was not detected (100 ppm or less). 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 97.0%. In elemental analysis, measured values (C: 37.25%, H: 5.67%, N: 4.18%) are theoretical values (C: 37.38%, H: 5.65%, N: 4. 36%). Chlorine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and their contents were 1 ppm or less.

Synthesis example 5
Under a nitrogen atmosphere, 40 g of N, N-dimethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd .: DMAEMA) and 110 g of butyl acetate are added to a 300 mL three-necked flask, the internal temperature is adjusted to 30 ° C., and trifluoro is stirred. 43.2 g of ethyl methane sulfonate was added dropwise, and a quaternization reaction was carried out at a reaction temperature of 30 ° C to 35 ° C. After 2 hours, the precipitated crystals were filtered and dried under reduced pressure at 40 ° C. and 5 torr. The gas chromatograph confirmed 1.6% of butyl acetate. Subsequently, the mixture was heated to 85 ° C. to melt the crystals, bubbled with dry air for 4 hours under normal pressure (flow rate: 50 mL / min), and the target product, methacryloyloxyethyldimethylethylammonium trifluoromethanesulfonate, was added. At room temperature, 76.4 g was obtained as white crystals that were smooth. By gas chromatography, butyl acetate was not detected (100 ppm or less), DMAMEA was 230 ppm, and ethyl trifluoromethanesulfonate was not detected (100 ppm or less). 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%. In elemental analysis, measured values (C: 39.28%, H: 5.99%, N: 4.15%) are theoretical values (C: 39.40%, H: 6.01%, N: 4. 18%). Chlorine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and their contents were 1 ppm or less.

Synthesis Example 6
Under a nitrogen atmosphere, 40 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) and 110 g of butyl acetate were added to a 300 mL three-necked flask, the internal temperature was adjusted to 30 ° C., and trifluoromethanesulfonic acid was stirred. 43.7 g of methyl was added dropwise, and a quaternization reaction was carried out at a reaction temperature of 30 ° C to 35 ° C. After 5 hours, the lower quaternary ammonium salt layer separated into two layers was taken out and concentrated under reduced pressure at 40 ° C. and 5 torr. A gas chromatograph confirmed 10.5% butyl acetate. Subsequently, bubbling was performed with dry nitrogen at 45 ° C. under normal pressure for 4 hours. By gas chromatograph, butyl acetate was not detected (100 ppm or less), DMAEA 1000 ppm, and methyl trifluoromethanesulfonate was not detected (100 ppm or less). As a result, 78.0 g of acryloyloxyethyltrimethylammonium trifluoromethanesulfonate was obtained as a transparent liquid. 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 93.8%. In elemental analysis, measured values (C: 35.13%, H: 5.32%, N: 4.55%) are theoretical values (C: 35.18%, H: 5.25%, N: 4. 56%). Chlorine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and their contents were 1 ppm or less.

Comparative Synthesis Example 1
In a 500 mL three-necked flask, 54.7 g of sodium trifluoromethanesulfonate was dissolved in ion-exchanged water to prepare an aqueous sodium trifluoromethanesulfonate solution. To this aqueous solution, 70 g of a 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) was added dropwise at 35 ° C. over 1 hour to obtain a uniform and transparent reaction solution. Subsequently, 200 g of ethyl acetate was added for extraction. Extraction was performed three times, and then the ethyl acetate layers were combined and concentrated by an evaporator. When the concentration of the quaternary ammonium salt in the concentrate was determined by potentiometric titration, it was not detected, and the target product was not obtained.

Comparative Synthesis Example 2
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, 49.4 g of sodium trifluoromethanesulfonate and 200 g of methanol were added to a 500 mL three-necked flask, and 100 g of the methanol solution containing DMAEA-Q 50% synthesized above was stirred at 25 ° C. for 1 hour while stirring the solution. And a white crystalline solid was deposited 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. Then, methanol in the filtrate was distilled off under reduced pressure to make acryloyloxyethyltrimethylammonium trifluoromethanesulfonate as a transparent liquid. 75.1 g was obtained. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 88.7% and the yield was 83.9%. Chlorine ion and sodium ion were quantified by ion chromatography, and the chlorine ion was 20800 ppm and the sodium ion was 2300 ppm.

Comparative Synthesis Example 3
Add 18.4 g of 2-aminoethyl methacrylate hydrochloride (Aldrich) and 500 mL of acetone to a 1 L three-necked flask, and add 65.7 g of methyl trifluoromethanesulfonate dropwise with stirring in an ice bath at 0 ° C. Subsequently, 83 g of potassium carbonate was added. The reaction solution was kept at 0 ° C. and stirred for 24 hours, and then acetone was distilled off under reduced pressure to obtain a suspended residue. Chloroform 500 mL and water 500 mL were added to the obtained residue, and the organic phase was separated with a separatory funnel and concentrated under reduced pressure to obtain a semi-solid product. Subsequently, ethyl acetate was added and stirred, insoluble solids were removed by filtration, and the filtrate was concentrated and dried under vacuum to obtain 18.5 g of a pale yellow solid powder. The gas chromatograph contained 2.3% ethyl acetate, and the generation of many impurities by-produced by the reaction of methyl trifluoromethanesulfonate and acetone was confirmed. When the purity of methacryloyloxyethyltrimethylammonium trifluoromethanesulfonate was determined by potentiometric titration, it was 57.5%. The yield was 33.1%.

Comparative Synthesis Example 4
Under a nitrogen atmosphere, 40 g of N, N-dimethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd .: DMAEMA) and 120 g of dichloromethane were added to a 300 mL three-necked flask, the internal temperature was adjusted to 35 ° C., and trifluoromethane was stirred. 41.8 g of methyl sulfonate was added dropwise, and a quaternization reaction was carried out at a reaction temperature of 35 to 40 ° C. After stirring for 8 hours, the reaction solution was concentrated under reduced pressure using an evaporator to obtain 52.5 g of a semi-solid product. The gas chromatograph confirmed the generation of a large number of impurities derived from 7.4% dichloromethane, 4.5% DMAEMA, and methyl trifluoromethanesulfonate. The purity of the quaternary ammonium salt methacryloyloxyethyltrimethylammonium trifluoromethanesulfonate was determined by potentiometric titration and found to be 74.8%. The yield was 48.1%. Chlorine ion was quantified by ion chromatography and found to be 79000 ppm.

As can be seen from the results of Synthesis Examples 1 to 6, according to the synthesis method of the present invention, no troubles such as polymerization occur, high purity and high yield, the target chloride ion free, metal ion free, and for reaction An unsaturated quaternary ammonium salt compound from which the organic solvent has been completely removed can be obtained.

On the other hand, from the results of Comparative Synthesis Examples 1 to 4, the target unsaturated quaternary ammonium salt compound and the by-product metal salt both dissolve in water when carried out in an anion exchange reaction performed in an aqueous solution. It was revealed that it was difficult to isolate an unsaturated quaternary ammonium salt compound, and an anion exchange reaction or an acid ester quaternization reaction was performed in an organic solvent such as methanol, acetone, or dichloromethane. However, there are many problems such as residual organic solvent, generation of by-products, residual chlorine ions and metal ions, and it is possible to obtain the desired unsaturated quaternary ammonium salt compound with high yield and high purity. Can not.

Examples and comparative examples in which an antistatic agent having an unsaturated quaternary ammonium salt compound 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 trifluoromethanesulfonate synthesized in Synthesis Example 1 in 120 parts by weight of IPA, pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate) PE-3A) 35 parts by weight, 3 parts by weight of Ciba Specialty Chemicals, trade name Darocure 1173 as a photoinitiator were added and mixed uniformly to obtain an anti-static hard coat agent capable of ultraviolet curing. 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 9, Comparative Examples A-10 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 acryloyloxyethyltrimethylammonium trifluoromethanesulfonate synthesized in Synthesis Example 1 and 0.2 parts by weight of azoisobutyronitrile (AIBN) were added to methanol. (MeOH) was mixed and dissolved in 120 parts by weight and polymerized at 60 ° C. for 8 hours under a nitrogen stream to obtain a quaternary ammonium salt homopolymer solution (a).
<Preparation of antistatic hard coating agent containing quaternary ammonium salt homopolymer>
10 parts by weight of the quaternary ammonium salt homopolymer solution (a), 50 parts by weight of pentaerythritol triacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-3A) and dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE) -6A) As a photoinitiator, 3 parts by weight of Ciba Specialty Chemicals, trade name Darocure 1173 as a photoinitiator was mixed and dissolved in 120 parts by weight of a 1: 1 solvent mixture of IPA and methyl ethyl ketone (MEK). 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>
In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, 10 parts by weight of acryloyloxyethyltrimethylammonium trifluoromethanesulfonate synthesized in Synthesis Example 1, 10 parts by weight of 2-ethylhexyl acrylate (EHA), and AIBN 0.2 Part by weight was 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 quaternary ammonium salt copolymer solution (b).
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 commercially available unsaturated quaternary ammonium salt has chlorine ions as anions, the coating film obtained therefrom is sticky and has transparency. It was found that a uniform coating film was not obtained due to these causes, the scratch resistance and hardness were lowered, and the antistatic effect was low. Furthermore, even when the metal ion concentration in the unsaturated quaternary ammonium salt compound is high, it becomes easy to absorb moisture, so that the resulting antistatic film has poor moisture resistance, causing problems such as whitening of the coating surface. To do. The unsaturated quaternary ammonium salt compound of the present invention is free of chloride ions, metal ions, does not contain organic solvents, has high compatibility with polyfunctional monomers and organic solvents, and is particularly nonpolar in antistatic agent compositions. Since it is compatible with the components, a uniform, transparent, non-colored antistatic coating can be obtained. The production method of the present invention is simple, and a high-purity target unsaturated quaternary ammonium salt compound can be obtained in high yield. Furthermore, the resulting high quality unsaturated quaternary ammonium salt compound 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 can be obtained.

As described above, the unsaturated quaternary ammonium salt compound of the present invention can be produced with high purity and high yield at a sufficient rate even at room temperature and normal pressure. In addition, it is free of chlorine ions, metal ions, and does not contain organic solvents, so it has low environmental impact, is applicable to electronic materials, and is compatible with antistatic compositions such as other polyfunctional monomers and organic solvents. Is good. The antistatic layer formed using the antistatic composition comprising this unsaturated quaternary ammonium salt compound is antistatic, transparent, scratch resistant, high in hardness, hardly colored, and has excellent moisture resistance. The antistatic layer comprising the unsaturated quaternary ammonium salt compound 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 (12)

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) An unsaturated quaternary ammonium salt represented by the general formula (2) in an organic solvent.

(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; A tertiary amine compound represented by formula (3):

(Wherein R ₄ represents an alkyl group having 1 to 3 carbon atoms or an aryl group) and is synthesized by a quaternization reaction with a trifluoromethanesulfonic acid ester represented by A method for producing a quaternary ammonium salt. In producing the unsaturated quaternary ammonium salt, an aprotic organic solvent composed of acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, methyl acetate, ethyl acetate, propyl acetate, and butyl acetate as an organic solvent The method for producing an unsaturated quaternary ammonium salt according to claim 1, wherein at least one selected from the group of solvents is used. 3. The method for producing an unsaturated quaternary ammonium salt according to claim 1, wherein the organic solvent is removed by inert gas bubbling in producing the unsaturated quaternary ammonium salt. In producing the unsaturated quaternary ammonium salt, the inert gas comprises dry noble gas such as dry nitrogen, dry air and dry helium, dry neon, dry argon, dry krypton, dry xenon and dry radon, The method for producing an unsaturated quaternary ammonium salt according to any one of claims 1 to 3, wherein at least one selected from a dry inert gas group that does not react with the unsaturated quaternary ammonium salt is used. . The chlorine ion-free (chlorine ion content is 1 ppm or less), metal ion-free (various metal ion content is 1 ppm or less) synthesized by the production method according to claim 1, and the content of the organic solvent is Unsaturated quaternary ammonium salt of less than 100 ppm. A chloride ion-free (chlorine ion content of 1 ppm or less) and metal ion-free (various metal ion content of 1 ppm or less) obtained by radical polymerization of the unsaturated quaternary ammonium salt according to claim 5 Oligomer or polymer. A chloride ion-free (chlorine ion content is 1 ppm or less) and metal ion-free (various metal ions) obtained by copolymerization of the unsaturated quaternary ammonium salt according to claim 5 and other copolymerizable vinyl monomers. A quaternary ammonium salt-containing co-oligomer or copolymer having a content of 1 ppm or less. A chlorine ion-free (chlorine ion content is 1 ppm or less) and metal ion-free (various metal ion content is 1 ppm or less) antistatic agent comprising the unsaturated quaternary ammonium salt and / or oligomer or polymer according to claim 5. The antistatic agent according to claim 8, or an antistatic composition containing the antistatic agent, comprising 0.1 to 90% by weight of the unsaturated quaternary ammonium salt as a constituent unit according to claim 5. . An antistatic composition comprising the antistatic agent according to claim 8 or 9, further comprising a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide. An antistatic layer formed by coating an antistatic agent or an antistatic composition according to any one of claims 8 to 10 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 11 on at least one side.