JP2011140448A - 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 highly pure ionic vinyl monomer; to provide the ionic vinyl monomer which is good in compatibility with resins and organic solvents, is high in hydrolysis resistance, is suitably used for various kinds of electrochemical devices, has an excellent antistatic effect, and is free from halogens and metal salts; and to provide an antistatic agent comprising the monomer. <P>SOLUTION: The method for producing 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 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) comprises the quaternization reaction of a tertiary amine compound with a thiocyanate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for producing a halogen-free and metal ion-free 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 known that acrylate and acrylamide cationic quaternary ammonium salts are used as base monomers for polymeric 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). 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, Patent Documents 7, 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. 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 the remaining halogen ions is high, and there is concern about corrosiveness to metals. Especially when it is used as an electronic material, it may cause functional deterioration and failure of electronic products. 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. As is well known, as a precondition for extraction from an aqueous solution into an organic solvent, it is essential that the target product is hardly soluble in water, soluble or easily soluble in an organic solvent, but is 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 these water-soluble thiocyanate anions, that is, the ionic vinyl of the present invention Monomers are of course also 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 is apparently 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 composed of an ammonium cation and a thiocyanate anion that is liquid at room temperature in a high yield, high purity and industrially has not been known. In addition, it has good compatibility with general-purpose acrylic monomers, has excellent hydrolysis resistance, can be applied to UV curing, and can maintain its antistatic effect for a long time after curing. A liquid ionic vinyl monomer, an antistatic agent comprising the monomer, and an antistatic composition 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 and is halogen-free and free of metal ions. 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.

（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。）

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、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。）

（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。）
As a result of intensive studies to solve these problems, the present inventor obtained an ionic vinyl monomer represented by the following general formula (1) as a tertiary amine compound represented by the following general formula (2): It has been found that it can be obtained by quaternizing a thiocyanate represented by the following general formula (3). Furthermore, the antistatic agent comprised with the said ionic vinyl monomer and / or the oligomer and polymer which consist of the said ionic monomer 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.

(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 represents an oxygen atom or —NH—, and Z represents an alkylene group of 1 to 3 carbon atoms.)

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 or different, and Y is an oxygen atom or —NH -Represents Z and an alkylene group having 1 to 3 carbon atoms. )

(In the formula, R ₄ represents an alkyl group having 1 to 3 carbon atoms or an aryl group.)

（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。）一般式（２）で表される３級アミン化合物、

（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、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。）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。）で表されるチオシアン酸エステルとの４級化反応により合成されることを特徴とする製造方法、
２）３級アミン化合物はＮ，Ｎ−二置換アミノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−二置換アミノアルキル（メタ）アクリレートであることを特徴とする前記１）記載の製造方法、
３）前記１）及び前記２）記載の製造方法で合成されるハロゲンフリー（各種ハロゲンイオン含量は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）のイオン性ビニルモノマー、４）前記３）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ハロゲンフリー各種ハロゲンイオン含量は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）のイオン性ホモオリゴマーとホモポリマー、
５）前記３）記載のイオン性ビニルモノマーと他の共重合可能のビニル系単量体との共重合で得られるハロゲンフリー（各種ハロゲンイオン含量は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）のイオン性コオリゴマーとコポリマー、
６）前記３）乃至前記５）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ハロゲンフリー各種ハロゲンイオン含量は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、
７）前記６）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３）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、８）前記６）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、９）基材上に前記６）〜８）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、１０）少なくとも片面に前記８）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.) General Formula (2) A tertiary amine compound represented by:

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 may be the same or different, and Y is an oxygen atom or — NH- represents Z represents an alkylene group having 1 to 3 carbon atoms) and general formula (3),

(Wherein R ₄ represents an alkyl group having 1 to 3 carbon atoms or an aryl group), and a quaternization reaction with a thiocyanate ester represented by
2) The production method according to 1) above, wherein the tertiary amine compound is N, N-disubstituted aminoalkyl (meth) acrylamide or N, N-disubstituted aminoalkyl (meth) acrylate,
3) Halogen-free (various halogen ion content is 1 ppm or less) and metal ion-free (various metal ion content is 1 ppm or less) synthesized by the production method according to 1) and 2), 4) 3) Halogen-free various halogen ion contents obtained by radical polymerization of the ionic vinyl monomer as described in 1 ppm or less) and metal ion-free (various metal ion content is 1 ppm or less) ionic homooligomers and homopolymers,
5) Halogen-free (various halogen ion content is 1 ppm or less) and metal ion-free (various metal ion content) obtained by copolymerization of the ionic vinyl monomer described in 3) above with other copolymerizable vinyl monomers Less than 1 ppm) ionic co-oligomer and copolymer,
6) Antistatic agent of halogen-free various halogen ions composed of the ionic vinyl monomer and / or oligomer or polymer described in 3) to 5) above and metal ion-free (various metal ion content of 1 ppm or less) ,
7) The antistatic agent described in 6) above or an antistatic composition containing the antistatic agent, which contains 0.1 to 90% by weight of the ionic vinyl monomer described in 3) above as a structural unit, 8) An antistatic composition containing the antistatic agent described in 6) above, further comprising a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide, 9) on a substrate An antistatic layer formed by applying an antistatic agent or an antistatic composition according to any one of 6) to 8) above and then polymerizing with an active energy ray or heat, 10) An antistatic film, a sheet comprising the antistatic layer described in 8) above on at least one surface;


Is to provide.

According to the method of the present invention, a high-purity ionic vinyl monomer that is liquid at room temperature and is free of metal ions and free of metal ions can be easily produced in a high yield. In addition, the antistatic agent and the antistatic composition comprising the ionic vinyl monomer as a constituent component have hydrolysis resistance, and are excellent in solubility and affinity in general-purpose acrylic monomers and organic solvents. It can be uniformly dispersed in the antistatic agent composition, 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 represents an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, Y represents an oxygen atom or —NH—, 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, methacryloyloxymethy Tripropylammonium thiocyanate, methacryloyloxyethyltrimethylammonium thiocyanate, methacryloyloxypropyltrimethylammonium thiocyanate, methacryloyloxypropylmethyldiethylammonium thiocyanate, methacryloyloxypropylethyldimethylammonium thiocyanate, methacryloyloxypropylmethyldi Propylammonium thiocyanate, methacryloyloxypropyltriethylammonium thiocyanate, methacryloyloxypropyltripropylammonium thiocyanate, methacryloyloxyethyldimethylbenzylammonium thiocyanate, methacryloyloxypropyldimethylbenzylammonium thiocyanate, methacrylate (Meth) acrylate-based ammonium alkyl thiocyanate quaternary cationic monomers such as Royloxypropyldiethylbenzylammonium thiocyanate, methacryloyloxypropylmethyldibenzylammonium thiocyanate, methacryloyloxypropylethyldibenzylammonium thiocyanate It is done. Among them, acryloylaminopropyltrimethylammonium thiocyanate, methacryloylaminopropyltrimethylammonium thiocyanate, acryloyloxyethyltrimethylammonium thiocyanate, methacryloyloxyethyltrimethylammonium ammonium are particularly easy to obtain inexpensive industrial raw materials. Thiocyanate is preferred.

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) acrylamide monomer and 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 Y Represents an oxygen atom or —NH—, and Z represents an alkylene group having 1 to 3 carbon atoms.

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

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 thiocyanate salt represented by the general formula (3). Specifically, methyl thiocyanate, ethyl thiocyanate, propyl thiocyanate, isopropyl thiocyanate, thiocyanbutyl, isobutyl thiocyanate, tert-butyl thiocyanate, pentyl thiocyanate, hexyl thiocyanate, heptyl thiocyanate, octyl thiocyanate Thiocyanate alkyl esters such as nonyl thiocyanate, decyl thiocyanate, thiocyanate cycloaliphatic esters such as cyclohexyl thiocyanate, thiocyanate such as phenyl thiocyanate, benzyl thiocyanate, tolyl thiocyanate, tolyl thiocyanate, xylyl thiocyanate An aryl ester is mentioned. Among these, methyl thiocyanate and ethyl thiocyanate are particularly preferable in terms of melting point and reactivity.

Although the molar ratio of the tertiary amine compound and the thiocyanate ester is arbitrary, the use of one of them in excess promotes the completion of the reaction. When the purpose is to use the polymerization characteristics of the ionic vinyl monomer of the present invention, excessive use of the polymerizable tertiary amine will affect the polymerization characteristics and antistatic performance of the ionic vinyl monomer even if a trace amount remains. Therefore, the molar ratio of tertiary amine / thiocyanate is 0.2 to 5 mol, preferably 0.5 to 2 mol.

The quaternization reaction of the present invention is possible even without solvent. Further, when the raw material tertiary amine or thiocyanate is solid at room temperature and has low solubility, it is preferable to add an organic solvent in order to carry out the reaction smoothly. The organic solvent to be used is not particularly limited as long as it is effective for dissolving the raw material. Examples thereof include alcohols such as methanol, ethanol, isopropanol, and propylene glycol monomethyl ether, and nonpolar organic solvents such as acetone, ethyl acetate, methyl ethyl ketone, and toluene. Further, the amount of the organic solvent used is not particularly limited, but a range in which the concentration of the raw thiocyanate is 1 to 95% is preferable. A range of 5 to 90 is particularly preferable. If it is less than 1%, the reaction rate is remarkably slow. If it exceeds 95%, the viscosity of the pre-reaction reaction solution is high, and the polymerizable compound in the reaction solution may be polymerized.

The reaction temperature when synthesizing the ionic vinyl monomer of the present invention is usually preferably 10 ° C or higher and 15 to 130 ° C, particularly preferably 40 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 the 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.

The moisture in the reaction system may cause by-product impurities of thiocyanate hydrolysis, and is preferably as low 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.

Of course, the ionic vinyl monomer of the present invention is a halogen-free and metal ion-free high-quality product. Of course, the total of various halogen ions contained in the aforementioned raw materials is 1 ppm or less, and various metal ions. Is required to be 1 ppm or less. Here, the halogen ion is an ion containing fluorine, chlorine, bromine or iodine, and the metal ion is a divalent metal ion such as sodium ion, lithium ion or potassium ion, calcium ion or magnesium ion. Metal ions, aluminum ions, iron ions, and other polyvalent metal ions.

After completion of the reaction, depending on the compatibility between the surplus raw material and the ionic vinyl monomer which is the product of the reaction solvent, it can be easily separated and recovered by distillation, extraction and thin film treatment, and can be used repeatedly. Moreover, it can also be used for the following superposition | polymerization process as a mixture or solution of an ionic vinyl monomer, and an antistatic film | membrane can also be produced as an antistatic agent composition.

By the above method, a high purity halogen-free and metal ion-free ionic vinyl monomer can be obtained. Furthermore, you may refine | purify by purification means, such as column chromatography, as needed.

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.

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

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

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

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

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

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

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

Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile.

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

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

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

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

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

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

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

The organic solvent is preferably one that can dissolve the ionic vinyl monomer of the present invention, oligomers and polymers containing the monomer as constituents. In particular, an organic solvent having a solubility parameter of 9 to 12 (cal / cm ³ ) ^0.5 is preferable for the ionic vinyl monomer and the oligomer and polymer obtained by homopolymerization.

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

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

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

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

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

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

In the following examples and comparative examples, the characteristics of the antistatic composition were evaluated by the following methods. (1) 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) Method for quantifying tertiary amine Titration was performed with an aqueous potentiometric titrator (device name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.) using a hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a concentration of 0.25 mol / L. And determine the tertiary amine concentration from the titer. (3) Coating 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. 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 (RDS12) so that an equal force is applied to the whole. The same speed without rotation (5 cm / sec) The film was pulled to the near side and applied, 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. (4) The surface of the ultraviolet curable coating was turned upward to be cured by irradiating with ultraviolet rays 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; △: Slightly cloudy or uneven; x: Extremely cloudy or uneven (5) Surface resistivity measurement type Using a plate (110 x 110 mm), cut the antistatic hard coat film with a cutter knife and place it in a constant temperature and constant temperature machine adjusted to a temperature of 25 ° C, relative humidity of 30%, 60% and 90%, and allowed to stand for 24 hours. The sample for surface resistivity measurement was obtained. Based on JIS K 6911, measurement was performed using a HIGH RESISTANFE METER 4329A manufactured by Yokogawa HEWLETT-PACKARD. (6) Scratch resistance test Using steel wool of # 0000, the steel wool was reciprocated 10 times on the antistatic hard coat film while applying a load of 200 g / cm ² to evaluate the presence or absence of scratches. Scratch resistance evaluation A: Almost no film peeling or scratching is observed; ○: Slight thin scratches are observed on the film; Δ: Striped scratches are observed on the entire surface of the film; X: Film peeling Arise. (7) Pencil hardness test An antistatic hard coat agent is dropped on 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. A pencil hardness test was performed based on JIS K 5400.

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 300 g of ethyl acetate were added to a 1 L three-necked flask, and the internal temperature was 50 ° C. While stirring and stirring, 47.3 g of methyl thiocyanate was added dropwise to carry out a quaternization reaction. After 16 hours, the lower layer separated into two layers was taken out and concentrated under reduced pressure. As a result, 143.5 g of acryloylaminopropyltrimethylammonium thiocyanate was obtained as a transparent liquid. When the quaternary ammonium salt concentration (purity of the target product) and tertiary amine concentration were determined by potentiometric titration, they were 99.4% and 0.11%, respectively. The yield was 99.3%. In elemental analysis, measured values (C: 52.12%, H: 8.21%, N: 18.18%) are theoretical values (C: 52.37%, H: 8.35%, N: 18. 32%). Chlorine ions, bromine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and the respective contents were 1 ppm or less.

Synthesis example 2
Under a nitrogen atmosphere, 100 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: DMAPAA) and 200 g of isopropanol (IPA) are added to a 1 L three-necked flask, adjusted to an internal temperature of 50 ° C., and stirred with methyl thiocyanate. 47g was dripped and quaternization reaction was implemented. After 12 hours, 338 g of an IPA solution of acryloylaminopropyltrimethylammonium thiocyanate was obtained as a clear liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the concentration of the target product was 42.6%, and the yield of the target product calculated from this was 98.6%. The tertiary amine concentration was 0.30%. In elemental analysis, the actual values (C: 52.22%, H: 8.13%, N: 18.25) are the theoretical values (C: 52.37%, H: 8.35%). , N: 18.32%). Chlorine ions, bromine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and the respective contents were 1 ppm or less.

Synthesis example 3
Under a nitrogen atmosphere, 100 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: DMAPAA) was added to a 300 mL three-necked flask, adjusted to an internal temperature of 50 ° C., and 47.3 g of methyl thiocyanate was added dropwise with stirring. A quaternization reaction was carried out. After 6 hours, 146.8 g of acryloylaminopropyltrimethylammonium thiocyanate was obtained as a transparent liquid. When the quaternary ammonium salt concentration (purity of the target product) and tertiary amine concentration were determined by potentiometric titration, they were 97.8% and 0.25%, respectively. The yield was 97.7%. In elemental analysis, actual values (C: 52.27%, H: 8.51%, N: 18.13%) are theoretical values (C: 52.37%, H: 8.35%) in elemental analysis. N: 18.32%). Chlorine ions, bromine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and the respective contents were 1 ppm or less.

Synthesis example 4
In Synthesis Example 1, 56.3 g of ethyl thiocyanate was used instead of methyl thiocyanate and reacted in the same manner as in Synthesis Example 1 to obtain 154.9 g of the desired product acryloylaminopropyldimethylethylammonium thiocyanate as a transparent liquid. . When the quaternary ammonium salt concentration (purity of the target product) and tertiary amine concentration were determined by potentiometric titration, they were 98.8% and 0.31%, respectively. The yield was 99.4%. In elemental analysis, measured values (C: 54.14%, H: 8.59%, N: 17.02%) are theoretical values (C: 54.29%, H: 8.70%, N: 17. 27%). Chlorine ions, bromine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and the respective contents were 1 ppm or less.

Synthesis Example 5 In Synthesis Example 1, 100 g of N, N-dimethylaminopropyl methacrylamide (manufactured by MRC Unitech Co., Ltd .: DMAPMA) was used instead of DMAPAA, and the reaction was conducted in the same manner as in Synthesis Example 1 to produce the desired product methacryloylaminopropyltrimethylammonium. 136.3 g of thiocyanate was obtained as a transparent liquid. When the quaternary ammonium salt concentration (purity of the target product) and tertiary amine concentration were determined by potentiometric titration, they were 97.5% and 0.27%, respectively. The yield was 96.3%. In elemental analysis, measured values (C: 54.12%, H: 8.43%, N: 17.03%) are theoretical values (C: 54.29%, H: 8.70%, N: 17.5%). 27%). Chlorine ions, bromine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and the respective contents were 1 ppm or less.

Synthetic Example 6 In Synthetic Example 2, 100 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) was used instead of DMAPAA and reacted in the same manner as in Synthetic Example 2, and the target product acryloyloxyethyltrimethylammonium thiocyanate 348 g of an IPA solution of natto was obtained as a clear liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the concentration of the target product was 41.1%, and the yield of the target product calculated from this was 95.1%. The tertiary amine concentration was 0.35%. In elemental analysis, the measured values (C: 50.04%, H: 7.53%, N: 13.05) are theoretical values (C: C: 49.98%, H: 7. 46%, N: 12.95%). Chlorine ions, bromine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and the respective contents were 1 ppm or less.

Synthesis Example 7 In Synthesis Example 3, 100 g of N, N-dimethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd .: DMAEMA) was used in place of DMAPAA and reacted in the same manner as in Synthesis Example 3 to produce the desired product methacryloyloxyethyltrimethyl. 145.6 g of ammonium thiocyanate was obtained as a transparent liquid. When the quaternary ammonium salt concentration (purity of the target product) and tertiary amine concentration were determined by potentiometric titration, they were 98.5% and 0.17%, respectively. The yield was 97.9%. In the elemental analysis, in the elemental analysis, the actual measurement values (C: 52.13%, H: 8.02%, N: 12.21%) are theoretical values (C: 52.15%, H: 7.88%, N: 12.16%). Chlorine ions, bromine ions, sodium ions, potassium ions, lithium ions, and calcium ions were quantified by ion chromatography, and the respective contents were 1 ppm or less.

Comparative Synthesis Example 11 In a three-necked flask of 11 L, 81.1 g of sodium thiocyanate was dissolved in 165 g of ion-exchanged water to obtain a sodium thiocyanate aqueous solution. A DMAPAA-Q 37% aqueous solution obtained by dissolving 286 g of 75% aqueous solution of acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: DMAPAA-Q) in 300 g of ion-exchanged water 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 21 In a three-necked flask of 21 L, 97 g of potassium thiocyanate was dissolved in 200 g of ion-exchanged water to obtain a potassium thiocyanate aqueous solution. A DMAPAA-Q 37% aqueous solution obtained by dissolving 286 g of 75% aqueous solution of acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: DMAPAA-Q) in 300 g of ion-exchanged water 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 33 In a 3 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. A 26% aqueous solution of DMAPMA-Q obtained by dissolving 261 g of methacryloylaminopropyltrimethylammonium chloride (manufactured by MRC Unitech Co., Ltd .: MAPTAC) in 1000 g of ion-exchanged water was added dropwise to this aqueous solution 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 41 In a three-necked flask of 41 L, 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, a DMAEA-Q 37% aqueous solution obtained by dissolving 250 g of 79% aqueous solution of acryloyloxyethyltrimethylammonium chloride (manufactured by Kojin: DMAEA-Q) in 280 g of ion-exchanged water 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 51 In a three-necked flask of 51 L, 97 g of potassium thiocyanate was dissolved in 1000 g of ion-exchanged water to obtain a potassium thiocyanate aqueous solution. To this aqueous solution, a DMAPAA-Q 20.5% aqueous solution obtained by dissolving 205 g of methacryloyloxyethyltrimethylammonium chloride (manufactured by Kyoeisha Chemical Co., Ltd .: DQ-100) in 1000 g of ion-exchanged water 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.

As can be seen from the results of Synthesis Examples 1 to 7, according to the synthesis method of the present invention, the target halogen-free and metal ion-free ionic vinyl can be obtained with high purity and high yield without causing problems such as polymerization. Monomer was obtained.

On the other hand, in Comparative Synthesis Examples 1 to 5 carried out in an anion exchange reaction carried out in an aqueous solution, 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.

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>
5 parts by weight of ionic homopolymer solution (a), 50 parts by weight of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate PE-3A) and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) 50 parts by weight and, as a photoinitiator, 5 parts by weight of Ciba Specialty Chemicals, trade name Darocure 1173, are mixed and dissolved in 120 parts by weight of a mixed solvent of 1: 1 weight ratio of IPA and methyl ethyl ketone (MEK), An antistatic hard coat agent containing an ultraviolet curable quaternary salt polymer 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 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 8, Comparative Examples B-9 to 10
An antistatic hard coat was prepared and evaluated in the same manner as in Example B-1, except that the composition shown in Table 3 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, is halogen-free and metal salt-free, has high compatibility with polyfunctional monomers and organic solvents, and is particularly nonpolar in an antistatic agent composition. Since it was compatible with the components, a uniform, transparent, non-colored antistatic coating film 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 is halogen-free and free of metal ions, it has little environmental impact, is applied to electronic materials, and has good compatibility with antistatic compositions such as other 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 (10)

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 is represented by the general formula (2)

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 may be the same or different, and Y is an oxygen atom or — A tertiary amine compound represented by the general formula (3): and NH—, Z represents an alkylene group having 1 to 3 carbon atoms.

(Wherein R ₄ represents an alkyl group having 1 to 3 carbon atoms or an aryl group), and a quaternization reaction with a thiocyanate ester represented by the production method. The production method according to claim 1, wherein the tertiary amine compound is N, N-disubstituted aminoalkyl (meth) acrylamide or N, N-disubstituted aminoalkyl (meth) acrylate. A halogen-free (various halogen content is 1 ppm or less) and metal ion-free (various metal ion content is 1 ppm or less) ionic vinyl monomer synthesized by the production method according to claim 1 or 2. A halogen-free (various halogen content is 1 ppm or less) and metal ion-free (various metal ion content is 1 ppm or less) ionic homo-oligomer and homopolymer obtained by radical polymerization of the ionic vinyl monomer according to claim 3. 4. Halogen-free (various halogen content is 1 ppm or less) and metal ion-free (various metal ion content is 1 ppm or less) obtained by copolymerization of the ionic vinyl monomer according to claim 3 and other copolymerizable vinyl monomers. ) Ionic co-oligomers and copolymers. 6. A halogen-free (various halogen content is 1 ppm or less) and metal ion-free (various metal ion content is 1 ppm or less) antistatic agent comprising the ionic vinyl monomer and / or oligomer or polymer according to claim 3. The antistatic agent according to claim 6 or an antistatic composition containing the antistatic agent, wherein the ionic vinyl monomer according to claim 3 is contained as a constituent unit in an amount of 0.1 to 90% by weight. An antistatic composition comprising the antistatic agent according to claim 6, 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 6 to 8 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 8 on at least one side.