JP5638250B2 - Antistatic agent and antistatic composition comprising unsaturated quaternary ammonium salt compound - Google Patents

Description

The present invention relates to an unsaturated quaternary ammonium salt compound which is highly safe and harmless to the environment and is liquid at room temperature, an antistatic agent comprising the unsaturated quaternary ammonium salt compound, and a charge containing the antistatic agent The present invention relates to a preventive resin composition.

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

Since acrylate-based and acrylamide-based cationic quaternary ammonium salts have polymerizability, they are known to be used as base monomers for polymer antistatic compositions (
Patent Documents 3-8). However, many polymerizable ammonium salts use halogen ions such as chlorine, bromo and iodine, and fluorine ions such as tetrafluoroborate, hexafluorophosphate and bis (trifluoromethanesulfonyl) imide as anions. These anions are low in raw material safety and extremely indegradable in the natural environment. Therefore, they are harmful to the environment, and there is concern about corrosiveness to metals. Especially when they are used as electronic materials, It may cause deterioration of function or failure.

JP 2008-231240 A JP 2008-13636 A JP 2008-231196 A Japanese Patent Laid-Open No. 63-201115 Japanese Patent Laid-Open No. 07-150130 JP 2007-51241 A JP 2007-9042 A JP 2005-255843 A

As mentioned above, it is an antistatic agent that is highly safe, harmless to the environment, can be polymerized by irradiation with energy rays such as UV, and has a long antistatic effect after polymerization, and contains halogens such as chlorine and fluorine. However, an unsaturated quaternary ammonium salt compound having excellent hydrolysis resistance has not yet been obtained.

The first object of the present invention is halogen-free, highly safe, harmless to the environment, easy to handle because it is liquid at room temperature, can be polymerized by irradiation with energy rays such as UV, and water, organic solvents,
An object of the present invention is to provide an unsaturated quaternary ammonium salt compound which has good compatibility with other antistatic agent compositions such as a common vinyl monomer and has excellent hydrolysis resistance. The second object of the present invention is to provide an efficient and economical method for producing the unsaturated quaternary ammonium salt compound. The third object of the present invention is to have a high safety comprising the unsaturated quaternary ammonium salt compound, a low environmental load, a long-lasting antistatic effect, excellent hydrolysis resistance, high hardness and high transparency. It is providing the antistatic agent which has the property, and the antistatic resin composition containing this antistatic agent.

As a result of intensive studies to solve these problems, the present inventor has found that these problems can be solved by using an unsaturated quaternary ammonium salt compound represented by the following general formula (1).

High purity of the unsaturated quaternary ammonium salt compound by anion exchange reaction of quaternary cationic vinyl monomer and saccharinate metal salt and acesulfamate metal salt, which are highly safe sweeteners used as food additives The present inventors have found a method that can be obtained in a high yield, and further found that the problems of the antistatic agent and the antistatic composition can be solved by using the unsaturated quaternary ammonium salt compound.

（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、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。）
２）上記１）記載の不飽和第４級アンモニウム塩化合物を構成成分として含むオリゴマー又はポリマー、
３）上記１）記載の不飽和第４級アンモニウム塩化合物及び／又は上記２）記載のオリゴマー若しくはポリマーからなる帯電防止剤、
４）上記３）記載の帯電防止剤を含有する帯電防止組成物であって、上記１）記載の不飽和第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、
５）上記３）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、
６）基材上に上記３）〜５）いずれか一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性ハードコート層、
７）少なくとも片面に上記６）記載の帯電防止性ハードコート層を有することを特徴とする帯電防止フィルム、
を提供するものである。 That the present invention, 1) a general formula (1) or general formula (2) that is represented by unsaturated quaternary ammonium salt compound, the compound is free of halogen, unsaturated fourth that is liquid at room temperature Quaternary ammonium salt compounds ,

(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 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.)
2) an oligomer or polymer containing the unsaturated quaternary ammonium salt compound according to 1) as a constituent;
3) An antistatic agent comprising the unsaturated quaternary ammonium salt compound described in 1) above and / or the oligomer or polymer described in 2) above,
4) An antistatic composition containing the antistatic agent described in 3) above , which contains 0.1 to 90% by weight of the unsaturated quaternary ammonium salt compound described in 1) as a structural unit;
5) An antistatic composition containing the antistatic agent described in 3) above, further comprising a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide,
6) Antistatic, characterized by being formed by coating the base material with the antistatic agent or antistatic composition according to any one of 3) to 5) above and then polymerizing with active energy rays or heat. Hard coat layer,
7) An antistatic film comprising the antistatic hard coat layer described in 6) above on at least one surface;
Is to provide.

The unsaturated quaternary ammonium salt compound of the present invention uses a saccharinate metal salt or an acesulfamate metal salt of a sweetener that is a food additive as a raw material, and thus is highly safe and harmless to the environment. Moreover, since it does not contain halogen, the antistatic agent and antistatic agent composition comprising the unsaturated quaternary ammonium salt compound are also suitably used for various electrochemical devices.

The unsaturated quaternary ammonium salt compound of the present invention is liquid at room temperature, and is excellent in solubility and affinity in water, organic solvents, and common vinyl monomers, so it can be handled easily and coated evenly on the substrate. It does not bleed out after curing by UV irradiation or the like, and the antistatic effect lasts.

The unsaturated quaternary ammonium salt compound of the present invention is a (meth) acrylamide monomer and a (meth) acrylate monomer that can be easily copolymerized with a common vinyl monomer, and is water-insoluble by copolymerization with a hydrophobic vinyl monomer. Thus, various novel antistatic agents and antistatic agent compositions having excellent hydrolysis resistance and having extremely little influence on the antistatic effect due to the humidity of the surrounding environment can be provided. Furthermore, it is possible to provide an antistatic layer, an antistatic film or an antistatic film having a high hardness, high wear resistance and excellent transparency.

Hereinafter, the present invention will be described in detail. The antistatic agent of the present invention comprises a quaternary ammonium (meth) acrylamide monomer represented by the general formula (1) or the general formula (2), a quaternary ammonium (meth) acrylate monomer, and those monomers. It consists of any one or more of oligomers or polymers to be constituted.

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

Specific examples of the quaternary ammonium monomer that is the antistatic agent of the present invention include acryloylaminomethyltrimethylammonium saccharinate, acryloylaminomethyltriethylammonium saccharinate, acryloylaminomethyltripropylammonium saccharinate, and acryloylamino. Ethyltrimethylammonium saccharinate,
Acryloylaminopropyltrimethylammonium saccharinate, acryloylaminopropylmethyldiethylammonium saccharinate, acryloylaminopropylethyldimethylammonium saccharinate, acryloylaminopropylmethyldipropylammonium saccharinate, acryloylaminopropyltriethylammonium saccharinate, acryloyl Aminopropyltripropylammonium saccharinate,
Acryloylaminoethyldimethylbenzylammonium saccharinate, acryloylaminopropyldimethylbenzylammonium saccharinate, acryloylaminopropyldiethylbenzylammonium saccharinate, acryloylaminopropylmethyldibenzylammonium saccharinate, acryloylaminopropylethyldibenzylammonium saccharide Methacryloylaminomethyltrimethylammonium saccharinate, methacryloylaminomethyltriethylammonium saccharinate, methacryloylaminomethyltripropylammonium saccharinate, methacryloylaminoethyltrimethylammonium saccharinate, methacryloylaminopropyltrimethylammonium saccharine Methacryloylaminopropylmethyldiethylammonium saccharinate, methacryloylaminopropylethyldimethylammonium saccharinate, methacryloylaminopropylmethyldipropylammonium saccharinate, methacryloylaminopropyltriethylammonium saccharinate, methacryloylaminopropyltripropylammonium saccharide Methacryloylaminoethyldimethylbenzylammonium saccharinate, methacryloylaminopropyldimethylbenzylammonium saccharinate, methacryloylaminopropyldiethylbenzylammonium saccharinate, methacryloylaminopropylmethyldibenzylammonium saccharinate, methacryloylaminopropyl (Meth) acrylamide-based ammonium alkyl saccharinates such as tildibenzylammonium saccharinate, or acryloyloxymethyltrimethylammonium saccharinate, acryloyloxymethyltriethylammonium saccharinate, acryloyloxymethyltripropylammonium saccharinate Linates, acryloyloxyethyltrimethylammonium saccharinate, acryloyloxypropyltrimethylammonium saccharinate, acryloyloxypropylmethyldiethylammonium saccharinate, acryloyloxypropylethyldimethylammonium saccharinate, acryloyloxypropylmethyldipropylammonium saccharide Nate, acryloyl oxyp Propyl triethylammonium saccharinate, acryloyloxypropyltripropylammonium saccharinate, acryloyloxyethyldimethylbenzylammonium saccharinate, acryloyloxypropyldimethylbenzylammonium saccharinate, acryloyloxypropyldiethylbenzylammonium saccharinate, acryloyloxy Propylmethyldibenzylammonium saccharinate, acryloyloxypropylethyldibenzylammonium saccharinate, methacryloyloxymethyltrimethylammonium saccharinate, methacryloyloxymethyltriethylammonium saccharinate, methacryloyloxymethyltripropylammonium saccharinate, methacryloyl Xylethyltrimethylammonium saccharinate, methacryloyloxypropyltrimethylammonium saccharinate, methacryloyloxypropylmethyldiethylammonium saccharinate, methacryloyloxypropylethyldimethylammonium saccharinate, methacryloyloxypropylmethyldipropylammonium saccharinate, methacryloyloxy Propyltriethylammonium saccharinate, methacryloyloxypropyltripropylammonium saccharinate, methacryloyloxyethyldimethylbenzylammonium saccharinate, methacryloyloxypropyldimethylbenzylammonium saccharinate, methacryloyloxypropyldiethylbenzylammonium saccharinate Sulfonates, methacryloyloxypropyl methyl dibenzyl ammonium saccharinate, etc. (meth) acrylate ammonium alkyl saccharinate such methacryloyloxypropyltrimethoxysilane ethyl dibenzyl ammonium saccharinate may be mentioned. Among them, acryloylaminopropyltrimethylammonium saccharinate, methacryloylaminopropyltrimethylammonium saccharinate, acryloyloxyethyltrimethylammonium saccharinate, methacryloyloxyethyltrimethylammonium ammonium are particularly easy to obtain inexpensive industrial raw materials. Saccharinate is preferred.

Specific examples of the quaternary ammonium monomer that is the antistatic agent of the present invention include acryloylaminomethyltrimethylammonium acesulfamate, acryloylaminomethyltriethylammonium acesulfamate, acryloylaminomethyltripropylammonium acesulfamate, acryloylamino. Ethyltrimethylammonium acesulfamate, acryloylaminopropyltrimethylammonium acesulfamate, acryloylaminopropylmethyldiethylammonium acesulfamate, acryloylaminopropylethyldimethylammonium acesulfamate, acryloylaminopropylmethyldipropylammonium acesulfamate, acryloylaminopropyl Triethylammoni Muacesulfamate, acryloylaminopropyltripropylammonium acesulfamate, acryloylaminoethyldimethylbenzylammonium acesulfamate, acryloylaminopropyldimethylbenzylammonium acesulfamate, acryloylaminopropyldiethylbenzylammonium acesulfamate, acryloylaminopropylmethyldi Benzylammonium acesulfamate, acryloylaminopropylethyldibenzylammonium acesulfamate, methacryloylaminomethyltrimethylammonium acesulfamate, methacryloylaminomethyltriethylammonium acesulfamate, methacryloylaminomethyltripropylammonium acesulfamate Methacryloylaminoethyltrimethylammonium acesulfamate, methacryloylaminopropyltrimethylammonium acesulfamate, methacryloylaminopropylmethyldiethylammonium acesulfamate, methacryloylaminopropylethyldimethylammonium acesulfamate, methacryloylaminopropylmethyldipropylammonium acesulfamate, methacryloyl Aminopropyltriethylammonium acesulfamate, methacryloylaminopropyltripropylammonium acesulfamate, methacryloylaminoethyldimethylbenzylammonium acesulfamate, methacryloylaminopropyldimethylbenzylammonium acesulfamate, methacryloyl (Meth) acrylamide ammonium alkyl acesulfamate quaternary cationic monomers such as ruaminopropyldiethylbenzylammonium acesulfamate, methacryloylaminopropylmethyldibenzylammonium acesulfamate, methacryloylaminopropylethyldibenzylammonium acesulfamate Named,
Or acryloyloxymethyltrimethylammonium acesulfamate, acryloyloxymethyltriethylammonium acesulfamate, acryloyloxymethyltripropylammonium acesulfamate, acryloyloxyethyltrimethylammonium acesulfamate, acryloyloxypropyltrimethylammonium acesulfamate, acryloyloxypropyl Methyldiethylammonium acesulfamate, acryloyloxypropylethyldimethylammonium acesulfamate, acryloyloxypropylmethyldipropylammonium acesulfamate, acryloyloxypropyltriethylammonium acesulfamate, acryloyloxypropyltripropyla Monium acesulfamate, acryloyloxyethyldimethylbenzylammonium acesulfamate, acryloyloxypropyldimethylbenzylammonium acesulfamate, acryloyloxypropyldiethylbenzylammonium acesulfamate, acryloyloxypropylmethyldibenzylammonium acesulfamate, acryloyloxypropylethyl Dibenzylammonium acesulfamate, methacryloyloxymethyltrimethylammonium acesulfamate, methacryloyloxymethyltriethylammonium acesulfamate,
Methacryloyloxymethyltripropylammonium acesulfamate, methacryloyloxyethyltrimethylammonium acesulfamate, methacryloyloxypropyltrimethylammonium acesulfamate, methacryloyloxypropylmethyldiethylammonium acesulfamate, methacryloyloxypropylethyldimethylammonium acesulfamate, methacryloyloxy Propylmethyldipropylammonium acesulfamate, methacryloyloxypropyltriethylammonium acesulfamate, methacryloyloxypropyltripropylammonium acesulfamate, methacryloyloxyethyldimethylbenzylammonium acesulfamate, methacryloyloxy Dimethyl benzyl ammonium acesulfamate, methacryloyloxypropyl diethyl benzyl ammonium acesulfamate,
And (meth) acrylate-based ammonium alkyl acesulfamate quaternary cationic monomers such as methacryloyloxypropylmethyldibenzylammonium acesulfamate and methacryloyloxypropylethyldibenzylammonium acesulfamate. Among these, acryloylaminopropyltrimethylammonium acesulfamate, methacryloylaminopropyltrimethylammonium acesulfamate, acryloyloxyethyltrimethylammonium acesulfamate, methacryloyloxyethyltrimethylammonium are particularly easy to obtain inexpensive industrial raw materials. Acesulfamate is preferred.

The unsaturated quaternary ammonium salt compound of the present invention can be produced by various methods. A typical method is shown in the following reaction 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, 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 1 to 3 carbon atoms. X ⁻ represents Cl ⁻ , B
r ⁻ , I ^{− and the} like halogen ions or OH ⁻ , CH ₃ COOH ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , HS
O ₄ ⁻ , CH ₃ SO ₃ ⁻ , CH ₃ C ₆ H ₆ SO ₃ ⁻ , SCN ⁻ or the like represents an inorganic acid anion or an organic acid anion, and M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , Ag ^+. , NH ₄ ⁺ , A−
Represents saccharinate and acesulfamate. ).

Reaction formula (1)

（式中、Ｒ_１は水素原子またはメチル基を、Ｒ_２及びＲ_３は各々独立に炭素数１〜３の
アルキル基で互いに同一であっても異なっていてもよく、Ｒ_４は炭素数１〜３のアルキル
基、炭素数１〜３のアルケニル基またはベンジル基を表し、Ｙは酸素原子または−ＮＨ−
を表し、Ｚは炭素数１〜３のアルキレン基を表し、Ｘ^-はＣｌ^-、Ｂｒ^-、Ｉ^-などハロゲン
イオンまたはＯＨ^-、ＣＨ_３ＣＯＯＨ^-、ＮＯ_３ ^-、ＣｌＯ_４ ^-、ＨＳＯ_４ ^-、ＣＨ_３ＳＯ_３ ^-
、ＣＨ_３Ｃ_６Ｈ_６ＳＯ_３ ^-、ＳＣＮ^-など無機酸アニオンまたは有機酸アニオンを表す）で
表されるアニオンを有する４級カチオン性ビニルモノマーと一般式（４）

（式中、Ｍ^＋はＨ^＋、Ｎａ^＋、Ｋ^＋、Ｌｉ^＋、Ａｇ^＋、ＮＨ_４ ^＋を表す）で表されるサ
ッカリネートの酸、金属塩または有機塩、一般式（５）

（式中、Ｍ^＋はＨ^＋、Ｎａ^＋、Ｋ^＋、Ｌｉ^＋、Ａｇ^＋、ＮＨ_４ ^＋を表す）で表されるア
セスルファメートの酸、金属塩または有機塩を溶媒中で中和またはアニオン交換により合
成することができる。 That is, the general formula (3)

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other, and R ₄ has 1 carbon atom) Represents an alkyl group of ˜3, an alkenyl group of 1 to 3 carbon atoms or a benzyl group, Y is an oxygen atom or —NH—
Z represents an alkylene group having 1 to 3 carbon atoms, X ⁻ represents a halogen ion such as Cl ⁻ , Br ⁻ and I ⁻ or OH ⁻ , CH ₃ COOH ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ and HSO ₄ ^−. , _{CH 3} SO 3 ^-
_{, CH 3 C 6 H 6 SO} 3 -, SCN - 4 quaternary cationic vinyl monomer of the general formula having an anion represented by such representative of an inorganic acid anion or an organic acid anion) (4)

(Wherein M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , Ag ⁺ , NH ₄ ⁺ ), a saccharinate acid, metal salt or organic salt, represented by the general formula (5)

(Wherein M ⁺ represents H ⁺ , Na ⁺ , K ⁺ , Li ⁺ , Ag ⁺ , NH ₄ ⁺ ) or neutralizing an acid, metal salt or organic salt of acesulfamate represented by It can be synthesized by anion exchange.

The reaction solvent is soluble in the quaternary cationic vinyl monomer represented by the general formula (3) and the acid, metal salt or organic salt of the saccharinate represented by the general formula (4). The acid, metal salt or organic salt of acesulfame represented by (5) is soluble, and the product is an unsaturated quaternary ammonium salt represented by general formula (1) or general formula (2). Widely used if the compound is soluble and the by-product M ⁺ X ⁻ is insoluble or hardly soluble (dissolves 5 g or less in 100 g of solvent) and does not adversely affect the reaction. be able to. For example, water, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and the like can be mentioned. Among these, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether are preferable because inexpensive industrial products can be easily obtained, safety is high, and handling is easy. These solvents can be used alone or in combination of two or more.

（式中、Ｒ_１は水素原子またはメチル基を、Ｒ_２及びＲ_３は各々独立に炭素数１〜３のア
ルキル基で互いに同一であっても異なっていてもよく、Ｒ_４は炭素数１〜３のアルキル基
、炭素数１〜３のアルケニル基またはベンジル基を表し、Ｙは酸素原子または−ＮＨ−を
表し、Ｚは炭素数１〜３のアルキレン基を表し、）で表されるＮ，Ｎ−ジアルキルアミノ
アルキル（メタ）アクリルアミド又は／及びＮ，Ｎ−ジアルキルアミノアルキル（メタ）
アクリレートに４級化剤としてのハロゲン化アルキルまたはジアルキル硫酸、炭酸ジアル
キルあるいはアルキルトルエンスルフォネート、チオシアン酸アルキルエステルを水また
は有機溶媒中で４級化反応させ、ジアルキルアミノアルキル（メタ）アクリルアミド４級
塩又は／及びＮ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート４級塩を得ること
ができる。 The quaternary cationic vinyl monomer used in the present invention can be produced using a known method. For example, the following general formula (6)

(In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other, and R ₄ has 1 carbon atom) Represents an alkyl group having 3 to 3, an alkenyl group having 1 to 3 carbon atoms or a benzyl group, Y represents an oxygen atom or -NH-, Z represents an alkylene group having 1 to 3 carbon atoms, and N represented by , N-dialkylaminoalkyl (meth) acrylamide or / and N, N-dialkylaminoalkyl (meth)
Alkyl halide or dialkyl sulfuric acid as a quaternizing agent, dialkyl carbonate or alkyltoluene sulfonate, and thiocyanic acid alkyl ester are quaternized in water or an organic solvent to form a quaternary dialkylaminoalkyl (meth) acrylamide quaternary. Salts and / or N, N-dialkylaminoalkyl (meth) acrylate quaternary salts can be obtained.

Examples of the N, N-dialkylaminoalkyl (meth) acrylamide include N,
N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N
-Diethylaminopropyl (meth) acrylamide, N, N-methylethylaminoethyl (meth) acrylamide, N, N-methylpropylaminoethyl (meth) acrylamide, N, N-methylethylaminopropyl (meth) acrylamide, N, N -Methylpropylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth)
Examples include acrylamide.

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

Further, as the quaternary cationic vinyl monomer, methyl chloride of N, N-dimethylaminopropyl acrylamide and methyl chloride of N, N-dimethylaminoethyl acrylate are particularly preferable from the viewpoint of being easily available as an inexpensive industrial raw material.

The reaction temperature when synthesizing the unsaturated quaternary ammonium salt compound of the present invention is usually 10 ° C. or higher, preferably 15-60 ° C., and particularly preferably 20-40 ° C. When reaction temperature is less than 10 degreeC, reaction rate becomes slow and the required reaction time to complete becomes long. On the other hand, when it exceeds 60 ° C., the vinyl monomer may be polymerized.

The unsaturated quaternary ammonium salt compound of the present invention is soluble in the reaction solvent, the by-product is insoluble or hardly soluble in the reaction solvent, and the by-product is separated from the reaction solvent by filtration after the reaction is completed. Further, by collecting the reaction solvent, a high-purity product can be easily obtained. If coloring becomes a problem, the unsaturated quaternary ammonium salt compound is dissolved in an appropriate solvent, treated with a decolorizing agent such as activated carbon, and then the solvent is removed by a conventional method and dried. be able to.

By the above method, 99% or more of a highly pure unsaturated quaternary ammonium salt compound can be obtained. As needed, you may refine | purify by refinement | purification means, such as reduction of the residual metal ion by an ion exchange resin process, reprecipitation, recrystallization, and column chromatography.

The antistatic quaternary ammonium salt compound and / or oligomer or / and polymer containing the compound as a constituent component of the present invention is applied to a molded article such as plastic,
When used in a dry state, even when used alone, antistatic properties, improved coating properties on plastics, scratch resistance,
The effect of increasing the hardness can be sufficiently shown. In addition, the original antistatic property, water resistance,
Multifunctional (having 2 or more ethylene groups) as long as the properties such as transparency and compatibility are not impaired
By adding meth) acrylate or polyfunctional (meth) acrylamide and forming a crosslinkable coating on the surface of the substrate, the coating performance such as further film-forming properties and scratch resistance can be improved.

As such polyfunctional (meth) acrylate, pentaerythritol tetra (meth)
Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate,
Dipentaerythritol tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, 6
-Hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ditetraethylene glycol di (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate And other monomers and oligomers.

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

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

These polyfunctional (meth) acrylates and polyfunctional (meth) acrylamides are one kind,
A plurality of polyfunctional monomers and oligomers may be used in combination. Moreover, when using such a polyfunctional monomer and an oligomer, it is preferable to make it contain 0.001-25000weight% with respect to the unsaturated quaternary ammonium salt compound structural unit of this invention, and 50-
It is particularly preferable to contain 20,000% by weight. If the content is less than 0.1% by weight, the effect of addition is not recognized. If the content exceeds 25000% by weight, the crosslinking rate increases, so that the hardness and scratch resistance of the coating film are improved, but the elasticity is lost. Easily break.

The 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 monomer, methylol group-containing monomer, alkoxymethyl group-containing monomer,
Examples thereof include radical polymerization compounds having a reactive double bond in the molecular chain, such as an epoxy group-containing monomer, a polyfunctional monomer, a vinyl ester, and an olefin.

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

Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth).
An acrylate etc. are mentioned.

Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile.

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

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

The 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. Examples of the polymerization method include emulsion polymerization, solution polymerization,
Methods such as suspension polymerization and bulk polymerization can be used.

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

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 90% by weight.
If it exceeds, transparency will be 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 the coating is coated on the substrate and cured to adjust to a paintable viscosity,
It preferably contains a reactive diluent or an organic solvent.

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

The organic solvent is preferably one that can dissolve the unsaturated quaternary ammonium salt compound of the present invention and the oligomer and polymer containing the compound as a constituent component. In particular, for the unsaturated quaternary ammonium salt compound and the oligomer and polymer obtained by homopolymerization, a solubility parameter of 9 to
An organic solvent of 15 (cal / cm ³ ) ^0.5 is preferred.

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 and trade name Darocure11.
16, Darocure 1173, IRGACURE 184, IRGACURE 369, IRGACURE 500, IRGACURE
651, IRGACURE754, IRGACURE819, IRGACURE907, IRGACURE1300, IRGACU
RE1800, IRGACURE1870, IRGACURE2959, IRGACURE4265, IRGACURE TPO,
UCB's product 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 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 Chemical) Titration is carried out, and the quaternary ammonium salt concentration is determined from the titration amount.

(2) A polyethylene terephthalate (PET) film having a coating thickness of 100 μm is pasted on a glass plate (length 200 × width 200 × thickness 5 mm),
It was fixed on a horizontal surface so that it did not 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 ◎: There is no cissing and it is a uniform coating film;
○: 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;
○: Slightly sticky;
Δ: Slight stickiness;
X: There is clear stickiness.

(3) The ultraviolet-cured coated surface was turned upward to be cured by irradiation 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
Δ: Slight cloudiness or unevenness;
×: Extremely cloudy or uneven

(4) Surface resistivity measurement Using a template (length 110 x width 110 mm), the antistatic hard coat film was cut with a cutter knife and placed in a constant temperature and constant temperature machine adjusted to a temperature of 25 ° C and a relative humidity of 60%. It left still for a time and 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.

(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) Pencil hardness test An antistatic hard coat agent is dropped in a strip shape on a glass plate (length 200 × width 200 × thickness 5 mm), and a uniform force is applied to the whole with a bar coater (RDS60). In this way, both ends were pressed, and the paint was drawn to the front at the same speed (5 cm / sec) without rotating, and the solvent was removed with a hot air dryer at 80 ° C. for 3 minutes. The coated surface of the obtained coating film was cured by irradiating with ultraviolet rays so as 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 unsaturated quaternary ammonium salt compounds are shown below.

<Synthesis of unsaturated quaternary ammonium salt compound>
Synthesis Example 1: In a nitrogen atmosphere, 300 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: DMAPAA) and 214 g of methanol were added to a 1 L autoclave glass container, and the internal temperature was adjusted to 30 ° C. or lower, and chlorinated with stirring. Methyl was injected to perform a quaternization reaction. When the residual free amine (residual DMAPAA) in the reaction solution became 0.2% or less, excess methyl chloride in the reaction solution was distilled off under reduced pressure, and methanol containing 65% acryloylaminopropyltrimethylammonium chloride (DMAPAA-Q) 590 g of liquid (yield 96.6%) was obtained. Subsequently, 102 g of sodium saccharinate and 392 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 150 g of DMAPAA-Q65% -containing methanol solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with methanol. The methanol in the filtrate was concentrated under reduced pressure to obtain the desired unsaturated quaternary ammonium salt compound, acryloylaminopropyltrimethyl. 156 g of ammonium saccharinate was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 93.5%. In elemental analysis, measured values (C: 54.32%, H: 6.13%, N: 11.65%) are theoretical values (C: 54.40%, H: 6.56%, N: 11. 90%).

Synthesis example 2
In Synthesis Example 1, potassium saccharinate 42.6 instead of sodium saccharinate
was used in the same manner as in Synthesis Example 1 to obtain 61 g of the desired product acryloylaminopropyltrimethylammonium saccharinate as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 91.4%. In elemental analysis, measured values (C: 54.11%, H: 6.45%, N
: 11.88%) agreed with the theoretical values (C: 54.40%, H: 6.56%, N: 11.90%).

Synthesis example 3
In Synthesis Example 1, 39 g of calcium saccharinate was used instead of sodium saccharinate and reacted in the same manner as in Synthesis Example 1 to obtain 59.3 g of the target product acryloylaminopropyltrimethylammonium saccharinate as a colorless transparent liquid. It was. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 88.9%. In elemental analysis, measured values (C: 54.13%, H: 6.76%, N: 12.02%) are theoretical values (C: 54.40%, H: 6.56%, N: 11.2. 90%).

Synthesis example 4
Under a nitrogen atmosphere, DMAPAA 300 g and ethanol 240 g were added to a 1 L autoclave glass container, the internal temperature was adjusted to 30 ° C. or lower, and methyl chloride was injected while stirring to carry out a quaternization reaction. When the residual free amine (residual DMAPAA) in the reaction solution became 0.2% or less, excess methyl chloride in the reaction solution was distilled off under reduced pressure, and ethanol containing 50% acryloylaminopropyltrimethylammonium chloride (DMAPAA-Q) was contained. 623 g (yield 98.1%) of liquid was obtained. Subsequently, 78.4 g of sodium saccharinate and 471 g of ethanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 150 g of the DMAPAA-Q 50% ethanol solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered and washed with ethanol. The ethanol in the filtrate was concentrated under reduced pressure to obtain the desired unsaturated quaternary ammonium salt compound, acryloylaminopropyltrimethyl. 121 g of ammonium saccharinate was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 94.3%. In elemental analysis, measured values (C: 54.34%, H: 6.52%, N: 11.75%) are theoretical values (C: 54.40%, H: 6.56%, N: 11.5). 90%).

Synthesis example 5
In a nitrogen atmosphere, 200 g of DMAPAA and 185.5 g of methanol were added to a 1 L three-necked flask, the internal temperature was adjusted to 25 ° C., and 235.5 g of methyl p-toluenesulfonate was added dropwise with stirring to carry out the quaternization reaction. Carried out. After confirming that the residual free amine (residual DMAPAA) in the reaction solution was 0.3% or less, it was confirmed by GC analysis that methyl p-toluenesulfonate was not detected, and acryloylaminopropyltrimethylammonium p -Toluenesulfonate (DMAPAA-TSMQ) 70% methanol solution 602g (yield 97.1%) was obtained. Subsequently, 61.8 g of sodium saccharinate and 237 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 140 g of DMAPAA-TSMQ-containing methanol solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered, washed with methanol, and concentrated under reduced pressure to give the objective unsaturated quaternary ammonium salt compound, acryloylaminopropyltrimethylammonium saccharinate colorless. As a clear liquid, 89 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 88.1%. In elemental analysis, measured values (C: 54.26%, H: 6.34%, N: 11.59%) are theoretical values (C: 54.40%, H: 6.56%, N: 11. 90%).

Synthesis Example 6
In Synthesis Example 1, a methanol solution containing 50% methacryloylaminopropyltrimethylammonium chloride (DMAPMA-Q) was synthesized using N, N-dimethylaminopropyl methacrylamide (manufactured by Degussa: DMAPMA) instead of DMAPAA. Subsequently, 58.7 g of sodium saccharinate and 293.5 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring this solution, 120 g of DMAPMA-Q 50% -containing methanol solution synthesized above was added dropwise at 25 ° C. over 1 hour and reacted in the same manner as in Synthesis Example 1 to obtain the desired product methacryloylaminopropyltrimethylammonium saccharide. 92.1 g of the nitrate was obtained as a colorless transparent liquid. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 99.9%. The yield was 92.3% theoretical (C: 55.60%, H: 6.86%, N: 11.44%
).

Synthesis example 7
Under a nitrogen atmosphere, add 180 g of N, N-dimethylaminoethyl acrylate (manufactured by Kojin: DMAEA) and 365 g of methanol to a 1 L autoclave glass container, adjust the internal temperature to 30 ° C. or less, and inject methyl chloride with 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) 40%. 596 g (yield 97.9%) of a liquid was obtained. Subsequently, 53.6 g of sodium saccharinate and 268 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 120 g of DMAEA-Q 40% -containing methanol solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered, washed with methanol, and concentrated under reduced pressure to give the objective unsaturated quaternary ammonium salt compound and acryloyloxyethyltrimethylammonium saccharinate colorless. As a clear liquid, 77.3 g was obtained. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 99%. The yield was 91.6%. In elemental analysis, measured values (C: 52.88%, H: 5.45%, N: 8.10%) are theoretical values (C: 52.97%, H: 5.93%, N: 8. 24%).

Synthesis Example 8
Under a nitrogen atmosphere, 130 g of DMAEA and 360.1 g of methanol were added to a 1 L three-necked flask, the internal temperature was adjusted to 25 ° C., and 166.7 g of methyl p-toluenesulfonate was added dropwise with stirring to perform the quaternization reaction. Carried out. The residual free amine (residual DMAEA) in the reaction solution was 0.3% or less, and it was confirmed by GC analysis that methyl p-toluenesulfonate was not detected, and acryloyloxyethyltrimethylammonium p-toluenesulfonate (DMAEA) was confirmed. -TSMQ) 645 g (yield 98.3%) of methanol solution containing 45% was obtained. Subsequently, 49 g of sodium saccharinate and 245 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 130 g of DMAEA-TSMQ-containing methanol solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered, washed with methanol, and concentrated under reduced pressure to give the objective unsaturated quaternary ammonium salt compound and acryloyloxyethyltrimethylammonium saccharinate colorless. As a clear liquid, 71 g was obtained. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 99%. The yield was 88.3%. In elemental analysis, measured values (C: 53.04%, H: 5.65%, N: 8.33%) are theoretical values (C: 52.97%, H: 5.93%, N: 8. 24%)

Synthesis Example 9
In Synthesis Example 1, a methanol solution containing 45% methacryloyloxyethyltrimethylammonium chloride (DMAEMA-Q) was synthesized using N, N-dimethylaminoethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd .: DMAEMA) instead of DMAPAA. Subsequently, 60.8 g of sodium saccharinate and 304 g of methanol were added to a 1 L three-necked flask, and a uniform solution was prepared while stirring. While stirring the solution, 130 g of DMAEMA-Q45% -containing methanol solution synthesized above was added dropwise at 25 ° C. over 1 hour, and at the same time, a white crystalline solid was precipitated. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours, and then the crystals were filtered, washed with methanol, and concentrated under reduced pressure to give the objective unsaturated quaternary ammonium salt compound and methacryloyloxyethyltrimethylammonium saccharinate colorless. As a clear liquid, 87 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 87.2%. In elemental analysis, measured values (C: 52.88%, H: 5.45%, N: 8.10%) are theoretical values (C: 54.23%, H: 6.26%, N: 7. 91%).

Synthesis Example 10
In Synthesis Example 1, 50.9 g of acesulfamate potassium was used in place of sodium saccharinate and reacted in the same manner as in Synthesis Example 1 to give the desired product acryloylaminopropyltrimethylammonium acesulfamate as a colorless transparent liquid. 6 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 91.2%. In elemental analysis, measured values (C: 57.54%, H: 6.81%, N: 12.42%) are theoretical values (C: 57.64%, H: 6.95%, N: 12.2. 60%).

Synthesis Example 11
In Synthesis Example 5, 45.7 g of acesulfamate potassium was used in place of sodium saccharinate and reacted in the same manner as in Synthesis Example 5 to give the desired product acryloylaminopropyltrimethylammonium acesulfamate as a colorless transparent liquid. 2 g was obtained. When the quaternary ammonium salt concentration was determined by potentiometric titration, the purity of the target product was 99.8%. The yield was 94.2%. In elemental analysis, measured values (C: 57.39%, H: 6.71%, N: 12.23%) are theoretical values (C: 57.64%, H: 6.95%, N: 12.2. 60%).

Synthesis Example 12
In Synthesis Example 6, 47 g of acesulfamate potassium was used instead of sodium saccharinate and reacted in the same manner as in Synthesis Example 6 to obtain 72.8 g of the target product methacryloylaminopropyltrimethylammonium acesulfamate as a colorless transparent liquid. It was. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 92.5%. In elemental analysis, measured values (C: 57.39%, H: 6.71%, N: 12.23%) are theoretical values (C: 48.40%, H: 7.25%, N: 12.2. 09%).

Synthesis Example 13
In Synthesis Example 7, 51.5 g of acesulfamate potassium was used in place of sodium saccharinate and reacted in the same manner as in Synthesis Example 7 to obtain the desired product acryloyloxyethyltrimethylammonium acesulfamate as a colorless transparent liquid. 5 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 93.7%. In elemental analysis, measured values (C: 45.03%, H: 6.23%, N: 8.60%) are theoretical values (C: 44.99%, H: 6.29%, N: 8. 74%).

Synthesis Example 14
In Synthesis Example 9, 49.4 g of acesulfamate potassium was used instead of sodium saccharinate, and the reaction was performed in the same manner as in Synthesis Example 9 to give the target product methacryloyloxyethyltrimethylammonium acesulfamate as a colorless transparent liquid. 7 g was obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 99.9%. The yield was 90.0%. In elemental analysis, measured values (C: 46.38%, H: 6.21%, N: 8.39%) are theoretical values (C: 46.69%, H: 6.63%, N: 8. 38%).

Preparation Example A-1 of Antistatic Hard Coating Agent
After dissolving 14 parts by weight of acryloylaminopropyltrimethylammonium saccharinate synthesized in Synthesis Example 1 in 120 parts by weight of isopropyl alcohol (IPA), pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-3A)
) 62 parts by weight, as photoinitiator, manufactured by Ciba Specialty Chemicals, Inc., trade name Darocu
3 parts by weight of re1173 was added and mixed uniformly to obtain an antistatic hard coat agent which can be cured by ultraviolet rays. 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 12, Comparative Examples A-13 to 20
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.

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 saccharinate synthesized in Synthesis Example 1 and 10 parts by weight of 2-ethylhexyl acrylate (2EHA) , 0.2 parts by weight of azoisobutyronitrile (AIBN) was mixed and dissolved in 60 parts by weight of isopropyl alcohol (IPA), and the mixture was dissolved at a temperature of 70 ° C. under a nitrogen stream.
Polymerization was performed for a time to obtain a copolymer solution (a).

Table 3 shows the mixing ratio of the monomers in the synthesis of the copolymer solution.

Preparation Example B-1 of Antistatic Hard Coating Agent Containing Quaternary Salt Polymer
5 parts by weight of copolymer 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, manufactured by Ciba Specialty Chemicals, Inc., trade name Darocure 1173
5 parts by weight was mixed and dissolved in 115 parts by weight of isopropyl alcohol (IPA) to obtain an antistatic hard coat agent containing an ultraviolet curable quaternary salt polymer. 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 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 synthesis examples and synthesis comparative examples, it was found that dialkylaminoalkyl (meth) acrylamide, dialkylaminoalkyl (meth) acrylate and methyl chloride or sulfonic acid ester 4
After the grading reaction, the metal salt exchange reaction with sodium saccharinate and potassium acesulfame proceeds in a protic polar solvent at a sufficient rate even at room temperature and normal pressure. A pure product was obtained in high yield. In addition, when quaternized with a sulfonic acid ester, the obtained unsaturated quaternary ammonium salt compound of the present invention is free of halogen ions and has a uniform transparency and moisture resistance. Can be formed. From the results of evaluating the UV curability and antistatic property of the coating film of Examples and Comparative Examples, the time required for UV curing due to the presence of chlorine ions is increased, the resulting coating film is sticky, the transparency is poor, and those As a result, a uniform coating film could not be obtained and the antistatic effect was low. Furthermore, since the unsaturated quaternary ammonium salt compound of the present invention is liquid at room temperature, it has good compatibility with nonpolar components such as polyfunctional acrylates in the antistatic agent composition, and a uniform coating film can be obtained. . Only the high-quality novel unsaturated quaternary ammonium salt compound obtained by the production method of the present invention requires less energy for UV curing, good transparency, high scratch resistance, high hardness, high moisture resistance and high resistance. It was clear that an antistatic agent having excellent hydrostatic properties and excellent antistatic performance can be provided.

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 reaction rate even at room temperature and normal pressure. In addition, it is harmless to the environment because it contains no halogen and uses a high-safety sweetener as a food additive. Further, since the unsaturated quaternary ammonium salt compound is liquid at room temperature and has good compatibility with other antistatic compositions and organic solvents, a charge formed using an antistatic composition comprising the same. The prevention layer is excellent in antistatic properties, transparency, scratch resistance, high hardness, moisture resistance and hydrolysis 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 (7)

Formula (1) or a general formula (2) is that the unsaturated quaternary ammonium salt compounds represented by the compound is free of halogen, unsaturated quaternary ammonium salt compound is liquid at room temperature.

(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 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.) The oligomer or polymer which contains the unsaturated quaternary ammonium salt compound of Claim 1 as a structural component. An antistatic agent comprising the unsaturated quaternary ammonium salt compound according to claim 1 and / or the oligomer or polymer according to claim 2. An antistatic composition containing the antistatic agent according to claim 3, wherein the unsaturated quaternary ammonium salt compound according to claim 1 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 3, further comprising a polyfunctional (meth) acrylate and / or a polyfunctional (meth) acrylamide. An antistatic hard material characterized by being formed by coating the base material with the antistatic agent or antistatic composition according to any one of claims 3 to 5 and then polymerizing with an active energy ray or heat. Coat layer. An antistatic film comprising the antistatic hard coat layer according to claim 6 on at least one side.