JP2015189680A - unsaturated quaternary ammonium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated quaternary ammonium salt with high purity including no halogen in the molecule, high in safety, harmless in the environment, including no moisture, also excellent in dissolubility to water, organic solvents, conventional vinyl monomers and resins, and suitably usable even to various electrochemical devices, to provide an efficient and economical production method for the unsaturated quaternary ammonium salt, and to provide a composition using the unsaturated quaternary ammonium salt as a constituting component.SOLUTION: Provided is an unsaturated quaternary ammonium salt represented by general formula (1). Also provided is a method for producing an unsaturated quaternary ammonium salt including a process where a cyclic ether group-containing compound and a tertiary amine compound are reacted without using water and/or a protonic organic solvent as a reaction solvent. Also provided is a composition comprising the unsaturated quaternary ammonium salt.

Description

The present invention relates to an unsaturated quaternary ammonium salt containing no halogen atom, a method for producing the same, and a composition containing the unsaturated quaternary ammonium salt as a constituent component.

The quaternary ammonium salt containing an unsaturated group can be homopolymerized or copolymerized with other monomers, so that the resulting polymer has functions such as cationicity, conductivity and adhesiveness. Can be widely used as a raw material monomer for flocculants, antistatic agents, soil improvers, conductive processing agents, dye improvers, paper strength enhancers, paper drainage improvers, cosmetics, resin modifiers, etc. Yes.

In particular, acrylate-based and acrylamide-based cationic quaternary ammonium salts are known to be used as base monomers for polymer antistatic compositions because of their excellent radical polymerizability (Patent Documents 1-6). 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.

Then, the polymeric ammonium salt which does not use a halogen-type ion as an anion is proposed (patent documents 7-10). In these patent documents, each polymerizable quaternary ammonium salt is reacted with water or a mixed solution of water and methanol using an inorganic or organic acid, a tertiary amine, and a monofunctional or polyfunctional epoxide. Is synthesized. However, in these patent documents, the tertiary amine, epoxide group, and double bond as raw materials are quantified after the reaction, but the purity and yield of the target product, the polymerizable quaternary ammonium salt, are determined. There is no mention of rates.

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 JP 2011-506749 A JP 2012-201764 A Japanese Patent Laid-Open No. 06-128105 Japanese Patent Laid-Open No. 08-92177

As described above, it does not contain halogen atoms such as chlorine and fluorine in the molecule, is highly safe, harmless to the environment, high purity, and soluble in water, organic solvents, common vinyl monomers, and resins. Unsaturated quaternary ammonium salt compounds that are excellent in properties and can be polymerized by irradiation with active energy rays such as ultraviolet rays (UV), and antistatic agents and antibacterial agents comprising the ammonium salts have not yet been obtained.

The first object of the present invention is to contain no halogen atoms in the molecule, high safety, harmless to the environment, high purity, and solubility in water, organic solvents, common vinyl monomers and resins. It is an object to provide an unsaturated quaternary ammonium salt that is excellent and can be polymerized by irradiation with an active energy ray such as UV. 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 provide a composition containing the unsaturated quaternary ammonium salt compound as a constituent component.

As a result of intensive studies to solve these problems, the present inventor has found that an unsaturated quaternary ammonium salt having a specific structure using an organic acid ion as a counter ion is an unsaturated compound containing a conventional halogen atom. The present invention was completed by discovering that it has physical properties equivalent to quaternary ammonium salts and can solve these problems.

（式中、Ｒ_１は水素原子またはメチル基、Ｒ_２、Ｒ_３は各々独立に炭素数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で、互いに同一であっても異なっていてもよく、Ｘは酸素原子またはＮＨ、Ｙは炭素数１〜３のアルキレン基を表し、ｎは１〜６の整数、Ｚは有機基、Ａ^ｎ-はｎ価の有機酸イオンを表す。）、
（２）前記ｎが１であり、且つ、Ｚが下記

（式中、Ｒ_４は、炭素数１〜２０のアルキル基、炭素数１〜３のアルケニル基、フェノール基またはベンジル基で、環状エーテル基で置換されていてもよく、Ｒ_５は水素原子またはメチル基であり、ｍは１〜３０の整数を示す。）で示される基である前記（１）記載の不飽和第四級アンモニウム塩、
（３）前記ｎが２〜６であり、且つ、Ｚが、下記

または

（式中、Ｒ_５は水素原子またはメチル基であり、ｍは１〜３０の整数を示し、ｐおよびｑは１〜２９の整数を表し、その合計は２〜３０である。）で示される基である前記（１）記載の不飽和第四級アンモニウム塩、
（４）不飽和第四級アンモニウム塩が、
（ａ）下記一般式（２）

（式中、Ｒ_１は水素原子またはメチル基、Ｒ_２、Ｒ_３は各々独立に炭素数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で互いに同一であっても異なっていてもよく、Ｘは酸素原子またはＮＨを表し、Ｙは炭素数１〜３のアルキレン基を表す。）
で表される三級アミン化合物と、有機酸と、
（ｂ）下記一般式（３）

または
（ｃ）下記一般式（４）

（式中、Ｒ_４は、炭素数１〜２０のアルキル基、炭素数１〜３のアルケニル基、フェノール基またはベンジル基で、環状エーテル基で置換されていてもよく、Ｒ_５は水素原子または炭素数１のアルキル基であり、ｍは１〜３０の整数を示す。）で表される環状エーテル基含有化合物を反応させることを特徴とする前記（１）乃至（３）のいずれか一項に記載の不飽和第四級アンモニウム塩の製造方法、
（５）前記反応において、三級アミン化合物と有機酸をｐＨ７以上、温度３５℃以下で反応させた後、環状エーテル基含有化合物とを反応させることを特徴とする前記（４）記載の不飽和第四級アンモニウム塩の製造方法、
（６）前記（１）乃至（３）のいずれか一項に記載の不飽和第四級アンモニウム塩の単独重合または他の共重合可能なビニル系単量体との共重合で得られるオリゴマーまたはポリマー、
（７）前記（１）乃至（３）のいずれか一項に記載の不飽和第四級アンモニウム塩、及び／または、前記（６）記載のオリゴマーまたはポリマーからなる帯電防止剤、
（８）前記（７）記載の帯電防止剤を含有する帯電防止性樹脂組成物であって、前記（１）乃至請求項３のいずれか一項に記載の不飽和第四級アンモニウム塩を構成単位として０．１〜９５重量％含有するもの、
（９）前記（８）記載の帯電防止性樹脂組成物であって、さらに多官能（メタ）アクリレート及び／または多官能（メタ）アクリルアミドを含有するもの、
（１０）基材上に前記（７）記載の帯電防止剤及び／または前記（８）または（９）記載の帯電防止組成物を塗装した後、活性エネルギー線または熱により硬化して形成されることを特徴とする帯電防止層、
（１１）少なくとも片面に前記（１０）記載の帯電防止層を有することを特徴とするフィルム又はシート状の帯電防止薄膜、
（１２）前記（１）乃至（３）のいずれか一項に記載の不飽和第四級アンモニウム塩、及び／または、前記（６）記載のオリゴマーまたはポリマーを用いることを特徴とする電池またはコンデンサ用電解質、
（１３）前記（１）乃至（３）のいずれか一項に記載の不飽和第四級アンモニウム塩、及び／または、前記（６）記載のオリゴマーまたはポリマーを用いることを特徴とする抗菌剤、
を提供するものである。 That is, the present invention
(1) A saturated quaternary ammonium salt represented by the following general formula (1).

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms or a benzyl group, may be different, X represents an oxygen atom or NH, Y represents an alkylene group having 1 to 3 carbon atoms, n represents an integer from 1 to 6, Z is an organic group, a ^n-is an n-valent organic acid ion Represent),
(2) n is 1 and Z is

(In the formula, R ₄ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, a phenol group or a benzyl group, which may be substituted with a cyclic ether group, and R ₅ is a hydrogen atom or An unsaturated quaternary ammonium salt according to the above (1), which is a methyl group, and m is an integer of 1 to 30).
(3) Said n is 2-6, and Z is the following

Or

(Wherein R ₅ is a hydrogen atom or a methyl group, m represents an integer of 1 to 30, p and q represent an integer of 1 to 29, and the sum thereof is 2 to 30). The unsaturated quaternary ammonium salt according to (1), which is a group,
(4) Unsaturated quaternary ammonium salt
(A) The following 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, an alkenyl group having 1 to 3 carbon atoms or a benzyl group, which may be the same or different. X represents an oxygen atom or NH, and Y represents an alkylene group having 1 to 3 carbon atoms.)
A tertiary amine compound represented by the formula:
(B) The following general formula (3)

Or (c) the following general formula (4)

(In the formula, R ₄ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, a phenol group or a benzyl group, which may be substituted with a cyclic ether group, and R ₅ is a hydrogen atom or (1) to (3), wherein the cyclic ether group-containing compound represented by (1) is an alkyl group having 1 carbon atom and m is an integer of 1 to 30. A method for producing the unsaturated quaternary ammonium salt according to claim 1,
(5) In the reaction, the tertiary amine compound and the organic acid are reacted at a pH of 7 or more and a temperature of 35 ° C. or less, and then reacted with a cyclic ether group-containing compound. Production method of quaternary ammonium salt,
(6) An oligomer obtained by homopolymerization of the unsaturated quaternary ammonium salt according to any one of (1) to (3) above or copolymerization with another copolymerizable vinyl monomer or polymer,
(7) An antistatic agent comprising the unsaturated quaternary ammonium salt according to any one of (1) to (3) and / or the oligomer or polymer according to (6),
(8) An antistatic resin composition containing the antistatic agent according to (7), wherein the unsaturated quaternary ammonium salt according to any one of (1) to (3) is configured. Containing 0.1 to 95% by weight as a unit;
(9) The antistatic resin composition described in (8) above, which further contains polyfunctional (meth) acrylate and / or polyfunctional (meth) acrylamide,
(10) After coating the antistatic agent described in (7) and / or the antistatic composition described in (8) or (9) on a base material, it is formed by curing with active energy rays or heat. An antistatic layer, characterized by
(11) A film or sheet-shaped antistatic thin film having the antistatic layer according to (10) on at least one surface;
(12) A battery or capacitor comprising the unsaturated quaternary ammonium salt according to any one of (1) to (3) and / or the oligomer or polymer according to (6). Electrolyte,
(13) An antibacterial agent characterized by using the unsaturated quaternary ammonium salt according to any one of (1) to (3) and / or the oligomer or polymer according to (6),
Is to provide.

The unsaturated quaternary ammonium salt compound of the present invention has excellent solubility and affinity in water, organic solvents, common vinyl monomers, and resins, so it can be applied evenly on the substrate, and active energy such as UV Since it does not bleed out even after being cured by irradiation with radiation and the antistatic effect and antibacterial effect are maintained, it is also suitably used for an antistatic coating agent and an antibacterial agent. Moreover, according to the method of the present invention, the unsaturated quaternary ammonium salt compound of the present invention can be easily produced with high purity and high yield.

Since the unsaturated quaternary ammonium salt compound of the present invention can be easily copolymerized with a common vinyl monomer, various water-insoluble antistatic compositions by copolymerization with a hydrophobic vinyl monomer can be provided.

Furthermore, since the unsaturated quaternary ammonium salt compound obtained by the production method of the present invention does not contain halogen or moisture, the composition of the present invention which does not contain halogen or moisture can be used in applications where corrosion is a problem, such as various types. It is also suitably used for electrochemical devices.

Hereinafter, the present invention will be described in detail.
The unsaturated quaternary ammonium salt of the present invention is a (meth) acrylate quaternary ammonium salt or a (meth) acrylamide quaternary ammonium salt represented by the general formula (1).

（式中、Ｒ_１は水素原子またはメチル基、Ｒ_２、Ｒ_３は各々独立に炭素数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で、互いに同一であっても異なっていてもよく、Ｘは酸素原子またはＮＨ、Ｙは炭素数１〜３のアルキレン基を表し、ｎは１〜６の整数、Ｚは有機基、Ａ^ｎ-はｎ価の有機酸イオンを表す。）

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, an alkenyl group having 1 to 3 carbon atoms or a benzyl group, may be different, X represents an oxygen atom or NH, Y represents an alkylene group having 1 to 3 carbon atoms, n represents an integer from 1 to 6, Z is an organic group, a ^n-is an n-valent organic acid ion Represents.)

で表される不飽和三級アミン化合物と、有機酸と、（ｂ）下記一般式（３）

または（ｃ）下記一般式（４）

で表される環状エーテル基含有化合物とを反応させることにより得ることができる。
（各式中、Ｒ_１は水素原子またはメチル基、Ｒ_２、Ｒ_３は各々独立に炭素数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で互いに同一であっても異なっていてもよく、Ｘは酸素原子またはＮＨを表し、Ｙは炭素数１〜３のアルキレン基を表す。また、Ｒ_４は、炭素数１〜２０のアルキル基、炭素数１〜３のアルケニル基、フェノール基またはベンジル基で、環状エーテル基で置換されていてもよく、Ｒ_５は水素原子または炭素数１のアルキル基であり、ｍは１〜３０の整数を示す。） The unsaturated quaternary ammonium salt represented by the general formula (1) of the present invention includes (a) the following general formula (2)

(B) the following general formula (3):

Or (c) the following general formula (4)

It can obtain by making it react with the cyclic ether group containing compound represented by these.
(In each 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, an alkenyl group having 1 to 3 carbon atoms, or a benzyl group, X may represent an oxygen atom or NH, Y represents an alkylene group having 1 to 3 carbon atoms, and R ₄ represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 1 to 3 carbon atoms. A group, a phenol group or a benzyl group, which may be substituted with a cyclic ether group, R ₅ is a hydrogen atom or an alkyl group having 1 carbon atom, and m is an integer of 1 to 30.)

Specific examples of the unsaturated tertiary amine compound represented by the general formula (2) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethyl. Aminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-methylethylaminoethyl (meth) acrylate, N, N-methylpropylaminoethyl (meth) acrylate, N, N-methylethyl Acrylates such as aminopropyl (meth) acrylate, N, N-methylpropylaminopropyl (meth) acrylate, N, N-dipropylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylami N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-methylethylaminoethyl (meth) acrylamide, N, N-methylpropylaminoethyl (meth) acrylamide, Examples thereof include acrylamides such as N, N-methylethylaminopropyl (meth) acrylamide, N, N-methylpropylaminopropyl (meth) acrylamide, and N, N-dipropylaminopropyl (meth) acrylamide.

Specific examples of the cyclic ether group-containing compound represented by the general formula (3) and the general formula (4) include glycidyl ethers of alkylene oxide adducts, and commercially available products include Denacol EX-171, 145, 810, 811, 850, 851, 821, 830, 832, 841, 861, 911, 941, 920, 931, 611, 612, 614, 614B, 622, 512, 521 (manufactured by Nagase ChemteX Corporation), Epolite 40E , 100E, 200E, 400E, 70P, 200P, 400P (manufactured by Kyoeisha Chemical Co., Ltd.).

In the method for producing an unsaturated quaternary ammonium salt represented by the general formula (1) of the present invention, the unsaturated tertiary amine compound represented by the general formula (2) and the general formula (3) or The reaction molar ratio with the cyclic ether group-containing compound represented by the formula (4) is 0.5 to 1.5 mol of the cyclic ether group-containing compound with respect to 1 mol of the tertiary amine compound, preferably 0. .8 to 1.2 moles. If the molar ratio is less than 0.5 mol or more than 1.5 mol, one of the raw materials remains excessively, so that purification after the reaction becomes difficult and the yield of the target product is lowered. . It is also economically disadvantageous.

The reaction conditions are not particularly limited as long as the unsaturated quaternary ammonium salt represented by the general formula (1) is obtained. Usually, after reacting the unsaturated tertiary amine compound represented by the general formula (2) and an organic acid, the cyclic ether group-containing compound represented by the general formula (3) or the general formula (4) Is generally reacted. Moreover, as an acid used for reaction of a tertiary amine compound and organic acid, when it becomes a quaternary ammonium salt, if it is an organic acid which does not have corrosivity with respect to a metal, it can use without a restriction | limiting especially.

Specific examples of the organic acid include mono- or dicarboxylic acids having 1 to 7 carbon atoms (formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), and sulfonic acids having 1 to 7 carbon atoms (methanesulfonic acid, trifluoromethane). Sulfonic acid and p-toluenesulfonic acid), hydroxycarboxylic acid (glycolic acid, lactic acid, hydroxyacrylic acid, oxybutyric acid, glyceric acid, malic acid, tartaric acid, citric acid, salicylic acid, etc.), aromatic carboxylic acid (salicylic acid, benzoic acid) Acid or the like), a linear or branched alkyl or alkenyl phosphate having 1 to 12 carbon atoms, a phosphorus-containing methacrylic acid ester such as acrylic acid, methacrylic acid, thiocyanic acid, acid phosphooxyethyl methacrylate, phosphorus-containing Suitable for organic acids that do not contain halogens in the molecule, such as acrylic esters It can be used.

The organic acid can be used in excess or in a small amount with respect to the unsaturated tertiary amine compound, but it is preferably carried out in the range where the pH of the solution is 7 or more, and particularly in the range of pH 7-9. In this way, it is preferable to control the supply amount of the organic acid because the reactivity of the tertiary amine can be improved.

When the pH is less than 7, the reactivity of the tertiary amine decreases, and the supplied organic acid may come into contact with the cyclic ether group-containing compound to cause a side reaction, which is not preferable.

When the tertiary amine compound and the organic acid are reacted, another basic compound may be added in order to adjust the pH of the reaction solution to 7 or more. The basic compound is not particularly limited, but examples thereof include quaternary ammonium salts such as tetramethylammonium hydroxide, alkali metals such as sodium hydroxide and potassium hydroxide, and alkaline earth metals such as calcium hydroxide. Kind. These can be used alone or in combination.

Moreover, it is preferable that reaction of said tertiary amine compound and organic acid is performed at 35 degrees C or less. If it exceeds 35 ° C., the temperature of the reaction solution due to the heat of neutralization generated during the reaction rises rapidly, and side reactions such as polymerization may occur.

In the production of the unsaturated quaternary ammonium salt of the present invention, a reaction product of an unsaturated tertiary amine and an organic acid is mixed with a cyclic ether group-containing compound represented by the general formula (3) or (4). The reaction temperature and reaction time can be appropriately set depending on the reaction, but it is effective to increase the reaction temperature in order to accelerate the reaction.

The reaction temperature is usually 10 ° C. or higher, preferably 15 to 150 ° C., and particularly preferably 20 to 120 ° 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 120 ° C., the reaction product of unsaturated tertiary amine and organic acid as an intermediate, and the product unsaturated quaternary ammonium salt may be polymerized.

In the present invention, the reaction can be carried out in the presence of a suitable solvent as necessary, but the reaction can also be carried out without using a solvent. When the reaction is carried out in the presence of a solvent, usable solvents are not particularly limited as long as they do not react with the cyclic ether group-containing compounds represented by the general formulas (3) and (4) at a low temperature at high speed. Proton polar solvents such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, acetonitrile, tetrahydrofuran, 1,4-dioxane, N, N-dimethylformamide , N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, aprotic polar solvents such as ethyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, linear aliphatic such as pentane, hexane, heptane Hydrocarbon, 2-me Branched aliphatic hydrocarbons such as tilbutane and 2-methylpentane, cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic halogen compounds such as dichloromethane and chloroform, chlorobenzene And aromatic halogen compounds such as dichlorobenzene. These organic solvents can be used alone or in admixture of two or more. The amount of these reaction solvents used is usually 0.01 to 20 times by weight with respect to the unsaturated quaternary ammonium salt of the present invention.

Since the unsaturated quaternary ammonium salt of the present invention contains an unsaturated group in the molecule, the organic solvent can be recovered and removed during the reaction, further by distillation under reduced pressure after completion of the reaction, and dry inert gas or dry air bubbling. It is preferable to carry out in the presence of a polymerization inhibitor.

Known polymerization inhibitors can be used, such as hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl parahydroquinone, 2,5-di-tert-butyl hydroquinone, 2, Phenol compounds such as 4-dimethyl-6-tertbutylphenol and hydroquinone monomethyl ether, N-isopropyl-N′-phenyl-para-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-para-phenylene Such as diamine, N- (1-methylheptyl) -N′-phenyl-para-phenylenediamine, N, N′-diphenyl-para-phenylenediamine, N, N′-di-2-naphthyl-para-phenylenediamine, etc. Paraphenylenediamines, thiodiphenylamine, etc. Amine compound, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 oxyl (4H-TEMPO), acetamide tetramethyl A radical scavenger group such as piperidine-1-oxyl (acetamide-TEMPO) can be exemplified. These polymerization inhibitors may be used alone or in combination of two or more.

The addition amount of the other polymerization inhibitor is 5 to 10000 ppm, preferably 10 to 5000 ppm, based on the unsaturated quaternary ammonium salt of the present invention.

The high-purity unsaturated quaternary ammonium salt obtained by the above production method can be widely used for coating agents, pressure-sensitive adhesives, adhesives, ink compositions and the like from the viewpoint of providing an antistatic effect. In addition, it can be suitably used in electrolytes utilizing high ionic conductivity and antibacterial agents utilizing antibacterial effects, and can be used as a monomer, or polymer or oligomer composition by thermal polymerization or active energy ray curing. It can be used by being incorporated into a part of

When the unsaturated quaternary ammonium salt of the present invention is used by incorporating it in a part of the polymer or oligomer composition, a method of tackling the polymer or oligomer includes a method of copolymerizing with a general-purpose vinyl monomer. . The copolymerization with the vinyl monomer is not particularly limited, and can be carried out by a known radical polymerization method. Examples thereof include a bulk polymerization method, a solution polymerization method in an organic solvent or in water, a suspension polymerization method, an emulsion polymerization method, and the like. When the solution polymerization method in an organic solvent is employed, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl alcohol, ethyl alcohol, or the like can be used alone or in combination as a polymerization solvent.

In the copolymerization with the vinyl monomer, examples of the polymerization initiator include generally known radical polymerization initiators such as azo, organic peroxide, inorganic peroxide, and redox. The amount of the radical polymerization initiator used is usually about 0.001 to 10% by weight based on the total amount of the polymerizable monomer components. Further, a normal radical polymerization technique such as adjustment of molecular weight by a chain transfer agent is applied.

The content of the unsaturated quaternary ammonium salt of the present invention in the copolymer with the vinyl monomer is 0.1 to 95% by weight, preferably 1 to 90% by weight. If it is 0.1% or less, the ion conduction performance is hardly exhibited, and if it exceeds 95%, the strength of the coating film may be lowered.

When using the unsaturated quaternary ammonium salt of this invention as a component of an active energy ray curable resin composition, the method of containing a photoinitiator and making it harden | cure with an active energy ray is mentioned.

Active energy rays are defined as energy rays that can generate active species by decomposing a compound that generates active species (photopolymerization initiator). Such active energy rays include visible light, ultraviolet rays ( UV), infrared rays, X-rays, α rays, β rays, γ rays and other light energy 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.

The photopolymerization initiator is not particularly required when an electron beam is used as the active energy ray, but is required when ultraviolet rays are used. The photopolymerization initiator may be appropriately selected from ordinary ones such as acetophenone, benzoin, benzophenone, and thioxanthone. Among these, as commercially available photopolymerization initiators, trade names Darocure 1116, Darocure 1173, IRGACURE 184, IRGACURE 369, IRGACURE 500, IRGACURE 651, IRGACURE 754, IRGACURE IR, IRGACURE 1800, IRGACURE 1800, IRGACURE 1800, IRGACURE1800, IRGACURE1800, IRGACURE1800, IRGACURE1800 TPO, a product made by UCB, a brand name Ubekrill P36, etc. can be used. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of these photopolymerization initiators is not particularly limited, but is generally 0.5 to 10% by weight, particularly 1 to 5% by weight based on the active energy ray-curable resin composition or coating agent. It is preferable. If it is less than 0.5% by weight, sufficient curability cannot be obtained, and if it exceeds 10%, the strength of the coating film may be lowered or yellowing may occur.

The polymer, oligomer and monomer used in combination with the unsaturated quaternary ammonium salt of the present invention may be added alone or in combination of two or more. For example, such polymers include homopolymers and copolymers such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyacrylamide, poly N-substituted acrylamide, polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol and the like. Examples of such oligomers include homo-oligomers and co-oligomers such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyacrylamide, poly N-substituted acrylamide, polyvinyl pyrrolidone, polyethylene oxide, and polyethylene glycol having a molecular weight of 10,000 or less. Such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) ) Acrylate, (meth) acrylate monomers such as N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylamide, propyl (meth) acrylamide, isopropyl (meth) acrylamide, butyl (meth) acrylamide, N-methyl ( (Meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- (Meth) acrylamide monomers such as ethylaminopropyl (meth) acrylamide and diacetone acrylamide, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide, N-methylhydroxyethyl (meth) acrylamide Hydroxyl group-containing (meth) acrylic monomers such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid and other carboxyl group-containing (meth) acrylic monomers, 2- ( Isocyanate group-containing (meth) acrylic monomers such as (meth) acryloyloxyethyl isocyanate, glycidyl group-containing (meth) acrylic monomers such as (meth) acrylic acid glycidyl, 2-vinyl-2-io Oxazoline group-containing (meth) acrylic monomers such as sazoline, cyano-containing monomers such as (meth) acrylonitrile, styrene monomers such as styrene and 2-methylstyrene, aromatic vinyl monomers such as vinylnaphthalene and divinylbenzene, vinyl acetate, Heterocyclic group-containing monomers such as vinyl ester monomers such as vinyl propionate, acryloylmorpholine, vinyl caprolactam, vinyl pyrrolidone, tetrahydrofurfuryl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, ethylene, propylene, Examples thereof include olefin monomers such as isoprene, butadiene and isobutylene, and vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether. These are not limited to one type, and a plurality of types may be used in combination.

When the unsaturated quaternary ammonium salt of the present invention is used as a component of the active energy ray-curable resin composition, it has a large number of two or more ethylene groups for the purpose of increasing the cohesive strength of the resin or improving the curability. Functional monomers and oligomers may be added. Specific examples of the polyfunctional monomer include (meth) acrylate pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol 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) a Relate, methylenebisacrylamide, methylenebisacrylamide methacrylamide, ethylene bisacrylamide, ethylene bis-methacrylamide, diallyl acrylamide, epoxy (meth) acrylates, polyester (meth) acrylate, urethane (meth) acrylate, urethane acrylamide.

These polyfunctional monomers and oligomers are not limited to one type and may be used in combination. In addition, when such a polyfunctional monomer or oligomer is used, the amount used thereof depends on the balance with the amount and molecular weight of the functional group contained in the active energy ray curable resin to be crosslinked, Although it can be appropriately selected depending on the purpose of use, it is usually preferably 0.05 to 99.9% by weight, preferably 0.1 to 99.5% by weight with respect to 100% by weight of the active energy ray-curable resin. More preferably it is contained. When the content is less than 0.05% by weight, the crosslinking formation by the crosslinking agent may be insufficient, and sufficient cohesive force may not be obtained. On the other hand, when the content exceeds 99.9% by weight, the polymer The cohesive force is large and the conformability (wetting property) to the adherend tends to be insufficient.

In this way, an antistatic resin composition comprising the unsaturated quaternary ammonium salt of the present invention is obtained. The antistatic resin composition includes various conventionally known tackifiers, surface lubricants, leveling agents, oxidation agents, and the like as long as the antistatic properties, transparency, compatibility, antibacterial properties and the like are not impaired. Inhibitors, UV absorbers, corrosion inhibitors, light stabilizers, polymerization inhibitors, silane coupling agents, inorganic or organic fillers, metal powders, pigments, dyes, powders, particles, foils Various conventionally known additives such as those can be appropriately added according to the intended use.

The antistatic resin composition of the present invention is made of paper, cloth, non-woven fabric, glass, polyethylene terephthalate, diacetate cellulose, triacetate cellulose, acrylic polymer, polyvinyl chloride, cellophane, celluloid, polycarbonate, polyimide, and other plastics and metals. A high-performance hard coat layer, pressure-sensitive adhesive layer, or adhesive layer can be obtained by coating between the surfaces of the material and curing by irradiation with active energy rays such as ultraviolet rays. Moreover, since the antistatic resin composition of the present invention is transparent, a transparent antistatic hard coat layer, a pressure-sensitive adhesive layer, and an adhesive layer can be obtained by using a transparent base material. As a method of applying this resin composition on a substrate, a normal coating film such as a spin coating method, a spray coating method, a dipping method, a gravure roll method, a knife coating method, a reverse roll method, a screen printing method, a bar coater method, etc. A forming method can be used. Moreover, as a method of apply | coating between base materials, the laminating method, the roll-to-roll method, etc. are mentioned.

The antistatic resin composition of the present invention is used for plastic products that are particularly prone to generate static electricity, and in particular, polarizing plates, retardation plates, optical compensation films, light diffusion sheets, reflection sheets and the like used for liquid crystal displays and the like. It can be suitably used as a surface protective film used for the purpose of protecting the surface of the optical member.

The unsaturated quaternary ammonium salt of the present invention has excellent ionic conductivity, water resistance and thermal stability in addition to antistatic coating applications. Also useful. Examples of the electrochemical device include an electric double layer capacitor, a lithium secondary battery, a fuel cell, a dye-sensitized solar cell, various electrochemical sensors, electrochromic blocking, and an electrochemical switching element. In addition, for use as an electrolytic solution, in addition to the unsaturated quaternary ammonium salt of the present invention alone, it can be used in a state dissolved in an organic solvent.

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

In the following synthesis examples and synthesis comparative examples, the analysis of unsaturated quaternary ammonium salts was performed by the following method.
[Method of measuring quaternary ammonium salt concentration (purity of the target product)]
Using an automatic potentiometric titrator (device name: AT-610, manufactured by Kyoto Electronics Industry Co., Ltd.), titration was performed with a sodium tetraphenylborate solution (manufactured by Kanto Chemical Co., Ltd.) having a concentration of 0.02 mol / L. The quaternary ammonium salt concentration was determined.

Synthesis Example 1 Unsaturated quaternary ammonium salt (1) (Synthesis of adduct of dimethylaminopropylacrylamide and lauryl alcohol (EO) 15 glycidyl ether / acetate)
A flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel was charged with 20.0 parts by weight (0.13 mol) of dimethylaminopropylacrylamide and 100.0 parts by weight of ion-exchanged water, and the temperature in the flask was adjusted. While maintaining the temperature at 35 ° C. or lower, 7.3 parts by weight (0.12 mol) of acetic acid was added dropwise. At this time, the pH of the reaction solution was 8.4. Next, the temperature in the flask was raised to 60 ° C., and 110.0 parts by weight (0.12 mol) of lauryl alcohol polyoxyethylene glycidyl ether (Denacol EX-171; manufactured by Nagase ChemteX Corporation) was added to 100% of ion-exchanged water. A solution dissolved in 0.0 part by weight was added dropwise over 1 hour, followed by stirring for 8 hours. Subsequently, 0.2 parts by weight of 4-methoxyphenol was added to the reaction solution, and concentrated under reduced pressure at 40 ° C. and 3 torr to remove ion-exchanged water, and the target unsaturated quaternary ammonium salt (1) was added to 135. 0 parts by weight were obtained. The product was a yellow viscous liquid. When the concentration of the quaternary ammonium salt (purity of the target product) was determined, it was 99.5%. The yield was 97.9%. In elemental analysis, measured values (C: 59.33%, H: 9.81%, N: 2.35%) are theoretical values (C: 59.01%, H: 9.90%, N: 2. 50%).

Synthesis Example 2 Unsaturated quaternary ammonium salt (2) (synthesis of adduct of dimethylaminopropylacrylamide and phenol (EO) 5 glycidyl ether / acetate)
A flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel was charged with 10.4 parts by weight (0.17 mol) of acetic acid and 100.0 parts by weight of ion-exchanged water, and the temperature in the flask was 35 ° C. or less. 30.0 parts by weight (0.19 mol) of dimethylaminopropylacrylamide was added dropwise. At this time, the pH of the reaction solution was 8.8. Next, the temperature of the flask was raised to 60 ° C., 64.0 parts by weight (0.17 mol) of phenol (EO) 5 glycidyl ether (Denacol EX-145; manufactured by Nagase ChemteX Corporation) was added to 100. What was dissolved in 0 part by weight was added dropwise over 1 hour, followed by stirring for 6 hours. Subsequently, 0.2 parts by weight of 4-methoxyphenol was added to the reaction solution, and concentrated under reduced pressure at 40 ° C. and 3 torr to remove ion-exchanged water, and 90.90 of the target unsaturated quaternary ammonium salt (2) was obtained. 0 parts by weight were obtained. The product was a light yellow viscous liquid. When the concentration of the quaternary ammonium salt (purity of the target product) was determined, it was 99.3%. The yield was 88.1%. In elemental analysis, measured values (C: 59.53%, H: 8.51%, N: 4.75%) are theoretical values (C: 59.37%, H: 8.59%, N: 4. 77%).

Synthesis Example 3 Unsaturated quaternary ammonium salt (3) (Synthesis of adduct of dimethylaminopropylacrylamide and polyethylene glycol (EO) 4 diglycidyl ether / propionate)
A flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel was charged with 20.0 parts by weight (0.13 mol) of dimethylaminopropylacrylamide and 100.0 parts by weight of ion-exchanged water, and the temperature in the flask was adjusted. While maintaining the temperature at 35 ° C. or lower, 9.5 parts by weight (0.12 mol) of propionic acid was added dropwise. At this time, the pH of the reaction solution was 8.4. Next, the temperature of the flask was raised to 60 ° C., and 18.6 parts by weight (0.06 mol) of polyethylene glycol (EO) 4 diglycidyl ether (Denacol EX-821; manufactured by Nagase ChemteX Corporation) was added to ion-exchanged water. What was dissolved in 100.0 parts by weight was added dropwise over 1 hour, followed by stirring for 8 hours. Subsequently, 0.05 parts by weight of 4-methoxyphenol was added to the reaction solution, and concentrated under reduced pressure at 40 ° C. and 3 torr to remove ion-exchanged water, and the desired unsaturated quaternary ammonium salt (3) was obtained in 41. 7 parts by weight were obtained. The product was a light yellow viscous liquid. When the concentration of the quaternary ammonium salt (purity of the target product) was determined, it was 99.2%. The yield was 88.7%. In elemental analysis, measured values (C: 56.13%, H: 9.11%, N: 7.05%) are theoretical values (C: 56.38%, H: 9.20%, N: 7.5). 31%).

Synthesis Example 4 Unsaturated quaternary ammonium salt (4) (Synthesis of adduct of dimethylaminoethyl acrylate and lauryl alcohol (EO) 15 glycidyl ether / acetate)
A flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel was charged with 20.0 parts by weight (0.14 mol) of dimethylaminoethyl acrylate and 100.0 parts by weight of ion-exchanged water, and the temperature in the flask was adjusted. While maintaining the temperature at 35 ° C. or lower, 8.0 parts by weight (0.13 mol) of acetic acid was added dropwise. At this time, since the pH of the reaction solution was 5.0, a 1% aqueous potassium hydroxide solution was added so that the pH was 7.0. Next, the temperature in the flask was raised to 60 ° C., and 119.9 parts by weight (0.13 mol) of lauryl alcohol polyoxyethylene glycidyl ether (Denacol EX-171; manufactured by Nagase ChemteX Corp.) A solution dissolved in 0.0 part by weight was added dropwise over 1 hour, followed by stirring for 8 hours. Subsequently, 0.1 part by weight of 4-methoxyphenol was added to the reaction solution, and the solution was concentrated under reduced pressure at 40 ° C. and 3 torr to remove ion-exchanged water, and the desired unsaturated quaternary ammonium salt (4) was 140. 2 parts by weight were obtained. The product was a yellow viscous liquid. When the concentration of the quaternary ammonium salt (purity of the target product) was determined, it was 99.4%. The yield was 94.9%. In elemental analysis, measured values (C: 59.02%, H: 9.72%, N: 1.25%) are theoretical values (C: 58.62%, H: 9.75%, N: 1. 27%).

Synthesis Example 5 Unsaturated quaternary ammonium salt (5) (Synthesis of adduct of dimethylaminoethyl methacrylate and polyethylene glycol (EO) 22 diglycidyl ether / succinate)
A flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel was charged with 20.0 parts by weight (0.13 mol) of dimethylaminoethyl methacrylate and 100.0 parts by weight of ion-exchanged water, and the temperature in the flask was adjusted. While maintaining the temperature at 35 ° C. or lower, 15.0 parts by weight (0.13 mol) of succinic acid was added dropwise. At this time, since the pH of the reaction solution was 5.7, a 1% aqueous sodium hydroxide solution was added so that the pH was 7.0. Next, the temperature of the flask was raised to 60 ° C., and 66.4 parts by weight (0.06 mol) of polyethylene glycol (EO) 22 diglycidyl ether (Denacol EX-861; manufactured by Nagase ChemteX Corporation) was added to ion-exchanged water. What was dissolved in 100.0 parts by weight was added dropwise over 1 hour, followed by stirring for 8 hours. Subsequently, 0.1 part by weight of 4-methoxyphenol was added to the reaction solution, and concentrated under reduced pressure at 40 ° C. and 3 torr to remove ion-exchanged water, and 90.90 of the target unsaturated quaternary ammonium salt (5) was obtained. 4 parts by weight were obtained. The product was a light yellow viscous liquid. When the concentration of the quaternary ammonium salt (purity of the target product) was determined, it was 98.8%. The yield was 89.6%. In elemental analysis, measured values (C: 53.99%, H: 8.48%, N: 1.73%) are theoretical values (C: 53.87%, H: 8.55%, N: 1. 70%).

Synthesis Example 6 Unsaturated Quaternary Ammonium Salt (6) (Synthesis of Adduct of Dimethylaminopropyl Methacrylamide and Ethylene Glycol (EO) 1 Diglycidyl Ether / Succinate)
A flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel was charged with 20.0 parts by weight (0.12 mol) of dimethylaminopropylmethacrylamide and 100.0 parts by weight of ion-exchanged water, and the temperature in the flask 13.9 parts by weight (0.12 mol) of succinic acid was added dropwise while keeping the temperature at 35 ° C. or lower. At this time, the pH of the reaction solution was 7.3. Next, the temperature of the flask was raised to 60 ° C., and 9.7 parts by weight (0.06 mol) of ethylene glycol (EO) 1 diglycidyl ether (Epolite 40E; manufactured by Kyoeisha Chemical Co., Ltd.) was added to 100.0 ion-exchanged water. A solution dissolved in parts by weight was added dropwise over 1 hour, followed by stirring for 8 hours. Subsequently, 0.04 part by weight of 4-methoxyphenol was added to the reaction solution, and the solution was concentrated under reduced pressure at 40 ° C. and 3 torr to remove ion-exchanged water, and the target unsaturated quaternary ammonium salt (6) was obtained by 38. 2 parts by weight were obtained. The product was a light yellow viscous liquid. When the concentration of the quaternary ammonium salt (purity of the target product) was determined, it was 99.0%. The yield was 90.3%. In elemental analysis, measured values (C: 54.44%, H: 8.38%, N: 7.52%) are theoretical values (C: 54.39%, H: 8.32%, N: 7. 46%).

Comparative Example 1
A flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel was charged with 20.0 parts by weight (0.13 mol) of dimethylaminoethyl methacrylate and 100.0 parts by weight of ion-exchanged water, and the temperature in the flask was adjusted. While maintaining the temperature at 35 ° C. or lower, 8.0 parts by weight (0.13 mol) of acetic acid was added dropwise. At this time, the pH of the reaction solution was 5.7. Without adjusting the pH of the reaction solution, the temperature of the flask was raised to 60 ° C., and 66.4 parts by weight (0.06) of polyethylene glycol (EO) 22 diglycidyl ether (Denacol EX-861; manufactured by Nagase ChemteX Corporation) Mol) was dissolved in 100.0 parts by weight of ion-exchanged water and added dropwise over 1 hour, followed by stirring for 8 hours. Subsequently, 0.1 part by weight of 4-methoxyphenol was added to the reaction solution, and vacuum exchange was performed at 40 ° C. and 3 torr to remove ion-exchanged water, thereby obtaining 86.6 parts by weight of a yellow viscous liquid. When the concentration of the quaternary ammonium salt was determined, it was 50.8%. The yield was 46.7%.

Comparative Example 2
In a flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, 20.0 parts by weight (0.13 mol) of dimethylaminopropylacrylamide, 7.3 parts by weight (0.12 mol) of acetic acid, 110.0 parts by weight (0.12 mol) of oxyethylene glycidyl ether (Denacol EX-171; manufactured by Nagase ChemteX Corporation) and 200.0 parts by weight of ion-exchanged water were charged, and the temperature in the flask rose to 85 ° C. . Then, the flask was cooled with a water bath, and the temperature of the reaction solution was stabilized at 60 ° C. At this time, the pH of the reaction solution was 7.4. Stirring was performed for 8 hours while maintaining the temperature in the flask at 60 ° C. Subsequently, 0.2 parts by weight of 4-methoxyphenol was added to the reaction solution, and the solution was concentrated under reduced pressure at 40 ° C. and 3 torr to remove ion-exchanged water, thereby obtaining 115.8 parts by weight of a yellow viscous liquid. The quaternary ammonium salt concentration was determined to be 8.6%. The yield was 7.2%.

About the unsaturated quaternary ammonium salt obtained by the production method of the present invention, the evaluation result of the active energy ray curability and the evaluation result of the characteristics in each application field when the active energy ray curable resin composition is used. It is shown below. The materials used in Examples and Comparative Examples are as follows.
IPA: isopropyl alcohol MEK: methyl ethyl ketone BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate “HEAA”: N-hydroxyethylacrylamide (trade name “HEAA” manufactured by Kojin Film & Chemicals Co., Ltd.)
MHEAA: N-methyl-N- (2-hydroxyethyl) acrylamide (manufactured by Kojin Film & Chemicals)
"ACMO": Acryloyl morpholine (product name "ACMO", manufactured by Kojin Film & Chemicals)
“DMAA”: N, N-dimethylacrylamide (manufactured by Kojin Film & Chemicals, trade name “DMAA”)
“DEAA”: N, N-diethylacrylamide (trade name “DEAA” manufactured by Kojin Film & Chemicals Co., Ltd.)
“NIPAM”: Isopropylacrylamide (manufactured by Kojin Films & Chemicals, Inc., trade name “NIPAM”)
“DMAPAA”: dimethylaminopropylacrylamide (manufactured by Kojin Film & Chemicals, trade name “DMAPAA”)
4HBA: 4-hydroxybutyl acrylate 2HEA: 2-hydroxyethyl acrylate PETA: pentaerythritol triacrylate DPHA: dipentaerythritol hexaacrylate IBOA: isobornyl acrylate HDDA: 1,6-hexanediol diacrylate DCP-A: dimethylol-tri Cyclodecanediacrylate UV-6640B: Polyurethane acrylate (manufactured by Nippon Synthetic Chemical)
CN2302: Hyperbranched polyester acrylate (manufactured by Sartomer)
DMAEA-Q: acryloyloxyethyltrimethylammonium chloride arton R5000: cyclic olefin-based protective film manufactured by JSR Corporation n-TAC: retardation film WV using a polymer mainly composed of cellulose ester manufactured by Konica Minoltaopt Co., Ltd. -SA: an optical compensation film in which a discotic liquid crystal is coated on a TAC film manufactured by Fuji Film Co., Ltd.

Evaluation Example A-1
20 parts by weight of unsaturated quaternary ammonium salt (1) synthesized in Synthesis Example 1, 40 parts by weight of PETA, 40 parts by weight of polyurethane acrylate (purple light UV-7600B manufactured by Nippon Gosei Kagaku), and 60 parts by weight of MEK are mixed, As a photopolymerization initiator, 3 parts by weight of Darocure 1173 was added and mixed uniformly to obtain an ultraviolet curable hard coat agent. Thereafter, using the obtained hard coat agent, an ultraviolet curable hard coat layer was produced by the following method.

Preparation method of UV curable hard coat layer Polyethylene terephthalate (PET) film with a thickness of 100 μm is fixed to a frame-like wooden frame, and the film is pressed onto the pedestal. The coating agent was dropped in a strip shape, both ends were pressed by a bar coater (RDS12) so that an even force was applied to the whole, and the coating was performed at the same speed (5 cm / sec) without rotating. After drying in an oven at 90 ° C. for 3 minutes, the coated surface is facing upward and irradiated with ultraviolet rays (apparatus: Inverter type conveyor device ECS-4011GX manufactured by iGraphics, metal halide lamp: M04-L41 manufactured by Eyegraphics, ultraviolet illuminance: 700 mW / Cm <2>, integrated light quantity: 1000 mJ / cm <2>) and cured to obtain an antistatic hard coat film.

The characteristics of the antistatic hard coat film were evaluated by the following methods. The results are shown in Table 1.
(1) Formability / stickiness / transparency of coating film The adhesion state and appearance of the antistatic hard coat film to the PET film were visually observed to evaluate the film formability, tackiness, and transparency.
Formability of coating film:
A: 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: There are many repellent and non-uniform coating films;
Stickiness ◎: No stickiness;
○: Slightly sticky;
Δ: Slight stickiness;
X: There is clear stickiness;
transparency:
A: Transparent and smooth surface;
○: Transparent but uneven
Δ: Slight cloudiness or unevenness;
X: Extreme cloudiness or unevenness;
(2) 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, the measurement was performed using a digital electrometer (R8252 type: manufactured by ADC Corporation).
(3) Scratch resistance test Using # 0000 steel wool, the steel wool was reciprocated 10 times on the antistatic hard coat film while applying a load of 200 g / cm <2>, and the presence or absence of scratches was evaluated.
Abrasion 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;
(4) Moisture resistance test The antistatic hard coat film was stored in a constant temperature bath at 40 ° C. and 90% RH for 3 days, and the change in the appearance of the film was visually evaluated.
A: No change in appearance;
○: A level in which a slight change in appearance such as whitening is observed but is not a problem;
Δ: Slight change in appearance such as whitening is observed;
×: Appearance change such as whitening is remarkably recognized;
(5) Pencil hardness test The antistatic hard coat film was subjected to a pencil hardness test based on JIS K 5400.
(6) Adhesion evaluation JIS K 5400 8.5 Create 100 squares of 1 mm square based on the cross-cut tape method (1990 version), apply cellophane tape, and hard coat on the substrate side when peeled off at once The number of eyes that left the layer was counted and evaluated.
A: 100/100 (number without peeling);
○: 95 to 99/100 (number without peeling);
(Triangle | delta): 90-94 / 100 (number without peeling);
X: 0-89 / 100 (number without peeling);

Evaluation Examples A-2 to A-10, Evaluation Comparative Examples A-11 to A-15
Except having changed into the composition of Table 1, the hard-coat layer was produced and evaluated similarly to evaluation example A-1. The results are shown in Tables 1 and 2.

Evaluation Example B-1
Synthesis of unsaturated quaternary ammonium salt homopolymer solution 20 wt. Of unsaturated quaternary ammonium salt (1) synthesized in Synthesis Example 1 in a flask equipped with a stirring blade, a reflux condenser, a thermometer, and a gas inlet. And 0.2 part by weight of azoisobutyronitrile (AIBN) are mixed and dissolved in 100 parts by weight of IPA, polymerized at 70 ° C. for 8 hours under a nitrogen stream, and a homopolymer solution of unsaturated quaternary ammonium salt (a) Got.
Synthesis of unsaturated quaternary ammonium salt copolymer solution 10 parts by weight of unsaturated quaternary ammonium salt (1) synthesized in Synthesis Example 1 in a flask equipped with a stirring blade, a reflux condenser, a thermometer, and a gas inlet 10 parts by weight of 2EHA and 0.2 parts by weight of AIBN were mixed and dissolved in 100 parts by weight of IPA and polymerized at 70 ° C. for 8 hours under a nitrogen stream to obtain a copolymer solution (b) of an unsaturated quaternary ammonium salt. Table 3 shows the mixing ratio of the monomers in the synthesis of the copolymer solution.

Preparation of Antistatic Hard Coating Agent Containing Unsaturated Quaternary Ammonium Salt Polymer Into 5 parts by weight of homopolymer solution (a) of unsaturated quaternary ammonium salt, 50 parts by weight of PETA and 50 parts by weight of DPHA, and photopolymerization As an initiator, 5 parts by weight of Darocure 1173 is mixed and dissolved in 120 parts by weight of a mixed solvent of 1: 1 weight ratio of IPA and MEK, and an antistatic hard coat containing an ultraviolet curable unsaturated quaternary ammonium salt homopolymer. An agent was obtained. Thereafter, the obtained hard coat agent was applied to a PET film having a thickness of 100 μm, and was subjected to ultraviolet curing in the same manner as in Evaluation Example A-1, thereby producing and evaluating an antistatic hard coat.

Evaluation Examples B-2 to B-11, Evaluation Comparative Examples B-12 to B-13
An antistatic hard coat was prepared and evaluated in the same manner as in Example B-1, except that the compositions shown in Table 4 and Table 5 were changed.

Evaluation Example C-1
Preparation method of antistatic pressure-sensitive adhesive In a flask equipped with a stirring blade, a reflux condenser, a thermometer, and a gas inlet, 4.0 parts by weight of the unsaturated quaternary ammonium salt (1) synthesized in Synthesis Example 1; Add 18.5 parts by weight of butyl acrylate, 74.0 parts by weight of 2-ethylhexyl acrylate, 3.5 parts by weight of 4-hydroxybutyl acrylate, 208 parts by weight of ethyl acetate and 42 parts by weight of acetone, and introduce nitrogen gas while stirring. After replacing the air in the apparatus with nitrogen, 0.2 part of AIBN was added, the temperature was raised to the reflux temperature, and the reaction was carried out for 7 hours. After completion of the reaction, the mixture was diluted with toluene to obtain a 35% solution (solid content 35%, viscosity 3000 mPa · s) of acrylic resin (I-1). The viscosity was measured at 20 ° C. according to JIS K5600-2-3 using a cone plate viscometer (device name: RE550 viscometer manufactured by Toki Sangyo Co., Ltd.). Subsequently, 2 parts of hexamethylene diisocyanate (Duranate 24A-100 manufactured by Asahi Kasei Kogyo Co., Ltd.) is added as a cross-linking agent to 100 parts of the solid content of the acrylic resin (I-1), and the mixture is sufficiently stirred. An antistatic pressure-sensitive adhesive was obtained.

Acrylic resin (I-2 to 11, B-1 to B-4)
Except for changing to the acrylic resins (A-2 to 11, B-1 to B-4) listed in Tables 6 and 7, the same as the acrylic resin (A-1) of Evaluation Example C-1 An antistatic pressure-sensitive adhesive was obtained.

Preparation method of antistatic pressure-sensitive adhesive sheet The antistatic pressure-sensitive adhesive prepared above was applied to a heavy release separator (silicone-coated PET film), dried at 90 ° C. for 3 minutes, and then lightly released separator (silicone-coated PET film). Then, using a desktop roll laminator machine (RSL-382S manufactured by Royal Sovereign) so as not to bite the bubbles, the adhesive layer was bonded to a thickness of 25 μm to form an adhesive layer. Then
(I) A test pressure-sensitive adhesive sheet (type i) was obtained by placing in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 1 day.
(ii) When cross-linking using a cross-linking agent, after aging in a constant temperature bath at 40 ° C. for 3 days, place it in an environment at a temperature of 23 ° C. and a relative humidity of 50% for 1 day, and attach the test adhesive sheet (type ii). Obtained.
(Iii) In the case of crosslinking by ultraviolet irradiation, ultraviolet irradiation is performed with the coated surface facing upward (apparatus: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm2 and integrated light quantity: 1000 mJ / cm2) to cure and obtain an ultraviolet-cured film, and then placed in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type iii).

The properties of the obtained antistatic pressure-sensitive adhesive sheet were evaluated by the following methods. The results are shown in Table 8.

(7) Transparency (haze value)
Under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, the peeled surface of the light release separator of the pressure-sensitive adhesive sheet cut to a width of 25 mm was attached to the glass substrate as the adherend, the heavy release separator was peeled off, and the haze value was measured. . The measurement was performed according to JIS K 7105 using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated according to the following criteria.
A: There is no problem in practical use. Haze: less than 0.5;
○: Clouding or the like is not recognized, but haze: 0.5 or more and less than 1;
Δ: Some cloudiness is observed. Haze 1 or more and less than 3;
X: Cloudiness is recognized and there is a problem in practical use. Or haze: 3 or more;
(8) Adhesive strength Under conditions of a temperature of 23 ° C. and a relative humidity of 50%, the adherend is transferred to acrylic (PMMA), polycarbonate (PC), polyethylene terephthalate (PET) and a glass substrate, sheet or film, and weight The pressure was applied by reciprocating twice using a 2 kg pressure roller, and the mixture was left for 30 minutes in the same atmosphere. Thereafter, 180 ° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min using a tensile tester (device name: Autograph AGXS-X 500N, manufactured by Shimadzu Corporation).
A: 3 (N / 25 mm) or more;
○: 0.5 (N / 25 mm) or more and less than 3 (N / 25 mm);
Δ: 0.1 (N / 25 mm) or more and less than 0.5 (N / 25 mm);
X: Less than 0.1 (N / 25 mm);
(9) Contamination resistance The adhesive sheet was adhered to the adherend in the same manner as in the measurement of the adhesive force described above, left at 80 ° C. for 24 hours, and then the contamination of the adherend surface after peeling the adhesive sheet was visually observed. Observed.
A: No contamination;
○: Slightly contaminated;
Δ: Slightly contaminated;
×: There is a residue of adhesive (adhesive);
(10) Light yellowing resistance The adhesive sheet was attached to a glass substrate, set in a xenon fade meter (SC-700-WA: manufactured by Suga Test Instruments Co., Ltd.), and irradiated with ultraviolet rays having an intensity of 70 mW / cm 2 for 120 hours. The color change of the adhesive sheet was observed visually.
A: No yellowing can be confirmed visually;
○: Yellowing can be confirmed very slightly by visual observation;
Δ: Yellowing can be visually confirmed;
X: Obvious yellowing can be confirmed visually;
(11) A durable adhesive sheet is attached to an adherend in the same manner as the measurement of the adhesive strength described above, and the presence / absence of floating / peeling, bubbles and cloudiness after holding for 100 hours under the conditions of 85 ° C. and 85% RH Were visually observed and evaluated.
◎: Transparent, no floating / peeling or bubbles generated;
○: There is very little cloudiness, but no floating / peeling or bubbles are generated;
Δ: Slight cloudiness or floating / peeling, air bubbles are present;
×: Extremely cloudy or floating / peeling, air bubbles are present;

Evaluation Examples C-2 to C-15, Evaluation Comparative Examples C-16 to C-21
An antistatic pressure-sensitive adhesive sheet was prepared in the same manner as in Evaluation Example C-1, and various physical properties were measured by the test methods described above. The obtained results are shown in Table 8 and Table 9. Evaluation Example C-8 produced an antistatic pressure-sensitive adhesive sheet (type i) in accordance with the pressure-sensitive adhesive sheet preparation method (i), and was evaluated as Evaluation Examples C-1 to C-7 and C-9 to C-11. Comparative Examples C-13 to C-16 produced antistatic pressure-sensitive adhesive sheets (type ii) according to the pressure-sensitive adhesive sheet production method (ii).

Evaluation Example C-17
To 10 parts by weight of the acrylic resin obtained in Comparative Production Example B-1, 0.5 part by weight of the unsaturated quaternary ammonium salt (1) synthesized in Synthesis Example 1, and dipentaerythritol hexa as an unsaturated group-containing compound Add 1.5 parts by weight of acrylate and 0.3 parts by weight of Darocure 1173 as a photopolymerization initiator, mix and dissolve in 10 parts by weight of an ethyl acetate / acetone mixed solvent (5/1 (v / v)), and then cure by UV. A possible resin composition solution containing an unsaturated quaternary ammonium salt was obtained. Using this antistatic pressure-sensitive adhesive, an antistatic pressure-sensitive adhesive sheet (type iii) was prepared by performing coating film and ultraviolet irradiation according to the above-mentioned pressure-sensitive adhesive sheet production method (iii).

Evaluation Examples C-18 to C-24, Evaluation Comparative Examples C-25 to C-26
An antistatic pressure-sensitive adhesive sheet (type iii) was prepared in the same manner as in Evaluation Example C-17, and various physical properties were measured by the test methods described above. Table 10 shows the obtained results.

Evaluation Example D-1
1 part by weight of unsaturated quaternary ammonium salt (1) synthesized in Synthesis Example 1, 60 parts by weight of “HEAA” and 24 parts by weight of “DMAA”, 5 parts by weight of HDDA, polyurethane acrylate (purchased UV- 6640B) An active energy ray-curable adhesive was prepared by mixing 10 parts by weight. To this, 3 parts by weight of Darocure 1173 and 1 part by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals) were added as a photopolymerization initiator and mixed uniformly.

Production method of polarizing plate by UV irradiation Using a table-type roll laminator (RSL-382S manufactured by Royal Sovereign), a polarizing film is sandwiched between two transparent films (protective film, retardation film or optical compensation film) Between the transparent film and the polarizing film, the adhesive of the evaluation example or the evaluation comparative example was bonded so as to have a thickness of 2 μm. Irradiate ultraviolet rays from the upper surface of the laminated transparent film (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, UV illuminance: 700 mW / cm2, integrated light amount: 1000 mJ / cm2 And a polarizing plate having a transparent film on both sides of the polarizing film was prepared.

Preparation method of polarizing plate by EB irradiation Without adding a photopolymerization initiator, similarly to the above, a transparent film such as a desktop roll laminator, a protective film, a retardation film or an optical compensation film, a polarizing film, and an evaluation example or Bonding was performed using the adhesive of the evaluation comparative example. An electron beam is irradiated from the upper surface of the bonded transparent film (apparatus: Nissin High Voltage Co., Ltd., trade name: Curetron EBC-200-AA3, acceleration voltage: 200 kV, irradiation dose 20 kGy), and both sides of the polarizing film A polarizing plate having a transparent film was prepared.

The properties of the obtained adhesive and polarizing plate were evaluated by the following methods. The results are shown in Table 11.

(12) Adhesive tape in which a polarizing plate (test piece) cut to 20 mm × 150 mm is attached to a tensile testing machine (Autograph AGXS-X 500N, manufactured by Shimadzu Corporation) under conditions of a peel strength of 23 ° C. and a relative humidity of 50% It peeled and stuck on the test board of the peeling test apparatus using the double-sided adhesive tape. One piece of the transparent protective film and the polarizing film to which the double-sided adhesive tape is not attached is peeled off in advance by about 20 to 30 mm, chucked on the upper gripping tool, and peeled at 90 ° peel strength (N / 20 mm).
A: 3.0 (N / 20 mm) or more;
○: 1.5 (N / 20 mm) or more and less than 3.0 (N / 20 mm);
Δ: 1.0 (N / 20 mm) or more and less than 1.5 (N / 20 mm);
X: Less than 1.0 (N / 20 mm);
(13) Measurement of surface resistivity The polyethylene terephthalate (PET) film having a thickness of 100 μm was coated with the adhesive liquid obtained in the evaluation examples and comparative examples using a bar coater (No. 3), and the upper surface of the film (Equipment: Inverter type ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 made by Eye Graphics, UV illumination: 700 mW / cm2, integrated light intensity: 1000 mJ / cm2), surface resistivity measurement A film was obtained. Subsequently, it was cut into 110 mm × 110 mm under conditions of a temperature of 23 ° C. and a relative humidity of 50% to obtain a test piece for measuring surface resistivity. Based on JIS K 6911, a digital electrometer (R8252 type: manufactured by ADC Corporation) Was used to measure the low surface efficiency.
(14) Appearance The transparency of the obtained polarizing plate was visually observed and evaluated according to the following criteria.
A: Neither fine streaks nor unevenness on the surface of the polarizing plate can be confirmed;
○: Minute streaks can be partially confirmed on the surface of the polarizing plate;
Δ: Minute streaks and unevenness on the surface of the polarizing plate can be confirmed;
X: Clear streaks and unevenness on the surface of the polarizing plate can be confirmed;
(15) Transparency (haze value)
The obtained polarizing plate was measured for the haze value using a haze meter (Nippon Denshoku Industries Co., Ltd. haze meter NDK2000) and evaluated according to the following criteria.
A: There is no problem in practical use. Haze: less than 0.5;
○: Clouding or the like is not recognized, but haze: 0.5 or more and less than 1;
Δ: Some cloudiness is observed. Haze 1 or more and less than 3;
X: Cloudiness is recognized and there is a problem in practical use. Or haze: 3 or more;
(16) Water resistance After the obtained polarizing plate was cut into 20 × 80 mm and immersed in warm water at 60 ° C. for 48 hours, the presence or absence of peeling at the interface between the polarizer and the protective film, retardation film, or optical compensation film was checked. confirmed. The determination was made according to the following criteria.
A: No peeling at the interface between the polarizer and the protective film (less than 1 mm);
○: There is peeling at a part of the interface between the polarizer and the protective film (1 mm or more and less than 3 mm);
(Triangle | delta): There exists peeling in a part of interface of a polarizer and a protective film (3 mm or more and less than 5 mm);
X: There is peeling at the interface between the polarizer and the protective film (5 mm or more);
(17) Durability The obtained polarizing plate was cut into 150 mm × 150 mm, put into a thermal shock apparatus (TSA-101L-A manufactured by Espec Corp.), and subjected to a heat shock of −40 ° C. to 80 ° C. for 30 minutes each 100 times. And evaluated according to the following criteria.
A: No cracking occurred;
○: Generation of a short crack of 5 mm or less only at the end;
(Triangle | delta): The crack has generate | occur | produced in the short linear form in places other than an edge part. However, the line does not separate the polarizer into two or more parts;
X: Cracks are generated in places other than the edges. The line separates the polarizer into two or more parts;

Evaluation Examples D-2 to D-9, Evaluation Comparative Examples D-10 to D-12
In Evaluation Example D-1, a polarizing plate was produced and evaluated in the same manner as in Example D-1, except that the compositions shown in Table 11 and Table 12 were changed. The results are shown in Table 7.

Evaluation Example E-1
Using the antistatic hard coat film prepared in Evaluation Example A-1, antibacterial evaluation was performed using Staphylococcus aureus and Escherichia coli as test bacteria according to JIS Z 2801.
In the determination, an antibacterial activity value for a raw sample (PET film) was obtained, and antibacterial evaluation was performed according to the following criteria.
A: Antibacterial activity value is 2.0 or more;
○: The antibacterial activity value is 1.5 or more and less than 2.0;
Δ: The antibacterial activity value is 0.5 or more and less than 1.5;
X: The antibacterial activity value is less than 0.5;

Evaluation Examples E-2 to 5 and Evaluation Comparative Example E-6
Evaluation was performed in the same manner as in Example E-1, except that the composition shown in Table 8 was used. The results are shown in Table 13.

As shown in the results of Synthesis Examples 1 to 6, the unsaturated quaternary ammonium salt of the present invention is synthesized by adjusting the pH at the time of reaction with an acid to 7 or more, and thus a cyclic ether group-containing compound Does not produce a by-product, and the target unsaturated quaternary ammonium salt can be obtained with high purity.

As shown in the results of the evaluation examples and evaluation comparative examples, the unsaturated quaternary ammonium salt of the present invention is amphiphilic, so it is a phase for various resin compositions, polymerizable monomers, oligomers, polymers, and organic solvents. Excellent solubility. For this reason, by blending the unsaturated quaternary ammonium salt, it is possible to obtain a resin composition having high functions such as high antistatic property, high transparency, and high adhesion. Resin compositions such as hard coats, pressure-sensitive adhesives, and adhesives can be obtained. In addition, since the unsaturated quaternary ammonium salt of the present invention has high purity and excellent conductivity, high ionic conductivity and thermal stability are required, and in electrolyte applications such as electric double layer capacitors and lithium secondary batteries. Can also be suitably used. Furthermore, since it has excellent antibacterial properties, it can be suitably used in antibacterial agent applications.

According to the present invention, an unsaturated quaternary ammonium salt can be produced industrially advantageously. The resulting unsaturated quaternary ammonium salt undergoes a curing reaction sensitively to active energy rays, and therefore can be suitably used for active energy ray curable resin applications. Suitable for antistatic agents such as adhesives, electronic materials, fibers and inks, electrolytes such as electric double layer capacitors and lithium secondary batteries using high conductivity, and antibacterial agents using antibacterial effects Can be used.
?

Claims (13)

A saturated quaternary ammonium salt represented by the following general formula (1).

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms or a benzyl group, may be different, X represents an oxygen atom or NH, Y represents an alkylene group having 1 to 3 carbon atoms, n represents an integer from 1 to 6, Z is an organic group, a ^n-is an n-valent organic acid ion Represents.) In the general formula (1), n is 1 and Z is

(In the formula, R ₄ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, a phenol group or a benzyl group, which may be substituted with a cyclic ether group, and R ₅ is a hydrogen atom or The unsaturated quaternary ammonium salt according to claim 1, which is a methyl group, and m is an integer of 1 to 30). N of general formula (1) is 2-6, and Z is the following

Or

(Wherein R ₅ is a hydrogen atom or a methyl group, m represents an integer of 1 to 30, p and q represent an integer of 1 to 29, and the sum thereof is 2 to 30). The unsaturated quaternary ammonium salt according to claim 1, which is a group. Unsaturated quaternary ammonium salt
(A) The following 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, an alkenyl group having 1 to 3 carbon atoms or a benzyl group, which may be the same or different. X represents an oxygen atom or NH, and Y represents an alkylene group having 1 to 3 carbon atoms.)
A tertiary amine compound represented by the formula:
(B) The following general formula (3)

Or (c) the following general formula (4)

(In the formula, R ₄ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, a phenol group or a benzyl group, which may be substituted with a cyclic ether group, and R ₅ is a hydrogen atom or (It is an alkyl group having 1 carbon atom, and m represents an integer of 1 to 30.)
The manufacturing method of the unsaturated quaternary ammonium salt as described in any one of Claim 1 thru | or 3 with which the cyclic ether group containing compound represented by these is made to react. 5. The method for producing an unsaturated quaternary ammonium salt according to claim 4, wherein the tertiary amine compound and the organic acid are reacted at a pH of 7 or more and a temperature of 35 ° C. or less and then reacted with a cyclic ether group-containing compound. An oligomer or a polymer obtained by homopolymerization of the unsaturated quaternary ammonium salt according to any one of claims 1 to 3 or copolymerization with another copolymerizable vinyl monomer. An antistatic agent comprising the unsaturated quaternary ammonium salt according to any one of claims 1 to 3 and / or the oligomer or polymer according to claim 6. An antistatic resin composition comprising the antistatic agent according to claim 7, wherein the unsaturated quaternary ammonium salt according to any one of claims 1 to 3 is 0.1 as a constituent unit. Contains ~ 95% by weight. The antistatic resin composition according to claim 8, further comprising polyfunctional (meth) acrylate and / or polyfunctional (meth) acrylamide. An antistatic layer formed by coating the base material with the antistatic agent according to claim 7 and / or the antistatic composition according to claim 8 or 9, and then curing with an active energy ray or heat. A film or sheet-shaped antistatic thin film having the antistatic layer according to claim 10 on at least one surface. An electrolyte for a battery or a capacitor using the unsaturated quaternary ammonium salt according to any one of claims 1 to 3 and / or the oligomer or polymer according to claim 6. The antibacterial agent using the unsaturated quaternary ammonium salt as described in any one of Claims 1 thru | or 3, and / or the oligomer or polymer of Claim 6.