JP2010229187A - Quaternary cationic antistatic agent, and antistatic composition and formed product containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic composition which has an adequate compatibility with a resin or an organic solvent, has excoriation resistance and transparency, is halogen-free, has a low environmental load, and has hydrolysis resistance and durability. <P>SOLUTION: An antistatic agent includes a (meth)acrylic amide-based onium salt monomer constituted by hydroxide ions and carboxy ions as negative ions and represented by formula (1). In addition, the antistatic agent also includes an oligomer or/and a polymer constituted by the monomer as a component. The antistatic agent or a composition containing it is applied onto a substrate to form an antistatic layer. (In the formula, R<SB>1</SB>represents a hydrogen atom or a methyl group; R<SB>2</SB>and R<SB>3</SB>independently represent a 1-3C alkyl group and may be the same or different; R<SB>4</SB>represents a 1-3C alkyl or benzyl group; A represents a 1-3C alkylene group; and X- represents a hydroxide ion or a carboxy ion). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to an antistatic agent comprising a quaternary cationic (meth) acrylamide monomer and an antistatic resin composition containing the antistatic agent.

In general, resin materials are excellent in electrical insulation, so they are extremely useful for applications that require electrical insulation, such as insulators. However, they are easy to be charged with static electricity on the surface, causing dust adsorption and problems caused by static electricity. Produce.

Cationic antistatic agents composed of quaternary ammonium bases are known to have excellent antistatic effects. For example, in Patent Documents 1 and 2, a non-polymerizable quaternary ammonium salt containing a halide ion or an alkyl sulfonate ion as a negative ion is added to a polymerizable compound such as an acrylate monomer, and antistatic properties are obtained by ultraviolet irradiation. A method for obtaining a resin composition has been reported. However, these non-polymerizable quaternary ammonium salts do not form an effective chemical bond with the resin, and gradually bleed out on the surface of the resin composition over time. The anti-static performance cannot be maintained.

In order to provide sustainable antistatic performance, a cationic vinyl monomer having a polymerizable group is copolymerized with another copolymerizable monomer such as methacryloyloxyethyltrimethylammonium chloride with 2-ethylhexyl acrylate, to form a polymer antistatic agent The method of using as is reported (patent document 3). However, since the cationic vinyl monomer has an ester acrylate skeleton, it has a drawback of being easily hydrolyzed. In addition, acrylic acid generated by hydrolysis may cause corrosion of electronic parts and optical materials.

It is publicly known to use an amide-based compound whose water resistance improvement is high in hydrolysis resistance.
However, many amide-based cationic vinyl monomers have high polarity, high hygroscopicity, and are commonly circulated in the form of an aqueous solution for manufacturing reasons. For example, there is a method in which methyl chloride is added as a quaternizing agent to unsaturated tertiary amine N, N-dimethylaminopropylacrylamide, and a quaternization reaction is performed in the presence of a mixed solvent composed of water and an aprotic organic solvent. It is often used (Patent Document 4). Of course, the amide-based cationic vinyl monomer solution obtained by these known methods is usually an aqueous solution, so the drying property at the time of coating is poor, and the general-purpose resin, polyfunctional acrylic monomer, oligomer, organic solvent, etc. There is a problem in that the compatibility of these materials is poor, they cannot be uniformly dispersed, and effective antistatic properties cannot be exhibited. Even if the amide-based cationic vinyl monomer is purified to a high purity and dissolved in a polar organic solvent, the monomer itself has high hydrophilicity, so when the organic solvent is removed, other components in the resin are used. Therefore, it cannot be formed into a continuous antistatic film, and the target antistatic performance cannot be achieved.

Various attempts have been made to simultaneously improve the water resistance and the compatibility with the resin and the organic solvent without using an amide-based cationic vinyl monomer. For example, a method of copolymerizing and using an acrylate cationic vinyl monomer and a polymerizable monomer having an amide group has been reported (Patent Documents 5 and 6). However, in these methods, since the content of the cationic vinyl monomer in the antistatic composition decreases, in order to obtain the target antistatic performance, it is necessary to add a large amount of this copolymer, As a result, there are problems that various properties of the resin are lowered and the price of the resin composition is increased.

In addition, for the purpose of improving the compatibility of the cationic vinyl monomer itself, for example,
Patent Document 7 proposes a polymerizable compound having a nitrogen onium cation and a weakly coordinating anion that coordinates weakly to the onium cation. However, the proposed alkali metal salts such as bis (trifluoromethanesulfonyl) imide are generally expensive and contain halogen ions, which may generate toxic gases during disposal and incineration. May adversely affect Furthermore, when such a nitrogen onium salt is used in an electronic component such as a battery or a capacitor, the electrode tends to be deteriorated by halogen ions, and is not suitable for use in contact with such a surface.

JP 2008-231240 A JP 2008-13636 A JP 2008-231196 A Japanese Patent Laid-Open No. 63-201115 JP 2007-332181 A JP 2000-129245 A JP 2007-9042 A

As described above, the water resistance and compatibility are essentially improved, the environmental load is small, and an amide-based cationic vinyl monomer as an effective antistatic agent composition has not yet been obtained. .

The present invention is an acrylamide that is excellent in compatibility with a base resin and an organic solvent, is halogen-free, has a low environmental impact, has high hydrolysis resistance, has an excellent antistatic effect, and can be produced at low cost. It is an object of the present invention to provide a cationic vinyl monomer, an antistatic agent comprising the monomer, and an antistatic resin composition containing the antistatic agent.
The present invention also provides an antistatic layer excellent in antistatic properties, transparency, and adhesion to various resin substrates, and such a charging agent, by using an antistatic composition comprising such an amide cationic vinyl monomer. It is an object of the present invention to provide an antistatic film including a prevention layer.

As a result of intensive studies to solve these problems, the inventor of the present invention has a general formula (1) in which an onium salt is composed of ammonium as a positive ion, a hydroxide ion as a negative ion, and a carboxy ion. R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ each independently represent an alkyl group having 1 to 3 carbon atoms, and may be the same or different, and R ₄ represents 1 to 3 carbon atoms.
A quaternary cationic (meth) acrylamide monomer represented by (A) represents an alkylene group having 1 to 3 carbon atoms, X ⁻ represents a hydroxide ion or a carboxy ion), and / or The present inventors have found an antistatic agent composed of an oligomer and a polymer comprising the monomer. The above problems were solved by forming the antistatic layer by dissolving the antistatic agent in an organic solvent and then coating and fixing the antistatic agent on the base material, thereby achieving the present invention.

（２）上記（１）記載の４級カチオン性（メタ）アクリルアミド系モノマーを構成成分と
して５〜１００重量％配合したオリゴマー又は／及びポリマーからなる帯電防止剤、
（３）上記（１）と（２）記載の４級カチオン性（メタ）アクリルアミド系モノマー、該
モノマーを配合したオリゴマー又は／及びポリマーを有機溶媒中に１〜９０重量％含有し
た溶液であることを特徴とする帯電防止剤、
（４）有機溶媒は、溶解度パラメーターが８〜１６
(cal/cm³)^0.5を有する有機溶媒からなる群から選択された１種または２種以上である上記
（３）記載の帯電防止剤、
（５）多官能（メタ）アクリレート又は／及び（メタ）アクリルアミドをさらに含有する
上記（１）乃至上記（４）記載の帯電防止組成物、
（６）上記（５）記載の多官能（メタ）アクリレート又は／及び（メタ）アクリルアミド
の配合量は上記（１）乃至上記（４）記載の４級カチオン性（メタ）アクリルアミド系モ
ノマー、該モノマーを配合したオリゴマー又は／及びポリマー対して１〜５０重量％含有
することを特徴とする帯電防止組成物、
（７）上記（１）記載の４級カチオン性（メタ）アクリルアミド系モノマーは構成単位と
して０．１〜９０重量％を含有した上記（１）乃至上記（６）記載の帯電防止剤および帯
電防止組成物
（８）基材上に上記（１）乃至上記（７）記載の帯電防止剤又は／及び帯電防止組成物を
塗布して形成されることを特徴とする帯電防止層、
（９）基材上に上記（１）乃至上記（７）記載の帯電防止剤又は／及び帯電防止組成物を
活性エネルギー線又は熱で重合して形成されることを特徴とする帯電防止層、
（１０）基材および基材上に上記（１）乃至上記（７）記載の帯電防止剤又は／及び帯電
防止層を有することを特徴とする帯電防止フィルム
を提供するものである。
That is, the present invention
(1) General formula (1) which is an onium salt composed of ammonium as a positive ion, hydroxide ion as a negative ion, and carboxy ion (wherein R ₁ represents 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, R ₄ represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, and A represents 1 carbon atom. An antistatic agent comprising a quaternary cationic (meth) acrylamide-based monomer represented by ˜3 alkylene group, X ⁻ represents a hydroxide ion or a carboxy ion),

(2) An antistatic agent comprising an oligomer and / or polymer containing 5 to 100% by weight of the quaternary cationic (meth) acrylamide monomer described in (1) above as a constituent component,
(3) A quaternary cationic (meth) acrylamide monomer described in (1) and (2) above, an oligomer or / and a polymer containing the monomer, and a solution containing 1 to 90% by weight in an organic solvent. Antistatic agent, characterized by
(4) The organic solvent has a solubility parameter of 8-16.
the antistatic agent according to the above (3), which is one or more selected from the group consisting of organic solvents having (cal / cm ³ ) ^0.5 ,
(5) The antistatic composition according to the above (1) to (4), further containing a polyfunctional (meth) acrylate or / and (meth) acrylamide,
(6) The amount of polyfunctional (meth) acrylate or (meth) acrylamide described in (5) above is the quaternary cationic (meth) acrylamide monomer described in (1) to (4) above, the monomer 1 to 50% by weight based on the oligomer or / and polymer blended with
(7) The quaternary cationic (meth) acrylamide monomer described in (1) above contains 0.1 to 90% by weight as a structural unit, and the antistatic agent and antistatic agent described in (1) to (6) above Composition (8) An antistatic layer formed by applying the antistatic agent or / and antistatic composition described in (1) to (7) above on a substrate,
(9) An antistatic layer formed by polymerizing the antistatic agent or / and antistatic composition according to (1) to (7) above on a substrate with active energy rays or heat,
(10) An antistatic film comprising the base material and the antistatic agent or / and the antistatic layer according to the above (1) to (7) on the base material is provided.

The antistatic agent comprising a quaternary cationic (meth) acrylamide monomer of the present invention has good compatibility with resins and organic solvents, good scratch resistance and transparency, and is halogen-free, resulting in low environmental impact. Thus, an antistatic resin composition having sufficient hydrolysis resistance and having an excellent antistatic effect that can be sustained can be obtained.
Among these effects, the antistatic property is particularly excellent because of its high compatibility with resins and organic solvents, so that the antistatic agent can be uniformly dispersed in the resin, and a continuous antistatic layer is formed. The present inventors speculate that this is easy. In addition, since the quaternary cationic (meth) acrylamide monomer of the present invention is excellent in its own compatibility, it becomes unnecessary to add a new compound for the purpose of improving the compatibility, and the content of the cationic monomer is relatively reduced. It was possible to suppress the deterioration of various properties of the resin.
Antistatic agent and antistatic composition comprising quaternary cationic (meth) acrylamide monomer of the present invention, and antistatic layer excellent in antistatic property, transparency and adhesion to various resin substrates, and such An antistatic film provided with an antistatic layer can be provided.

Hereinafter, the present invention will be described in detail.
The quaternary cationic (meth) acrylamide monomer, which is an active ingredient of the antistatic agent of the present invention, is an onium salt composed of ammonium as a positive ion, hydroxide ion as a negative ion, and carboxy ion. It is a compound linked to (meth) acrylamide.
In the compound represented by the general formula (1), R ₁ represents 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;
R ₄ represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, A represents an alkylene group having 1 to 3 carbon atoms, and X ⁻ represents a hydroxide ion or a carboxy ion, specifically, acryloyl Aminomethyltrimethylammonium hydroxide, acryloylaminomethyltriethylammonium hydroxide, acryloylaminomethyltripropylammonium hydroxide, acryloylaminoethyltrimethylammonium hydroxide,
Acryloylaminopropyltrimethylammonium hydroxide, acryloylaminopropylmethyldiethylammonium hydroxide, acryloylaminopropylethyldimethylammonium hydroxide, acryloylaminopropylmethyldipropylammonium hydroxide, acryloylaminopropyltriethylammonium hydroxide, acryloylaminopropyltripropylammonium hydroxide Hydroxide, acryloylaminoethyldimethylbenzylammonium hydroxide, acryloylaminopropyldimethylbenzylammonium hydroxide, acryloylaminopropyldiethylbenzylammonium hydroxide, acryloylaminopropylmethyldibenzylammonium hydroxide, acrylo Ruaminopropylethyl dibenzylammonium hydroxide, methacryloylaminomethyltrimethylammonium hydroxide, methacryloylaminomethyltriethylammonium hydroxide, methacryloylaminomethyltripropylammonium hydroxide, methacryloylaminoethyltrimethylammonium hydroxide, methacryloylaminopropyltrimethylammonium hydroxide ,
Methacryloylaminopropylmethyldiethylammonium hydroxide, methacryloylaminopropylethyldimethylammonium hydroxide, methacryloylaminopropylmethyldipropylammonium hydroxide, methacryloylaminopropyltriethylammonium hydroxide, methacryloylaminopropyltripropylammonium hydroxide, methacryloylaminoethyldimethylbenzyl Ammonium hydroxide, methacryloylaminopropyldimethylbenzylammonium hydroxide, methacryloylaminopropyldiethylbenzylammonium hydroxide, methacryloylaminopropylmethyldibenzylammonium hydroxide, methacryloylaminopropylethyldibenzylammonium (Meth) acrylamide-based ammonium hydroxide quaternary cationic monomers such as methoxide, or acryloylaminomethyltrimethylammonium acetate, acryloylaminomethyltriethylammonium acetate, acryloylaminomethyltripropylammonium acetate, acryloylaminoethyltrimethylammonium acetate , Acryloylaminopropyltrimethylammonium acetate, acryloylaminopropylmethyldiethylammonium acetate, acryloylaminopropylethyldimethylammonium acetate,
Acryloylaminopropylmethyldipropylammonium acetate, acryloylaminopropyltriethylammonium acetate, acryloylaminopropyltripropylammonium acetate, acryloylaminoethyldimethylbenzylammonium acetate, acryloylaminopropyldimethylbenzylammonium acetate, acryloylaminopropyldiethylbenzylammonium acetate, acryloylamino Propylmethyldibenzylammonium acetate, acryloylaminopropylethyldibenzylammonium acetate, methacryloylaminomethyltrimethylammonium acetate, methacryloylaminomethyltriethylammonium acetate, methacryloylaminomethyltrimethyl Propylammonium acetate, methacryloylaminoethyltrimethylammonium acetate, methacryloylaminopropyltrimethylammonium acetate, methacryloylaminopropylmethyldiethylammonium acetate, methacryloylaminopropylethyldimethylammonium acetate, methacryloylaminopropylmethyldipropylammonium acetate, methacryloylaminopropyltriethylammonium acetate , Methacryloylaminopropyltripropylammonium acetate, methacryloylaminoethyldimethylbenzylammonium acetate, methacryloylaminopropyldimethylbenzylammonium acetate,
Examples include (meth) acrylamide-based ammonium acetate quaternary cationic monomers such as methacryloylaminopropyl diethylbenzylammonium acetate, methacryloylaminopropylmethyldibenzylammonium acetate, and methacryloylaminopropylethyldibenzylammonium acetate. Furthermore, acryloylaminomethyltrimethyl Ammonium propionate, acryloylaminomethyltriethylammonium propionate, acryloylaminomethyltripropylammonium propionate, acryloylaminoethyltrimethylammonium propionate, acryloylaminopropyltrimethylammonium propionate, acryloylaminopropylmethyldiethylammonium propionate Pionate, acryloylaminopropylethyldimethylammonium propionate, acryloylaminopropylmethyldipropylammonium propionate, acryloylaminopropyltriethylammonium propionate, acryloylaminopropyltripropylammonium propionate, acryloylaminopropyltrimethylammonium propionate Acrylate, acryloylaminopropyldimethylbenzylammonium propionate, acryloylaminopropyldiethylbenzylammonium propionate, acryloylaminopropylmethyldibenzylammonium propionate, acryloylaminopropylethyldibenzylammonium propionate, methacryloylaminomethyltrimethyl Nmo chloride propionate,
Methacryloylaminomethyltriethylammonium propionate, methacryloylaminomethyltripropylammonium propionate, methacryloylaminoethyltrimethylammonium propionate, methacryloylaminopropyltrimethylammonium propionate, methacryloylaminopropylmethyldiethylammonium propionate, methacryloylaminopropyl Ethyldimethylammonium propionate,
Methacryloylaminopropylmethyldipropylammonium propionate, methacryloylaminopropyltriethylammonium propionate, methacryloylaminopropyltripropylammonium propionate, methacryloylaminoethyldimethylbenzylammonium propionate, methacryloylaminopropyldimethylbenzylammonium propionate, (Meth) acrylamide-based ammonium propionate quaternary cationic monomers such as methacryloylaminopropyldiethylbenzylammonium propionate, methacryloylaminopropylmethyldibenzylammonium propionate, methacryloylaminopropylethyldibenzylammonium propionate . In the present embodiment, one or more monomers may be arbitrarily selected from these quaternary cationic monomers and combined. And among these,
From the viewpoint of easy availability of industrial raw materials and low cost and easy production, acryloylaminopropyltrimethylammonium hydroxide and acryloylaminopropyltrimethylammonium acetate are particularly preferred.

The quaternary cationic (meth) acrylamide monomer of the present invention can be produced using a known method. For example, N, N-dialkylaminoalkyl (meth) acrylamide represented by the following general formula (2) is mixed with an alkyl halide or dialkyl sulfuric acid, dialkyl carbonate or alkyltoluene sulfonate as a quaternizing agent in water or an organic solvent. 4 in
To obtain a quaternary salt of dialkylaminoalkyl (meth) acrylamide,
It can be obtained by performing an anion exchange reaction step using sodium or potassium salt having the target negative ion. Since the dialkylaminoalkyl (meth) acrylamide quaternary salt obtained in the quaternization reaction step has high hydrophilicity, particularly when an organic solvent is used as a reaction solvent, the organic solvent is 8 to 16 (cal / cm ³ ) ^0.5. One or two or more solvents selected from the group consisting of solvents having a solubility parameter of 2 are preferable, and the concentration of the dialkylaminoalkyl (meth) acrylamide quaternary salt after the reaction is 1 to 90%. It is particularly preferable to carry out the treatment so that the content becomes 5 to 70%. If it exceeds 90%, crystals of diaminoalkyl (meth) acrylamide quaternary salt precipitate and form a slurry, which may cause a polymerization reaction due to heat of crystallization. On the other hand, when it is 1% or less, the reaction efficiency is significantly lowered due to the dilution effect by the solvent. The negative ion exchange reaction in the next step is also performed using the same organic solvent as the reaction solvent,
Precipitated sodium or potassium salt is removed by filtration and concentrated so that the quaternary cationic acrylamide monomer has the desired concentration, thereby achieving the desired amide cationic vinyl monomer solution with good solubility in organic solvents. Can be obtained.

一般式（２）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、Ａは炭素数１〜３のアル
キレン基を表し、具体的には、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、
Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピ
ル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、
Ｎ，Ｎ−メチルエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−メチルプロピルア
ミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−メチルエチルアミノプロピル（メタ）アク
リルアミド、Ｎ，Ｎ−メチルプロピルアミノプロピル（メタ）アクリルアミドＮ，Ｎ−ジ
プロピルアミノプロピル（メタ）アクリルアミド等が例示される。また、４級化剤として
は、メチルクロライド、エチルクロライド、メチルブロマイド、エチルブロマイド等のア
ルキルハライド、ベンジルクロライド、及びベンジルブロマイド等のアラルキルハライド
、ジメチル硫酸、ジエチル硫酸等のアルキル硫酸、パラトルエンスルホン酸メチル、パラ
トルエンスルホン酸エチル等のアルキルトルエンスルフォネートが挙げられる。

In General Formula (2), R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ each independently represent 1 carbon atom.
-3 alkyl groups which may be the same as or different from each other, A represents an alkylene group having 1 to 3 carbon atoms, specifically, 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) Examples include acrylamide N, N-dipropylaminopropyl (meth) acrylamide and the like. As quaternizing agents, alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and ethyl bromide, aralkyl halides such as benzyl chloride and benzyl bromide, alkyl sulfuric acids such as dimethyl sulfate and diethyl sulfate, paratoluenesulfonic acid Examples thereof include alkyltoluenesulfonates such as methyl and ethyl paratoluenesulfonate.

Examples of the negative ion of the quaternary cationic (meth) acrylamide monomer of the present invention include hydroxide ions and carboxy ions. Carboxy ions include aliphatic carboxylic acids having 1 to 18 carbon atoms in the alkyl group such as formic acid, acetic acid, propionic acid, myristic acid, stearic acid, aromatic carboxylic acids such as benzoic acid, or lactic acid, salicylic acid, glycol. Negative ions such as oxycarboxylic acids having 1 to 18 carbon atoms such as acids can be used, and acetic acid and propionic acid are particularly preferable.

The organic solvent for dissolving the quaternary cationic (meth) acrylamide monomer of the present invention has a solubility parameter (SP value) in the range of 8 to 16 (cal / cm ³ ) ^0.5 , more preferably 9 to 15. is there. When it is in the range of 8 to 16, both the solubility and dispersibility of the quaternary cationic acrylamide monomer of the present invention are improved. The solubility parameter of the present invention is H.
Burrell's Polymer Handbook, 2nd edition (edited by J. Brandrup and EHImmergut) Wiley
Values shown by pages IV-337 to IV-359 of Interscience, New York, (1975).

Examples of such an organic solvent include methanol, ethanol, 1-propanol, 2
-Propanol, 1-butanol, 2-butanol, tert-butanol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether and the like can be mentioned.

Usually, since the cationic vinyl monomer has high hydrophilicity, the compatibility with general-purpose resins and organic solvents is poor, and there is a problem that a uniform antistatic effect cannot be obtained. Even if it is dissolved in an organic solvent, The solubility is low, and it was necessary to add a large amount in order to give the target antistatic performance. However, since the quaternary cationic (meth) acrylamide monomer of the present invention has improved solubility in organic solvents, it can be dissolved in various resin compositions usually mixed in organic solvents at a high concentration. It was. As a result, the obtained antistatic composition is applied to a molded article such as plastic and then dried (application method), or used by adding and kneading to a resin or the like before molding and curing in advance. Any method (kneading method) can be used.

When the quaternary cationic (meth) acrylamide monomer of the present invention is applied to a molded article such as plastic and then dried, the antistatic property, the coating property on the plastic,
The effect of scratch resistance can be sufficiently shown. In addition, a polyfunctional (meth) acrylate or polyfunctional (meth) acrylamide having two or more ethylene groups is added to the extent that does not impair the characteristics such as the antistatic property and compatibility of the present invention. By forming the film on the surface of the base material, it is possible to improve the performance of the coating film such as further film-forming properties and scratch resistance.

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
Examples thereof include D-310, D-330, DPHA, DPHA-2C (manufactured by Nippon Kayaku Co., Ltd.), Nicalak 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) and the like.

These polyfunctional (meth) acrylates and polyfunctional (meth) acrylamides are not limited to one type, and a plurality of polyfunctional monomers and oligomers may be used in combination. When such a polyfunctional monomer or oligomer is used, it is preferably contained in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight, based on the quaternary cationic acrylamide monomer of the present invention.
It is particularly preferable to contain it. If the content is less than 1% by weight, the addition effect is not recognized,
If it exceeds 50% by weight, the crosslinking rate is increased, so that the hardness and scratch resistance of the coating film are improved, but the elasticity is lost and the film is easily cracked.

The quaternary cationic (meth) acrylamide monomer of the present invention is prepared by mixing and copolymerizing other polymerizable compounds when adjusting various properties of the antistatic layer such as hardened or softened properties. As the polymerizable compound, acrylic (meth) acrylate, hydroxyalkyl (meth) acrylate, unsaturated nitrile monomer, unsaturated carboxylic acid, amide group-containing monomer, methylol group-containing monomer, alkoxymethyl group-containing monomer, epoxy group Examples thereof include a radical polymerization compound having a reactive double bond in the molecular chain, such as a monomer containing, a polyfunctional monomer, a vinyl ester, and an olefin.

Examples of acrylic (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 polymers may be used in combination.

The quaternary cationic acrylamide monomer of the present invention can be made into a polymer or copolymer by a known method with a polymerizable compound. As the polymerization method, for example, methods such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization and the like can be used. Of these methods, solution polymerization using a radical polymerization initiator is preferred. Examples of the solution used for solution polymerization include alcohols such as methanol, ethanol and isopropanol, glycol ethers such as ethyl cellosolve and butyl cellosolve, propylene glycol ethers such as propylene glycol monomethyl ether, tetrahydrofuran, 1,4- Ethers such as dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, hydrocarbons such as toluene, xylene, hexane and heptane, esters such as ethyl acetate and butyl acetate, water and the like can be used. These solvents may be used alone or in admixture of two or more depending on the type of monomer to be polymerized and the mixing ratio in the case of copolymerization. In these cases, 5% by weight or more is blended as a constituent of the quaternary cationic acrylamide monomer. Below this value, a sufficient antistatic effect cannot be obtained.

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 quaternary cationic (meth) acrylamide monomer 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. Since it depends on the physical properties of the antistatic composition, it is not particularly limited, but is 0.1 to 90% by weight, preferably 1 to 60% by weight, as a solid content ratio in the antistatic composition. When the content of the quaternary cationic (meth) acrylamide monomer is 0.1% by weight or less, the antistatic performance is insufficient, and when it exceeds 90% by weight, the transparency is inferior.

The antistatic composition comprising the quaternary cationic (meth) acrylamide monomer of the present invention is
Since it can be cured by active energy rays or heat, it can be used as an antistatic hard coat resin composition by applying to a molded article such as plastic, drying and curing.

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 optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays because it has a certain energy level, has a high curing rate, is relatively inexpensive, and is compact.

When photocuring the quaternary cationic (meth) acrylamide monomer of the present invention, a photoinitiator is added. The photoinitiator is not particularly necessary when an electron beam is used as the active energy ray, but is necessary when ultraviolet rays are used. The photoinitiator may be appropriately selected from ordinary ones such as acetophenone, benzoin, benzophenone, and thioxanthone.
Among the photoinitiators, commercially available photoinitiators are trade names Darocure 1116, Darocure 1173, IRGACURE 184, IRGACURE 369, IRGACURE 5 manufactured by Ciba Specialty Chemicals.
00, IRGACURE651, IRGACURE754, IRGACURE819, IRGACURE907, IRGACURE1
300, IRGACURE 1800, IRGACURE 1870, IRGACURE 2959, IRGACURE 4265,
IRGACURE TPO, manufactured by UCB, trade name Ubekrill P36, etc. can be used.

As long as the properties such as antistatic properties and compatibility of the quaternary cationic (meth) acrylamide monomer of the present invention are not impaired, pigments, dyes, surfactants, antiblocking agents, binders,
You may use together other arbitrary components, such as a crosslinking agent, antioxidant, and an ultraviolet absorber.

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) A glass sample plate (length 200 x width 200 x thickness 5 mm) with a polyethylene terephthalate (PET) film with a thickness of 100 μm painted and UV-cured is fixed on the horizontal surface so that it does not move. The antistatic hard coat agent is dropped in the form of a strip on the end of the wire, and both ends are pressed with a bar coater (RDS60) so that an equal force is applied to the whole, and it is pulled to the front at the same speed (5 cm / sec) without rotating. Then, 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 (（: excellent; ○: good; Δ: somewhat bad; ×: bad). Next, the coated surface was turned upward to be cured by irradiating with ultraviolet rays to obtain an antistatic hard coat film. UV curing conditions are 300W output and 50W output per unit.
/ Cm UV irradiation equipment with one high-pressure mercury lamp (Oak Seisakusho Model OHD320
M) was used, and the distance between the sample plate and the lamp was adjusted so that the ultraviolet energy was 10 mJ / cm ² per ^second . The irradiation time required until the surface of the coating film was not sticky was measured as the curing time. After curing, the surface resistivity and scratch resistance test of the coating film on each test plate were conducted. Further, the transparency of the coating film was visually observed and evaluated (◎: transparent and smooth surface; ○: transparent but uneven; Δ: slight cloudiness and unevenness; x: extreme cloudiness and unevenness; is there).
(2) Surface resistivity measurement Using a template (length 110 x width 110 mm), the antistatic hard coat film was cut with a cutter to obtain a sample for measuring surface resistivity. Based on JIS K 6911, Y made by Yokogawa HEWLETT-PACKARD
Measurement was performed using IGH RESISTANFE METER 4329A.
(3) Scratch resistance test Using steel wool of # 0000, the steel wool was reciprocated 10 times while applying a load of 200 g / cm ² , and the presence or absence of scratches was evaluated (◎: peeling of film or occurrence of scratches) Is scarcely observed; ◯: slight thin scratches are observed on the film; Δ: streaky scratches are observed on the entire surface of the film; ×: peeling of the film occurs.

The components used in Examples and Comparative Examples are as follows.

<Synthesis of cationic vinyl monomer>
Synthesis example 1
Under a nitrogen atmosphere, in a 1 L autoclave glass container, 100 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: trademark “DMAPAA”), isopropanol (IPA) 52
9 g was added, the internal temperature was adjusted to 30 ° C. or less, 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 N, N-dimethylaminopropylacrylamide-methyl chloride salt ( 640 g of DMAPAA-Q) containing 20% IPA solution was obtained.
Subsequently, 109 g of a saturated solution of sodium hydroxide in isopropanol (sodium hydroxide concentration 1.8% by weight) was added to a 200 mL three-necked flask, and DMAPAA- synthesized above was added.
50 g of 20% IPA solution of Q was added and stirred at an internal temperature of 25 ° C. for 1 hour. Precipitated sodium chloride was removed by filtration, and the filtrate was collected. Half of this filtrate was concentrated under reduced pressure, and an IPA solution containing 50% acryloylaminopropyltrimethylammonium hydroxide (DMAPAA-
16.6 g (yield 91%) of 50% IPA solution of OH was obtained. The remaining half of the filtrate was neutralized by adding acetic acid, concentrated under reduced pressure, and an IPA solution containing 50% acryloylaminopropyltrimethylammonium acetate (DMAPAA-acetic acid 50% IPA solution).
20.1 g (90% yield) was obtained.

Example A-1
Preparation of antistatic hard coat agent 62 parts by weight of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-3A), 50% IPA solution of DMAPAA-OH synthesized in Synthesis Example 1
8 parts by weight (14 parts by weight as DMAPAA-OH), as a photoinitiator, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Darocure 1173, 3 parts by weight are mixed and dissolved in 106 parts by weight of IPA, and UV curable antistatic A hard coating agent was obtained. Thereafter, the obtained hard coat agent was applied to a PET film having a thickness of 100 μm and subjected to ultraviolet curing to produce an antistatic hard coat.

Examples A-2 to 6, Comparative Examples A-1 to A-3
Except having changed into the composition of Table 1, it produced similarly to Example A-1.

ＤＭＡＰＡＡ−ＯＨ：アクリロイルアミノプロピルトリメチルアンモニウムヒドロキシド
ＤＭＡＰＡＡ−酢酸：アクリロイルアミノプロピルトリメチルアンモニウムアセテート
ＤＭＡＰＡＡ−Ｑ：アクリロイルアミノプロピルトリメチルアンモニウムクロライド
ＤＭＡＥＭＡ−Ｑ：メタクリロイルオキシエチルトリメチルアンモニウムクロライド
ＰＥＴＡ：ペンタエリスリトールトリアクリレート
ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート

DMAPAA-OH: acryloylaminopropyltrimethylammonium hydroxide DMAPAA-acetic acid: acryloylaminopropyltrimethylammonium acetate DMAPAA-Q: acryloylaminopropyltrimethylammonium chloride DMAEMA-Q: methacryloyloxyethyltrimethylammonium chloride PETA: pentaerythritol triacrylate DPHA: di Pentaerythritol hexaacrylate

Example B-1
Synthesis of copolymer solution DMAPA synthesized in Synthesis Example 1 in a flask equipped with a stirring blade, a reflux condenser, and a gas inlet.
20 parts by weight of a 50% IPA solution of A-OH (10 parts by weight as DMAPAA-OH) and 2-
10 parts by weight of ethylhexyl acrylate (EHA), azoisobutyronitrile (AIBN)
) 0.2 parts by weight of IPA was mixed and dissolved in 30 parts by weight, and polymerized at 70 ° C. for 8 hours under a nitrogen stream
A copolymer solution (a) was obtained.
Preparation of antistatic hard coat agent To 5 parts by weight of copolymer solution (a), dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) and pentaerythritol triacrylate (Kyoeisha Chemical Co., Ltd.) Company: Light acrylate PE-3A) and photoinitiator
Product name Darocure 1173, 5 parts by weight IPA, manufactured by Ciba Specialty Chemicals
It was mixed and dissolved in 120 parts by weight to obtain an antistatic hard coat agent capable of ultraviolet curing. Thereafter, the obtained hard coat agent was applied to a PET film having a thickness of 100 μm and subjected to ultraviolet curing to produce an antistatic hard coat.

Table 2 shows the mixing ratio of the monomers in the synthesis of the copolymer solution.

Examples B-2 to 6, Comparative Examples B-1 to B-3
Except having changed into the composition of Table 3, it produced similarly to Example B-1.

ＤＭＡＰＡＡ−ＯＨ：アクリロイルアミノプロピルトリメチルアンモニウムヒドロキシド
ＤＭＡＰＡＡ−酢酸：アクリロイルアミノプロピルトリメチルアンモニウムアセテート
ＤＭＡＰＡＡ−Ｑ：アクリロイルアミノプロピルトリメチルアンモニウムクロライド
ＤＭＡＥＭＡ−Ｑ：メタクリロイルオキシエチルトリメチルアンモニウムクロライド
２ＥＨＡ：２−エチルヘキシルアクリレート
ＢＡ：ブチルアクリレート、
２ＨＥＡ：２−ヒドロキシエチルアクリレート

DMAPAA-OH: acryloylaminopropyltrimethylammonium hydroxide DMAPAA-acetic acid: acryloylaminopropyltrimethylammonium acetate DMAPAA-Q: acryloylaminopropyltrimethylammonium chloride DMAEMA-Q: methacryloyloxyethyltrimethylammonium chloride 2EHA: 2-ethylhexyl acrylate BA: butyl Acrylate,
2HEA: 2-hydroxyethyl acrylate

ＰＥＴＡ：ペンタエリスリトールトリアクリレート
ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート

PETA: Pentaerythritol triacrylate DPHA: Dipentaerythritol hexaacrylate

According to the characteristics evaluation of the examples and comparative examples, the quaternary cationic acrylamide monomer of the present invention is mixed with a polymerizable compound and copolymerized with or without the conventional highly hydrophilic cation. Excellent compatibility with the improved vinyl monomer, forming a highly transparent and uniform coating film, resulting in antistatic performance equivalent to or better than that of acrylate antistatic agents used in the past I understand that. Further, the energy required for curing is small, and the obtained coating film has high scratch resistance and hydrolysis resistance.

As described above, the quaternary cationic (meth) acrylamide monomer of the present invention is
It is halogen-free, has a low environmental impact, and has good compatibility with other antistatic compositions and organic solvents, so it is formed using an antistatic composition comprising this quaternary cationic (meth) acrylamide monomer. The antistatic layer is excellent in antistatic properties, transparency, scratch resistance and hydrolysis resistance. The antistatic layer comprising the quaternary cationic (meth) acrylamide monomer of the present invention can be suitably used when it is added to a resin such as an ultraviolet curable resin composition or an adhesive composition in advance.

Claims (10)

General formula (1) which is an onium salt composed of ammonium as a positive ion, hydroxide ion as a negative ion, and carboxy ion, wherein R ₁ is a hydrogen atom or a methyl group, and R ₂ and R ₃ are each independently The alkyl group having 1 to 3 carbon atoms, which may be the same or different, R ₄ represents an alkyl group having 1 to 3 carbon atoms or a benzyl group; A represents an alkylene group having 1 to 3 carbon atoms; ^- is the hydroxide ion, antistatic agent comprising quaternary cationic (meth) acrylamide monomer represented by carboxymethyl exhibits ionic).

An antistatic agent comprising an oligomer and / or a polymer comprising the quaternary cationic (meth) acrylamide monomer according to claim 1 as a constituent component. A quaternary cationic (meth) acrylamide monomer according to claim 1 or claim 2, an oligomer containing the monomer, and / or a solution containing 1 to 90% by weight in an organic solvent. Antistatic agent. The antistatic agent according to claim 3, wherein the organic solvent is one or more selected from the group consisting of organic solvents having a solubility parameter of 8 to 16 (cal / cm ³ ) ^0.5 . The antistatic composition according to claim 1, further comprising polyfunctional (meth) acrylate or / and (meth) acrylamide. The blending amount of the polyfunctional (meth) acrylate or / and (meth) acrylamide according to claim 5 is the quaternary cationic (meth) acrylamide monomer according to claims 1 to 4, an oligomer blended with the monomer, or / And 1 to 50% by weight based on the polymer. The quaternary cationic (meth) acrylamide monomer according to claim 1 has a structural unit of 0.
The antistatic agent and antistatic composition according to claim 1 to 6 containing 1 to 90% by weight. An antistatic layer formed by applying an antistatic agent or / and an antistatic composition according to claim 1 on a substrate. An antistatic layer formed by polymerizing the antistatic agent or / and antistatic composition according to claim 1 on the substrate with an active energy ray or heat. An antistatic film comprising the base material and the antistatic agent or / and antistatic layer according to claim 1 on the base material.