JP2011012240A - Quaternary cationic antistatic agent, antistatic composition and molded product containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic agent with a preferable compatibility to a resin and an organic solvent, a high hydrolysis resistance, free of a halogen and a metal ion so as to have little load to the environment, and an antistatic composition containing the antistatic agent.SOLUTION: An antistatic layer is formed by coating or fixing on a substrate as an antistatic agent a (meth)acrylamide monomer of an onium salt including as a positive ion an ammonium and as a negative ion at least one ion selected from the group consisting of a 1-20C alkyl sulfonic acid, a benzene sulfonic acid, a p-toluene sulfonic acid, and a trifluoromethane sulfonic acid represented by general formula (1), (wherein R1 is a hydrogen atom or a methyl group, R2 and R3, which may be same or different, each independently are a 1-3C alkyl group, R4 is a 1-3C alkyl group or a benzyl group, A is a 1-3C alkylene group, and X- is an anion), or an oligomer and/or a polymer made of the monomer.

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 easily charged with static electricity on the surface, causing problems due to dust adsorption and 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. Hydrolysis results in the generation of non-polymerizable quaternary ammonium salts having acrylic acid and terminal hydroxyl groups, losing the expected sustainable antistatic performance. In addition, acrylic acid generated by hydrolysis may cause corrosion of electronic parts and optical materials.

In order to improve water resistance, it is known to use an amide compound having high hydrolysis resistance. However, many amide-based cationic vinyl monomers have high polarity and high hygroscopicity, and are usually distributed in an aqueous solution for manufacturing reasons. For example, methyl chloride as a quaternizing agent is added to unsaturated tertiary amine N, N-dimethylaminopropylacrylamide, and quaternization reaction is performed in the presence of a mixed solvent composed of water and an aprotic organic solvent. The method is often used (Patent Document 4). Of course, 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. In some cases, it is difficult to form a continuous antistatic film due to condensation in the resin or precipitation from the resin, 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 example, in Patent Documents 7 and 8, for the purpose of improving the compatibility of the cationic vinyl monomer itself, a polymerizable compound having a nitrogen onium cation and a weakly coordinating anion that coordinates weakly to the onium cation is disclosed. is suggesting. However, the polymerizable compound having the proposed bis (trifluoromethanesulfonyl) imide as an anion is usually synthesized by quaternization with an alkyl halide and salt exchange with an alkali metal salt. Therefore, mixing of alkali metal ions and halogen ions is inevitable. In addition, since the alkali metal salt is generally expensive and contains halogen ions, it may generate toxic gas during disposal and incineration, which may adversely affect the human body and the natural environment. Furthermore, when such nitrogen onium salts are used in electronic parts such as batteries and capacitors, the halogen ions tend to cause deterioration of the electrodes, moisture resistance due to hygroscopicity of metal ions, and decrease in water resistance. Not suitable for.

In order to remove halogen ions and metal ions, a purification step such as ion exchange resin treatment is usually required. However, after the cationic vinyl monomer, which is a solid or highly viscous liquid, is dissolved and diluted with an appropriate solvent. It needs to be introduced into the ion exchange resin tower, requires a large amount of solvent, and cannot be said to be an effective method in terms of cost such as solvent recovery.

As a halogen-free production method, a quaternization reaction of a tertiary amine with a quaternizing agent other than an alkyl halide has been studied. For example, quaternization methods using dialkyl sulfates shown in Patent Document 7 and Patent Document 9 have been proposed. In Patent Document 7, dimethylaminoethyl methacrylate and excess diethylsulfuric acid were reacted in a solvent-free system, diluted in ion-exchanged water, and anion exchange was performed by a metal salt reaction with potassium bis (trifluoromethanesulfonyl) imide. In Patent Document 9, dimethyl sulfate and dimethylaminopropyl methacrylamide were reacted in the presence of alcohol as a solvent, and then a radical polymerization initiator was added to perform polymerization. However, there is no description about the purity, yield, isolation and purification method and the like of the obtained methacrylate series and methacrylamide series quaternary salt monomers.

In order to obtain high-purity products of these quaternary vinyl monomers, the reaction solvent must usually be removed from the reaction solution after the reaction by a method such as distillation. However, since the quaternary vinyl salt monomer has high polarity and high hygroscopicity, it is extremely difficult to isolate it by distillation or the like. Further, since the cationic vinyl monomer has a polymerizable group, it may be polymerized during distillation. Furthermore, dialkyl sulfates, which are these proposed quaternizing agents, have high toxicity such as carcinogenicity, skin corrosiveness and irritation, and the resulting cationic vinyl monomer has a problem in terms of safety.

In Patent Document 9, quaternization with sulfonic acid esters was proposed at the same time, but there was no description about the actual synthesis. Even if a sulfonic acid vinyl monomer is synthesized in the same alcohol solvent, it cannot be separated and purified in the same way as dimethyl sulfate, and it is clear that a high-purity cationic vinyl monomer required for UV curing cannot be obtained. It has become.

On the other hand, Patent Document 10 proposed the use of N-methacrylamideamidopropyl-N, N, N, -trimethylammonium-p-toluenesulfonate as a constituent component of a silver halide photographic light-sensitive material. According to the patent document, when a mixed solvent of ethyl acetate and n-hexane is used, the reaction solution is cooled after reacting dimethylaminopropylmethacrylamide and the same mole of methyl p-toluenesulfonate at 40 ° C. Thus, the target product can be separated from the reaction solution and separated. However, the yield of the reaction was as low as 83.6%, and there was no detailed description such as the purity of the objective quaternary salt vinyl monomer obtained. Toluenesulfonic acid-based quaternary salt vinyl monomers obtained by this method can be used to synthesize crosslinkable polymers by copolymerizing with other divinyl monomers proposed in the literature, for example, where high purity is not required. However, it cannot be said that it is applicable to the application to the UV curing field where high purity and high quality are required.

JP 2008-231240 A JP 2008-13636 A JP 2008-231196 A Japanese Patent Laid-Open No. 63-201115 JP 2007-332181 A JP 2000-129245 A JP 2007-9042 A JP 2005-255843 A JP 2001-323029 A Japanese Patent Laid-Open No. 61-279853

As described above, in the production of a cationic vinyl monomer using an alkyl halide as a conventional quaternizing agent, an anion is exchanged with an expensive alkali metal salt via an onium salt using a halogen ion as a counter anion. Therefore, halogen ions and metal ions remain in the product, and when such cationic vinyl monomers are used for electronic parts such as batteries and capacitors, there are problems such as corrosion. Also in the production of cationic vinyl monomers that do not use alkyl halides, alkyl sulfates having a safety problem were used as counter anions. Furthermore, methyl p-toluenesulfonate can be used as another quaternizing agent, but it has been difficult to obtain a cationic vinyl monomer having a high yield and a high purity. In other words, amide-based cationic vinyl, which has an essentially improved water resistance and compatibility, has a low environmental impact, is suitably used in various electrochemical devices, and can be applied to UV curing. At present, no method has yet been obtained for obtaining high-quality monomer crystals in high yield.

The present invention has excellent compatibility with the base material and other antistatic agent compositions, high hydrolysis resistance, low hygroscopicity, excellent antistatic effect, halogen-free, metal ion-free and into the environment. High-purity acrylamide-based cationic vinyl monomer that is suitable for use in various electrochemical devices and can be produced at low cost and in high yield, and contains an antistatic agent comprising the monomer and the antistatic agent It is an object to provide an antistatic resin composition.
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 present inventor has found that the following general formula (1) (wherein R1 is a hydrogen atom or a methyl group, and R2 and R3 are each independently of 1 to 3 carbon atoms). An alkyl group which may be the same as or different from each other, R4 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 an anion). A tertiary amine compound represented by the following general formula (2) and the following general formula (3) in the presence of an aprotic organic solvent compatible with water. And an antistatic agent composed of the quaternary cationic (meth) acrylamide monomer, and / or an oligomer or polymer composed of 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.


(In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and A represents an alkylene having 1 to 3 carbon atoms. Represents a group.)

(In the formula, R 4 represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X represents an alkylsulfonyl group having 1 to 20 carbon atoms, a benzenesulfonyl group, a p-toluenesulfonyl group, and a trifluoromethanesulfonyl group.)

That is, the present invention
(1) Onium composed of ammonium as a positive ion and at least one ion selected from alkylsulfonic acid having 1 to 20 carbon atoms, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid as a negative ion General formula (1) which is a salt (wherein R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other; An antistatic agent comprising a quaternary cationic (meth) acrylamide monomer represented by: 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 an anion) ,
(2) The quaternary cationic (meth) acrylamide monomer described in (1) above is represented by the general formula (2)


(In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and A represents an alkylene having 1 to 3 carbon atoms. A dialkylaminoalkyl (meth) acrylamide represented by the general formula (3)
(In the formula, R 4 represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X represents an alkylsulfonyl group having 1 to 20 carbon atoms, a benzenesulfonyl group, a p-toluenesulfonyl group, and a trifluoromethanesulfonyl group.) An antistatic agent comprising a quaternary cationic (meth) acrylamide monomer according to claim 1, wherein the antistatic agent is obtained by reacting with a quaternizing agent represented by the formula:
(3) In producing the quaternary cationic (meth) acrylamide monomer described in (1) above, acetone, acetonitrile, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, And quaternary cationic (meth) acrylamide according to (1) above, wherein at least one selected from the group of aprotic organic solvents compatible with water, comprising N-methylpyrrolidone and N-methylpyrrolidone, is used. An antistatic agent containing a monomer,
(4) In producing the quaternary cationic (meth) acrylamide monomer described in (1) above, the blending amount of the organic solvent described in (3) is based on the concentration of the quaternary cationic (meth) acrylamide monomer. The method for producing the quaternary cationic (meth) acrylamide monomer according to claim 1, wherein the quaternary cationic (meth) acrylamide monomer is 10 to 1000% by volume.
(5) An antistatic agent comprising an oligomer and / or polymer comprising the quaternary cationic (meth) acrylamide monomer described in (1) above as a constituent component,
(6) The antistatic composition according to the above (1) to (5), further containing a polyfunctional (meth) acrylate or / and (meth) acrylamide,
(7) The amount of polyfunctional (meth) acrylate and / or (meth) acrylamide described in (6) above is the quaternary cationic (meth) acrylamide monomer described in (1) to (5) above, the monomer 1 to 50% by weight based on the oligomer or / and polymer blended with
(8) The antistatic agent and antistatic composition according to the above (1) to (7), wherein the quaternary cationic (meth) acrylamide monomer according to (1) is contained in an amount of 0.1 to 90% by weight as a structural unit. (9) An antistatic layer formed by applying the antistatic agent or / and antistatic composition according to (1) to (7) above on a substrate,
(10) 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,
(11) Provided is an antistatic film comprising the base material and the antistatic agent or / and the antistatic layer described in the above (1) to (7) on the base material.

The antistatic agent comprising the quaternary cationic (meth) acrylamide monomer of the present invention has good compatibility with the resin, good scratch resistance and transparency, no contamination with metal ions, and halogen free. An antistatic resin composition having a low environmental load, sufficient hydrolysis resistance, extremely low hygroscopicity, and an excellent antistatic effect that can be sustained can be obtained.
Among these effects, the antistatic property is particularly excellent because the quaternary cationic (meth) acrylamide monomer has high purity and is highly compatible with resins and organic solvents. The present inventors speculate that the inhibitor can be uniformly dispersed and it is easy to form a continuous antistatic layer.

The quaternary cationic (meth) acrylamide monomer of the present invention is synthesized by a quaternization reaction of a dialkylaminoalkyl (meth) acrylamide and a quaternizing agent of a sulfonic acid ester. The present inventors have made extensive insights into the fact that this is a bimolecular nucleophilic substitution reaction between a nitrogen nucleophilic species and a sulfonylated alkyl, and the reaction yield varies greatly depending on the type of reaction solvent. That is, non-polar solvents such as n-hexane, toluene, and ethyl acetate have a low quaternization yield of 90% or less, and polar solvents generate large charges as the reaction progresses, so they are subject to a large solvent effect and the reaction Proceeds quickly and can reach a yield of 99% or more in a short time. Further, it is most preferable to use an aprotic organic solvent in which the raw material for the quaternization reaction is soluble and the quaternary cationic (meth) acrylamide monomer that is the product is insoluble. In this case, as the reaction proceeds, the target quaternary salt monomer precipitates as a crystal or solvent-insoluble liquid, and the quaternization reaction can be completed at a high speed, high selectivity, and high yield. Furthermore, the crystal or the liquid insoluble in the reaction solvent thus obtained is non-viscous and easy to handle and can be obtained with high purity without containing unreacted substances. On the other hand, in the case of a protic strong polar solvent, the reaction rate is further increased, but the selectivity for producing a target quaternary salt is low, and the produced target quaternary salt monomer has an affinity for a protic strong polar solvent. In addition, since the quaternary salt monomer is often dissolved, troubles such as polymerization of the target quaternary salt monomer in a purification step such as removal of the reaction solvent after completion of the reaction may not be avoided.

By using the aprotic polar organic solvent of the present invention, the quaternization reaction proceeds at a sufficient rate even at ordinary temperature and pressure, and the desired quaternary cationic (meth) acrylamide monomer can be obtained efficiently. In addition, because it is free of halogen ions and metal ions, the new quaternary cationic (meth) acrylamide monomer of the present invention is excellent in its own compatibility, so there is no need to add a new compound for the purpose of improving compatibility. Thus, it was possible to suppress a decrease in various properties of the resin due to a relative decrease in the content of the cationic monomer.

With the antistatic agent and antistatic composition comprising the quaternary cationic (meth) acrylamide monomer of the present invention, there is no mixing of metals such as alkali ions, and there is little environmental impact because it is halogen-free, antistatic properties, transparency, An antistatic layer excellent in adhesion to various resin substrates and an antistatic film including such 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 ammonium as a positive ion, alkyl sulfonic acid having 1 to 20 carbon atoms as a negative ion, benzene sulfonic acid, p-toluene sulfone. An onium salt composed of at least one ion selected from an acid and trifluoromethanesulfonic acid, and further a compound linked to polymerizable (meth) acrylamide.

In the compound represented by the general formula (1), R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same or different. , R4 represents a C 1-3 alkyl group or benzyl group, A represents a C 1-3 alkylene group, and X − represents an anion, specifically, acryloylaminomethyltrimethylammonium methylsulfo. Nert, acryloylaminomethyltriethylammonium methylsulfonate, acryloylaminomethyltripropylammonium methylsulfonate, acryloylaminoethyltrimethylammonium methylsulfonate, acryloylaminopropyltrimethylammonium methylsulfonate, acryloylaminopropylmethyldiethylarate Ammonium methylsulfonate, acryloylaminopropylethyldimethylammonium methylsulfonate, acryloylaminopropylmethyldipropylammonium methylsulfonate, acryloylaminopropyltriethylammonium methylsulfonate, acryloylaminopropyltripropylammonium methylsulfonate, acryloylaminoethyldimethylbenzyl Ammonium methylsulfonate, acryloylaminopropyldimethylbenzylammonium methylsulfonate, acryloylaminopropyldiethylbenzylammonium methylsulfonate, acryloylaminopropylmethyldibenzylammonium methylsulfonate, acryloylaminopropylethyldibenzylammonium methyl Sulfonate, methacryloylaminomethyltrimethylammonium methylsulfonate, methacryloylaminomethyltriethylammonium methylsulfonate, methacryloylaminomethyltripropylammonium methylsulfonate, methacryloylaminoethyltrimethylammonium methylsulfonate, methacryloylaminopropyltrimethylammonium methylsulfonate, methacryloylamino Propylmethyldiethylammonium methylsulfonate, methacryloylaminopropylethyldimethylammonium methylsulfonate, methacryloylaminopropylmethyldipropylammonium methylsulfonate, methacryloylaminopropyltriethylammonium methylsulfonate, methacryloyl Aminopropyltripropylammonium methylsulfonate, methacryloylaminoethyldimethylbenzylammonium methylsulfonate, methacryloylaminopropyldimethylbenzylammonium methylsulfonate, methacryloylaminopropyldiethylbenzylammonium methylsulfonate, methacryloylaminopropylmethyldibenzylammonium methylsulfonate, (Meth) acrylamide-based ammonium alkylsulfonate quaternary cationic monomers such as methacryloylaminopropylethyldibenzylammonium methylsulfonate, or acryloylaminomethyltrimethylammonium benzylsulfonate, acryloylaminomethyltriethylammonium benzylsulfone Narate, acryloylaminomethyltripropylammonium benzylsulfonate, acryloylaminoethyltrimethylammonium benzylsulfonate, acryloylaminopropyltrimethylammonium benzylsulfonate, acryloylaminopropylmethyldiethylammonium benzylsulfonate, acryloylaminopropylethyldimethylammonium benzylsulfonate, Acryloylaminopropylmethyldipropylammonium benzylsulfonate, acryloylaminopropyltriethylammonium benzylsulfonate, acryloylaminopropyltripropylammonium benzylsulfonate, acryloylaminoethyldimethylbenzylammonium benzylsulfonate, acryloyl Aminopropyldimethylbenzylammonium benzylsulfonate, acryloylaminopropyldiethylbenzylammonium benzylsulfonate, acryloylaminopropylmethyldibenzylammonium benzylsulfonate, acryloylaminopropylethyldibenzylammonium benzylsulfonate, methacryloylaminomethyltrimethylammonium benzylsulfonate, Methacryloylaminomethyltriethylammonium benzylsulfonate, methacryloylaminomethyltripropylammonium benzylsulfonate, methacryloylaminoethyltrimethylammonium benzylsulfonate, methacryloylaminopropyltrimethylammonium benzylsulfonate, methacryloylamino Propylmethyldiethylammonium benzylsulfonate, methacryloylaminopropylethyldimethylammonium benzylsulfonate, methacryloylaminopropylmethyldipropylammonium benzylsulfonate, methacryloylaminopropyltriethylammonium benzylsulfonate, methacryloylaminopropyltripropylammonium benzylsulfonate, methacryloylamino Ethyl dimethyl benzyl ammonium benzyl sulfonate, methacryloylaminopropyl dimethyl benzyl ammonium benzyl sulfonate, methacryloyl aminopropyl diethyl benzyl ammonium benzyl sulfonate, methacryloyl aminopropyl methyl dibenzyl ammonium benzyl sulfonate, (Meth) acrylamide-based ammonium benzyl sulfonate quaternary cationic monomers such as methacryloylaminopropylethyldibenzylammonium benzylsulfonate, or acryloylaminomethyltrimethylammonium tosylate, acryloylaminomethyltriethylammonium tosylate, acryloylamino Methyltripropylammonium tosylate, acryloylaminoethyltrimethylammonium tosylate, acryloylaminopropyltrimethylammonium tosylate, acryloylaminopropylmethyldiethylammonium tosylate, acryloylaminopropylethyldimethylammonium tosylate, acryloylaminopropylmethyldipropylammonium tosylate Acryloylaminopropyltriethylammonium tosylate, acryloylaminopropyltripropylammonium tosylate, acryloylaminoethyldimethylbenzylammonium tosylate, acryloylaminopropyldimethylbenzylammonium tosylate, acryloylaminopropyldiethylbenzylammonium tosylate, acryloylaminopropylmethyldibenzyl Ammonium tosylate, acryloylaminopropylethyldibenzylammonium tosylate, methacryloylaminomethyltrimethylammonium tosylate, methacryloylaminomethyltriethylammonium tosylate, methacryloylaminomethyltripropylammonium tosylate, methacryloylaminoethyltrimethyl Ruammonium tosylate, methacryloylaminopropyltrimethylammonium tosylate, methacryloylaminopropylmethyldiethylammonium tosylate, methacryloylaminopropylethyldimethylammonium tosylate, methacryloylaminopropylmethyldipropylammonium tosylate, methacryloylaminopropyltriethylammonium tosylate, methacryloyl Aminopropyltripropylammonium tosylate, methacryloylaminoethyldimethylbenzylammonium tosylate, methacryloylaminopropyldimethylbenzylammonium tosylate, methacryloylaminopropyldiethylbenzylammonium tosylate, methacryloylaminopropylmethyldibenzylammonium (Meth) acrylamide-based ammonium tosylate quaternary cationic monomers such as nitrotosylate and methacryloylaminopropylethyldibenzylammonium tosylate, and acryloylaminomethyltrimethylammonium trifluoromethanesulfonate, acryloylaminomethyltriethylammonium Trifluoromethanesulfonate, acryloylaminomethyltripropylammonium trifluoromethanesulfonate, acryloylaminoethyltrimethylammonium trifluoromethanesulfonate, acryloylaminopropyltrimethylammonium trifluoromethanesulfonate, acryloylaminopropylmethyldiethylammonium trifluoromethanesulfonate, acrylo Ruaminopropylethyldimethylammonium trifluoromethanesulfonate, acryloylaminopropylmethyldipropylammonium trifluoromethanesulfonate, acryloylaminopropyltriethylammonium trifluoromethanesulfonate, acryloylaminopropyltripropylammonium trifluoromethanesulfonate, acryloylaminoethyldimethylbenzylammonium Trifluoromethanesulfonate, acryloylaminopropyldimethylbenzylammonium trifluoromethanesulfonate, acryloylaminopropyldiethylbenzylammonium trifluoromethanesulfonate, acryloylaminopropylmethyldibenzylammonium trifluoromethanesulfonate, Acryloylaminopropylethyldibenzylammonium trifluoromethanesulfonate, methacryloylaminomethyltrimethylammonium trifluoromethanesulfonate, methacryloylaminomethyltriethylammonium trifluoromethanesulfonate, methacryloylaminomethyltripropylammonium trifluoromethanesulfonate, methacryloylaminoethyltrimethylammonium trifluoro Lomethanesulfonate, methacryloylaminopropyltrimethylammonium trifluoromethanesulfonate, methacryloylaminopropylmethyldiethylammonium trifluoromethanesulfonate, methacryloylaminopropylethyldimethylammonium trifluoromethanesulfonate, methacrylate Liloylaminopropylmethyldipropylammonium trifluoromethanesulfonate, methacryloylaminopropyltriethylammonium trifluoromethanesulfonate, methacryloylaminopropyltripropylammonium trifluoromethanesulfonate, methacryloylaminoethyldimethylbenzylammonium trifluoromethanesulfonate, methacryloylaminopropyldimethylbenzyl Ammonium trifluoromethanesulfonate, methacryloylaminopropyldiethylbenzylammonium trifluoromethanesulfonate, methacryloylaminopropylmethyldibenzylammonium trifluoromethanesulfonate, methacryloylaminopropylethyldibenzylammonium trifluoro Such as Tan sulfonate (meth) acrylamide ammonium trifluoromethanesulfonate quaternary cationic monomer. In the present embodiment, one or more monomers may be arbitrarily selected from these quaternary cationic monomers and combined. Among these, acryloylaminopropyltrimethylammonium tosylate is particularly preferable from the viewpoint of easy availability of industrial raw materials and low cost and easy production.

The quaternary cationic (meth) acrylamide monomer of the present invention has the following general formula (2)
(In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and A represents an alkylene having 1 to 3 carbon atoms. A dialkylaminoalkyl (meth) acrylamide represented by the general formula (3)

(In the formula, R 4 represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X represents an alkylsulfonyl group having 1 to 20 carbon atoms, a benzenesulfonyl group, a p-toluenesulfonyl group, and a trifluoromethanesulfonyl group.)
It can obtain by making it react with quaternizing agent represented by presence of an organic solvent.

An aprotic organic solvent compatible with water, wherein the dialkylaminoalkyl (meth) acrylamide comprises acetone, acetonitrile, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, and N-methylpyrrolidone When reacted with the quaternizing agent in at least one solvent selected from the group, the quaternary cationic (meth) acrylamide monomer of the present invention can be obtained in a high yield and handled in a non-viscous manner. It is easy and high purity without containing unreacted substances.

The compounding amount of the organic solvent used in the quaternization reaction varies depending on the type, but it is in the range of 10 to 1000% by volume with respect to the quaternary cationic (meth) acrylamide monomer concentration of the present invention. preferable. If it is less than 10%, the reaction cannot be controlled, and the selectivity may decrease. In addition, problems such as polymerization trouble due to heat generation may occur. On the other hand, when it exceeds 1000%, the contact efficiency of the raw materials is lowered, and the reaction rate may be slow.

In general formula (2), R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and A is 1 to 1 carbon atom. 3 represents an alkylene group, 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) acrylamide N, N-dipropylaminopropyl (me ) Acrylamide and the like. Further, as the quaternizing agent, the general formula (3)

In the formula, R4 represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, X represents an alkylsulfonyl group having 1 to 20 carbon atoms, a benzenesulfonyl group, a p-toluenesulfonyl group, or a trifluoromethanesulfonyl group. Include sulfonic acid esters such as methyl methanesulfonate and methyl paratoluenesulfonate.

The negative ion of the quaternary cationic (meth) acrylamide monomer of the present invention is at least one selected from alkyl sulfonic acids having 1 to 20 carbon atoms, benzene sulfonic acid, p-toluene sulfonic acid, and trifluoromethane sulfonic acid. Ions. As the alkylsulfonic acid ion, negative ions such as methanesulfonic acid and ethanesulfonic acid can be used, and p-toluenesulfonic acid ion is particularly preferable.

When the quaternary cationic (meth) acrylamide monomer of the present invention is applied to a molded article such as plastic and then dried, it alone has the effect of antistatic property, coating property on plastic, and scratch resistance. Can show enough. 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.

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

As a commercial item of such a polyfunctional (meth) acrylate, for example, Aronix M-400, M-450, M-305, M-309, M-310, M-315, M-320, TO-1200, TO-1231, TO-595, TO-756 (above, manufactured by Toagosei), KAYARD
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.

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

These polyfunctional (meth) acrylates and polyfunctional (meth) acrylamides are not limited to one type, and a plurality of polyfunctional monomers and oligomers may be used in combination. Moreover, when using such a polyfunctional monomer and oligomer, it is preferable to contain 1 to 50 weight% with respect to the quaternary cationic acrylamide type monomer of this invention, and to contain 2 to 30 weight%. Particularly preferred. When the content is less than 1% by weight, the effect of addition is not recognized. When the content exceeds 50% by weight, the crosslinking rate increases, so the hardness and scratch resistance of the coating film are improved, but the elasticity is lost and cracking occurs. It becomes easy.

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) acrylate.

Examples of unsaturated nitrile monomers include acrylonitrile and methacrylonitrile.

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

Such a polymerizable compound is not limited to one type, and a plurality of 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. Solvents 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.

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. The solid content ratio in the antistatic composition is 0.1 to 90% by weight, preferably 1 to 60% by weight, although it is not particularly limited. 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.

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

The active energy ray of the present invention is defined as an energy ray capable of decomposing a compound (photopolymerization initiator) that generates active species to generate active species. Examples of such active energy rays include 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 manufactured by Ciba Specialty Chemicals, Inc., trade names Darocure 1116, Darocure 1173, IRGACURE 184, IRGACURE 369, IRGACURE 500, IRGACURE 651, IRGACURE 754, IRGACURE 819, IRGACURE 129, IRGACURE 1800, IRGACURE IRGACURE TPO, manufactured by UCB, trade name Ubekrill P36, etc. can be used.

As long as the properties such as antistatic properties and compatibility of the quaternary cationic (meth) acrylamide monomer of the present invention are not impaired, pigments, dyes, surfactants, antiblocking agents, binders, crosslinking agents, antioxidants, You may use together other arbitrary components, such as a 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) Quaternary salt determination method

Automatic potentiometric titrator (device name: AT-610)
Titration is performed using a sodium tetraphenylborate solution (manufactured by Kanto Chemical Co., Ltd.) having a concentration of 0.02 mol / L using Kyoto Electronics Industry Co., Ltd., and the quaternary ammonium salt concentration is determined from the titration amount.


(2) Painting and UV curing

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 is fixed on a horizontal surface so that it does not move, and an antistatic hard coat is applied to the front edge of the plate. The agent is dropped in a strip shape, and both ends are pressed with a bar coater (RDS60) so that a uniform force is applied to the whole, and it is applied by pulling it to the front at the same speed (5 cm / sec) without rotating. Hot air dryer The solvent was removed at 80 ° C. for 3 minutes 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. The UV curing conditions were as follows: UV irradiation equipment (Oak Seisakusho Model OHD320M) equipped with one high-pressure mercury lamp with an output of 300 W and an output of 50 W / cm per unit was used so that the UV energy was 10 mJ / cm 2 per second. The distance between the plate and the lamp was adjusted. The irradiation time required until the surface of the coating film was not sticky was measured as the curing time. After curing, the 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).


(3) Surface resistivity measurement

Using a template (110 × 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, measurement was performed using a HIGH RESISTANFE METER 4329A manufactured by Yokogawa HEWLETT-PACKARD.


(4) Scratch resistance test

Using steel wool of # 0000, the steel wool was reciprocated 10 times while applying a load of 200 g / cm 2 to evaluate the presence or absence of scratches (◎: almost no film peeling or scratches were 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: Acrylylaminopropyltrimethylammonium p-toluenesulfonate 100 g of N, N-dimethylaminopropylacrylamide (trade name “DMAPAA”), methyl ethyl ketone (MEK) in a 1 L three-necked flask under nitrogen atmosphere 185 g was added, the internal temperature was adjusted to 20 ° C. or lower, and 119 g of methyl p-toluenesulfonate was added dropwise with stirring to carry out a quaternization reaction. After 1 hour, the precipitated crystals were filtered and dried under reduced pressure. As a result, 218 g of white crystals of acryloylaminopropyltrimethylammonium p-toluenesulfonate were obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 99.6%.

Synthesis example 2: acryloylaminopropyltrimethylammonium trifluoromethanesulfonate In a nitrogen atmosphere, 100 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: trademark “DMAPAA”) and 200 g of tetrahydrofuran were added to a 1 L three-necked flask. While adjusting the internal temperature to 20 ° C. or lower and stirring, 107 g of methyl trifluoromethanesulfonate was added dropwise to carry out a quaternization reaction. After 1 hour, the oily liquid layer part of the lower layer obtained by separating the two layers was taken out and washed three times with tetrahydrofuran, and then the remaining trace amount of tetrahydrofuran was removed under reduced pressure to give acryloylaminopropyltrimethylammonium trifluoride as a colorless transparent liquid. 206 g of romethanesulfonate was obtained. As a result of analysis by potentiometric titration, the purity of the target product was 100%. The yield was 99.5%.

Synthesis Example 3: Methacryloylaminopropyltrimethylammonium p-toluenesulfonate In a nitrogen atmosphere, 100 g of N, N-dimethylaminopropylmethacrylamide and 185 g of methyl ethyl ketone (MEK) were added to a 1 L three-necked flask, and the internal temperature was 20 ° C. While adjusting and stirring below, 109 g of methyl p-toluenesulfonate was added dropwise to carry out a quaternization reaction. After 1 hour, the precipitated crystals were filtered and dried under reduced pressure. As a result, 208 g of white crystals of methacryloylaminopropyltrimethylammonium p-toluenesulfonate were obtained. When the concentration of the quaternary ammonium salt was determined by potentiometric titration, the purity of the target product was 100%. The yield was 99.7%.

Synthesis Example 4: Methacryloylaminopropyltrimethylammonium trifluoromethanesulfonate In a nitrogen atmosphere, 100 g of N, N-dimethylaminopropylmethacrylamide and 200 g of tetrahydrofuran were added to a 1 L three-necked flask, and the internal temperature was adjusted to 20 ° C. or lower and stirred. Then, 98 g of methyl trifluoromethanesulfonate was added dropwise to carry out a quaternization reaction. After 1 hour, the oily liquid layer part of the lower layer obtained by separating the two layers was taken out, washed with tetrahydrofuran three times, then the remaining trace amount of tetrahydrofuran was removed under reduced pressure, and methacryloylaminopropyltrimethylammonium trifluoride was obtained as a colorless transparent liquid. 195 g of romethanesulfonate was obtained. As a result of analysis by potentiometric titration, the purity of the target product was 100%. The yield was 99.4%.

Synthesis Comparative Example 1: Acrylylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl) imide (see Patent Document 9)
While stirring 100 g of a 75% aqueous solution of acryloylaminopropyltrimethylammonium chloride (manufactured by Kojin: trademark “DMAPAA-Q”) in a 1 L three-necked flask, 116 g of potassium bis (trifluoromethanesulfonyl) imide was added to 80 mL of ion-exchanged water. The diluted one was added under heating at 60 ° C. After 2 hours, the lower oil layer part separated into two layers was taken out, washed with ion-exchanged water three times, and then the remaining trace water was removed under reduced pressure to obtain 93% acryloylaminopropyltrimethylammonium bis (trifluoromethanesulfonyl). ) 156 g of imide liquid was obtained. The yield was 88%. Further, chlorine and potassium ions were quantified by ion chromatography, and the respective contents were 7000 ppm and 12000 ppm.

Synthesis comparative example 2: acryloylaminopropyltrimethylammonium p-toluenesulfonate (see Patent Document 10)
Under a nitrogen atmosphere, 136 g of N, N-dimethylaminopropylacrylamide (Kohjin: trademark “DMAPAA”) was added to a 3 L three-necked flask, and 1 L of ethyl acetate and 1 L of n-hexane were added as solvents. While stirring and stirring, 162 g of methyl p-toluenesulfonate was added dropwise over 1 hour to carry out a quaternization reaction. After 1 hour, the precipitated crystals were filtered and dried under reduced pressure. As a result, 233 g of acryloylaminopropyltrimethylammonium p-toluenesulfonate white crystals were obtained. The quaternary ammonium salt concentration was 100%, but the yield was 78%.

Synthesis Comparative Example 3: Acrylylaminopropyltrimethylammonium p-toluenesulfonate In a nitrogen atmosphere, 100 g of N, N-dimethylaminopropylacrylamide (manufactured by Kojin: trademark “DMAPAA”) and 185 g of methanol were added to a 1 L three-necked flask. In addition, 119.2 g of methyl p-toluenesulfonate was added dropwise while adjusting and stirring to an internal temperature of 20 ° C. or lower to carry out a quaternization reaction. After 1 hour, the obtained uniform liquid was concentrated under reduced pressure. As a result, the liquid thickened during the concentration, and a waxy solid with high hygroscopicity was obtained. The double bond rate was measured according to JIS K 0700. As a result, the content of the target quaternary salt monomer in the solid was 8%.

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), 14 parts by weight of acryloylaminopropyltrimethylammonium p-toluenesulfonate synthesized in Synthesis Example 1 As a photoinitiator, 3 parts by weight of trade name Darocure 1173 manufactured by Ciba Specialty Chemicals was mixed and dissolved in 120 parts by weight of isopropyl alcohol (IPA) to obtain an ultraviolet curable antistatic hard coat agent. 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 8, Comparative Examples A-1 to A-4

Except having changed into the composition of Table 1, it produced similarly to Example A-1.

Example B-1

Synthesis of copolymer solution

In a flask equipped with a stirring blade, a reflux condenser, and a gas inlet, 10 parts by weight of DMAPAA-PTS synthesized in Synthesis Example 1, 10 parts by weight of 2-ethylhexyl acrylate (EHA), 0.2% of azoisobutyronitrile (AIBN) Part by weight was mixed and dissolved in 40 parts by weight of IPA and polymerized at 70 ° C. for 8 hours under a nitrogen stream to obtain a copolymer solution (a).
Preparation of antistatic hard coat agent To 5 parts by weight of copolymer solution (a), pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate PE-3A) and dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd.) Company: Light acrylate DPE-6A) and photoinitiator, Ciba Specialty Chemicals, trade name Darocure 1173 5 parts by weight IPA
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 10 and Comparative Examples B-1 to B-4

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

From the results of the synthesis example and the synthesis comparison example, the quaternization reaction between the dialkylaminoalkyl (meth) acrylamide and the sulfonic acid ester proceeds only at a sufficient rate even at room temperature and normal pressure in only an aprotic polar solvent, No troubles such as polymerization occurred, and high-purity products could be obtained in high yield. Further, the quaternary salt monomer obtained by the acid ester method is free from the mixing of halogen ions and metal ions such as alkali, and can form a highly transparent and uniform antistatic coating film. From the results of evaluating the UV curability and antistatic property of the coating film of Examples and Comparative Examples, the time required for UV curing due to the remaining metal ions and chlorine ions is increased, the resulting coating film is sticky, and the transparency is poor. Moreover, the uniform coating film was not obtained by those causes, and the antistatic effect was low. Only the high-quality novel quaternary salt (meth) acrylamide monomer obtained by the production method of the present invention requires less energy for UV curing, has good transparency, and has both high scratch resistance and high hydrolysis resistance. It was clear that an antistatic agent having excellent antistatic performance could be provided.

As described above, the quaternary cationic (meth) acrylamide monomer of the present invention can be obtained at a high rate with high purity because the reaction proceeds at a sufficient rate even at room temperature and normal pressure. In addition, it does not contain metal ions such as alkalis, is halogen-free, has a low environmental impact, and has good compatibility with other antistatic compositions and organic solvents, so this quaternary cationic (meth) acrylamide monomer The antistatic layer formed using the antistatic composition comprising the above 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 (11)

An onium salt composed of at least one ion selected from ammonium as a positive ion and alkylsulfonic acid having 1 to 20 carbon atoms as a negative ion, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. Formula (1) (wherein R1 is a hydrogen atom or a methyl group, R2 and R3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other; An antistatic agent comprising a quaternary cationic (meth) acrylamide monomer represented by 3 alkyl group or benzyl group, A represents an alkylene group having 1 to 3 carbon atoms, and X − represents an anion).
The quaternary cationic (meth) acrylamide monomer has the general formula (2)
(In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and A represents an alkylene having 1 to 3 carbon atoms. A dialkylaminoalkyl (meth) acrylamide represented by the general formula (3)
(In the formula, R 4 represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X represents an alkylsulfonyl group having 1 to 20 carbon atoms, a benzenesulfonyl group, a p-toluenesulfonyl group, and a trifluoromethanesulfonyl group.) The antistatic agent containing a quaternary cationic (meth) acrylamide monomer according to claim 1, wherein the antistatic agent is obtained by reacting with a quaternizing agent represented by the formula: In producing the quaternary cationic (meth) acrylamide monomer, the organic solvent comprises acetone, acetonitrile, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, and N-methylpyrrolidone. The antistatic agent containing a quaternary cationic (meth) acrylamide monomer according to claim 1, wherein at least one selected from the group of aprotic organic solvents compatible with water is used. In producing the quaternary cationic (meth) acrylamide monomer, the blending amount of the organic solvent according to claim 3 is 10 to 1000% by volume with respect to the quaternary cationic (meth) acrylamide monomer concentration. The method for producing the quaternary cationic (meth) acrylamide monomer according to claim 1. 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. The antistatic composition according to any one of claims 1 to 5, further comprising polyfunctional (meth) acrylate or / and (meth) acrylamide. The blending amount of the polyfunctional (meth) acrylate or / and (meth) acrylamide according to claim 6 is the quaternary cationic (meth) acrylamide monomer according to claims 1 to 5, an oligomer blended with the monomer or / And 1 to 50% by weight based on the polymer. 8. An antistatic agent and an antistatic composition according to claim 1, which contain 0.1 to 90% by weight of the quaternary cationic (meth) acrylamide monomer according to claim 1 as a structural unit. 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.