JP5610209B2 - Antistatic agent and coating composition using the same - Google Patents

Description

  The present invention relates to an antistatic agent, and further relates to a coating composition using the antistatic agent.

  In recent years, information devices such as notebook computers and televisions equipped with display devices such as a liquid crystal display (LCD), a plasma display (PDP), and an organic EL display that can clearly display images and characters have become widespread. Here, for example, a triacetyl cellulose (TAC) film used for a polarizing plate for a liquid crystal display has an active energy ray curable composition or thermosetting on the film surface for the purpose of protecting the film surface or imparting a function. Applying the coating composition of the composition to form a coating film on the film surface that has antifouling properties to prevent fingerprints and dirt, scratch resistance to prevent scratches, antistatic properties to prevent dust adhesion, etc. To be done. In particular, the adhesion of dust due to the generation of static electricity on the film surface lowers the visibility of the image displayed on the display device, and in order to prevent this, an improvement in the antistatic performance of the film surface is required. .

  Antistatic agents for imparting antistatic properties to the coating composition include various surfactants such as cations, anions, and nonionics that have been used for a long time as low molecular weight antistatic agents, metal particles, and carbon black. Conductive fillers such as carbon nanotubes and conductive whiskers, ion conductive polymers that are complexes of polyethylene oxide (PEO) with alkali metals such as sodium and potassium, and conductive polymers such as polyaniline, polythiophene, and polyacetylene. Are known. These antistatic agents can be applied directly to the surface of the substrate to which antistatic properties are to be imparted, blended inside the substrate, or added to the coating composition and then applied to the substrate to which antistatic properties are to be imparted. Used.

  The reason why the above-mentioned antistatic agent can prevent electrification is, for example, in the case of the surfactant, since it has a hydrophilic group and a hydrophobic group in the chemical structure of the surfactant, it was applied to the substrate. At this time, it is considered that the hydrophilic group adsorbs moisture in the air on the surface and releases the static electricity charged on the substrate surface. For this reason, the antistatic agent needs to be present on the surface of the substrate to be antistatic. However, when the antistatic agent is blended into the plastic base material, it is once taken into the base material, so that the antistatic effect cannot be obtained immediately, and the antistatic agent bleeds out from the base material. The antistatic performance can be obtained only after shifting to the material surface. Therefore, a method using a higher alcohol or the like in combination for the purpose of accelerating the bleeding out of the antistatic agent has been proposed, but the transparency is impaired, and it is unsuitable for applications requiring transparency. In addition, there is an antistatic agent that does not migrate to the surface of the base material while being incorporated into the base material. About these problems, it is the same also about the coating composition which added antistatic property, and in order to acquire sufficient antistatic property, it is necessary to increase the addition amount of an antistatic agent, and the coating film of coating composition There was a problem that the scratch resistance, transparency, and surface smoothness of the resin were impaired. Furthermore, when the compatibility between the antistatic agent and the base resin of the coating composition is low, these problems are significant.

  Therefore, as an antistatic agent that solves the above problem, a fluorinated cationic surfactant having a perfluoroalkyl group in the molecule has been proposed (for example, see Patent Document 1). However, this fluorinated cationic surfactant can provide antistatic properties when it is applied to the surface of a plastic substrate by a coating method such as spraying or dipping, but is dissolved in a fluorine-based solvent. When used by adding to a product, there is a problem that a smooth and transparent coating film cannot be obtained due to poor solubility in the base resin, organic solvent, etc. in the coating composition.

  In addition, a perfluoroalkyl group-containing quaternary ammonium salt has been proposed as an antistatic agent that solves the above problems (see, for example, Patent Document 2). When this perfluoroalkyl group-containing quaternary ammonium salt is used by being added to a coating composition, the solubility in the base resin, organic solvent, etc. in the coating composition is higher than that of the antistatic agent described in Patent Document 1. Although the prevention performance was improved, it was still insufficient when higher transparency of the coating film and smoothness of the coating film surface were required.

JP 55-89376 JP 2008-231240 A

  The problem to be solved by the present invention is that, when added to a coating composition, it has high solubility in resins, various monomers, organic solvents, etc., which are components in the composition, and it has excellent antistatic properties when added in a small amount. It is providing the antistatic agent which can be provided to a coating composition, and the coating composition using this antistatic agent.

  As a result of intensive studies to solve the above problems, the present inventors have incorporated a quaternary ammonium salt having a fluorinated organic group such as a fluorinated alkyl group and a nitrogen-containing heterocyclic ring into the coating composition. When used as an antistatic agent, the antistatic agent is applied to the coating film when the composition is applied to a substrate by the action of minimizing the surface free energy peculiar to fluorine atoms present in the antistatic agent. It was segregated on the surface, and it was found that an excellent antistatic property could be imparted to the coating film of the composition, and a coating film having excellent transparency and surface smoothness could be obtained, and the present invention was completed.

  That is, the present invention relates to an antistatic agent comprising a quaternary ammonium salt having a nitrogen-containing heterocycle represented by the following general formula (1) as an essential component and a coating composition using the same.

（式中、Ｒｆは下記（Ｒｆ−１）で表されるフッ素化アルキル基を表し、Ａはエチレン基を表す。Ｒ^１及びＲ^２は含窒素複素環を形成する炭素原子又は窒素原子を表し、Ｒ^１及びＲ^２は２価の有機基を介して、Ｒ^１及びＲ^２が結合している４級窒素原子とともに複素環を形成する。なお、この複素環にさらに他の環が縮合した縮合環となっていてもよい。Ｒ^３は炭素数１〜３の範囲のアルキル基を表し、Ｘ⁻はアニオンを表す。）

（ｎは１〜８の整数を表す。）

(In the formula, Rf represents a fluorinated alkyl group represented by the following (Rf-1) , A represents an ethylene group, and R ¹ and R ² represent a carbon atom or a nitrogen atom forming a nitrogen-containing heterocyclic ring. , R ¹ and R ² form a heterocyclic ring with a quaternary nitrogen atom to which R ¹ and R ² are bonded via a divalent organic group, and another ring is condensed to this heterocyclic ring. (R ³ represents an alkyl group having 1 to ³ carbon atoms, and X ⁻ represents an anion.)

(N represents an integer of 1 to 8.)

  The coating composition containing the antistatic agent of the present invention can impart excellent antistatic properties to the substrate surface by coating the substrate and forming a coating film on the substrate. In addition, since the antistatic agent of the present invention has a high solubility in the base resin, organic solvent, etc. in the coating composition, and a coating film excellent in transparency and surface smoothness is obtained, high transparency and surface smoothness are obtained. Can be suitably used as a material for imparting antistatic properties to the surface of an optical film such as a TAC film used for polarizing plates for liquid crystal displays.

1 is a chart of the infrared absorption spectrum of the compound (3-1) obtained in Synthesis Example 1. FIG. FIG. 2 is a chart of the ¹ H-NMR spectrum of the compound (3-1) obtained in Synthesis Example 1. FIG. 3 is a chart of ¹³ C-NMR spectrum of the compound (3-1) obtained in Synthesis Example 1. 4 is a chart of the infrared absorption spectrum of the compound (4-1) obtained in Example 1. FIG. 5 is a chart of ¹ H-NMR spectrum of the compound (4-1) obtained in Example 1. FIG. 6 is a chart of ¹³ C-NMR spectrum of the compound (4-1) obtained in Example 1. FIG.

  The antistatic agent of the present invention comprises a quaternary ammonium salt having a nitrogen-containing heterocycle represented by the following general formula (1) as an essential component.

（式中、Ｒｆはフッ素化アルキル基（ただし、前記アルキル基は酸素原子によるエーテル結合を有するものも含む。）を表し、Ａは２価の有機基を表す。Ｒ^１及びＲ^２は含窒素複素環を形成する炭素原子又は窒素原子を表し、Ｒ^１及びＲ^２は２価の有機基を介して、Ｒ^１及びＲ^２が結合している４級窒素原子とともに複素環を形成する。なお、この複素環にさらに他の環が縮合した縮合環となっていてもよい。Ｒ^３は炭素数１〜３の範囲のアルキル基を表し、Ｘ⁻はアニオンを表す。）

Wherein Rf represents a fluorinated alkyl group (wherein the alkyl group includes those having an ether bond with an oxygen atom), A represents a divalent organic group, and R ¹ and R ² represent nitrogen-containing groups. represents a carbon atom or a nitrogen atom to form a heterocyclic ring, R ¹ and R ² through a bivalent organic group, together with quaternary nitrogen atom to which R ¹ and R ² are attached form a heterocyclic ring. Note The heterocyclic ring may be condensed with another ring, R ³ represents an alkyl group having 1 to ³ carbon atoms, and X ⁻ represents an anion.)

  Rf in the general formula (1) is a fluorinated alkyl group, but includes those having an ether bond with an oxygen atom. Specific examples of the fluorinated alkyl group include the following (Rf-1) to (Rf-7).

（上記式（Ｒｆ−１）及び（Ｒｆ−２）中のｎは１〜８の整数を表す。上記式（Ｒｆ−３）中のｎは２〜８の整数を表す。上記式（Ｒｆ−４）中のｎは３〜８の整数を表す。上記式（Ｒｆ−５）中のｍは１〜５の整数であり、ｎは０〜４の整数であり、かつｍ及びｎの合計は１〜５である。上記式（Ｒｆ−６）中のｍは０〜４の整数であり、ｎは１〜４の整数であり、ｐは０〜４の整数であり、かつｍ、ｎ及びｐの合計は１〜５である。）

(N in the above formulas (Rf-1) and (Rf-2) represents an integer of 1 to 8. n in the above formula (Rf-3) represents an integer of 2 to 8. The above formula (Rf- 4) n represents an integer of 3 to 8. m in the above formula (Rf-5) is an integer of 1 to 5, n is an integer of 0 to 4, and the sum of m and n is M in the above formula (Rf-6) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 0 to 4, and m, n and The total of p is 1-5.)

  Among the above Rf, the antistatic agent of the present invention (Rf-1) where n is 4 or 6 is the surface of the coating film of the composition when the antistatic agent of the present invention is blended with the resin composition. Since the segregation ability of the antistatic agent of the present invention is increased, it is preferable because more excellent antistatic properties can be imparted to the coating film and compatibility with other components in the composition is improved.

  A in the general formula (1) is a divalent organic group, and specifically, an alkylene group having 1 to 3 carbon atoms is preferable. Further, among the alkylene groups, an ethylene group from which raw materials are easily available is more preferable.

In the general formula (1), R ¹ and R ² represent a carbon atom or a nitrogen atom that forms a nitrogen-containing heterocycle, and R ¹ and R ² are divalent organic groups, and R ¹ and R ² are Forms a heterocycle with the quaternary nitrogen atom attached. Note that this heterocyclic ring may be a condensed ring obtained by further condensing another ring. Specific examples of such nitrogen-containing heterocycle include pyrrole, imidazole, pyrazole, pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperidine, piperazine, isoindole, indole, 1H-indazole, purine, indoline, iso Preferred are those derived from nitrogen-containing heterocycles such as indoline, morpholine, carbazole, β-carboline, phenothiazine, phenoxazine and the like. Among these nitrogen-containing heterocycles, imidazole and imidazoline are more preferable because solubility in other resins and organic solvents is improved.

R ³ in the general formula (1) is preferably an alkyl group having 1 to 12 carbon atoms, and a methyl group is more preferable because of easy production.

X ⁻ in the general formula (1) is an anion, specifically, halide ion, OH ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , CH ₃ SO ₄ ⁻ , CH ₃ CO ₂ ⁻ , CF _3. SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , CH ₃ PhSO ₃ ^{— and the} like can be mentioned. Among these anions, CH ₃ PhSO ₃ ^— is more preferable because it has a high solubility in the base resin and organic solvent in the coating composition and can provide a coating film having excellent transparency and surface smoothness.

  As a manufacturing method of the quaternary ammonium salt which is an essential component of the antistatic agent of this invention, the method through the following processes 1-3 is mentioned, for example.

(Process 1)
A step of reacting a compound having a fluorinated alkyl group and a hydroxyl group with epichlorohydrin or β-methylepichlorohydrin to obtain a compound having an epoxy group.
(Process 2)
A step of reacting the compound having an epoxy group obtained in Step 1 with a nitrogen-containing heterocyclic compound having a secondary amine in the heterocyclic ring to obtain a nitrogen-containing heterocyclic compound having a tertiary amine in the heterocyclic ring.
(Process 3)
A step of obtaining a quaternary ammonium compound by quaternizing the tertiary amine in the nitrogen-containing heterocyclic compound having the tertiary amine obtained in Step 2 in the heterocyclic ring.

  A method for obtaining a compound having an epoxy group by reacting a compound having a fluorinated alkyl group and a hydroxyl group with epichlorohydrin or β-methylepichlorohydrin in Step 1 will be described below.

  As the reaction in the above step 1, for example, a compound having a fluorinated alkyl group and a hydroxyl group and epichlorohydrin or β-methylepichlorohydrin are made into a solution in the presence of a solvent or without a solvent, and a catalyst is added as necessary. The method of obtaining the compound which has an epoxy group by dripping a base and making it epoxidize is mentioned. As reaction temperature at the time of performing this epoxidation reaction, the range of 0-80 degreeC is preferable.

  Examples of the compound having a fluorinated alkyl group and a hydroxyl group include a compound represented by the following chemical formula (2).

（式中のＲｆ及びＡは、上記一般式（１）で示したものと同じである。）

(Rf and A in the formula are the same as those shown in the general formula (1).)

  Here, the charge ratio of the compound having a fluorinated alkyl group and a hydroxyl group and the epichlorohydrin or β-methylepichlorohydrin (a compound having a fluorinated alkyl group and a hydroxyl group / epichlorohydrin or β-methylepichlorohydrin) is 1 in molar ratio. The range of 1/1 to 1/15 is preferable, and the range of 1 / 1.05 to 1/10 is more preferable.

  Examples of the solvent used in the production of the above step 1 include a polar solvent and a two-phase solvent of an organic phase and an aqueous phase. Examples of the polar solvent include benzene, toluene, diethyl ether, tetrahydrofuran, isopropyl ether, dimethyl sulfoxide, 1,4-bis (trifluoromethyl) benzene, and the solvent used for the organic phase includes benzene, toluene. , Diethyl ether, isopropyl ether, cyclohexane, 1,4-bis (trifluoromethyl) benzene, dimethyl sulfoxide and the like.

  Examples of the base used in the production of Step 1 above include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrides such as sodium hydride and potassium hydride; lithium, sodium, potassium and the like. Alkali metals; amines such as triethylamine. These bases can also be used as an aqueous solution. The amount of the base used is preferably in the range of 1.05 to 20 mol% based on the total amount of the compound having a fluorinated alkyl group and a hydroxyl group and epichlorohydrin or β-methylepichlorohydrin. More preferably, it is used in the range of 1 to 10 mol%.

  Moreover, as a catalyst used as needed in manufacture of said process 1, a quaternary ammonium salt is preferable and phase transfer catalysts, such as a quaternary ammonium chloride and a quaternary ammonium bromide, are mentioned. Specific examples of this phase transfer catalyst include benzyltriethylammonium chloride, benzyldimethylphenylammonium chloride, tetra-n-butylammonium hydrogen sulfate, tetramethylammonium bromide and the like. The amount of the catalyst used is preferably in the range of 1 to 200% by mass, and in the range of 3 to 100% by mass, based on the total amount of the compound having a fluorinated alkyl group and a hydroxyl group and epichlorohydrin or β-methylepichlorohydrin. More preferred.

  The compound having an epoxy group represented by the following general formula (3) is obtained by the reaction in the above step 1.

（式中のＲｆ及びＡは、上記一般式（１）で示したものと同じである。）

(Rf and A in the formula are the same as those shown in the general formula (1).)

  After completion of the reaction, the compound having an epoxy group obtained by the reaction in the above step 1 is a compound having a fluorinated alkyl group and a hydroxyl group, excess epichlorohydrin or β-methylepichlorohydrin, and these unclosed products, and other by-products. It is preferable to remove the product by performing an isolation operation such as distillation under reduced pressure.

  Next, in step 2 above, the compound having an epoxy group obtained in step 1 is reacted with a nitrogen-containing heterocyclic compound having a secondary amine in the heterocyclic ring, and the nitrogen-containing compound having a tertiary amine in the heterocyclic ring. A method for obtaining a heterocyclic compound will be described below.

  Examples of the nitrogen-containing heterocyclic compound having a secondary amine in the heterocyclic ring include pyrrole, imidazole, pyrazole, pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperidine, piperazine, isoindole, indole, 1H- Indazole, purine, indoline, isoindoline, morpholine, carbazole, β-carboline, phenothiazine, phenoxazine and the like can be mentioned. In addition, as nitrogen-containing heterocyclic compounds having these secondary amines in the heterocyclic ring, it is also possible to use derivatives having substituents and compounds in which other rings are condensed to these heterocyclic rings to form condensed rings. .

  Among the nitrogen-containing heterocyclic compounds having the secondary amine in the heterocyclic ring, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole Imidazole such as 2-phenyl-4-methylimidazole or a derivative thereof; imidazoline such as imidazoline or 2-phenylimidazoline or a derivative thereof is preferable.

  As the reaction in the above step 2, for example, the nitrogen-containing heterocyclic compound having the secondary amine in the heterocyclic ring is dissolved in a solvent, and the solution is heated in the range of 60 to 160 ° C. and obtained in the step 1. The method of dripping the compound which has the obtained epoxy group, and making it react is mentioned.

  By the reaction in the above step 2, a nitrogen-containing heterocyclic compound having a tertiary amine represented by the following general formula (4) in the heterocyclic ring is obtained.

（式中のＲｆ、Ａ、Ｒ^１及びＲ^２は、上記一般式（１）で示したものと同じである。）

(Rf, A, R ¹ and R ² in the formula are the same as those shown in the general formula (1).)

  Further, in the above step 3, a method for obtaining a quaternary ammonium compound by quaternizing the tertiary amine in the nitrogen-containing heterocyclic compound having the tertiary amine obtained in step 2 in the heterocyclic ring will be described below. To do.

As a reagent (hereinafter abbreviated as “quaternizing agent”) used to quaternize the nitrogen atom bonded to R ¹ and R ² in the compound having a heterocyclic ring obtained in Step 2. Examples thereof include alkyl halide, methyl p-toluenesulfonate, dimethyl sulfate and the like. Among these quaternizing agents, methyl p-toluenesulfonate is preferable since the compatibility with the resin component in the composition is improved when the antistatic agent of the present invention is added to the resin composition.

  The method of using the quaternizing agent can be selected depending on the properties of the quaternizing agent. When the quaternizing agent is a gas having a temperature of 25 ° C. or a gas having a boiling point of less than 50 ° C., it can be introduced into the reaction vessel in a gaseous state. At this time, it can be introduced into either the gas phase portion or the liquid phase in the reaction vessel, or can be introduced into both. Here, it is preferable to introduce the quaternizing agent by bubbling it into the liquid phase and dissolve it in the liquid phase because the introduction efficiency of the quaternizing agent is increased. Further, since the dissolution efficiency of the quaternizing agent in the liquid can be improved, it is preferable to introduce the quaternizing agent in a pressurized state. The introduction pressure (gauge pressure) of the quaternizing agent is preferably 0 to 1500 kPa, more preferably 10 to 300 kPa. On the other hand, when the quaternizing agent is a liquid at 25 ° C., it may be dropped onto the liquid surface of the liquid phase in the reaction vessel.

  In Step 3, the quaternizing agent is directly introduced into the reaction solution obtained in Step 2 above, or the solvent is distilled off from the reaction solution obtained in Step 2 above to have a heterocyclic ring. You may carry out after taking out a compound. In order to increase the purity of the target product, step 3 is preferably performed after removing the compound having a heterocyclic ring by distilling off the solvent from the reaction solution obtained in step 2 above.

  When the reaction of Step 3 is carried out after removing the compound having a heterocyclic ring by distilling off the solvent from the reaction solution obtained in Step 2, the reaction can be carried out by adding a quaternizing agent without solvent. From the viewpoint of high reaction efficiency, it is preferred to dissolve a compound having a heterocyclic ring in a reaction solvent and add a quaternizing agent for reaction. As the reaction solvent, a solvent in which the compound having a heterocyclic ring obtained in Step 2 and a quaternizing agent are dissolved may be used. For example, ketones, esters, amides, sulfoxides, ethers, hydrocarbons More specifically, methanol, ethanol, butanol, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N- Examples include methyl pyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  The amount of the quaternizing agent used is such that the charged molar ratio of the quaternizing agent is 0.90 to 1.0.1 with respect to the nitrogen-containing heterocyclic compound having the tertiary amine obtained in Step 2 in the heterocyclic ring. A range of 10 is preferred.

  The reaction temperature at the time of quaternizing the compound having a heterocyclic ring obtained in Step 2 above is preferably 0 to 100 ° C, more preferably 20 to 80 ° C. The reaction temperature may be controlled before the introduction of the quaternary ammonium agent or after the introduction, but is preferably controlled after the introduction of the quaternary ammonium agent.

  Specific examples of the quaternary ammonium salt obtained by the above production method include the following formulas (1-1) to (1-6).

  The quaternary ammonium salt obtained by the above production method can impart antistatic properties to the surface of the substrate by applying it to the substrate as it is or as a solution dissolved in an organic solvent. In addition, since the quaternary ammonium salt has a fluorinated alkyl group in the molecule, the surface free energy peculiar to fluorine atoms is minimized when the coating composition containing the quaternary ammonium salt is applied to a substrate. Since the quaternary ammonium salt segregates on the coating film surface, the antistatic property is imparted to the coating film surface even if the amount of the quaternary ammonium salt added to the coating composition is small. be able to. Therefore, the antistatic agent of the present invention containing the quaternary ammonium salt as an essential component is preferably added to the coating composition.

  The coating composition of the present invention is obtained by adding the antistatic agent of the present invention containing the quaternary ammonium salt as an essential component as an antistatic agent. The amount added to the antistatic agent in the coating composition varies depending on the type of resin in the coating composition, the coating method, the target film thickness, etc., but imparts sufficient antistatic properties to the coating surface. Therefore, 0.0001-20 mass parts is preferable with respect to 100 mass parts of solid content in a coating composition, 0.001-10 mass parts is more preferable, and 0.01-5 mass parts is further more preferable.

  In addition, the types of coating compositions include evaporation-drying, which forms a coating film by evaporating a solvent based on a solvent-soluble resin, and thermal curing, in which a resin precursor is polymerized by heat to form a coating film Any type of active energy ray curable type in which a resin precursor is polymerized by irradiation with active energy rays such as a mold and ultraviolet rays to form a coating film may be used.

  Examples of the base resin of the evaporation-drying or thermosetting coating composition include natural resins such as petroleum resins, shellac resins, rosin resins, cellulose resins, rubber resins, lacquers, cashew resins, and oil-based vehicles. Paints used: phenol resins, alkyd resins, unsaturated polyester resins, amino resins, epoxy resins, vinyl resins, acrylic resins, polyurethane resins, silicone resins, fluororesins, and other synthetic resins.

  The active energy ray curable coating composition contains an active energy ray curable resin or an active energy ray curable monomer as a main component. These active energy ray-curable resins and active energy ray-curable monomers may be used alone or in combination.

  Examples of the active energy ray-curable resin include urethane (meth) acrylate resins, unsaturated polyester resins, epoxy (meth) acrylate resins, polyester (meth) acrylate resins, acrylic (meth) acrylate resins, and maleimide group-containing resins. However, in the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency and low shrinkage. In the present invention, “(meth) acryloyl group” means one or both of methacryloyl group and acryloyl group, and “(meth) acrylic acid” means one or both of methacrylic acid and acrylic acid. , “(Meth) acrylate” refers to one or both of methacrylate and acrylate.

  The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound. Is mentioned.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  On the other hand, examples of the hydroxy group-containing acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, Monovalent dihydric alcohols such as 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate ( (Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) Mono- or di (meth) acrylates of trivalent alcohols such as acrylate and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Containing mono- and di (meth) acrylates; monofunctional hydroxyl groups such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and more than trifunctional (meth) acryloyl groups Or a hydroxyl group-containing polyfunctional (meth) acrylate further modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene (Meth) acrylate compounds having an oxyalkylene chain such as polyethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxy group-containing acrylate compound can be carried out by a conventional method in the presence of a urethanization catalyst. Specific examples of urethanization catalysts that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, phosphines such as triphenylphosphine and triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, and octyl. Examples thereof include organotin compounds such as tin diacetate, dibutyltin diacetate, and tin octylate, and organometallic compounds such as zinc octylate.

  Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound are excellent in transparency of the cured coating film and have good sensitivity to active energy rays. It is preferable from the viewpoint of excellent curability.

  Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols. The α, β-unsaturated dibasic acid or its acid anhydride includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples include esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  Next, as an epoxy vinyl ester resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. What is obtained is mentioned.

  As the maleimide group-containing resin, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like. These active energy ray-curable resins can be used alone or in combination of two or more.

  Examples of the active energy ray-curable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene having a number average molecular weight in the range of 150 to 1,000. Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) having a number average molecular weight in the range of 150 to 1000 Acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl ( (Meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate Rate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, aliphatic alkyl (meth) acrylate such as isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropy Glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N -Octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) Carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-dimale And maleimides such as midcyclohexane.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra ( A trifunctional or higher polyfunctional (meth) acrylate such as (meth) acrylate is preferred. These active energy ray-curable monomers can be used alone or in combination of two or more.

  The said active energy ray hardening-type coating composition can be made into a cured coating film by irradiating an active energy ray after apply | coating to a base material. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator is added to the fluorine-containing curable resin or active energy ray curable coating composition to improve curability. Is preferred. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α ray, β ray, and γ ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no need to add a photosensitizer.

  Examples of the photopolymerization initiator include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Acetophenone-based compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos In'okishido, bis (2,4,6-trimethylbenzoyl) - acyl phosphine oxide-based compounds such as triphenylphosphine oxide; benzyl, and methyl phenylglyoxylate ester.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  Among the above photopolymerization initiators, 1-hydroxycyclohexylphenyl is preferable because it has excellent compatibility with the active energy ray-curable resin and the active energy ray-curable monomer in the active energy ray-curable coating composition. Ketones and benzophenones are preferred, and 1-hydroxycyclohexyl phenyl ketone is particularly preferred. These photopolymerization initiators can be used alone or in combination of two or more.

  Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. And sulfur compounds.

  The amount of these photopolymerization initiator and photosensitizer used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable coating composition, 15 mass% is more preferable, and 0.3-7 mass parts is further more preferable.

  Further, in the coating composition of the present invention, an organic solvent; a colorant such as a pigment, a dye, or carbon; if necessary, silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, calcium carbonate, or the like. Inorganic powder: Higher fatty acid, acrylic resin, phenol resin, polyester resin, polystyrene resin, urethane resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluororesin (PTFE (polytetrafluoro) Ethylene) etc.), various resin fine powders such as polyethylene and polypropylene; antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, weather stabilizer, heat stabilizer, antioxidant, rust inhibitor, slip agent, Silicone type, fluorine type, other leveling agents, wax, gloss adjusting agent, Type agents, compatibilizers, conductive modifiers, dispersants, dispersion stabilizers, thickeners, anti-settling agents can be appropriately added various additives such as a silicone-based or hydrocarbon-based surfactants.

  The organic solvent is useful in appropriately adjusting the viscosity of the coating composition of the present invention. In particular, in order to perform thin film coating, it is easy to adjust the film thickness. Examples of the organic solvent that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents can be used alone or in combination of two or more.

  Further, the coating method of the coating composition of the present invention varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping , Screen printing, spraying, applicator, bar coater, coating method using electrostatic coating, or molding methods using various molds.

  Examples of articles that can be imparted with antifouling properties (ink repellency, fingerprint resistance, etc.) using the coating composition of the present invention include TAC film and other liquid crystal display (LCD) polarizing film; plasma display (PDP), Various display screens such as organic EL displays; touch panels; mobile phone cases or mobile phone screens; optical recording media such as CDs, DVDs, and Blu-ray discs; transfer films for insert molds (IMD, IMF); copiers, printers, etc. Rubber rollers for OA equipment; Glass surfaces of reading parts of OA equipment such as copiers and scanners; Optical lenses such as cameras, video cameras, and glasses; Windshields and glass surfaces of watches such as watches; Various vehicles such as automobiles and railway vehicles Windows; various building materials such as decorative panels; window glass for houses; woodwork materials such as furniture; Leather, home appliances of the housing or the like of various plastic molded products, such as FRP bathtubs and the like. By applying the coating composition of the present invention to these article surfaces to form a coating film, antistatic properties can be imparted to the article surfaces. Further, the antistatic property of the present invention can be imparted to the surface of the article by adding the antistatic agent to various paints suitable for each article, and applying and drying.

  In addition, since the essential component of the antistatic agent of the present invention has a fluorinated organic group such as a fluorinated alkyl group, it also has a leveling effect, and has excellent antistatic properties for coating films of various coating materials. In addition to imparting, leveling properties can also be imparted. Examples of the coating material to which the antistatic agent of the present invention can be applied include a hard coating material for an LCD polarizing plate such as a TAC film, an anti-glare (AG) coating material or an anti-reflection (LR) coating material; a plasma display ( PDP), hard coating materials for various display screens such as organic EL displays; hard coating materials for touch panels; colors for forming RGB pixels used in color filters for liquid crystal displays (hereinafter referred to as “CF”) Resist, printing ink, inkjet ink or paint; black resist for CF black matrix, printing ink, inkjet ink or paint; resin composition for pixel partition such as plasma display (PDP), organic EL display; Paint or hard coat material; mobile phone Hard coating materials for screens; Hard coating materials for optical recording media such as CDs, DVDs, Blu-ray discs; Hard coating materials for transfer films for insert molds (IMD, IMF); Coated for rubber rollers for OA equipment such as copiers and printers Materials: Glass coating materials for reading parts of OA equipment such as copiers, scanners, etc .; Coating materials for optical lenses such as cameras, video cameras and glasses; Windshields for watches such as watches; Glass coating materials; Automobiles, railway vehicles, etc. Coating materials for windows of various vehicles; printing inks or paints for various building materials such as decorative panels; coating materials for window glass of houses; wood coating materials for furniture, etc .; coating materials for artificial and synthetic leather; Various plastic molded article paints or coating materials; FRP bathtub paints or coating materials, and the like.

  In particular, when the coating composition of the present invention is used as an anti-glare coating material among coating materials for protective films of polarizing plates for liquid crystal displays (LCD), among the above-mentioned compositions, silica fine particles, acrylic resin fine particles, polystyrene resin Excellent anti-glare properties by blending inorganic or organic fine particles such as fine particles at a ratio of 0.1 to 0.5 times the total mass of the curing component in the active energy ray-curable coating composition of the present invention. This is preferable.

  When the coating composition of the present invention is used as an antiglare coating material for a protective film of a polarizing plate for a liquid crystal display (LCD), after the coating material is brought into contact with a mold having an uneven surface shape before curing, It can also be applied to a transfer method in which an active energy ray is irradiated from the opposite side of the mold and cured, and the surface of the coat layer is embossed to impart antiglare properties.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the measuring method of the infrared absorption spectrum and NMR spectrum of the compound manufactured by the following synthesis example or Example is as follows.

[Infrared absorption spectrum measurement method]
Using a measuring device of “IR Prestige-21” manufactured by Shimadzu Corporation, a very small amount of the sample solution was dropped on a KBr plate and the solvent was dried, and then the measurement was performed.

[Method for measuring ¹ H-NMR and ¹³ C-NMR spectrum]
Using “AL-400” manufactured by JEOL Ltd., the acetone-d ₆ solution of the sample was analyzed for structural analysis.

(Synthesis Example 1)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 350 parts by mass of 2- (perfluorohexyl) ethanol, 534 parts by mass of epichlorohydrin and 176 parts by mass of a 50% by mass aqueous solution of benzyltriethylammonium chloride were charged. Stir. Next, stirring was started under an air stream, the temperature in the flask was raised to 40 ° C., and 23.6 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 2 hours. After completion of dropping, the temperature was raised to 60 ° C. and stirred for 1 hour. Thereafter, 94 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 4 hours, followed by reaction for 5 hours. After completion of the reaction, the produced salt was filtered off, the filtrate was allowed to stand, and the aqueous layer separated into the upper layer was removed. To the remaining reaction solution, 500 parts by mass of water was added to perform water washing, and this water washing was performed three times in total. After washing with water, epichlorohydrin was distilled off while concentrating with an aspirator using an oil bath set at 120 ° C. and a rotary evaporator. Subsequently, the compound (3-1) which has an epoxy group was obtained by taking out the component distilled off on conditions with a temperature of 120-130 degreeC, and a pressure of 1.3 kPa. About the obtained compound (3-1), the infrared absorption spectrum, < ¹ > H-NMR, and < ¹³ > C-NMR spectrum were measured, and it identified that it was a compound represented by following formula (3-1). In addition, the charts of the infrared absorption spectrum, ¹ H-NMR and ¹³ C-NMR spectrum of this compound (3-1) are shown in FIGS.

(Synthesis Example 2)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 344 parts by mass of 2- (perfluorobutyl) ethanol, 710 parts by mass of epichlorohydrin and 105 parts by mass of a 50% by mass aqueous solution of benzyltriethylammonium chloride were charged. Stir. Next, stirring was started under an air stream, the temperature in the flask was raised to 40 ° C., and 69.2 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 2 hours. After completion of dropping, the temperature was raised to 60 ° C. and stirred for 1 hour. Thereafter, 65 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 4 hours, followed by reaction for 5 hours. After completion of the reaction, the produced salt was filtered off, the filtrate was allowed to stand, and the aqueous layer separated at the top was removed. To the remaining reaction solution, 500 parts by mass of water was added to perform water washing, and this water washing was performed three times in total. After washing with water, epichlorohydrin was distilled off while concentration using an oil bath at 108 ° C. and a rotary evaporator. Subsequently, the compound (3-2) which has an epoxy group represented by the following formula (3-2) was obtained by taking out the component distilled out using aspirator at the temperature of 118-135 degreeC. In the same manner as in Synthesis Example 1, the compound represented by the following formula (3-2) was identified.

Example 1
6 parts by mass of imidazole and 65 parts by mass of toluene were placed in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and imidazole was dissolved in toluene at 85 ° C. in the flask while stirring. Subsequently, 37 mass parts of compounds (3-1) obtained by the synthesis example 1 were dripped over 1 hour. After further stirring for 2 hours, the reaction was carried out at a temperature in the flask of 106 ° C. for 3 hours. After the reaction, toluene was distilled off under reduced pressure to obtain a viscous liquid of a nitrogen-containing heterocyclic compound (4-1) having a tertiary amine in the heterocyclic ring. The compound (4-1) was identified as a compound represented by the following formula (4-1) by measuring an infrared absorption spectrum, ¹ H-NMR and ¹³ C-NMR spectrum. In addition, the charts of the infrared absorption spectrum, ¹ H-NMR, and ¹³ C-NMR spectrum of this compound (4-1) are shown in FIGS.

  Next, 40 parts by mass of methyl ethyl ketone was added to 20 parts by mass of the compound (4-1) and dissolved, and then 7.6 parts by mass of methyl p-toluenesulfonate was added dropwise at 40 ° C. over 15 minutes. Thereafter, the reaction was carried out at 60 ° C. for 3 hours. After completion of the reaction, the reaction solution was filtered, and then methyl ethyl ketone was added to obtain a 30% by mass methyl ethyl ketone solution of a quaternary ammonium salt of the compound (4-1) represented by the following formula (1-1).

(Example 2)
10 parts by mass of 2-ethyl-4-methylimidazole and 72 parts by mass of methyl isobutyl ketone were placed in a glass flask equipped with a stirrer, thermometer, condenser, and dropping device. -Ethyl-4-methylimidazole was dissolved in methyl isobutyl ketone. Subsequently, 38 mass parts of compounds (3-1) obtained by the synthesis example 1 were dripped over 1 hour. The mixture was further stirred for 2 hours, and reacted at a flask internal temperature of 110 ° C. for 3 hours so that a 30% by mass methyl isobutyl ketone solution of a nitrogen-containing heterocyclic compound (4-2) having a tertiary amine in the heterocyclic ring was obtained. Prepared. The compound (4-2) was identified as a compound represented by the following formula (4-2) by measuring an infrared absorption spectrum, ¹ H-NMR and ¹³ C-NMR spectrum.

  Next, a 30 mass% methyl isobutyl ketone solution 60 of a nitrogen-containing heterocyclic compound (4-2) having the tertiary amine in the heterocyclic ring in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device. The mass part was heated to 40 ° C., and 6.3 parts by mass of methyl p-toluenesulfonate was added dropwise over 10 minutes, followed by reaction at 60 ° C. for 3 hours. After completion of the reaction, the reaction solution is filtered, and then methyl isobutyl ketone is added to obtain a 30% by mass methyl isobutyl ketone solution of a quaternary ammonium salt of the compound (4-2) represented by the following formula (1-2). It was.

(Example 3)
6 parts by mass of 2-phenylimidazole and 72 parts by mass of methyl isobutyl ketone are placed in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and 2-phenylimidazole is added at a temperature of 95 ° C. while stirring. Dissolved in methyl isobutyl ketone. Next, 17.2 parts by mass of the compound (3-1) obtained in Synthesis Example 1 was added dropwise over 1 hour. The mixture was further stirred for 2 hours, and then reacted at a temperature in the flask of 110 ° C. for 3 hours so that a 30% by mass methyl isobutyl ketone solution of a nitrogen-containing heterocyclic compound (4-3) having a tertiary amine in the heterocyclic ring was obtained. Prepared. The compound (4-3) was identified as a compound represented by the following formula (4-3) by measuring an infrared absorption spectrum, ¹ H-NMR and ¹³ C-NMR spectrum.

  Next, a 30% by mass methyl isobutyl ketone solution 60 of a nitrogen-containing heterocyclic compound (4-3) having the tertiary amine in the heterocyclic ring in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device. The mass part was heated to 40 ° C., and 5.9 parts by mass of methyl p-toluenesulfonate was added dropwise over 10 minutes, followed by reaction at 60 ° C. for 3 hours. After completion of the reaction, the reaction solution is filtered, and then methyl isobutyl ketone is added to obtain a 30% by mass methyl isobutyl ketone solution of a quaternary ammonium salt of the compound (4-3) represented by the following formula (1-3). It was.

Example 4
Put 6 parts by mass of 2-phenylimidazoline and 35 parts by mass of methyl isobutyl ketone in a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and stir 2-phenylimidazoline at 95 ° C in the flask while stirring. Dissolved in methyl isobutyl ketone. Next, 17.2 parts by mass of the compound (3-1) obtained in Synthesis Example 1 was added dropwise over 1 hour. The mixture was further stirred for 2 hours, and then reacted at a temperature in the flask of 106 ° C. for 3 hours so that a 30% by mass methyl isobutyl ketone solution of a nitrogen-containing heterocyclic compound (4-4) having a tertiary amine in the heterocyclic ring was obtained. Prepared. The compound (4-4) was identified as a compound represented by the following formula (4-4) by measuring an infrared absorption spectrum, ¹ H-NMR and ¹³ C-NMR spectrum.

  Next, a 30% by mass methyl isobutyl ketone solution 60 of a nitrogen-containing heterocyclic compound (4-3) having the tertiary amine in the heterocyclic ring in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device. After adding a mass part, 5.9 mass parts of methyl p-toluenesulfonate was dripped at 40 degreeC over 10 minutes, and it was made to react at 60 degreeC after completion | finish of dripping. After completion of the reaction, the reaction solution is filtered, and then methyl isobutyl ketone is added to obtain a 30% by mass methyl isobutyl ketone solution of a quaternary ammonium salt of the compound (4-4) represented by the following formula (1-4). It was.

(Example 5)
Put 8 parts by mass of imidazole and 69 parts by mass of methyl isobutyl ketone in a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and dissolve the imidazole in methyl isobutyl ketone at 90 ° C. in the flask while stirring. It was. Next, 38 parts by mass of the compound (3-2) obtained in Synthesis Example 2 was added dropwise over 1 hour. The mixture was further stirred for 2 hours, and then reacted at a temperature in the flask of 110 ° C. for 3 hours so that a 30% by mass methyl isobutyl ketone solution of a nitrogen-containing heterocyclic compound (4-5) having a tertiary amine in the heterocyclic ring was obtained. Prepared. The compound (4-5) was identified as a compound represented by the following formula (4-5) by measuring an infrared absorption spectrum, ¹ H-NMR and ¹³ C-NMR spectrum.

  Next, a 30% by mass methyl isobutyl ketone solution 60 of a nitrogen-containing heterocyclic compound (4-5) having the tertiary amine in the heterocyclic ring in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device. After adding mass part, 6.5 mass parts of methyl iodide was dripped at 40 degreeC over 10 minutes, and it was made to react at 60 degreeC after completion | finish of dripping for 3 hours. After completion of the reaction, the reaction solution was filtered, and then methyl isobutyl ketone was added to obtain a 30% by mass methyl isobutyl ketone solution of a quaternary ammonium salt of a compound represented by the following formula (1-5).

(Example 6)
30% by mass methyl of the nitrogen-containing heterocyclic compound (4-5) having the tertiary amine in the heterocyclic ring in the glass flask equipped with the stirrer, thermometer, condenser, and dropping device obtained in Example 5 After adding 60 parts by mass of an isobutyl ketone solution, 8.5 parts by mass of methyl p-toluenesulfonate was added dropwise at 40 ° C. over 1 hour, and reacted at 60 ° C. for 3 hours after completion of the addition. After completion of the reaction, the reaction solution is filtered, and then methyl isobutyl ketone is added to obtain a 30% by mass methyl isobutyl ketone solution of a quaternary ammonium salt of the compound (4-5) represented by the following formula (1-6). It was.

(Comparative Example 1)
10.5 parts by mass of diethanolamine was placed in a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the compound (3-1) 42.2 obtained in Synthesis Example 1 was stirred at 40 ° C. A part by mass was dropped and reacted for 3 hours. Furthermore, it was made to react at 110 degreeC for 1 hour, and the compound represented by a following formula (C1'-1) was obtained.

  Next, 50 parts by mass of isopropanol was added to obtain a uniform solution, and then 18.2 parts by mass of methyl p-toluenesulfonate was added dropwise over 30 minutes, and the mixture was further reacted at 60 ° C. for 2 hours. After completion of the reaction, isopropanol was distilled off under reduced pressure and dried to obtain a quaternary ammonium salt represented by the following formula (C1-1).

[Preparation of Base Composition for Evaluation Coating Composition]
As a coating composition for evaluation, pentafunctional non-yellowing urethane acrylate 50 parts by mass, dipentaerythritol hexaacrylate 50 parts by mass, butyl acetate 25 parts by mass, photopolymerization initiator (“Irgacure 184” manufactured by BASF Japan Ltd .; 1- (Hydroxycyclohexyl phenyl ketone) 5 parts by weight, 54 parts by weight of toluene as a solvent, 28 parts by weight of 2-propanol, 28 parts by weight of ethyl acetate and 28 parts by weight of propylene glycol monomethyl ether are uniformly mixed to form a UV curable coating composition. A base composition was obtained.

[Preparation of coating composition for evaluation]
To 268 parts by mass of the base composition obtained above, the quaternary ammonium salt obtained in Examples 1 to 12 and Comparative Examples 1 to 2 is 1 part by mass (1 phr), or 3 parts by mass (3 phr). Were mixed and dissolved uniformly, followed by microfiltration with a 0.1 μm polytetrafluoroethylene (PTFE) filter to obtain a coating composition for evaluation. Further, nothing was added and only a base composition was prepared and used as Comparative Example 3.

[Preparation of coating film for evaluation]
The coating composition for evaluation obtained above was measured using a bar coater No. 13 was applied to a polyethylene terephthalate (PET) film having a thickness of 188 μm, and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent. Next, the dried coating film was cured by irradiating with ultraviolet rays (UV) using an ultraviolet curing device (under a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ).

[Measurement of haze value]
About the coating film for evaluation obtained above, the haze value was measured using a turbidimeter (Nippon Denshoku Industries Co., Ltd., model: NDH5000).

[Evaluation of surface smoothness]
The surface appearance of the coating film for evaluation obtained above was visually observed, and surface smoothness was evaluated according to the following criteria.
○: The surface is smooth.
Δ: Slightly uneven on the surface.
X: Not smooth, but whitening and cloudiness are observed.

[Measurement of surface resistivity]
A digital superinsulator / microammeter (manufactured by Hioki Electric Co., Ltd., model: DSM-8103) was used in the apparatus under the conditions of the surface resistivity of the coating film for evaluation obtained above at a temperature of 23 ° C. and a humidity of 50%. , And an electrode for a flat plate sample (manufactured by Hioki Electric Co., Ltd., model: SME-8311).

  The measurement and evaluation results are shown in Table 1.

The cured coating film of the coating composition to which the quaternary ammonium salt having a nitrogen-containing heterocycle obtained in Examples 1 to 6, which is the antistatic agent of the present invention, is compatible with the resin component in the coating composition. It was found that the transparency was very high. It was also found that the surface smoothness was very high. This is because the surface smoothness is higher than that of the cured coating film (Comparative Example 3) to which no antistatic agent was added, and thus it is considered that the antistatic agent of the present invention also acts as a leveling agent. Further, the surface specific resistance value of the cured coating film (Comparative Example 3) to which no antistatic agent was added was 1.2 × 10 ¹⁷ Ω / □, whereas 10 ¹⁰ to 10 ¹² even when a small amount of 1 phr was added. It was found that the resistance was reduced to the order of Ω / □, and excellent antistatic properties could be imparted to the cured coating film.

  On the other hand, in the example using the quaternary ammonium salt having no nitrogen-containing heterocycle obtained in Comparative Example 1, although the surface resistivity was decreased, the compatibility with each component in the coating composition was It was bad and it turned out that a cured coating film becomes cloudy and is inferior to transparency.

It was found that Comparative Example 3 in which no antistatic agent was added had a high surface resistivity of 1.2 × 10 ¹⁷ Ω / □ and the surface smoothness of the cured coating film was insufficient.

Claims (10)

An antistatic agent comprising a quaternary ammonium salt having a nitrogen-containing heterocycle represented by the following general formula (1) as an essential component.

(In the formula, Rf represents a fluorinated alkyl group represented by the following (Rf-1) , A represents an ethylene group, and R ¹ and R ² represent a carbon atom or a nitrogen atom forming a nitrogen-containing heterocyclic ring. , R ¹ and R ² form a heterocyclic ring with a quaternary nitrogen atom to which R ¹ and R ² are bonded via a divalent organic group, and another ring is condensed to this heterocyclic ring. (R ³ represents an alkyl group having 1 to ³ carbon atoms, and X ⁻ represents an anion.)

(N represents an integer of 1 to 8.) The antistatic agent according to claim 1, wherein in (Rf-1), n is 4 or 6. R ³ The antistatic agent according to claim 1, wherein is a methyl group. In the general formula (1), the heterocyclic ring containing R ¹ and R ² is pyrrole, imidazole, pyrazole, pyrrolidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperidine, piperazine, isoindole, indole, 1H-indazole The antistatic agent according to claim 1, wherein the antistatic agent is derived from one or more heterocyclic compounds selected from the group consisting of quinone, purine, indoline, isoindoline, morpholine, carbazole, β-carboline, phenothiazine and phenoxazine. In the general formula (1), R ¹ And R ² Is selected from the group consisting of pyrrole, imidazole, pyrazole, pyrrolidine, pyrroline, imidazoline, piperidine, piperazine, indole, 1H-indazole, purine, indoline, morpholine, carbazole, β-carboline, phenothiazine and phenoxazine. The antistatic agent according to claim 1, which is derived from one or more heterocyclic compounds. In the general formula (1), R ¹ And R ² The antistatic agent according to claim 1, wherein the heterocyclic ring containing is imidazole or imidazoline. In the general formula (1), X ⁻ is a halide ion, OH ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , CH ₃ SO ₄ ⁻ , CH ₃ CO ₂ ⁻ , CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO _3. ^- and _CH 3 PhSO ₃ ^- 1 monovalent antistatic agent according to claim 1 Symbol mounting an anion least one selected from the group consisting of. In the general formula (1), X ⁻ Is a halide ion or CH ₃ PhSO ₃ ⁻ The antistatic agent according to claim 1. The antistatic agent of Claim 1 represented by following formula (1-1)-(1-6).

  A coating composition comprising the antistatic agent according to claim 1.

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