Antistatic agent and resin composition

Abstract

Provided is an antistatic agent capable of exhibiting the antistatic performance even without containing fluorine atoms.　An antistatic agent according to one embodiment of the present invention contains an ion pair of a quaternary ammonium cation and a carboxylate anion having a carbon-carbon double bond. The antistatic agent optionally contains a substance obtained by mixing a quaternary ammonium bicarbonate and a carboxylic acid having a carbon-carbon double bond. A resin composition according to one embodiment of the present invention contains a resin and an ion pair of a quaternary ammonium cation and a carboxylate anion having a carbon-carbon double bond.

Description

Antistatic agents and resin compositions

[0001] Embodiments of the present invention relate to antistatic agents and resin compositions.

[0002] Conventionally, antistatic agents such as surfactants, conductive fillers, conductive polymers, and ionic liquids have been used to prevent electrostatic discharge. For example, Patent Document 1 proposes using a compound combining a phosphonium cation having a fluoroalkyl group and an anion having a fluorine atom as an antistatic agent for resins.

[0003] Japanese Patent Publication No. 2023-181119

[0004] As mentioned above, it is known that ionic liquids are used as antistatic agents, but these ionic liquids are compounds containing fluorine atoms. In recent years, from the perspective of the impact on the global environment, there has been a demand for products that do not contain fluorine compounds, and therefore, it is desirable that antistatic agents also do not contain fluorine atoms.

[0005] The embodiment of the present invention aims to provide an antistatic agent that can exhibit antistatic properties even without containing fluorine atoms.

[0006] The present invention includes the embodiments shown below: [1] An antistatic agent comprising an ion pair of a carboxylic acid anion having a carbon-carbon double bond and a quaternary ammonium cation. [2] The carboxylic acid anion is represented by the following general formula (1), In formula (1), R １ and R ２ The antistatic agent according to [1], wherein each independently represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a nitrogen atom and / or an oxygen atom. [3] R in formula (1) １ R represents a hydrogen atom or a methyl group. ２ The antistatic agent described in [2], where is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. [4] The quaternary ammonium cation is represented by the following general formula (2), In formula (2), R ３ , R ４ , R ５ and R ６each independently represent a monovalent hydrocarbon group having 1 to 5 carbon atoms which may contain an oxygen atom, the antistatic agent according to any one of [1] to [3]. [5] R in the formula (2) ３ represents an alkyl group having 1 to 5 carbon atoms that is substituted or unsubstituted with a hydroxy group, and R ４ , R ５ and R ６ each independently represent an alkyl group having 1 to 5 carbon atoms, the antistatic agent according to [4].

[0007] [6] An antistatic agent comprising a substance obtained by mixing a carboxylic acid having a carbon-carbon double bond and a quaternary ammonium bicarbonate. [7] The carboxylic acid is represented by the following general formula (3), In the formula (3), R １ and R ２ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a nitrogen atom and / or an oxygen atom, the antistatic agent according to [6]. [8] R in the formula (3) １ represents a hydrogen atom or a methyl group, and R ２ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, the antistatic agent according to [7]. [9] The quaternary ammonium bicarbonate is represented by the following general formula (4), In the formula (4), R ３ , R ４ , R ５ and R ６ each independently represent a monovalent hydrocarbon group having 1 to 5 carbon atoms which may contain an oxygen atom, the antistatic agent according to any one of [6] to [8].

[10] R in the formula (4) ３ represents an alkyl group having 1 to 5 carbon atoms that is substituted or unsubstituted with a hydroxy group, and R ４ , R ５ and R ６ each independently represent an alkyl group having 1 to 5 carbon atoms, the antistatic agent according to [9].

[0008]

[11] A resin composition comprising an ion pair of a carboxylic acid anion having a carbon-carbon double bond and a quaternary ammonium cation, and a resin.

[12] A resin composition comprising a substance obtained by mixing a carboxylic acid having a carbon-carbon double bond and a quaternary ammonium bicarbonate, and a resin.

[13] The resin composition according to

[11] or

[12] , wherein the resin comprises an acrylic resin and / or a polycarbonate resin.

[0009] According to this embodiment, it is possible to provide an antistatic agent that can exhibit antistatic properties even without containing fluorine atoms.

[0010] [Antistatic Agent] An antistatic agent according to one embodiment contains an ion pair of a carboxylic acid anion having a carbon-carbon double bond and a quaternary ammonium cation. When an ionic pair is formed between a carboxylic acid anion having a carbon-carbon double bond and a quaternary ammonium cation, it is possible to form an ion pair that exhibits antistatic performance even without containing a fluorine atom.

[0011] The ion pair may also be a salt of the carboxylic acid anion and a quaternary ammonium cation, in which case the ion pair may be an ionic liquid. In one embodiment, the ion pair may have a melting point of 100°C or less (i.e., liquid at 100°C and 1 atm), a melting point of 50°C or less (i.e., liquid at 50°C and 1 atm), or a melting point of 25°C or less (i.e., liquid at 25°C and 1 atm). Thus, the ion pair may be a liquid or a solid at room temperature (25°C) and atmospheric pressure (1 atm). If it is a liquid at room temperature and atmospheric pressure, it is easily mixed into low-viscosity resin compositions, for example, those produced by solvent casting. If it is a solid at room temperature and atmospheric pressure, it is easily mixed by melting it during kneading, for example, in kneaded-type resin compositions.

[0012] In one embodiment, the antistatic agent may comprise a substance containing an ion pair (hereinafter referred to as "ion pair-containing substance"). The ion pair-containing substance may be composed solely of an ion pair of a carboxylate anion having a carbon-carbon double bond and a quaternary ammonium cation, or may be composed of the ion pair together with a carboxylic acid having a carbon-carbon double bond as a hydrogen bond donor described below and / or a quaternary ammonium bicarbonate as a hydrogen bond acceptor, and these may form a hydrogen bond network. The ion pair-containing substance may be liquid, solid or gel at 25°C and 1 atm, and in one embodiment may be liquid, that is, an ion pair-containing liquid. The content of ion pairs in the ion pair-containing substance is not particularly limited, and may be, for example, 25% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass.

[0013] As the carboxylate anion that is the anionic component constituting the ion pair, an anion represented by the following general formula (1) is preferred.

[0014] In formula (1), R １ and R ２ each independently represent a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 6) that may optionally contain a nitrogen atom and / or an oxygen atom. As such, the monovalent hydrocarbon group may or may not contain a nitrogen atom and / or an oxygen atom as a heteroatom, but preferably does not contain a heteroatom. It should be noted that the heteroatom may be contained in a substituent of the monovalent hydrocarbon group, and therefore the monovalent hydrocarbon group may be a hydrocarbon group unsubstituted or substituted with a substituent containing a nitrogen atom and / or an oxygen atom. Preferably, R １ represents a hydrogen atom or a methyl group, and R ２represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 6). Examples of the monovalent hydrocarbon group include saturated or unsaturated chain hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. More specifically, an alkyl group (which may be linear or branched), an alkenyl group (which may be linear or branched), and an aryl group (e.g., a phenyl group) are preferred.

[0015] Specific examples of carboxylate anions include geranate anion, sorbate anion, 2-butenoate anion, 2-pentenoate anion, 2-hexenoate anion, 2-heptenoate anion, 2-octenoate anion, cinnamate anion, 3-methylcinnamate anion, 4-methylcinnamate anion, α,4-dimethylcinnamate anion, acrylate anion, methacrylate anion, and the like. Any one or more of these may be used. Among these, at least one selected from the group consisting of geranate anion, cinnamate anion, sorbate anion, acrylate anion, and methacrylate anion is particularly preferred.

[0016] As the quaternary ammonium cation which is the cation component constituting the above ion pair, a cation represented by the following general formula (2) is preferred.

[0017] In formula (2), R ３ , R ４ , R ５ and R ６ each independently represent a monovalent hydrocarbon group having 1 to 5 carbon atoms (preferably 1 to 3, more preferably 1 or 2) which may contain an oxygen atom. As described above, the monovalent hydrocarbon group may or may not contain an oxygen atom as a heteroatom. The heteroatom may be included in a substituent of the monovalent hydrocarbon group, and therefore, the monovalent hydrocarbon group may be a hydrocarbon group that is substituted or unsubstituted with a substituent containing an oxygen atom. Preferably, R ３ , R ４ , R ５ and R ６Each of these independently represents an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms), which may have a hydroxyl group as a substituent. More preferably, R ３ R represents an alkyl group having 1 to 5 carbon atoms, substituted or unsubstituted with a hydroxyl group. ４ , R ５ and R ６ Each independently represents an alkyl group having 1 to 5 carbon atoms, and more preferably, R ３ R represents a methyl group, ethyl group, propyl group, hydroxymethyl group, hydroxyethyl group, or hydroxypropyl group. ４ , R ５ and R ６ Each of these independently represents a methyl group, an ethyl group, or a propyl group. Note that the alkyl group may be linear or branched.

[0018] Specific examples of quaternary ammonium cations include choline cations, tetramethylammonium cations, tetraethylammonium cations, tetrapropylammonium cations, and tetrabutylammonium cations. One or more of these can be used. Among these, choline cations and / or tetraethylammonium cations are particularly preferred.

[0019] Specific examples of preferred ion pairs include geranate anion / choline cation, geranate anion / tetraethylammonium cation, cinnamate anion / choline cation, cinnamate anion / tetraethylammonium cation, sorbate anion / choline cation, sorbate anion / tetraethylammonium cation, acrylate anion / choline cation, acrylate anion / tetraethylammonium cation, methacrylate anion / choline cation, and methacrylate anion / tetraethylammonium cation.

[0020] An antistatic agent according to one embodiment includes a substance obtained by mixing a carboxylic acid having a carbon-carbon double bond with a quaternary ammonium bicarbonate (hereinafter sometimes referred to as the "product"). By mixing a carboxylic acid having a carbon-carbon double bond with a quaternary ammonium bicarbonate, a substance with excellent antistatic performance can be produced even without containing fluorine atoms, and an antistatic agent that does not contain fluorine atoms can be provided. The product may be a liquid, a solid, or a gel at 25°C and 1 atm. In one embodiment, the product may be a liquid at 25°C and 1 atm without the use of a separate solvent.

[0021] In detail, when a carboxylic acid having a carbon-carbon double bond as a hydrogen bond donor is mixed with a quaternary ammonium bicarbonate as a hydrogen bond acceptor, the hydrogen (H) of the carboxyl group of the donor reacts with the bicarbonate of the acceptor to produce carbon dioxide and water. Also, the oxygen of the donor... － and the N of the acceptor ＋ It is believed that ionic bonding occurs to form an ionic pair between a carboxylic acid anion having a carbon-carbon double bond and a quaternary ammonium cation. The resulting product may contain, along with the ionic pair, a carboxylic acid having a carbon-carbon double bond as a hydrogen bond donor, and / or a quaternary ammonium bicarbonate as a hydrogen bond acceptor, and these may form a hydrogen bond network. Thus, the product is formed by mixing a hydrogen bond donor as a parent component and a hydrogen bond acceptor, and among these, the liquid substance that causes freezing point depression for the parent component is also called a deep eutectic solvent.

[0022] In preparing the product, a carboxylic acid having a carbon-carbon double bond and a quaternary ammonium bicarbonate may be (i) mixed as is, (ii) one of them may be dissolved in water and / or an organic solvent and mixed with the other, or (iii) both may be dissolved in water and / or an organic solvent and then mixed together. Since carbon dioxide is produced by mixing, the produced carbon dioxide may be released, and the produced water, and in the case of the above-mentioned mixed solutions, the solvents, may be removed by distillation or the like.

[0023] Here, "product" is defined as a substance that does not include the solvent (i.e., the water produced and the solvent used to form a solution during mixing). Therefore, as a component of the antistatic agent, the solvent is a separate component from the product, and thus the antistatic agent may consist only of the product, or it may contain the solvent together with the product. Preferably, it does not contain the solvent.

[0024] The content of ion pairs in the generated substance is not particularly limited and may be, for example, 25% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass.

[0025] As carboxylic acids having a carbon-carbon double bond, compounds represented by the following general formula (3) are preferred. R in equation (3) １ and R ２ R in equation (1) １ and R ２ It is similar to that.

[0026] Specific examples of carboxylic acids having a carbon-carbon double bond include geranic acid, sorbic acid, 2-butenoic acid, 2-pentenoic acid, 2-hexenoic acid, 2-heptenoic acid, 2-octenoic acid, cinnamic acid, 3-methylcinnamic acid, 4-methylcinnamic acid, α,4-dimethylcinnamic acid, acrylic acid, and methacrylic acid. One or more of these can be used. Among these, at least one selected from the group consisting of geranic acid, cinnamic acid, sorbic acid, acrylic acid, and methacrylic acid is particularly preferred.

[0027] As the quaternary ammonium bicarbonate, the compound represented by the following general formula (4) is preferred. R in equation (4) ３ , R ４ , R ５ and R ６ R in equation (2) ３ , R ４ , R ５ and R ６ It is similar to that.

[0028] Specific examples of quaternary ammonium bicarbonates include choline bicarbonate, tetramethylammonium bicarbonate, tetraethylammonium bicarbonate, tetrapropylammonium bicarbonate, and tetrabutylammonium bicarbonate. One or more of these can be used. Among these, choline bicarbonate and / or tetraethylammonium bicarbonate are particularly preferred.

[0029] The mixing ratio (donor:acceptor) of a carboxylic acid having a carbon-carbon double bond (donor) and a quaternary ammonium bicarbonate (acceptor) is not particularly limited, but may be 6:1 to 1:6, 4:1 to 1:4, 2:1 to 1:2, 3:2 to 2:3, or 1:1 in molar ratio.

[0030] The antistatic agent contains the above-mentioned ion pairs, ion pair-containing substances, or generated substances as active ingredients. The antistatic agent may consist only of ion pairs, ion pair-containing substances, or generated substances, or may contain other components as needed. Examples of other components include antioxidants, UV inhibitors, weather-resistant agents, anti-blocking agents, pigments, reinforcing agents, lubricants, plasticizers, and other antistatic components.

[0031] Antistatic agents can be applied to various materials that are prone to static electricity, for example, and can prevent them from becoming charged. Such materials are not particularly limited and include, for example, resins such as synthetic resins, rubber, and fibers (woven fabrics, knitted fabrics, nonwoven fabrics). The application method is also not particularly limited; for example, the agent may be added internally to the above materials, or it may be applied to the surface of molded articles made of these materials.

[0032] [Resin Composition] The resin composition according to this embodiment comprises the above-mentioned ion pair, ion pair-containing substance or generated substance, and resin. For example, the resin composition can be obtained by blending the above-mentioned antistatic agent with the resin, thereby reducing the surface resistance of a molded article made of the resin composition and preventing dust from adhering to the surface of the molded article.

[0033] The above-mentioned resin is not particularly limited, and examples include acrylic resins and polycarbonate resins. One or more of these can be used. Among these, acrylic resins and / or polycarbonate resins are preferred, and it is preferable that they be the main components. For example, 100% by mass of the resin preferably contains 50% by mass or more of acrylic resin and / or polycarbonate resin, more preferably 80% by mass or more, and may contain 100% by mass.

[0034] Acrylic resins are polymers of acrylic acid esters and / or methacrylic acid esters, and may be incorporated into resin compositions as pre-polymerized polymers, or as photocurable resins that polymerize and harden under ultraviolet light or the like. Examples of (meth)acrylates used as photocurable resins include phenoxybenzyl (meth)acrylate, ethoxylated phenylphenol (meth)acrylate, biphenylyl (meth)acrylate, butyl acrylate, and dipentaerythritol hexaacrylate. One or more of these may be used. Among these, aromatic group-containing (meth)acrylates are preferred as acrylic resins, more preferably aromatic group-containing monofunctional (meth)acrylates, and even more preferably phenoxybenzyl (meth)acrylate and / or ethoxylated phenylphenol (meth)acrylate. Here, (meth)acrylate is a general term for acrylate and methacrylate.

[0035] In the resin composition, the content of the above-mentioned ion pair is not particularly limited; for example, it may be 0.01 to 10 parts by mass, 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass per 100 parts by mass of resin. The content of the ion pair-containing substance or the generated substance is also not particularly limited; for example, it may be 0.01 to 10 parts by mass, 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass per 100 parts by mass of resin.

[0036] The resin composition may contain, as needed, other components along with the above-mentioned ion pairs, ion pair-containing substances or generated substances, and the resin. Examples of other components include antioxidants, UV inhibitors, weather-resistant agents, anti-blocking agents, pigments, reinforcing agents, lubricants, plasticizers, and other antistatic agents.

[0037] The applications of the resin composition are not particularly limited and include, for example, optical applications, semiconductor applications, and medical device applications.

[0038] The present invention will be described in more detail below based on examples and comparative examples, but it is not limited thereto.

[0039] [Production Example 1] 66 parts by mass of geranic acid (85% purity) were added to 34 parts by mass of an 80% by mass aqueous solution of choline bicarbonate (geranic acid:choline bicarbonate (molar ratio) = 2:1), and the mixture was stirred at room temperature until the release of carbon dioxide stopped. The resulting mixture was distilled at 70°C for 1 hour to remove water and obtain liquid L1, which is liquid at room temperature and atmospheric pressure. Since carbon dioxide was generated by the above mixing, it can be seen that geranic acid and choline bicarbonate react to form an ion pair of geranic acid anion and choline cation, and that liquid L1 contains this ion pair. Furthermore, since it was prepared by adding an excess of geranic acid, it can be seen that liquid L1 contains geranic acid as a hydrogen bond donor along with the ion pair.

[0040] [Production Example 2] 66 parts by mass of geranic acid (purity 85% by mass) were mixed with 34 parts by mass of a 50% methanol solution of tetraethylammonium bicarbonate (purity 95% by mass) (geranic acid:tetraethylammonium bicarbonate (molar ratio) = 4:1), and the mixture was stirred at room temperature until the release of carbon dioxide stopped. The resulting mixture was distilled at 70°C for 1 hour to remove water and methanol, thereby obtaining liquid L2, which is liquid at room temperature and pressure. Since carbon dioxide was generated by the above mixing, it can be seen that geranic acid and tetraethylammonium bicarbonate react to form an ion pair of geranic acid anion and tetraethylammonium cation, and that liquid L2 contains this ion pair. Furthermore, since it was prepared by adding an excess of geranic acid, it can be seen that liquid L2 contains geranic acid as a hydrogen bond donor along with the ion pair.

[0041] [Production Example 3] 59 parts by mass of a 50% methanol solution of cinnamic acid were added to 41 parts by mass of an 80% aqueous solution of choline bicarbonate (cinnamic acid:choline bicarbonate (molar ratio) = 1:1), and the mixture was stirred at room temperature until the release of carbon dioxide stopped. The resulting mixture was distilled at 70°C for 1 hour to remove water and methanol, thereby obtaining liquid L3, which is liquid at room temperature and pressure. Since carbon dioxide was generated by the above mixing, it can be seen that cinnamic acid and choline bicarbonate react to form an ion pair of cinnamate anion and choline cation, and that liquid L3 contains this ion pair.

[0042] [Production Example 4] 42 parts by mass of a 50% methanol solution of cinnamic acid were added to 58 parts by mass of a 50% methanol solution of tetraethylammonium bicarbonate (95% purity) (cinnamic acid:tetraethylammonium bicarbonate (molar ratio) = 1:1), and the mixture was stirred at room temperature until the release of carbon dioxide stopped. The resulting mixture was distilled at 70°C for 1 hour to remove water and methanol, thereby obtaining liquid L4, which is liquid at room temperature and atmospheric pressure. Since carbon dioxide was generated by the above mixing, it can be seen that cinnamic acid and tetraethylammonium bicarbonate react to form an ion pair of cinnamate anion and tetraethylammonium cation, and that liquid L4 contains this ion pair.

[0043] [Comparative Manufacturing Example 1] 65 parts by mass of citric acid were added to 35 parts by mass of an 80% by mass aqueous solution of choline bicarbonate (citric acid:choline bicarbonate (molar ratio) = 2:1), and the mixture was stirred at room temperature until the release of carbon dioxide stopped. The resulting mixture was distilled at 70°C for 1 hour to remove water, thereby obtaining liquid L5, which is a liquid at room temperature and atmospheric pressure. Since carbon dioxide was generated by the above mixing, it can be seen that the reaction between citric acid and choline bicarbonate formed an ion pair of citrate anion and choline cation, and that liquid L5 contains this ion pair.

[0044] [Comparative Production Example 2] 58 parts by mass of 2-ethylhexanoic acid were added to 42 parts by mass of an 80% by mass aqueous solution of choline bicarbonate (2-ethylhexanoic acid:choline bicarbonate (molar ratio) = 2:1), and the mixture was stirred at room temperature until the release of carbon dioxide stopped. The resulting mixture was distilled at 70°C for 1 hour to remove water and obtain liquid L6, which is a liquid at room temperature and atmospheric pressure. Since carbon dioxide was generated by the above mixing, it can be seen that 2-ethylhexanoic acid and choline bicarbonate react to form an ion pair of 2-ethylhexanoic acid anion and choline cation, and that liquid L6 contains this ion pair.

[0045] [Comparative Production Example 3] 74 parts by mass of a 50% methanol solution of geranic acid (purity 85% by mass) were added to 26 parts by mass of a 50% aqueous solution of choline chloride (geranic acid:choline chloride (molar ratio) = 2:1), and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was distilled at 70°C for 1 hour to remove water and methanol, thereby obtaining liquid L7, which is a liquid at room temperature and atmospheric pressure.

[0046] [Comparative Production Example 4] 51 parts by mass of a 50% by mass ethanol solution of cinnamic acid was added to 49 parts by mass of a 50% by mass aqueous solution of choline chloride (cinnamic acid:choline chloride (molar ratio) = 1:1), and the mixture was stirred at room temperature for 30 minutes. The resulting mixture was distilled at 70°C for 1 hour to remove water and methanol, thereby obtaining liquid L8, which is a liquid at room temperature and atmospheric pressure.

[0047] [Test Example 1: Evaluation of Antistatic Performance] A coating agent was prepared using phenoxybenzyl acrylate (Kyoeisha Chemical Co., Ltd.'s "Light Acrylate POB-A") as the acrylic resin, with 3 parts by mass of liquids L1 to L8 each added as antistatic agents per 100 parts by mass of the acrylic resin, and 3 parts by mass of Omnirad 184 (IGM Resins B.V.) added as a photopolymerization initiator. Meanwhile, a polyethylene terephthalate film (product name: Cosmoshine A4360, manufactured by Toyobo Engineering Co., Ltd.) was prepared as the substrate, and the coating agent was applied to this substrate using a bar coater to form a coating film with a thickness of 50 μm. Next, the coating film was subjected to a high-pressure mercury lamp with an integrated charge of 1000 mJ / cm². ２ Test specimens were prepared by irradiating them with light to harden the coating.

[0048] The surface resistance of the fabricated test specimens was measured using a digital ultra-high resistance / micro-current meter (Advantest Corporation). The results are shown in Table 1 below.

[0049] As Comparative Example 1, test specimens were prepared in the same manner for acrylic resin without an antistatic agent, and the surface resistance was measured. Furthermore, as a reference example, test specimens prepared using "Elexel AS-110" (EMIm (1-ethyl-3-methylimidazolium)・FSI (bis(fluorosulfonyl)imide)) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as an antistatic agent, with the other ingredients added to the acrylic resin in the same manner as in Examples 1 to 4, were also measured for surface resistance.

[0050]

[0051] As shown in Table 1, Examples 1 to 4, which incorporated liquids L1 to L4 according to Production Examples 1 to 4, showed a significantly lower surface resistance compared to Comparative Example 1, which did not contain any additives, demonstrating superior antistatic performance. Although Examples 1 to 4 did not contain fluorine atoms, they had antistatic performance roughly equivalent to that of the Reference Example, which incorporated an ionic liquid containing fluorine atoms. Therefore, they provided antistatic performance while minimizing environmental impact. Furthermore, compared to the ionic liquid in the Reference Example, which generally requires multiple chemical synthesis and purification steps, these examples could be easily synthesized and were cost-effective.

[0052] In contrast, Comparative Examples 2 and 3, which contained liquids L5 and L6 obtained by mixing citric acid or 2-ethylhexanoic acid, which are carboxylic acids without carbon-carbon double bonds, with choline bicarbonate, showed surface resistance values ​​approximately the same as Comparative Example 1, which had no antistatic agent added, and no antistatic performance was observed. Furthermore, Comparative Examples 4 and 5, which contained liquids L7 and L8 obtained by mixing carboxylic acids having carbon-carbon double bonds with choline chloride, showed surface resistance values ​​approximately the same as Comparative Example 1, which had no antistatic agent added, and no antistatic performance was observed.

[0053] [Test Example 2: Evaluation of Antistatic Performance] Using ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as the acrylic resin and liquid L1 as the antistatic agent, a test specimen for Example 5 was prepared in the same manner as in Test Example 1. The surface resistance value of the prepared test specimen was measured in the same manner as in Test Example 1.

[0054] As Comparative Example 6, a test specimen was similarly prepared and its surface resistance value measured for an acrylic resin (ethoxylated-o-phenylphenol acrylate) without an antistatic agent.

[0055]

[0056] The results are shown in Table 2. Even when ethoxylated-o-phenylphenol acrylate was used as the acrylic resin, Example 5, which contained liquid L1, showed a significantly lower surface resistance compared to Comparative Example 6, which did not contain the additive, demonstrating superior antistatic performance.

[0057] [Test Example 3: Evaluation of Antistatic Performance] A coating agent was prepared by dissolving polycarbonate resin ("Toughlon™ A2200" manufactured by Idemitsu Kosan Co., Ltd.) in a chloroform solution at a concentration of 10% by mass, and adding liquids L1 to L4 as antistatic agents at a concentration of 3 parts by mass per 100 parts by mass of polycarbonate resin. On the other hand, polyethylene terephthalate film (product name: Cosmoshine A4360 manufactured by Toyobo Engineering Co., Ltd.) was prepared as a substrate, and the coating agent was applied to this substrate using a bar coater. A coating film with a thickness of 50 μm was formed by the solvent casting method (drying at 80°C for 1 minute), thereby producing test pieces for Examples 6 to 9. The surface resistance values ​​of the prepared test pieces were measured in the same manner as in Test Example 1.

[0058] As Comparative Example 7, test specimens were similarly prepared and their surface resistance values ​​measured for polycarbonate resin without added antistatic agents.

[0059]

[0060] The results are shown in Table 3. Even when polycarbonate resin was used instead of acrylic resin, Examples 6 to 9, which incorporated liquids L1 to L4 according to Production Examples 1 to 4, showed a significantly lower surface resistance compared to Comparative Example 7, which did not contain any additives, demonstrating superior antistatic performance.

[0061] [Production Example 5] 26 parts by mass of acrylic acid was mixed with 74 parts by mass of an 80% by mass aqueous solution of choline bicarbonate (acrylic acid:choline bicarbonate (molar ratio) = 1:1), and the mixture was stirred at room temperature until the release of carbon dioxide stopped. The resulting mixture was distilled at 70°C for 1 hour to remove water, thereby obtaining liquid L9, which is a liquid at room temperature and atmospheric pressure. Since carbon dioxide was generated by the above mixing, it can be seen that an ion pair of acrylate anion and choline cation is formed by the reaction of acrylic acid and choline bicarbonate, and that liquid L9 contains this ion pair.

[0062] [Test Example 4: Evaluation of Antistatic Performance] A coating agent was prepared using dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as the polyfunctional acrylic resin. Liquids L1 and L9 were added in 3 parts by mass per 100 parts by mass of the polyfunctional acrylic resin as antistatic agents, and Omnirad 184 (IGM Resins B.V.) was added in 3 parts by mass as a photopolymerization initiator. On the other hand, polyethylene terephthalate film (product name: Cosmoshine A4360, manufactured by Toyobo Engineering Co., Ltd.) was prepared as the substrate, and the coating agent was applied to this substrate with a bar coater to form a coating film with a thickness of 20 μm. Next, the coating film was subjected to a high-pressure mercury lamp with an integrated charge of 1000 mJ / cm². ２ Test specimens were prepared by irradiating them with light to harden the coating. The surface resistance of the prepared test specimens was measured in the same manner as in Test Example 1.

[0063] As Comparative Example 8, a test specimen was similarly prepared and its surface resistance measured for a polyfunctional acrylic resin (dipentaerythritol hexaacrylate) without an antistatic agent.

[0064]

[0065] The results are shown in Table 4. Even when using a polyfunctional acrylic resin (dipentaerythritol hexaacrylate), Examples 10 and 11, which incorporated liquids L1 and L9, showed a significantly lower surface resistance compared to Comparative Example 8, which did not contain these additives, demonstrating superior antistatic performance.

[0066] Furthermore, the various numerical ranges described in this specification can be any combination of their upper and lower limits, and all such combinations are described herein as preferred numerical ranges. Also, the description of a numerical range as "X to Y" means X or greater and Y or less.

[0067] Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the spirit of the invention. These embodiments and their omissions, substitutions, and modifications are included in the scope and spirit of the invention, as well as in the claims and their equivalents.

Claims

1. An antistatic agent comprising an ion pair of a carboxylic acid anion having a carbon-carbon double bond and a quaternary ammonium cation.

2. The carboxylic acid anion is represented by the following general formula (1), In formula (1), R １ and R ２ The antistatic agent according to claim 1, wherein each of the following independently represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a nitrogen atom and / or an oxygen atom.

3. R ​​in formula (1) above １ R represents a hydrogen atom or a methyl group. ２ The antistatic agent according to claim 2, wherein is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

4. The quaternary ammonium cation is represented by the following general formula (2), In formula (2), R ３ , R ４ , R ５ and R ６ The antistatic agent according to any one of claims 1 to 3, wherein each of these independently represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, which may contain an oxygen atom.

5. In the above formula (2), R ３ represents an alkyl group having 1 to 5 carbon atoms which is substituted or unsubstituted with a hydroxy group, and R ４ , R ５ and R ６ each independently represent an alkyl group having 1 to 5 carbon atoms. The antistatic agent according to claim 4.

6. An antistatic agent comprising a substance obtained by mixing a carboxylic acid having a carbon-carbon double bond with a quaternary ammonium bicarbonate.

7. The carboxylic acid is represented by the following general formula (3), In formula (3), R １ and R ２ The antistatic agent according to claim 6, wherein each of these independently represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a nitrogen atom and / or an oxygen atom.

8. R in formula (3) above １ R represents a hydrogen atom or a methyl group. ２ The antistatic agent according to claim 7, wherein is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

9. The quaternary ammonium bicarbonate is represented by the following general formula (4), In formula (4), R ３ , R ４ , R ５ and R ６ The antistatic agent according to any one of claims 6 to 8, wherein each of these independently represents a monovalent hydrocarbon group having 1 to 5 carbon atoms, which may contain an oxygen atom.

10. R in equation (4) above ３ R represents an alkyl group having 1 to 5 carbon atoms, either substituted or unsubstituted with a hydroxyl group. ４ , R ５ and R ６ The antistatic agent according to claim 9, wherein each of these independently represents an alkyl group having 1 to 5 carbon atoms.

11. A resin composition comprising an ion pair of a carboxylic acid anion having a carbon-carbon double bond and a quaternary ammonium cation, and a resin.

12. A resin composition comprising a substance obtained by mixing a carboxylic acid having a carbon-carbon double bond with a quaternary ammonium bicarbonate, and a resin.

13. The resin composition according to claim 11 or 12, wherein the resin comprises an acrylic resin and / or a polycarbonate resin.

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