Compound and antistatic agent containing the same as an active ingredient

Abstract

To provide a compound that is stably immobilized on the surface of a resin while having excellent compatibility with the resin, and that is suitable as an antistatic agent that can express high antistatic performance even with a small quantity.SOLUTION: The present invention provides a compound represented by the general formula (1) in the figure. (In the formula, R1, R2 and R3 each independently represent a linear or branched alkyl group having 1-20 carbon atoms, R4 represents a linear or branched fluoroalkyl group having 1-20 carbon atoms, and A represents an anion having a fluorine atom.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound which is a phosphonium salt having a fluoroalkyl group and an antistatic agent containing the same as an active ingredient. [Background technology]

[0002] Various methods for preventing electrostatic damage have been proposed, but most solutions rely on the use of antistatic agents. Antistatic agents include surfactants, conductive fillers, conductive polymers, and ionic liquids. The mechanism by which ionic liquids exhibit their antistatic properties differs from that of other antistatic agents. For example, when ionic liquids are used as antistatic agents for resins, the static electricity generated on the resin surface is neutralized by the uneven concentration of ionic liquid in the resin, resulting in antistatic properties that are less susceptible to external environmental factors such as temperature and humidity. Furthermore, molecular design is possible through the combination of positive and negative ions, making it easy to adjust compatibility with resins and providing the advantage of maintaining excellent appearance properties, such as transparency.

[0003] Various proposals have been made regarding technologies using ionic liquids as antistatic agents, depending on the purpose. For example, Patent Document 1 discloses an antistatic agent containing an inclusion compound formed by encapsulating an ionic liquid in cyclodextrin as an antistatic agent with excellent water resistance and solvent resistance, and describes specific ammonium salts or phosphonium salts as ionic liquids that can be encapsulated in cyclodextrin. Patent Document 2 also discloses an antistatic agent that is miscible with hydrocarbons due to the inclusion of the anion of docusate, a so-called bis(2-ethylhexyl) ester of sulfonosuccinic acid, and describes its use as an antistatic additive for fuels and polymers. Furthermore, Patent Document 3 describes the use of a compound containing a polymerizable anion of a predetermined structure having a perfluoroalkyl group and a polymerizable functional group in the molecule, and a monovalent cation, as a polymerizable ionic liquid, as an antistatic agent with excellent voltage resistance. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-52859 [Patent Document 2] Special Publication No. 2006-510581 [Patent Document 3] International Publication No. WO2020 / 031836 Brochure Summary of the Invention [Problem to be solved by the invention]

[0005] As mentioned above, the antistatic properties imparted by ionic liquids are not easily affected by the external environment, and if their compatibility with resins can be improved, they can be expected to be used as permanent antistatic agents. However, because resins have very high insulating properties, they are very susceptible to charging, and this charging can easily cause contamination of the resin surface by the adsorption of dust and the like. Therefore, in order to obtain sustained antistatic properties, it is necessary to stably fix the ionic liquid to the resin surface.

[0006] However, while previously proposed antistatic agents using ionic liquids have excellent antistatic properties, it has been difficult to stably fix them to the resin surface. One method for solving this problem is to use a polymerizable ionic liquid as described in Patent Document 3, which increases the contact area with the resin and fixes it, but this requires a large amount of ionic liquid to improve the antistatic properties, which causes problems such as impairing the properties and appearance required of the resin.

[0007] Therefore, an object of the present invention is to provide a compound suitable as an antistatic agent that has excellent compatibility with resins, is stably fixed on the resin surface, and can exhibit high antistatic performance even in small amounts. [Means for solving the problem]

[0008] In light of the above-mentioned circumstances, the present inventors have conducted extensive research and have found that, in a phosphonium-type ionic liquid, by introducing a functional group into the phosphonium cation and further combining it with an anion having a fluorine atom, the ionic liquid is stably immobilized on the resin surface, and therefore excellent permanent antistatic properties are exhibited even in small amounts, which led to the completion of the present invention.

[0009] That is, the present invention provides a compound represented by the following general formula (1). [ka] (In the formula, R 1 , R 2 and R 3 each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms; R 4 represents a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, and A represents an anion having a fluorine atom. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a compound suitable as an antistatic agent, which has excellent compatibility with resins, is stably fixed on the resin surface, and has high antistatic performance even in small amounts. DETAILED DESCRIPTION OF THE INVENTION

[0011] The compound of the present invention is a phosphonium salt having a fluoroalkyl group, represented by the following general formula (1). [ka]

[0012] In general formula (1), R 1 , R 2 and R 3 R represents a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms, and particularly preferably 3 to 15 carbon atoms. 1 , R 2 and R 3may be the same or different, but are preferably the same from the viewpoint of synthesis.

[0013] R in general formula (1) 4 represents a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, preferably 2 to 18, and particularly preferably 3 to 15. Also, A represents an anion having a fluorine atom.

[0014] R 1 , R 2 and R 3 Specific examples of the linear alkyl group having 1 to 20 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group.

[0015] R 1 , R 2 and R 3 Specific examples of the branched alkyl group having 1 to 20 carbon atoms represented by the formula (I) include an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, an isopentyl group, an s-pentyl group, a t-pentyl group, an isohexyl group, an s-hexyl group, a t-hexyl group, and an ethylhexyl group.

[0016] R 4 Examples of the fluoroalkyl group having 1 to 20 carbon atoms represented by the formula (I) include groups in which at least one hydrogen atom in the linear or branched alkyl group having 1 to 20 carbon atoms is substituted with a fluorine atom.

[0017] R 4 As the fluoroalkyl group having 1 to 20 carbon atoms represented by the formula (1), a group represented by the following general formula (2) is particularly preferred, in that it can achieve both compatibility with the resin and immobilization.

[0018] [ka] (In the formula, R 5 represents a linear or branched perfluoroalkyl group having 1 to 18 carbon atoms.

[0019] Examples of the linear or branched perfluoroalkyl group having 1 to 18 carbon atoms include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluorooctyl group, and a perfluorodecyl group.

[0020] In general formula (1), A represents an anion having a fluorine atom, and examples thereof include tetrafluoroborate (BF), hexafluorophosphate (PF), bis(trifluoromethanesulfonyl)imide (N(SOCF), bis(fluorosulfonyl)imide (N(SOF)), trifluoromethanesulfonate (SOCF), tris(pentafluoroethyl)trifluorophosphate ((CFPF), and trifluoroacetic acid (CFCOO). Of these, bis(fluorosulfonyl)imide (N(SOF)) and bis(trifluoromethanesulfonyl)imide (N(SOCF)) are preferred because they can achieve both compatibility with the resin and good immobilization.

[0021] Specific examples of the compound represented by general formula (1) of the present invention include tributyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(trifluoromethanesulfonyl)imide, tributyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(fluorosulfonyl)imide, tributyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium bis(trifluoromethanesulfonyl)imide, tributyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium bis(trifluoromethanesulfonyl)imide, Tributyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium bis(trifluoromethanesulfonyl)imide, Triethyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(trifluoromethanesulfonyl)imide, Triethyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(fluorosulfonyl)imide, Triethyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(fluorosulfonyl)imide, Triethyl(1H,1H,2H,2H-nonaf Triethyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium bis(fluorosulfonyl)imide, Triethyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium bis(trifluoromethanesulfonyl)imide, Trioctyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(trifluoromethanesulfonyl)imide, Trioctyl(1H,1H, Examples include (2H,2H-heptadecafluorodecyl)phosphonium bis(fluorosulfonyl)imide, trioctyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium bis(trifluoromethanesulfonyl)imide, trioctyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium bis(fluorosulfonyl)imide, and trioctyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium bis(trifluoromethanesulfonyl)imide.

[0022] The compound represented by the general formula (1) can be obtained, for example, by reacting a trialkylphosphine with a fluoroalkyl halide under an inert gas atmosphere to obtain a phosphonium salt whose anion is a halogen, followed by neutralization and oxidation treatment as desired, and then adding a desired anion component dropwise to the obtained phosphonium salt and mixing it to perform anion exchange. The compound represented by the general formula (1) obtained after the anion exchange can be used as an active ingredient of an antistatic agent, as described below, by optionally undergoing steps such as washing, concentration, drying, and pulverization.

[0023] The antistatic agent of the present invention is characterized by containing, as an active ingredient, a phosphonium salt, which is a compound represented by the general formula (1). While ammonium salts and sulfonium salts are also known as similar cationic antistatic agents, phosphonium salts are known to have higher heat resistance than other onium salts, can be kneaded and molded with resins at relatively high temperatures, and do not undergo thermal decomposition. Therefore, even in cases where other onium salts cannot be used due to thermal decomposition, phosphonium salts can be used without any problems.

[0024] In the compound represented by the general formula (1), three of the four substituents in the cation moiety are relatively short alkyl groups having 1 to 8 carbon atoms, and the remaining one is a long-chain fluoroalkyl group having 1 to 20 carbon atoms, so that the compound has excellent antistatic properties and is stably fixed to a resin. Furthermore, the anion moiety contains a fluorine atom, which allows the compound to be both compatible with the resin and fixed.

[0025] The antistatic agent of the present invention can be either water-soluble or oil-soluble depending on the physical properties of the compound represented by general formula (1). When using the antistatic agent, if necessary, resin additives such as antioxidants, ultraviolet inhibitors, weathering agents, antiblocking agents, pigments, reinforcing agents, lubricants, plasticizers, and other antistatic agents may be used in combination.

[0026] The antistatic agent of the present invention is solid or liquid at room temperature. If it is solid at room temperature, it is preferably in powder form, from the viewpoint of easily becoming liquid upon heating when kneaded with a resin and being able to be uniformly dispersed, and the average particle size measured by a laser diffraction scattering method is preferably 100 μm or less, more preferably 0.1 to 50 μm or less, particularly preferably 0.5 to 20 μm.

[0027] Furthermore, when the antistatic agent of the present invention is liquid at room temperature, from the viewpoint of uniform dispersion when kneaded with a resin and obtaining an excellent antistatic effect, it is preferable that the viscosity at 25° C. is 10 to 300 cP, particularly 15 to 250 cP. The viscosity at 25° C. can be measured using a rotational viscometer, a vibration viscometer, or the like.

[0028] The material to be blended with the antistatic agent of the present invention may be any material that is charged with static electricity, and examples thereof include polymeric materials such as synthetic resins and rubbers, and molded articles, fibers, films, nonwoven fabrics, beads, etc.

[0029] The type of polymer material to which the antistatic agent of the present invention can be applied is not particularly limited, and examples thereof include polyolefins such as polyethylene, polypropylene, and polystyrene, and copolymers thereof, thermoplastic resins such as polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polybutylene terephthalate, polycaprolactam, amide resins, phenylene oxide resins, vinyl resins, acetal resins, ketone resins, sulfide resins, and urethane resins, and copolymers thereof, as well as fluorine-based resins obtained by fluorinating these polymer materials. In particular, application to fluorine-based resins tends to provide the advantages of compatibility with the resin and fixation.

[0030] Examples of the fluorine-based resin include polytetrafluoroethylene, polyhexafluoropropylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxyalkane, polychlorotrifluoroethene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (ethylene / tetrafluoroethylene) copolymer, (propylene / hexafluoropropylene) copolymer, (vinylidene fluoride / ethylene) copolymer, and (vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene) copolymer.

[0031] Examples of rubber include styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, urethane rubber, silicone rubber, NBR, EPM, hydrogenated nitrile rubber, polysulfide rubber, acrylic rubber, ethylene acrylic rubber, and fluorinated rubbers obtained by fluorinating these rubbers.

[0032] Examples of the fluorine-based rubber include tetrafluoroethylene-based rubber, tetrafluoroethylene propylene-based rubber, vinylidene fluoride-based rubber, hexafluorobutadiene-based rubber, fluorosilicone-based rubber, tetrafluoroethylene-propylene-based rubber, and tetrafluoroethylene-perfluoroalkyl vinyl ether-based rubber.

[0033] The antistatic agent of the present invention may be applied to a polymeric material by any method, including, for example, a method of adding it internally to a desired polymeric material, and a method of applying it to the surface of a molded article made of a polymeric material.

[0034] The method of internally adding the antistatic agent of the present invention to a polymeric material includes adding and mixing the antistatic agent of the present invention during polymer processing or production. The method of adding the antistatic agent during polymer processing involves directly adding the antistatic agent of the present invention to a desired polymeric material, mixing the material in a tumbler, ribbon blender, high-speed mixer, or the like, and melt-mixing the material to achieve a uniform distribution in the polymeric material, or adding the antistatic agent of the present invention in the form of master chips containing the antistatic agent at a high concentration, and melt-mixing the material. The antistatic agent of the present invention can also be added and mixed before or during polymerization of polyethylene terephthalate or the like.

[0035] The amount of the antistatic agent of the present invention added internally to a polymer material is usually 0.01 to 10% by mass, preferably 0.1 to 5% by mass. If the amount is less than 0.01% by mass, the amount of antistatic agent present near the surface of the molded article is insufficient, resulting in a weak antistatic effect. If the amount is more than 10% by mass, the transparency of the molded article may decrease, impairing its appearance, and the resulting high cost is economically disadvantageous.

[0036] The method of using the antistatic agent of the present invention by coating it on the surface of a molded article made of a polymer material can be carried out, for example, by uniformly coating the antistatic agent of the present invention alone or together with other substances on the surface, and is particularly effective for imparting antistatic properties to polymer materials that have problems with the dispersibility of the antistatic agent in the resin, surface migration, compatibility, etc. The coating liquid used in this case may be a solution in which the antistatic agent of the present invention is dissolved in a solvent such as water, a lower alcohol, or a ketone, or may be a dispersion or emulsion in which the antistatic agent is dispersed in such a solvent.

[0037] Examples of means for applying the antistatic agent of the present invention to the surface of a molded article made of a polymer material include immersion, spraying, roller coating, gravure coating, and other methods using a solution, dispersion, emulsion, or the like containing the antistatic agent of the present invention. If necessary, the surface to be treated may be subjected to a physical treatment such as corona treatment or plasma treatment, or a pretreatment such as application of an anchor coating agent, before application. It is not necessary to apply a solution containing only the antistatic agent with the primary purpose of providing antistatic properties, but it is also possible to add the agent to a treatment agent used for other purposes to simultaneously impart antistatic properties.

[0038] For example, when a coating agent is used to impart adhesion, printability, gas barrier properties, water resistance, vapor permeability, hardness, etc. to the surface of a molded article made of a polymer material, good antistatic properties can be imparted by using the antistatic agent in combination with such a coating agent. Furthermore, the antistatic agent may also be used in combination with low-molecular organic substances such as inks, paints, and lubricating components. [Example]

[0039] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0040] [Manufacturing Example 1] A 300 ml four-neck flask equipped with a thermometer, dropping funnel, and magnetic stirrer was thoroughly purged with nitrogen and charged with 20.2 g (0.1 mol) of tributylphosphine and 100 ml of acetonitrile. The temperature was heated to 75 °C, and 57.4 g (0.1 mol) of 1H,1H,2H,2H-heptadecafluorodecyl iodide was added dropwise from the dropping funnel over 1 hour under light-shielded conditions. The mixture was then aged at 80 °C for 4 hours. A sample of the reaction solution was subjected to a color test with carbon disulfide, revealing no trace of tributylphosphine. The mixture was then cooled to room temperature. The solvent was concentrated using an evaporator to obtain 74.5 g of a pale yellow solid (96% crude yield) with a melting point of 66.2-67.6 °C. The NMR identification data for the resulting pale yellow solid are as follows: (Identification data) 31 P-NMR: 34.88 ppm. 1 H-NMR; 0.98ppm (CH3,9H), 1.56ppm (-CH2-CH2-, 12H), 2.63ppm (P-CH2-, 8H), 2.64ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium iodide.

[0041] Next, 23.3 g (0.03 mol) of the tributyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium iodide obtained above was placed in a 200 ml two-neck flask equipped with a thermometer and magnetic stirrer and dissolved in 50 ml of dichloromethane. An aqueous solution of 9.6 g (0.03 mol) of potassium bis(trifluoromethanesulfonyl)imide in 50 ml of purified water was added and mixed at room temperature for anion exchange. After stirring for 30 minutes, the dichloromethane layer was washed three times with purified water in a separatory funnel. Concentration in an evaporator yielded 26.5 g (95% crude yield) of a pale yellow solid with a melting point of 48.5-49.2 °C. The NMR identification data for the resulting pale yellow solid are as follows: 31 P-NMR: 35.30 ppm. 1 H-NMR; 0.94ppm (CH3,9H), 1.48ppm (-CH2-CH2-, 12H), 2.25ppm (P-CH2-, 8H), 2.45ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(trifluoromethanesulfonyl)imide.

[0042] [Manufacturing Example 2] The same procedure as in Production Example 1 was repeated, except that anion exchange was performed with potassium bis(fluorosulfonyl)imide instead of potassium bis(trifluoromethanesulfonyl)imide, to obtain 23.6 g (crude yield 95%) of a pale yellow solid having a melting point of 40.7-41.3°C. The NMR identification data of the resulting pale yellow solid are as follows: 31 P-NMR: 35.37 ppm. 1 H-NMR; 0.96ppm (CH3,9H), 1.51ppm (-CH2-CH2-, 12H), 2.22ppm (P-CH2-, 8H), 2.45ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(fluorosulfonyl)imide.

[0043] [Manufacturing Example 3] In Preparation Example 1, 37.4 g (0.1 mol) of 1H,1H,2H,2H-nonafluorohexyl iodide was reacted with 20.2 g (0.1 mol) of tributylphosphine instead of 1H,1H,2H,2H-heptadecafluorodecyl iodide to obtain 54.1 g (crude yield 94%) of a pale yellow viscous liquid. The NMR identification data of the obtained pale yellow viscous liquid are as follows: 31 P-NMR: 34.87 ppm. 1 H-NMR; 0.94ppm (CH3,9H), 1.56ppm (-CH2-CH2-, 12H), 2.60ppm (P-CH2-, 8H), 2.74ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium iodide.

[0044] Next, the same procedure as in Preparation Example 1 was repeated except that the obtained tributyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium iodide was used, to obtain 20.6 g (crude yield 94%) of a pale yellow viscous liquid. The NMR identification data of the obtained pale yellow solid are as follows: 31 P-NMR: 35.31 ppm. 1 H-NMR; 0.94ppm(CH3,9H), 1.49ppm(-CH2-CH2-,12H), 2.23ppm(P-CH2-,8H), 2.43ppm(-CH2-CF2-,2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium bis(trifluoromethanesulfonyl)imide.

[0045] [Manufacturing Example 4] The same procedure as in Preparation 3 was repeated, except that tributyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium iodide and potassium bis(fluorosulfonyl)imide were subjected to anion exchange, to obtain 17.9 g of a pale yellow viscous liquid (crude yield 95%). The NMR identification data of the resulting pale yellow solid are as follows: 31 P-NMR: 35.37 ppm. 1 H-NMR; 0.95ppm (CH3,9H), 1.50ppm (-CH2-CH2-, 12H), 2.25ppm (P-CH2-, 8H), 2.42ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-nonafluorohexyl)phosphonium bis(fluorosulfonyl)imide.

[0046] [Manufacturing Example 5] 20.2 g (0.1 mol) of tributylphosphine and 47.4 g (0.1 mol) of 1H,1H,2H,2H-tridecafluoro-n-octyl iodide were reacted without solvent to obtain 62.2 g (crude yield 92%) of a pale yellow solid having a melting point of 41.7 to 43.3 °C. The NMR identification data of the resulting pale yellow solid was as follows: 31 P-NMR: 34.88 ppm. 1 H-NMR; 0.94ppm (CH3,9H), 1.54ppm (-CH2-CH2-, 12H), 2.60ppm (P-CH2-, 8H), 2.79ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium iodide.

[0047] The resulting tributyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium iodide and potassium bis(trifluoromethanesulfonyl)imide were then subjected to anion exchange in the same manner as in Production Example 1, yielding 23.4 g (crude yield 94%) of a pale yellow solid having a melting point of 40.8-41.3°C. The NMR identification data of the resulting pale yellow solid are as follows: 31 P-NMR: 35.33 ppm. 1 H-NMR; 0.94ppm (CH3,9H), 1.51ppm (-CH2-CH2-, 12H), 2.24ppm (P-CH2-, 8H), 2.45ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium bis(trifluoromethanesulfonyl)imide.

[0048] [Manufacturing Example 6] The same procedure as in Preparation 3 was repeated, except that tributyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium iodide and potassium bis(fluorosulfonyl)imide were subjected to anion exchange, to obtain 20.6 g of a pale yellow viscous liquid (crude yield 94%). The NMR identification data for the resulting pale yellow liquid are as follows: 31 P-NMR: 35.39 ppm. 1 H-NMR; 0.94ppm (CH3,9H), 1.51ppm (-CH2-CH2-, 12H), 2.20ppm (P-CH2-, 8H), 2.50ppm (-CH2-CF2-, 2H). As a result, it was confirmed that the compound was tributyl(1H,1H,2H,2H-tridecafluoro-n-octyl)phosphonium bis(fluorosulfonyl)imide.

[0049] [Comparative Manufacturing Example 1] A 300 ml four-neck flask equipped with a thermometer, dropping funnel, and magnetic stirrer was thoroughly purged with nitrogen, and 15.2 g (0.15 mol) of triethylamine and 57.4 g (0.1 mol) of 1H,1H,2H,2H-heptadecafluorodecyl iodide were added. The mixture was reacted at 80 °C for 6 hours in the dark. After cooling to room temperature, the solvent was concentrated using an evaporator, and the resulting crystals were washed with ethanol. 50.6 g (75% crude yield) of a white solid with a melting point of 59.4-61.8 °C was obtained. The NMR identification data for the resulting white solid are as follows: 1 H-NMR;2.67~2.74ppm(-CH3,9H),3.22~3.25ppm(N-CH2-CH2-,10H). As a result, it was confirmed that the compound was triethyl(1H,1H,2H,2H-heptadecafluorodecyl)ammonium iodide.

[0050] Next, 20.2 g (0.03 mol) of the triethyl(1H,1H,2H,2H-heptadecafluorodecyl)ammonium iodide obtained above was placed in a 200 ml two-neck flask equipped with a thermometer and magnetic stirrer and dissolved in 50 ml of dichloromethane. An aqueous solution of 9.6 g (0.03 mol) of potassium bis(trifluoromethanesulfonyl)imide in 50 ml of purified water was added and mixed at room temperature for anion exchange. After stirring for 30 minutes, the dichloromethane layer was washed three times with purified water in a separatory funnel. The mixture was concentrated in an evaporator to obtain 14.7 g (crude yield 59%) of a white solid with a melting point of 57.6-59.5 °C. NMR identification data for the resulting white solid are as follows: 1 H-NMR;2.69~2.74ppm(-CH3,9H),3.22~3.25ppm(N-CH2-CH2-,10H). As a result, it was confirmed that the compound was triethyl(1H,1H,2H,2H-heptadecafluorodecyl)ammonium bis(trifluoromethanesulfonyl)imide.

[0051] [Comparative Manufacturing Example 2] The same procedure as in Comparative Production Example 1 was repeated, except that anion exchange was performed with potassium bis(fluorosulfonyl)imide instead of potassium bis(trifluoromethanesulfonyl)imide, to obtain 16.4 g (crude yield 75%) of a white solid having a melting point of 56.6-58.0°C. The NMR identification data of the obtained white solid are as follows: 1 H-NMR; 2.67~2.74ppm(-CH3,9H), 3.22~3.26ppm(N-CH2-CH2-,10H). As a result, it was confirmed that the compound was triethyl(1H,1H,2H,2H-heptadecafluorodecyl)phosphonium bis(fluorosulfonyl)imide.

[0052] [Examples 1 to 11] The phosphonium salt obtained in each Production Example was added to the thermoplastic resin shown in Table 1 in the amount shown in Table 1, and the mixture was kneaded at 250 to 260°C in Examples 1 to 10, and at 285 to 295°C in Example 11. The kneaded resin obtained was then fitted into a stainless steel mold measuring 10 cm x 10 cm and t = 2 mm and pressed to prepare test specimens.

[0053] The volume resistivity and surface resistivity of this test piece were measured according to JIS K6911-1995 to evaluate its antistatic performance. A super insulation meter (Toa Denpa Kogyo Co., Ltd. SM-8220, plate sample electrode SME-8310) was used as the measuring instrument, and measurements were taken one day after the test piece was prepared, and then five days later. The measurement conditions were 30°C and 25% RH. The test piece was sandwiched between plate electrodes, and a voltage of 100 V was applied for 10 seconds. The measured value was the average of three measurements taken 60 seconds later. Next, to evaluate organic solvent resistance, the test specimens were wiped with methanol on both sides after 5 days, air-dried, and then the volume resistivity and surface resistivity were measured. Furthermore, after 6 days, the test specimens were immersed in 100 mL of methanol, left to stand for 10 minutes, removed, air-dried for 1 hour, and then the volume resistivity and surface resistivity were measured. The measurement results are shown in Table 1. To evaluate water resistance, the test specimens were wiped 50 times with a cloth while exposed to running water after 5 days, and then air-dried for 1 hour. The volume resistivity and surface resistivity of the test specimens were measured. The measurement results are shown in Table 1.

[0054] [Comparative Examples 1 to 3] Test pieces were prepared from the thermoplastic resins used in the examples without adding any phosphonium salt. The test pieces were subjected to the same measurements as in the examples. The measurement results are shown in Table 2.

[0055] [Comparative Examples 4 to 5] The ammonium salts obtained in each Comparative Production Example were added to the thermoplastic resin used in the Examples in the amounts shown in Table 2, and the mixture was kneaded at 250 to 260°C to prepare test pieces measuring 10 cm x 10 cm and t = 2 mm. The test pieces obtained were subjected to the same measurements as in the Examples. The measurement results are shown in Table 2.

[0056] [Table 1]

[0057] [Table 2]

[0058] The results shown in Tables 1 and 2 reveal that the test pieces of Examples 1 to 11, to which the phosphonium salts of the respective production examples were added, had low volume resistivity and surface resistivity, with no significant changes observed. On the other hand, the test pieces of Comparative Examples 1 to 3, to which no phosphonium salt was added, maintained high volume resistivity and surface resistivity. Furthermore, the test pieces of Comparative Examples 4 and 5, to which an ammonium salt was added, had higher volume resistivity and surface resistivity than the examples to which the same amount of phosphonium salt was added, demonstrating that the phosphonium salts of the present invention have high antistatic properties even in small amounts.

Claims

1. A compound represented by the following general formula (1): 【Chemical 1】 (In the formula, R １ , R ２ and R ３ each independently represents a linear alkyl group having 2 to 4 carbon atoms; R ４ represents a group represented by the following general formula (2), and A represents bis(fluorosulfonyl)imide or bis(trifluoromethanesulfonyl)imide. 【Chemistry 2】 (In the formula, R ５ represents a linear perfluoroalkyl group having 4 to 8 carbon atoms.

2. An antistatic agent comprising the compound according to claim 1 as an active ingredient.

3. A resin composition comprising the antistatic agent according to claim 2 and a resin.

4. 4. The resin composition according to claim 3, wherein the resin is a fluorine-containing resin.

Images