Fluorine-containing ammonium salt, aqueous composition using same, and surface modifier

Abstract

To provide an aqueous composition, which exhibits excellent functions such as detachability, water and oil repellency, and the like, by using a fluorine-containing ammonium salt constituted of a perfluoroalkyl group having 6 or less carbon atoms which is considered to have low accumulation property.SOLUTION: Provided are a fluorine-containing ammonium salt represented by the following general formula (1) and an aqueous composition comprising the same: Rf1-CH=CH-Rf2-(CH2)n-X (1). {In formula (1), Rf1 is a C1-6 perfluoroalkyl group; Rf2 is a C1-6 perfluoroalkylene group; n is an integer of 1-4; and X is represented by the following general formula (2) or the following general formula (3): -P(=O)(OM1)(OM2) (2) and -O-P(=O)(OM1)(OM2) (3) (M1 and M2 are each independently a hydrogen atom or a water-soluble organic ammonium, where M1 and M2 are not hydrogen atoms at the same time)}.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel fluorine-containing ammonium salt, and an aqueous composition and a surface modifier each using the same. [Background technology]

[0002] Fluorine-containing compounds have unique properties based on the properties of the carbon-fluorine bond, such as heat resistance, chemical resistance, water and oil repellency, low friction, and release properties, and are used as functional materials. In particular, fluorine-containing ammonium salts obtained by neutralizing phosphoric or phosphonic acids having perfluoroalkyl groups with amines are used as active ingredients in surface modifiers, for example, as release agents required for molding polymeric materials in a mold, and as water and oil repellents for treating the surfaces of paper, textiles, leather, etc.

[0003] Up to now, compounds having a perfluoroalkyl group with 8 or more carbon atoms have been used as highly functional surface modifiers containing fluorine-containing ammonium salts (see, for example, Patent Document 1). However, compounds having a perfluoroalkyl group with 8 or more carbon atoms have problems such as their tendency to accumulate in the environment and living organisms. For this reason, studies are being conducted to replace them with fluorine-containing compounds having a perfluoroalkyl group with six or fewer carbon atoms, which are considered to have low bioaccumulation potential. However, it is known that the smaller the carbon number of the perfluoroalkyl group, the poorer the release performance becomes compared to compounds having a perfluoroalkyl group with eight or more carbon atoms.

[0004] Patent Document 2 discloses a fluorine-containing compound that is composed of a perfluoroalkyl group having 6 or less carbon atoms and exhibits high surface modification performance, and a surface modifier using the same, but there is no description regarding the uniformity or storage stability of the aqueous solution. As a surface modifier, an aqueous composition containing water as the main solvent is preferably used from the viewpoint of safety and ease of handling, but the longer the carbon number of the perfluoroalkyl group in the fluorine-containing ammonium salt, the lower the water solubility, which causes problems in the uniformity and storage stability of the aqueous composition, and therefore further improvements have been required. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2-45572 [Patent Document 2] International Publication No. 2017 / 119371 Summary of the Invention [Problem to be solved by the invention]

[0006] The object of the present invention is to provide a novel fluorine-containing ammonium salt which is composed of a perfluoroalkyl group having 6 or less carbon atoms and has excellent water solubility and which is considered to have low bioaccumulation potential, as well as an aqueous composition and a surface modifier which each use the same. [Means for solving the problem]

[0007] The present inventors have discovered that ammonium salts obtained by neutralizing a fluorine-containing phosphate compound or a fluorine-containing phosphonic acid compound, which is composed of perfluoroalkyl groups having 6 or less carbon atoms and has an unsaturated bond in the molecule, as shown below, with an appropriate water-soluble organic amine, exhibit high water solubility, and that aqueous compositions using such salts exhibit high surface modification performance, which has led to the completion of the present invention.

[0008] That is, the present invention relates to the following. [1] A fluorine-containing ammonium salt represented by the following general formula (1): Rf 1 -CH=CH-Rf 2 -(CH2) n -X (1) {In formula (1), Rf 1 is a perfluoroalkyl group having 1 to 6 carbon atoms, Rf 2 is a perfluoroalkylene group having 1 to 6 carbon atoms, n is an integer from 1 to 4, X is represented by the following general formula (2) or the following general formula (3): -P(=O)(OM 1 )(OM 2 ) (2) -OP(=O)(OM 1 )(OM 2 ) (3) (M 1 and M 2 are each independently a hydrogen atom or a water-soluble organic ammonium; M 1 and M 2 is not a hydrogen atom at the same time) [2] In the general formula (1), Rf 1 is a linear perfluoroalkyl group having 4 to 6 carbon atoms, and Rf 2 The fluorine-containing ammonium salt according to [1], wherein [3] The fluorine-containing ammonium salt according to [1] or [2], wherein the water-soluble organic ammonium is an ammonium derived by protonation of a water-soluble organic amine. [4] The fluorine-containing ammonium salt according to any one of [1] to [3], wherein the water-soluble organic ammonium is an ammonium derived by protonation of a water-soluble organic amine having at least one oxygen atom. [5] The fluorine-containing ammonium salt according to claim 1 or claim 2, wherein the water-soluble organic ammonium is a quaternary ammonium. [6] An aqueous composition comprising the fluorine-containing ammonium salt according to any one of [1] to [5] and water as a solvent. [7] The aqueous composition described in [6], characterized in that the water content in the solvent is 50% by weight or more. [8] The aqueous composition described in [6], characterized in that the water content in the solvent is 90% by weight or more. [9] A surface modifier comprising the aqueous composition according to any one of [6] to [7].

[0009] The present invention will be described in detail below. In the above general formula (1), Rf1 The group is preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a linear perfluoroalkyl group. 1 The group structure may have a branched structure, but a linear perfluoroalkyl group is likely to form an aggregate and a monomolecular film on the surface of the substrate. In the above general formula (1), Rf 2 The Rf group is preferably a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms, more preferably a linear perfluoroalkylene group. 2 The group structure may have a branched structure, but a linear perfluoroalkylene group is likely to form an aggregate and a monomolecular film on the surface of a substrate. Among them, Rf 1 is a linear perfluoroalkyl group having 4 to 6 carbon atoms, and Rf 2 is preferably a linear perfluoroalkylene group having 4 to 6 carbon atoms.

[0010] In the above general formula (1), Rf 1 -CH=CH-Rf 2 Specific structures of the - portion include C2F5-CH=CH-C4F8-, C2F5-CH=CH-C6F 12 -, C4F9-CH=CH-C4F8-, C4F9-CH=CH-C6F 12 , C6F 13 -CH=CH-C4F8-, C6F 13 -CH=CH-CF 12 - and the like, but are not limited to these.

[0011] In general formula (1), n ​​is an integer of 1 to 4. Of these, n is preferably an integer of 2 to 4, and more preferably 2 or 3, from the viewpoint of ease of production.

[0012] In the general formula (1), M 1 and M 2 are each independently a hydrogen atom or a water-soluble organic ammonium; M 1 and M 2is not a hydrogen atom at the same time. Here, the water-soluble organic ammonium is an ammonium or quaternary ammonium derived by protonation of a water-soluble organic amine. Among them, it is preferable that the water-soluble organic ammonium is an ammonium or quaternary ammonium derived by protonation of a water-soluble organic amine having at least one oxygen atom. Specific examples of water-soluble organic amines having at least one oxygen atom include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dimethyl-2,3-dihydroxypropylamine, diglycolamine, morpholine, and N-methylmorpholine. Specific examples of the quaternary ammonium include benzyltrimethylammonium, benzyltriethylammonium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, etc. Among them, benzyltrimethylammonium, tetramethylammonium, tetraethylammonium, etc. are preferred from the viewpoints of availability and water solubility. In the general formula (1), M 1 and M 2 may be the same or different, but are not hydrogen atoms. 1 or M 2 One of the groups is a hydrogen atom and the other is a water-soluble organic ammonium, or M 1 and M 2 are preferably the same water-soluble organic ammonium salt.

[0013] The fluorine-containing ammonium salt represented by the general formula (1) of the present invention can be produced from a terminally iodized fluoroalkyl compound represented by the following general formula (4) as a starting material. The terminally iodized fluoroalkyl compound (4) is a known compound and is described in Patent Document 2 (WO 2017 / 119371). Rf 1 -CH=CH-Rf 2 -I (4)

[0014] In the fluorine-containing ammonium salt represented by the general formula (1) of the present invention, the fluorine-containing ammonium phosphonate in which X is represented by the general formula (2) can be obtained by the method exemplified below. That is, the fluoroalkyl ethylene iodide obtained by adding the fluoroalkyl compound (4) having iodized terminals to ethylene is reacted with trialkyl phosphite P(OR)3, and then the fluorine-containing phosphonic acid (5) obtained by hydrolysis is neutralized with a water-soluble organic amine to obtain the product. Alternatively, a terminally iodized fluoroalkyl compound (4) can be added to a phosphonic acid diester having a vinyl group, a 2-propenyl group or a 3-butenyl group by a known method, followed by reductive elimination of the iodine, and then hydrolysis of the ester to give a fluorine-containing phosphonic acid (5), which can be neutralized with a water-soluble organic amine or a quaternary ammonium hydroxide. Rf 1 -CH=CH-Rf 2 -(CH2) n -P(=O)(OH)2(5)

[0015] In the fluorine-containing ammonium salt represented by general formula (1) of the present invention, the fluorine-containing ammonium phosphate in which X is represented by general formula (3) can be produced using the fluorine-containing phosphate compound described in Patent Document 2 as a raw material. That is, it can be obtained by neutralizing a fluorine-containing phosphate compound represented by the following formula (6) with a water-soluble organic amine or a quaternary ammonium hydroxide. Rf 1 -CH=CH-Rf 2 -(CH2) n -OP(=O)(OH)2(6)

[0016] The water-soluble organic amine used in the production of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention is preferably a water-soluble organic amine having at least one oxygen atom, specifically, for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dimethyl-2,3-dihydroxypropylamine, morpholine, N-methylmorpholine, etc. The amount of the water-soluble organic amine used in the production of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention is preferably 0.1 to 5 equivalents, more preferably 0.5 to 4 equivalents, and particularly preferably 1 to 3 equivalents, relative to the fluorine-containing phosphonic acid compound or fluorine-containing phosphate compound used in the neutralization reaction. Specific examples of the quaternary ammonium hydroxide used in the production of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention include benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, etc. Among these, benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide are preferred from the viewpoints of availability and water solubility. The amount of the quaternary ammonium hydroxide used in the production of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention is preferably 0.1 to 5 equivalents, more preferably 0.5 to 4 equivalents, and particularly preferably 1 to 3 equivalents, relative to the fluorine-containing phosphonic acid compound or fluorine-containing phosphate compound used in the neutralization reaction. In the production of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention, the fluorine-containing phosphonic acid compound, the fluorine-containing phosphate compound, the water-soluble organic amine and the quaternary ammonium hydroxide may each be used alone or in combination of two or more kinds.

[0017] In the production of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention, the solvent applicable to the neutralization reaction may be any solvent that is inert to the reaction, such as hydrocarbon solvents or halogenated hydrocarbon solvents, such as hexane, heptane, toluene, dichloromethane, chloroform, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers, such as tetrahydrofuran, diethyl ether, diisopropyl ether, esters, such as methyl acetate, ethyl acetate, butyl acetate, acetonitrile, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, polar aprotic solvents, water, etc. Among them, acetone, tetrahydrofuran, N-methyl-2-pyrrolidone, and water are preferred. These solvents may be used alone or in combination of two or more. The solvent to be used can be appropriately selected depending on the compound to be subjected to the reaction, and if the compound to be subjected to the reaction is liquid, a solvent may not be used.

[0018] The purification method of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention can be carried out by a known method, for example, purification by solvent extraction, decantation, drying, filtration, concentration, recrystallization, etc., can be performed to obtain the target fluorine-containing ammonium salt represented by the general formula (1).

[0019] The fluorine-containing ammonium salt represented by the general formula (1) of the present invention is useful in that it has high solubility in a solvent containing water, shows high uniformity when dissolved in a solvent containing water, does not produce aggregates or precipitates during storage, and can be diluted with water at any ratio. 1 , Rf 2 The larger the carbon number of the fluorine-containing ammonium salt, the lower the water solubility. However, the fluorine-containing ammonium salt of the present invention is useful in that it retains high water solubility.

[0020] The fluorine-containing ammonium salt of the present invention represented by the general formula (1) can be dissolved in water or a mixed solvent such as water and an organic solvent, and can be used as a surface modifier consisting of an aqueous composition containing the fluorine-containing ammonium salt and a solvent. The fluorine-containing ammonium salt may be used alone, or a plurality of fluorine-containing ammonium salts may be mixed in any ratio. Here, the fluorine-containing ammonium salt in the aqueous composition may be solid, and can be dissolved in a solvent containing water to form a solution-like composition that can be applied to a substrate.

[0021] The aqueous composition of the present invention containing the fluorine-containing ammonium salt represented by general formula (1) and water as a solvent may be prepared by mixing the fluorine-containing phosphonic acid compound represented by general formula (6) or the fluorine-containing phosphate compound represented by general formula (7) and a water-soluble organic amine in water or a mixed solvent of water and an organic solvent, etc. The fluorine-containing phosphonic acid compound, the fluorine-containing phosphate compound and the water-soluble organic amine may each be used alone or in a mixture of two or more kinds.

[0022] In a surface modifier comprising an aqueous composition containing the fluorine-containing ammonium salt of the present invention and water as a solvent, the concentration of the fluorine-containing ammonium salt as a solid content, i.e., the solid content concentration, is preferably 0.01% by weight to 10% by weight, more preferably 0.05% by weight to 5% by weight. In the surface modifier comprising an aqueous composition containing the fluorine-containing ammonium salt of the present invention and water as a solvent, any organic solvent that is miscible with water can be used as the organic solvent in the mixed solvent, including alcohols such as methanol, ethanol, isopropyl alcohol, etc., ketones such as acetone, etc., ethers such as tetrahydrofuran, acetonitrile, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, etc.

[0023] In the surface modifier of the present invention, which is an aqueous composition containing a fluorine-containing ammonium salt and water as a solvent, the water content in the solvent is preferably 50% by weight or more, more preferably 90% by weight or more, and even more preferably 90% by weight or more and 99.99% by weight or less. The greater the water content in the solvent, the more the toxicity, flammability, etc. caused by the organic solvent are reduced, making it more useful from the viewpoint of safety.

[0024] The aqueous composition containing the fluorine-containing ammonium salt represented by the general formula (1) of the present invention and the above-mentioned solvent may be prepared by diluting the fluorine-containing ammonium salt represented by the general formula (1) with a solvent, or by mixing the fluorine-containing phosphonic acid represented by the general formula (5) or the fluorine-containing phosphoric acid compound represented by the general formula (6) with a water-soluble organic amine or a quaternary ammonium hydroxide in a solvent.

[0025] An aqueous composition containing the fluorine-containing ammonium salt of the present invention represented by the general formula (1) and the above-mentioned solvent is advantageous in that, for example, when the fluorine-containing ammonium salt is solid, it can be easily applied to a substrate in the form of a solution.

[0026] An aqueous composition containing the fluorine-containing ammonium salt of the present invention and water as a solvent can be used as a surface modifier such as a water and oil repellent, a rust inhibitor, an antifouling agent, a water resistance agent, a stripping agent, a mold releasing agent, an oil barrier agent, or an agent for preventing flux creeping up.

[0027] Substrates to be treated with the surface modifier of the present invention are not particularly limited, and examples thereof include metals, fibers, leather, cloth products, paper, etc. Among them, the fluorine-containing ammonium salt, which is an active ingredient, exhibits chemical adsorption to metal oxides, and therefore exhibits high durability as a surface modifier when treating metal substrates.

[0028] The treatment of a substrate with the surface modifier of the present invention can be carried out by any commonly used method, such as brush application, application with a wipe or rag, immersion, spraying with a mister, spraying with a spray gun, or aerosol spraying.

[0029] In addition, although there is no particular limitation on the use, when the surface modifier according to the present invention is used as a mold release agent, it can be used as an internal mold release agent added to a molding resin, or as an external mold release agent applied to a molding die, but it is preferable to use it as an external mold release agent applied to a molding die. Molded products molded in a mold are not particularly limited, and include, for example, resins such as polyurethane, epoxy resin, phenolic resin, unsaturated polyester resin, polyimide, ABS resin, acrylic resin, fluororesin, polycarbonate, and polyester, and rubbers such as chloroprene rubber and fluororubber. Effect of the Invention

[0030] By using the fluorine-containing ammonium salt represented by the general formula (1) of the present invention, an aqueous composition with excellent uniformity can be prepared using an active ingredient composed of a perfluoroalkyl group having 6 or less carbon atoms, which is considered to have low bioaccumulation properties, and a surface modifier with high surface modification performance can be provided. EXAMPLES

[0031] Examples of the present invention are shown below, but the present invention is not limited to these examples. The following instruments were used for the analysis: 1 H-NMR, 19 F-NMR: Bruker AVANCE II 400

[0032] Reference example 1 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid (3) 1-1) Synthesis of 1-iodo-3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecene (1) [ka] 1,1,2,2,3,3,4,4,5,5,6,6,9,9,10,10,11,11,12,12,13,13,14,14,14-pentacosafluoro-1-iodo-7-tetradecene 100.00g (0.130mol) and di-tert-butyl peroxide 0.13g (0.003mol) were charged into a 150ml SUS autoclave, sealed, and the inside was replaced with nitrogen. The temperature was then raised to 115°C, and 2.00g (0.142mol) of ethylene was added while maintaining the pressure at 0.5-1.0MPa. After further reacting at 115°C for 1 hour, the mixture was cooled to obtain 103.50g of compound (1). The yield was 99.9%. 1 H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) δ(ppm): 6.48(m, 2H, CF 13 CH=CH C6F 12 ),3.17(m,2H, CH 2I), 2.65(m, 2H, CH 2CF2) 19 F-NMR (solvent: deuterated chloroform, internal standard: trifluoromethylbenzene) δ(ppm): -81.41(t,3F,CF3), -114.39(m,4F, CF 2CH), -115.50(m,2F, CF 2CH2),-122.08(m,6F,CF2CF2CF2), -123.33(m,2F,CF2),-123.89(m,6F,CF2CF2CF2),-126.69(m,2F,CF2)

[0033] 1-2) Synthesis of diethyl 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecen-1-ylphosphonate (2) [ka] 10.00 g (12.50 mmol) of compound (1) and 31.15 g (187.5 mmol) of triethyl phosphite were charged into a 100 mL three-neck flask and reacted at 150° C. for 20 hours. The reaction solution was diluted with 50 g of diisopropyl ether and washed three times with 30 g of water. The organic layer was concentrated under reduced pressure and then recrystallized with heptane to obtain 7.61 g of compound (2). The yield was 75.1%.

[0034] The analysis results were as follows: 1 H-NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) δ(ppm): 6.48(m, 2H, CF 13 CH=CH C6F 12 ), 4.13(m,4H, CH 2CH3), 2.41(m, 2H, CH 2CF2), 1.99(m, 2H, CH 2P), 1.33(m, 6H, CH2 CH 3) 19 F-NMR (solvent: deuterated chloroform, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,3F,CF3), -114.36(m,4F, CF 2CH), -115.76(m,2F, CF 2CH2),-122.05(m,6F,CF2CF2CF2), -123.30(m,2F,CF2),-123.83(m,6F,CF2CF2CF2),-126.64(m,2F,CF2)

[0035] 1-3) Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid (3) [ka] In a 100 ml recovery flask equipped with a reflux condenser, 5.00 g (6.17 mmol) of compound (2) and 20 g of 35% hydrochloric acid were charged and reacted at 100° C. for 48 hours. After cooling to room temperature, the mixture was filtered by suction and washed with water to obtain 4.56 g of compound (3) as a white solid. The yield was 98.0%.

[0036] The analysis results were as follows: 1 H-NMR (solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm)::6.93(m,2H,CF 13 CH=CH C6F 12 ), 3.31(m,2H, CH 2CF2), 1.95(m, 2H, CH 2P) 19 F-NMR (solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.41(t,3F,CF3), -113.85(m,4F, CF 2CH), -115.50(m,2F, CF 2CH2),-121.57(m,6F,CF2CF2CF2), -122.93(m,2F,CF2),-123.46(m,6F,CF2CF2CF2),-126.40(m,2F,CF2)

[0037] Example 1 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid monoethanolammonium salt (4) [ka] 85 mg of monoethanolamine (FUJIFILM Wako Pure Chemical Industries, Ltd., 1.39 mmol) and 20 g of tetrahydrofuran (Kishida Chemical Industries, Ltd.) were charged into a 50 mL recovery flask, and 1.00 g (1.33 mmol) of compound (3) was added with stirring. After stirring for 30 minutes at room temperature, the supernatant was removed by decantation, and the resulting precipitate was concentrated under reduced pressure of 0.1 kPa or less to obtain 1.01 g of fluorine-containing ammonium salt (4) as a white solid.

[0038] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.93(m, 2H, CF 13 CH=CH C6F 12 ), 3.75(t, J=5.2Hz, 2H, NH3CH2 CH 2OH), 3.01(t, J=5.2Hz, 2H, NH3 CH 2CH2OH), 2.46(m,2H, CH 2CF2), 1.80(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=10.2Hz,3F,CF3), -113.77(m,4F, CF 2CH),-115.40(m,2F, CF 2CH2),-121.56(m,4F,CF2CF2),-121.85(m,2F,CF2),-122.91(m,2F,CF2),-123.48(m,6F,CF2CF2CF2),-126.30(m,2F,CF2)

[0039] Example 2 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid diethanolammonium salt (5) [ka] The same procedure as in Example 1 was carried out except that 146 mg of diethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.01 g of a fluorine-containing ammonium salt (5) as a white solid.

[0040] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.92(m, 2H, CF 13 CH=CH C6F 12 ), 3.83(t, J=5.6Hz, 4H, NH2CH2 CH 2OH), 3.14(t, J=5.2Hz, 4H, NH2 CH 2CH2OH), 2.48(m,2H, CH 2CF2), 1.82(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=10.2Hz,3F,CF3), -113.77(m,4F, CF 2CH),-115.41(m,2F, CF 2CH2),-121.56(m,4F,CF2CF2),-121.85(m,2F,CF2),-122.91(m,2F,CF2),-123.52(m,6F,CF2CF2CF2),-126.30(m,2F,CF2)

[0041] Example 3 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid triethanolammonium salt (6) [ka] The same procedure as in Example 1 was carried out except that 208 mg of triethanolamine (Sigma-Aldrich, 1.39 mmol) was used instead of monoethanolamine, to obtain 1.02 g of a fluorine-containing ammonium salt (6) as a white solid.

[0042] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.91(m, 2H, CF 13 CH=CH C6F 12 ), 3.87(t, J=5.2Hz, 6H, NHCH2 CH 2OH), 3.34(t, J=5.2Hz, 6H, NH CH 2CH2OH), 2.46(m,2H, CH 2CF2), 1.77(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=11.3Hz,3F,CF3), -113.78(m,4F, CF 2CH),-115.42(m,2F, CF 2CH2),-121.56(m,4F,CF2CF2),-122.92(m,2F,CF2),-123.44(m,2F,CF2),-123.53(m,6F,CF2CF2CF2),-126.36(m,2F,CF2)

[0043] Example 4 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid isopropanol ammonium salt (7) [ka] The same procedure as in Example 1 was carried out except that 105 mg of isopropanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.01 g of a fluorine-containing ammonium salt (7) as a white solid.

[0044] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.92(m, 2H, CF 13 CH=CH C6F 12 ), 3.96(m,1H,NH3CH2 CH OH),2.96(dd,J=12.8Hz,3.2Hz,1H,NH3 CH 2CHOH),2.74(dd,J=12.8Hz,9.2Hz,1H,NH3 CH 2CHOH), 2.47(m, 2H, CH 2CF2), 1.81(m, 2H, CH 2P), 1.23(d, J=6.4Hz, 3H, CH3) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.40(t,J=9.8Hz,3F,CF3), -113.80(m,4F, CF 2CH),-115.41(m,2F, CF 2CH2),-121.58(m,4F,CF2CF2),-121.86(m,2F,CF2),-122.93(m,2F,CF2),-123.49(m,6F,CF2CF2CF2),-126.32(m,2F,CF2)

[0045] Example 5 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid diisopropanol ammonium salt (8) [ka] The same procedure as in Example 1 was carried out except that 185 mg of diisopropanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.02 g of a fluorine-containing ammonium salt (8) as a white solid.

[0046] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.93(m, 2H, CF 13 CH=CH C6F 12 ), 4.06(m,2H,NH2CH2 CH OH), 3.08(m, 2H, NH2 CH 2CHOH), 2.88(m,2H,NH2 CH 2CHOH), 2.47(m, 2H, CH 2CF2), 1.77(m, 2H, CH 2P),1.24(dd,J=6.0Hz,1.2Hz,6H,CH3) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=10.4Hz,3F,CF3), -113.78(m,4F, CF 2CH),-115.43(m,2F, CF 2CH2),-121.57(m,4F,CF2CF2),-121.87(m,2F,CF2),-122.92(m,2F,CF2),-123.49(m,6F,CF2CF2CF2),-126.31(m,2F,CF2)

[0047] Example 6 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid triisopropanol ammonium salt (9) [ka] The same procedure as in Example 1 was carried out except that 266 mg of triisopropanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.02 g of a fluorine-containing ammonium salt (9) as a white solid.

[0048] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.92(m, 2H, CF 13 CH=CH C6F 12 ), 4.15(m,3H,NHCH2 CH OH), 3.25(m, 3H, NH2 CH 2CHOH), 3.13(m, 3H, NH CH 2CHOH), 2.48(m, 2H, CH 2CF2), 1.78(m, 2H, CH 2P), 1.25(m,9H,CH3) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=9.8Hz,3F,CF3), -113.77(m,4F, CF 2CH),-115.41(m,2F, CF 2CH2),-121.56(m,4F,CF2CF2),-121.85(m,2F,CF2),-122.92(m,2F,CF2),-123.48(m,6F,CF2CF2CF2),-126.30(m,2F,CF2)

[0049] Example 7 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid N-methylethanolammonium salt (10) [ka] The same procedure as in Example 1 was carried out except that 105 mg of N-methylethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.01 g of a fluorine-containing ammonium salt (10) as a white solid.

[0050] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.93(m, 2H, CF 13 CH=CH C6F 12 ), 3.80(t, J=5.2Hz, 2H, NH2CH2 CH 2OH), 3.09(t, J=5.2Hz, 2H, NH2 CH 2CH2OH),2.71(s,3H,CH3),2.48(m,2H, CH 2CF2), 1.81(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=10.2Hz,3F,CF3), -113.77(m,4F, CF 2CH),-115.40(m,2F, CF 2CH2),-121.55(m,4F,CF2CF2),-121.85(m,2F,CF2),-122.91(m,2F,CF2),-123.49(m,6F,CF2CF2CF2),-126.29(m,2F,CF2)

[0051] Example 8 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid diglycol ammonium salt (11) [ka] The same procedure as in Example 1 was carried out except that 146 mg of diglycolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.01 g of a fluorine-containing ammonium salt (11) as a white solid.

[0052] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.92(m, 2H, CF 13 CH=CH C6F 12 ), 3.71(m,4H,NH3CH2 CH 2 OCH 2CH2OH),3.61(t,J=5.2Hz,2H,OCH2 CH 2OH), 3.12(t, J=5.2Hz, 2H, NH3 CH 2CH2O), 2.48(m, 2H, CH 2CF2), 1.82(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.38(t,J=9.8Hz,3F,CF3), -113.74(m,4F, CF 2CH),-115.37(m,2F, CF 2CH2),-121.53(m,4F,CF2CF2),-121.83(m,2F,CF2),-122.89(m,2F,CF2),-123.46(m,6F,CF2CF2CF2),-126.27(m,2F,CF2)

[0053] Example 9 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid morpholine salt (12) [ka] The same procedure as in Example 1 was carried out except that 121 mg of morpholine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.01 g of a fluorine-containing ammonium salt (12) as a white solid.

[0054] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.94(m, 2H, CF 13 CH=CH C6F 12 ),3.89(m,4H, CH 2O CH 2), 3.21(m, 4H, CH 2NH2 CH 2), 2.48(m, 2H, CH 2CF2), 1.82(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=10.2Hz,3F,CF3), -113.78(m,4F, CF 2CH),-115.37(m,2F, CF 2CH2),-121.53(m,4F,CF2CF2),-121.82(m,2F,CF2),-122.89(m,2F,CF2),-123.50(m,6F,CF2CF2CF2),-126.27(m,2F,CF2)

[0055] Example 10 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid bis(triethanolammonium) salt (13) [ka] The same procedure as in Example 3 was carried out except that the amount of triethanolamine was 495 mg (3.31 mmol), to obtain 1.03 g of a fluorine-containing ammonium salt (13) as a white solid.

[0056] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.95(m, 2H, CF 13 CH=CH C6F 12 ), 3.85(t, J=5.2Hz, 12H, NHCH2 CH 2OH), 3.31(t, J=5.2Hz, 12H, NH CH 2CH2OH), 2.43(m,2H, CH 2CF2), 1.76(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.39(t,J=11.8Hz,3F,CF3), -113.68(m,4F, CF 2CH),-115.35(m,2F, CF 2CH2),-121.59(m,4F,CF2CF2),-122.89(m,2F,CF2),-123.45(m,2F,CF2),-123.61(m,6F,CF2CF2CF2),-126.35(m,2F,CF2)

[0057] Example 11 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid 4-methylmorpholine salt (14) [ka] The same procedure as in Example 1 was carried out except that 141 mg of 4-methylmorpholine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.01 g of a fluorine-containing ammonium salt (12) as a white solid.

[0058] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.82(m, 2H, CF 13 CH=CH C6F 12 ),3.96(m,4H, CH 2O CH 2), 3.38(m, 2H, CH 2NHCH3), 3.10(m, 2H, CH 2NHCH3), 2.86(m,3H,CH2NH CH 3), 2.49(m,2H, CH 2CF2), 1.86(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.46(t,J=9.8Hz,3F,CF3), -113.95(m,4F, CF 2CH),-115.50(m,2F, CF 2CH2),-121.54(m,4F,CF2CF2),-121.86(m,2F,CF2),-122.97(m,2F,CF2),-123.50(m,6F,CF2CF2CF2),-126.42(m,2F,CF2)

[0059] Example 12 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid benzyltrimethylammonium salt (15) [ka] The same procedure as in Example 1 was carried out except that 582 mg of a 40% benzyltrimethylammonium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.33 g of a fluorine-containing ammonium salt (15) as a white solid.

[0060] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 7.63-7.55(m, 5H, C 6 H 5), 6.87(m,2H,C6F 13 CH=CH C6F 12 ),4.58(s,2H, CH 2N(CH3)3), 3.15(s, 9H, CH2N (CH 3 ) 3), 2.47(m,2H, CH 2CF2), 1.76(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.48(t,J=8.3Hz,3F,CF3), -114.00(m,4F, CF 2CH),-115.40(m,2F, CF 2CH2),121.69(m,4F,CF2CF2),121.89(m,2F,CF2),-123.02(m,2F,CF2),-123.61(m,6F,CF2CF2CF2),-126.46(m,2F,CF2)

[0061] Example 13 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid benzyltrimethylammonium salt (16) [ka] The same procedure as in Example 1 was carried out except that 1.55 g of a 15% tetramethylammonium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.25 g of a fluorine-containing ammonium salt (16) as a white solid.

[0062] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.86(m, 2H, CF 13 CH=CH C6F 12 ),3.23(m,12H,N(CH3)4),2.59(m,2H, CH 2CF2), 1.72(m, 2H, CH 2P) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.46(t,J=9.8Hz,3F,CF3), -113.89(m,4F, CF 2CH),-115.10(m,2F, CF 2CH2),-121.56(m,4F,CF2CF2),-121.84(m,2F,CF2),-122.98(m,2F,CF2),-123.51(m,6F,CF2CF2CF2),-126.44(m,2F,CF2)

[0063] Example 14 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid benzyltrimethylammonium salt (17) [ka] The same procedure as in Example 1 was carried out except that 1.16 g of a 20% tetraethylammonium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.21 g of a fluorine-containing ammonium salt (17) as a white solid.

[0064] The analysis results were as follows: 1 H-NMR (400MHz, solvent: methanol-d4, internal standard: tetramethylsilane) δ(ppm): 6.85(m, 2H, CF 13 CH=CH C6F 12 ), 3.31(q, J=7.2Hz, 8H, N( CH 2CH3)4),2.48(m,2H, CH 2CF2), 1.81(m, 2H, CH 2P),1.30(tt,J=7.2Hz,2.0Hz,12H,N(CH2 CH 3)4) 19 F-NMR (376MHz, solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ(ppm): -81.48(t,J=9.8Hz,3F,CF3), -113.93(m,4F, CF 2CH),-115.44(m,2F, CF 2CH2),-121.58(m,4F,CF2CF2),-121.89(m,2F,CF2),-123.00(m,2F,CF2),-123.54(m,6F,CF2CF2CF2),-126.45(m,2F,CF2)

[0065] Comparative Example 1 Synthesis of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-Pentacosafluoro-10-heptadecen-1-yl ammonium phosphate (18) [ka] In a 50 ml recovery flask, 20 g of tetrahydrofuran (Kishida Chemical Co., Ltd.), 1.00 g of 4,4,5,5,6,6,7,7,8,8,9,9,12,12,13,13,14,14,15,15,16,16,17,17,17-pentacosafluoro-10-heptadecen-1-yl phosphoric acid (compound (14), 1.28 mmol) synthesized according to the method described in Patent Document 2, and 86 mg (1.40 mmol) of 25 wt % aqueous ammonia were charged, and the mixture was stirred at room temperature for 30 minutes, after which the supernatant was removed by decantation, and the resulting precipitate was concentrated under reduced pressure of 0.1 kPa or less to obtain 1.01 g of a fluorine-containing ammonium salt (18) as a white solid.

[0066] Comparative Example 2 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid sodium salt (19) [ka] The same operation as in Example 1 was carried out except that 56 mg (1.39 mmol) of a 48 wt % aqueous sodium hydroxide solution was used instead of monoethanolamine, to obtain 1.01 g of a fluorine-containing sodium salt (19) as a white solid.

[0067] Comparative Example 3 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid ammonium salt (20) [ka] The same procedure as in Example 1 was carried out except that 89 mg of 28 wt % aqueous ammonia solution (Kishida Chemical, 1.46 mmol) was used instead of monoethanolamine, to obtain 1.00 g of a fluorine-containing ammonium salt (20) as a white solid.

[0068] Comparative Example 4 Synthesis of 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-Pentacosafluoro-9-hexadecen-1-ylphosphonic acid triethylammonium salt (21) [ka] The same procedure as in Example 1 was carried out except that 141 mg of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) was used instead of monoethanolamine, to obtain 1.00 g of a fluorine-containing ammonium salt (21) as a colorless wax.

[0069] Example 15 Evaluation of water solubility of fluorine-containing ammonium salts The fluorine-containing ammonium salt (4) obtained in Example 1 and pure water were mixed in a prescribed ratio in a 20 mL screw tube bottle, and the mixture was stirred at room temperature for 30 minutes at a rotation speed of 400 rpm using a magnetic stirrer. The appearance of the mixture was then visually confirmed to evaluate its water solubility, which is shown in Table 1. Water solubility when the fluorine-containing ammonium salt content was 1% by weight and the appearance was a homogeneous solution was indicated by ⊚, water solubility when the fluorine-containing ammonium salt content was in the range of 0.1% by weight or more and less than 1% by weight and the appearance was a homogeneous solution was indicated by ◯, and water solubility when a precipitate was formed when the fluorine-containing ammonium salt content was 0.1% by weight and the content was x. The following examples and comparative examples were also evaluated in the same manner.

[0070] Examples 16 to 28 The water solubility was evaluated in the same manner as in Example 15, except that the fluorine-containing ammonium salts (5) to (17) obtained in Examples 2 to 14 were mixed with pure water in a given ratio. The results are shown in Table 1.

[0071] Comparative Example 5 The water solubility was evaluated in the same manner as in Example 15, except that the compound (3) obtained in Reference Example 1 was mixed with pure water in a predetermined ratio, and the results are shown in Table 1.

[0072] Comparative Example 6 The water solubility was evaluated in the same manner as in Example 11, except that the compound (18) synthesized according to the method described in Patent Document 2 was mixed with pure water in a predetermined ratio. The results are shown in Table 1.

[0073] Comparative Examples 7 to 10 The water solubility was evaluated in the same manner as in Example 11, except that the salts (19) to (22) obtained in Comparative Examples 1 to 4 were mixed with pure water in a given ratio. The results are shown in Table 1.

[0074] [Table 1]

[0075] The results in Table 1 show that the fluorine-containing ammonium salts exhibit excellent water solubility in Examples 15 to 28. On the other hand, in Comparative Examples 5 to 10, when the fluorine-containing phosphonic acid compound or the fluorine-containing phosphate compound was used without neutralization, or when the fluorine-containing phosphonic acid compound or the fluorine-containing phosphate compound was used in the form of a metal salt, an inorganic ammonium salt, or an ammonium salt derived by protonation of a water-insoluble organic amine, the water solubility was significantly inferior to that of Examples 15 to 28.

[0076] Example 29 A surface modifier solution was prepared containing 0.1% by weight of the fluorine-containing ammonium salt (4) obtained in Example 1 and 99.9% by weight of pure water. Using this surface modifier solution, the surface modification performance was evaluated by the following measurement method.

[0077] Water and oil repellency evaluation A stainless steel plate (material: SUS304, 30 mm x 15 mm x 2 mm thick, surface 2B polished) was degreased by immersing in a solution consisting of 5% by weight sodium hydroxide, 47.5% by weight pure water, and 47.5% by weight ethanol for 1 hour, and then washed with pure water. The plate was then surface-modified by immersing in 10 mL of a surface modifier solution in a 50 mL sample bottle at room temperature for 1 hour. The surface-modified stainless steel plate was then washed with 2-propanol and air-dried. The contact angles of water and hexadecane were then measured using a contact angle meter DMs-401 manufactured by Kyowa Interface Science. The droplet volume was 2 μL in the measurement, and the θ / 2 method was used to analyze the contact angle.

[0078] Examples 30 to 42 In Example 21, a stainless steel sheet was treated in the same manner, except that the fluorine-containing ammonium salt (4) was replaced with the fluorine-containing ammonium salts (5) to (17), respectively, and the water and oil repellency were evaluated in the same manner. The results are shown in Table 2.

[0079] Example 43 100 g of pure water and 21 mg of triethanolamine (Sigma-Aldrich) were charged into a 200 mL recovery flask, and 100 mg of compound (3) was added with stirring. The mixture was stirred at room temperature for 30 minutes, and the resulting homogeneous aqueous solution of fluorine-containing ammonium salt (6) was used as a surface modifier. The water and oil repellency was evaluated in the same manner as in Example 21, and the results are shown in Table 2.

[0080] Example 44 100 g of pure water and 12 mg of morpholine were charged into a 200 mL recovery flask, and 100 mg of compound (3) was added with stirring. The mixture was stirred at 80°C for 2 hours and cooled to room temperature to obtain a homogeneous aqueous solution of fluorine-containing ammonium salt (12). The water and oil repellency was evaluated in the same manner as in Example 29, and the results are shown in Table 2.

[0081] Example 45 The same procedure as in Example 44 was repeated except that 42 mg of triethanolamine was used instead of morpholine, and the resulting homogeneous aqueous solution of fluorine-containing ammonium salt (13) was used as a surface modifier, and the water and oil repellency were evaluated in the same manner as in Example 29. The results are shown in Table 2.

[0082] Example 46 The same procedure as in Example 44 was repeated except that 14 mg of 4-methylmorpholine was used instead of morpholine, and the resulting homogeneous aqueous solution of fluorine-containing ammonium salt (14) was used as a surface modifier, and the water and oil repellency were evaluated in the same manner as in Example 29. The results are shown in Table 2.

[0083] Comparative Example 11 In Example 21, the same measurements were carried out on a stainless steel plate without surface modification, and the results are shown in Table 2.

[0084] [Table 2]

[0085] The results in Table 2 show that the surface modifier comprising the fluorine-containing ammonium salt aqueous composition of the present invention imparts excellent water and oil repellency to a substrate, and is therefore useful as a surface modifier for water and oil repellents, rust inhibitors, antifouling agents, water resistance agents, stripping agents, mold release agents, oil barrier agents, flux creep-up inhibitors, and the like. [Industrial Applicability]

[0086] The fluorine-containing ammonium salt of the present invention and the aqueous composition using the same can be used as a surface modifier exhibiting excellent water and oil repellency, etc., by using an active ingredient composed of a perfluoroalkyl group having 6 or less carbon atoms, which is considered to have low accumulation in the environment and living organisms.

Claims

1. A fluorine-containing ammonium salt represented by the following general formula (1): Rf １ -CH=CH-Rf ２ -(CH ２ ) ｎ -X (1) {In formula (1), Rf １ is a perfluoroalkyl group having 1 to 6 carbon atoms, Rf ２ is a perfluoroalkylene group having 1 to 6 carbon atoms, n is an integer from 1 to 4, X is represented by the following general formula (2) or the following general formula (3): -P(=O)(OM) １ )(OM ２ ) (2) -O-P(=O)(OM １ )(OM ２ ) (3) (M １ and M. ２ are each independently a hydrogen atom or an ammonium derived by protonation of a water-soluble organic amine having at least one oxygen atom; M １ and M. ２ is not a hydrogen atom at the same time)

2. Rf １ is a linear perfluoroalkyl group having 4 to 6 carbon atoms, Rf ２ The fluorine-containing ammonium salt according to claim 1, wherein is a linear perfluoroalkylene group having 4 to 6 carbon atoms.

3. 3. An aqueous composition comprising the fluorine-containing ammonium salt according to claim 1 or 2 and water as a solvent.

4. 4. The aqueous composition according to claim 3, wherein the solvent contains 50% by weight or more of water.

5. 4. The aqueous composition according to claim 3, wherein the solvent contains 90% by weight or more of water.

6. A surface modifier comprising the aqueous composition according to any one of claims 3 to 5.

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