JP7649683B2 - Fluorine-containing ammonium salt, aqueous composition using same, and surface modifier - Google Patents

Description

The present invention relates to a novel fluorine-containing ammonium salt and an aqueous composition and a surface modifier using the same.

Fluorine-containing compounds have unique functions 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.

To date, 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.

Patent Document 2 discloses a fluorine-containing compound composed of perfluoroalkyl groups having 6 or less carbon atoms and exhibiting high surface modification performance, and a surface modifier using the same, but makes no mention of the uniformity or storage stability of the aqueous solution. As a surface modifier, an aqueous composition in which water is 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 with the uniformity and storage stability of the aqueous composition, and further improvements were therefore required.

Special Publication No. 2-45572 International Publication No. 2017/119371

The object of the present invention is to provide a novel fluorine-containing ammonium salt that is composed of a perfluoroalkyl group having 6 or less carbon atoms and has excellent water solubility, and an aqueous composition and a surface modifier that use the same.

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

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 -(CH ₂ ) _n -X (1)
In formula (1),
^Rf1 is a perfluoroalkyl group having 1 to 6 carbon atoms;
^Rf2 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 a water-soluble organic ammonium, and M ¹ and M ² are not both hydrogen atoms.)
[2] The fluorine-containing ammonium salt according to [1], wherein, in the general formula (1), Rf ¹ is a linear perfluoroalkyl group having 4 to 6 carbon atoms, and Rf ² is a linear perfluoroalkylene group having 4 to 6 carbon atoms.
[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 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 according to [6], wherein the solvent has a water content of 50% by weight or more.
[8] The aqueous composition according to [6], wherein the solvent has a water content of 90% by weight or more.
[9] A surface modifier comprising the aqueous composition according to any one of [6] to [7].

The present invention will be described in detail below.
In the above general formula (1), the ^Rf1 group is preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a linear perfluoroalkyl group. ^{The Rf1} group may have a branched structure, but a linear perfluoroalkyl group is likely to form an aggregate and a monomolecular film on the surface of a substrate.
In the above general formula (1), the ^Rf2 group is preferably a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms, more preferably a linear perfluoroalkylene group. ^{The Rf2} group 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 these, it is preferable that Rf ¹ is a linear perfluoroalkyl group having 4 to 6 carbon atoms, and Rf ² is a linear perfluoroalkylene group having 4 to 6 carbon atoms.

Specific structures of the Rf ¹ -CH=CH-Rf ² - portion in the above general formula (1) include, but are not limited to, C ₂ F ₅ -CH=CH-C ₄ F ₈ -, C ₂ F ₅ -CH=CH-C ₆ F ₁₂ -, C ₄ F ₉ -CH=CH-C ₄ F ₈ -, C ₄ F ₉ -CH=CH-C ₆ F ₁₂ , C ₆ F ₁₃ -CH=CH-C 4 F _{8 -} , C ₆ F ₁₃ -CH=CH-C ₆ F ₁₂ -, and the like.

In general formula (1), n is an integer from 1 to 4. From the viewpoint of ease of production, n is preferably 2 to 4, and more preferably 2 or 3.

In general formula (1), ^M1 and ^M2 are each independently a hydrogen atom or a water-soluble organic ammonium, and ^M1 and ^M2 are not simultaneously a hydrogen atom. 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), ^M1 and ^M2 may be the same or different, but are not both hydrogen atoms. From the viewpoint of ease of production, it is preferred that one of ^M1 and ^M2 is a hydrogen atom and the other is a water-soluble organic ammonium, or that ^M1 and ^M2 are the same water-soluble organic ammonium.

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)

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, a fluoroalkyl ethylene iodide obtained by adding a terminally iodized fluoroalkyl compound (4) to ethylene is reacted with a trialkyl phosphite P(OR) ₃ , and then the resulting fluorine-containing phosphonic acid (5) is hydrolyzed and neutralized with a water-soluble organic amine to obtain the compound.
Alternatively, a terminally iodized fluoroalkyl compound (4) is added to a phosphonic acid diester having a vinyl group, a 2-propenyl group or a 3-butenyl group by a known method, and the iodine is reductively eliminated. The ester is then hydrolyzed to give a fluorine-containing phosphonic acid (5), which is then neutralized with a water-soluble organic amine or a quaternary ammonium hydroxide to obtain the fluorine-containing phosphonic acid.
Rf ¹ -CH=CH-Rf ² -(CH ₂ ) _n -P(=O)(OH) ₂ (5)

In the fluorine-containing ammonium salt represented by the general formula (1) of the present invention, the fluorine-containing ammonium phosphate in which X is represented by the 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 -(CH ₂ ) _n -OP(=O)(OH) ₂ (6)

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, 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, 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.

In the production of the fluorine-containing ammonium salt represented by the general formula (1) of the present invention, any solvent that is inert to the reaction can be used as the solvent applicable to the neutralization reaction, such as hydrocarbon solvents or halogenated hydrocarbon solvents, such as hexane, heptane, toluene, dichloromethane, chloroform, etc., ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., ethers, such as tetrahydrofuran, diethyl ether, diisopropyl ether, etc., esters, such as methyl acetate, ethyl acetate, butyl acetate, etc., polar aprotic solvents, such as acetonitrile, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, etc., and water. 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 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.

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

The fluorine-containing ammonium salt of the present invention represented by the general formula (1) 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. Usually, the water solubility decreases as the carbon numbers of Rf ¹ and Rf ² in the general formula (1) increase, but the fluorine-containing ammonium salt of the present invention is useful in that it maintains high water solubility.

The fluorine-containing ammonium salt of the present invention represented by the general formula (1) is 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 multiple fluorine-containing ammonium salts may be mixed in any ratio. Here, the fluorine-containing ammonium salt in the aqueous composition may be in the form of a solid, and can be dissolved in a solvent containing water to form a solution-like composition that can be applied to a substrate.

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) with a water-soluble organic amine in water or a mixed solvent of water and an organic solvent or the like. 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.

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.

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 less toxicity and flammability caused by the organic solvent, making it more useful from the standpoint of safety.

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

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

The 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, rust inhibitor, stain inhibitor, water resistance agent, stripping agent, mold release agent, oil barrier agent, flux creep-up inhibitor, etc.

Substrates that can be treated with the surface modifier of the present invention include, but are not limited to, metals, fibers, leather, cloth products, paper, etc. Among them, the active ingredient, fluorine-containing ammonium salt, exhibits chemical adsorption to metal oxides, and therefore exhibits high durability as a surface modifier when treating metal substrates.

The surface modifier of the present invention can be used to treat a substrate by any commonly used method, such as brushing, applying with a wipe or rag, dipping, spraying with a mister, spraying with a spray gun, or aerosol spraying.

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 the molding resin, or as an external mold release agent applied to the molding die, but it is preferable to use it as an external mold release agent applied to the molding die. Molded products molded in a die include, but are not limited to, resins such as polyurethane, epoxy resin, phenolic resin, unsaturated polyester resin, polyimide, ABS resin, acrylic resin, fluororesin, polycarbonate, polyester, and rubbers such as chloroprene rubber and fluororubber.

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, and a surface modifier with high surface modification performance can be provided.

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: AVANCE II 400 manufactured by Bruker

１５０ｍｌのＳＵＳ製オートクレーブに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-ペンタコサフルオロ-1-ヨード-7-テトラデセン１００．００ｇ（０．１３０ｍｏｌ）及びジターシャリブチルペルオキシド（Di-tert-butyl Peroxide）０．１３ｇ（０．００３ｍｏｌ）を仕込み、密閉後内部を窒素置換した。その後１１５℃に昇温し、エチレン２．００ｇ（０．１４２ｍｏｌ）を０．５～１．０ＭＰａの圧力を保ちながら添加した。さらに１１５℃で１時間反応した後、冷却して化合物（１）１０３．５０ｇを得た。収率は９９．９％であった。
^１Ｈ－ＮＭＲ （溶媒：重クロロホルム、内部標準：テトラメチルシラン） δ（ｐｐｍ）：６．４８（ｍ，２Ｈ，Ｃ_６Ｆ_１３ ＣＨ＝ＣＨＣ_６Ｆ_１２），３．１７（ｍ，２Ｈ，ＣＨ _２ Ｉ），２．６５（ｍ，２Ｈ，ＣＨ _２ ＣＦ_２）
^１９Ｆ－ＮＭＲ （溶媒：重クロロホルム、内部標準：トリフルオロメチルベンゼン） δ（ｐｐｍ）：－８１．４１（ｔ，３Ｆ，ＣＦ_３），－１１４．３９（ｍ，４Ｆ，ＣＦ _２ ＣＨ）， －１１５．５０（ｍ，２Ｆ，ＣＦ _２ ＣＨ_２），－１２２．０８（ｍ，６Ｆ，ＣＦ_２ＣＦ_２ＣＦ_２）， －１２３．３３（ｍ，２Ｆ，ＣＦ_２），－１２３．８９（ｍ，６Ｆ，ＣＦ_２ＣＦ_２ＣＦ_２），－１２６．６９（ｍ，２Ｆ，ＣＦ_２） 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)

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 (0.003mol) were charged into a 150ml SUS autoclave, and the inside was replaced with nitrogen after sealing. The temperature was then raised to 115°C, and 2.00g (0.142mol) of ethylene was added while maintaining the pressure at 0.5 to 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%.
^1H -NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) δ (ppm) _: 6.48 (m, 2H, _C6F13CH = _CHC6F12 ), 3.17 (m _, 2H, _CH2I ), 2.65 (m , _2H , CH2CF2 ₎
^19F -NMR (solvent: deuterated chloroform, internal standard: trifluoromethylbenzene) δ (ppm) _: -81.41 (t, 3F, _CF3 ), -114.39 (m, 4F, _CF2CH ), -115.50 ( m _{, 2F} , CF2CH2 ), -122.08 (m, 6F, CF2CF2CF2), -123.33 (m, _2F , _CF2 ), -123.89 (m, 6F, _{CF2CF2CF2 ) ,} -126.69 (m, 2F, _{CF2 )}

１００ｍＬの３つ口フラスコに化合物（１）１０．００ｇ（１２．５０ｍｍｏｌ）及び亜リン酸トリエチル３１．１５ｇ（１８７．５ｍｍｏｌ）を仕込み、１５０℃で２０時間反応した。反応液をジイソプロピルエーテル５０ｇで希釈し、水３０ｇで３回洗浄した。有機層を減圧濃縮した後、ヘプタンで再結晶して化合物（２）７．６１ｇを取得した。収率は７５．１％であった。 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)

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%.

The analysis results were as follows:
^1H -NMR (solvent: deuterated chloroform, internal standard: tetramethylsilane) δ (ppm) _: 6.48 (m, 2H, _C6F13CH = CHC6F12), 4.13 ( _{m , 4H} , _CH2CH3 ), 2.41 (m, 2H, CH2CF2 _{) ,} 1.99 ₍ m, 2H, CH2P ) _, 1.33 (m, 6H, CH2CH3 ₎
^19F -NMR (solvent: deuterated chloroform, internal standard: trifluoromethylbenzene) δ (ppm) _: -81.39 (t, 3F, _CF3 ), -114.36 (m, 4F, _CF2CH ), -115.76 ( m _{, 2F} , CF2CH2 ), -122.05 (m, 6F, CF2CF2CF2), -123.30 (m, _2F , _CF2 ), -123.83 (m, 6F, _{CF2CF2CF2 ) ,} -126.64 (m, 2F, _{CF2 )}

還流冷却器を備えた１００ｍｌのナスフラスコに化合物（２）５．００ｇ（６．１７ｍｍｏｌ）及び３５％塩酸２０ｇを仕込み、１００℃で４８時間反応した。室温に冷却後吸引ろ過し、水洗して化合物（３）４．５６ｇを白色固体として取得した。収率は９８．０％であった。 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)

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 suction filtered and washed with water to obtain 4.56 g of compound (3) as a white solid. The yield was 98.0%.

The analysis results were as follows:
^1H -NMR (solvent: methanol-d4, internal standard: tetramethylsilane) δ (ppm) _: 6.93 (m, _2H , _C6F13CH = CHC6F12), 3.31 (m, 2H , _{CH2CF2 ) ,} 1.95 (m, 2H, CH2P ₎
^19F -NMR (solvent: methanol-d4, internal standard: trifluoromethylbenzene) δ (ppm): -81.41 (t _, 3F, _CF3 ), -113.85 (m, 4F, CF2CH), -115.50 ( _{m , 2F} , CF2CH2 ), -121.57 (m, 6F, CF2CF2CF2), -122.93 (m, _2F , _CF2 ), -123.46 (m, 6F, _{CF2CF2CF2 ) ,} -126.40 ₍ m, 2F, _CF2 )

５０ｍＬのナスフラスコにモノエタノールアミン８５ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）及びテトラヒドロフラン２０ｇ（キシダ化学製）を仕込み、撹拌しながら化合物（３）１．００ｇ（１．３３ｍｍｏｌ）を加えた。室温下で３０分間撹拌した後、デカンテーションにより上澄みを除去し、得られた沈殿物を０．１ｋＰａ以下で減圧濃縮して含フッ素アンモニウム塩（４）１．０１ｇを白色固体として取得した。 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)

85 mg of monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 1.39 mmol) and 20 g of tetrahydrofuran (manufactured by Kishida Chemical Industries, Ltd.) were charged into a 50 mL recovery flask, and 1.00 g (1.33 mmol) of compound (3) was added thereto with stirring. After stirring at room temperature for 30 minutes, the supernatant was removed by decantation, and the resulting precipitate was concentrated under reduced pressure at 0.1 kPa or less to obtain 1.01 g of fluorine-containing ammonium salt (4) as a white solid.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.93 (m, 2H, _C6F13CH = CHC6F12) _, 3.75 _{( t} , J=5.2Hz, _2H , NH3CH2CH2OH) _, 3.01 (t, _{J=5.2Hz, 2H, NH3CH2CH2OH), 2.46 (m, 2H, CH2CF2 )} , _{1.80 (} m _{, 2H ,} CH2P )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=10.2Hz, 3F, _CF3 ), -113.77 (m, 4F, CF2CH ), -115.40 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてジエタノールアミン１４６ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（５）１．０１ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.92 (m, 2H, _C6F13CH = CHC6F12) _, 3.83 _{( t} , J=5.6Hz, _4H , NH2CH2CH2OH) _, 3.14 (t, _{J=5.2Hz, 4H, NH2CH2CH2OH), 2.48 (m, 2H, CH2CF2 )} , _{1.82 (} m _{, 2H ,} CH2P )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=10.2Hz, 3F, _CF3 ), -113.77 (m, 4F, CF2CH ), -115.41 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてトリエタノールアミン２０８ｍｇ（シグマアルドリッチ製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（６）１．０２ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was carried out except that 208 mg of triethanolamine (manufactured by 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.91 (m, 2H, _C6F13CH = CHC6F12) , 3.87 _{( t , J} =5.2Hz, 6H, NHCH2CH2OH) _, 3.34 (t, J=5.2Hz, _6H , NHCH2CH2OH), 2.46 (m, _2H , CH2CF2 _{) ,} 1.77 ( _m , 2H, CH2P )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=11.3Hz, 3F, _CF3 ), -113.78 (m, 4F, CF2CH ), -115.42 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてイソプロパノールアミン１０５ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（７）１．０１ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.92 ( _m , 2H, _C6F13CH = CHC6F12), 3.96 ( _{m, 1H, NH3CH2CHOH )} , _2.96 (dd, J=12.8Hz, 3.2Hz, 1H, NH3CH2CHOH) _, 2.74 (dd, J=12.8Hz, 9.2Hz, 1H, _NH3CH2CHOH ) , 2.47 ( _{m ,} 2H, CH2CF2 ), 1.81 ( _m , 2H, _CH2P ), 1.23 ( _d , J= _6.4Hz , 3H , _CH3 )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.40 (t, J=9.8Hz, 3F, _CF3 ), -113.80 (m, 4F, CF2CH ), -115.41 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてジイソプロパノールアミン１８５ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（８）１．０２ｇを白色固体として取得した。 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)

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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm) _: 6.93 ( _m , 2H, _C6F13CH = CHC6F12), 4.06 ( _{m, 2H , NH2CH2CHOH ) ,} 3.08 (m, 2H, NH2CH2CHOH) _, 2.88 (m, 2H, _NH2CH2CHOH ), 2.47 ( _m , 2H, CH2CF2 ) , 1.77 ( _m , 2H, CH2P ₎ , 1.24 (dd, J = 6.0Hz, 1.2Hz, 6H, CH3 ₎
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=10.4Hz, 3F, _CF3 ), -113.78 (m, 4F, CF2CH ), -115.43 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてトリイソプロパノールアミン２６６ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（９）１．０２ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.92 (m, 2H, _C6F13CH = CHC6F12), 4.15 ( _{m , 3H , NHCH2CHOH} ), 3.25 (m, 3H, NH2CH2CHOH ) _, 3.13 ( _m , 3H, NHCH2CHOH ), 2.48 (m, 2H, CH2CF2 ), 1.78 ( _m , 2H, _CH2P ), _1.25 (m, 9H, CH3 ₎ .
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=9.8Hz, 3F, _CF3 ), -113.77 (m, 4F, CF2CH ), -115.41 (m _{, 2F} , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてＮ－メチルエタノールアミン１０５ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（１０）１．０１ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated 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.

The analysis results were as follows:
¹ H-NMR (400 MHz, solvent: methanol-d ₄ , internal standard: tetramethylsilane) δ (ppm): 6.93 (m, 2H, C ₆ F ₁₃ CH=CH C ₆ F ₁₂ ), 3.80 (t, J=5.2 Hz, 2H, NH ₂ CH ₂ CH ₂ OH), 3.09 (t, J=5.2Hz, 2H, NH ₂ CH ₂ CH ₂ OH), 2.71 (s, 3H, CH ₃ ), 2.48 (m, 2H, CH ₂ CF ₂ ), 1.81 (m, 2H, CH ₂ P)
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=10.2Hz, 3F, _CF3 ), -113.77 (m, 4F, CF2CH ), -115.40 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてジグリコールアミン１４６ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（１１）１．０１ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) _δ (ppm): 6.92 (m, 2H, _C6F13CH = CHC6F12), 3.71 _{( m , 4H} , NH3CH2CH2OCH2CH2OH ), 3.61 (t, _J = _5.2Hz , _{2H ,} OCH2CH2OH ) _, 3.12 (t, J=5.2Hz, 2H, NH3CH2CH2O _{) , 2.48} (m, 2H, CH2CF2 ) _, 1.82 ( _m , 2H, CH2P ₎
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.38(t,J=9.8Hz,3F, _CF3 ), -113.74(m,4F, CF2CH ), -115.37(m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えてモルホリン１２１ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（１２）１．０１ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.94 ( _{m, 2H, C6F13CH=CHC6F12), 3.89 (m, 4H ,} CH2OCH2 ) _, 3.21 _{( m ,} 4H, _CH2NH2CH2 ), 2.48 ( _{m , 2H} , CH2CF2 ) _, 1.82 ( _m , 2H, CH2P )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=10.2Hz, 3F, _CF3 ), -113.78 (m, 4F, CF2CH ), -115.37 (m, _2F , CF2CH2 ), -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 ₎

実施例３において、トリエタノールアミンの量を４９５ｍｇ（３．３１ｍｍｏｌ）とした以外、同様の操作を行い、含フッ素アンモニウム塩（１３）１．０３ｇを白色固体として取得した。 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)

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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.95 (m, 2H, _C6F13CH = CHC6F12) _, 3.85 ( _t , J=5.2Hz, _12H , NHCH2CH2OH) _, 3.31 (t, J=5.2Hz, _12H , _NHCH2CH2OH ), 2.43 (m, _2H , CH2CF2 ₎ , 1.76 ( _m , 2H, CH2P ₎
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.39 (t, J=11.8Hz, 3F, _CF3 ), -113.68 (m, 4F, CF2CH ), -115.35 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えて４－メチルモルホリン１４１ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（１２）１．０１ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ(ppm): 6.82 (m, 2H, _C6F13CH = CHC6F12 ) , 3.96 ( _{m , 4H , CH2OCH2} ) , 3.38 (m, 2H, CH2NHCH3 ), 3.10 ( _m , _2H , _{CH2NHCH3 )} , 2.86 (m, 3H, _CH2NHCH3 ) , 2.49 ( _m , _2H , _CH2CF2 ), 1.86 ( _m , 2H, CH2P )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.46(t,J=9.8Hz,3F, _CF3 ), -113.95(m,4F, CF2CH ), -115.50(m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えて４０％ベンジルトリメチルアンモニウムヒドロキシド溶液５８２ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（１５）１．３３ｇを白色固体として取得した。 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)

The same operation 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ(ppm): 7.63-7.55 ( _{m, 5H, C6H5 )} , 6.87 ( m , 2H, C6F13CH _{= CHC6F12} ), 4.58 ( _s , _2H , _CH2N (CH3 ) ₃ ), 3.15 (s, 9H, CH2N ( _{CH3 ) 3} ), 2.47 (m _{, 2H} , CH2CF2 ) , 1.76 ₍ m, 2H, _CH2P )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.48(t,J=8.3Hz,3F, _CF3 ), -114.00(m,4F, CF2CH ), -115.40(m, _2F , CF2CH2 ), 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 )

実施例１において、モノエタノールアミンに替えて１５％テトラメチルアンモニウムヒドロキシド溶液１．５５ｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（１６）１．２５ｇを白色固体として取得した。 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)

The same operation 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm): 6.86 (m, 2H, _C6F13CH = CHC6F12), 3.23 _{(m, 12H, N(CH3)4 ) , 2.59 ( m} , 2H, CH2CF2 ₎ , 1.72 (m, _2H , CH2P )
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.46 (t, J=9.8Hz, 3F, _CF3 ), -113.89 (m, 4F, CF2CH ), -115.10 (m, _2F , CF2CH2 ), -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 ₎

実施例１において、モノエタノールアミンに替えて２０％テトラエチルアンモニウムヒドロキシド溶液１．１６ｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（１７）１．２１ｇを白色固体として取得した。 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)

The same operation 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.

The analysis results were as follows:
^1H -NMR (400MHz, solvent: methanol- _d4 , internal standard: tetramethylsilane) δ (ppm) _: 6.85 (m, 2H, _C6F13CH = CHC6F12), 3.31 _{(q, J=7.2Hz, 8H, N(CH2CH3 )} 4 _{) ,} 2.48 ( _{m , 2H} , CH2CF2), 1.81 (m, 2H, CH2P ) , 1.30 ₍ tt, J=7.2Hz, 2.0Hz, 12H, N(CH2CH3 _{) 4} ) _.
^19F -NMR (376MHz, solvent: methanol- _d4 , internal standard: trifluoromethylbenzene) δ(ppm): -81.48(t,J=9.8Hz,3F, _CF3 ), -113.93(m,4F, CF2CH ), -115.44(m, _2F , CF2CH2 ), -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 ₎

５０ｍｌのナスフラスコに、テトラヒドロフラン２０ｇ（キシダ化学製）と、特許文献２に記載の方法に従い合成した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-ペンタコサフルオロ-10-ヘプタデセン-1-イルリン酸１．００ｇ（化合物（１４）、１．２８ｍｍｏｌ）及び２５ｗｔ％アンモニア水８６ｍｇ（１．４０ｍｍｏｌ）を仕込み、室温下で３０分間撹拌した後、デカンテーションにより上澄みを除去し、得られた沈殿物を０．１ｋＰａ以下で減圧濃縮して含フッ素アンモニウム塩（１８）１．０１ｇを白色固体として取得した。 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)

Into 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 stirred at room temperature for 30 minutes, after which the supernatant was removed by decantation and the resulting precipitate was concentrated under reduced pressure at 0.1 kPa or less to obtain 1.01 g of a fluorine-containing ammonium salt (18) as a white solid.

実施例１において、モノエタノールアミンに替えて４８ｗｔ％水酸化ナトリウム水溶液５６ｍｇ（１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素ナトリウム塩（１９）１．０１ｇを白色固体として取得した。 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)

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.

実施例１において、モノエタノールアミンに替えて２８ｗｔ％アンモニア水溶液８９ｍｇ（キシダ化学製、１．４６ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（２０）１．００ｇを白色固体として取得した。 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)

The same procedure as in Example 1 was repeated except that 89 mg of a 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.

実施例１において、モノエタノールアミンに替えてトリエチルアミン１４１ｍｇ（富士フイルム和光純薬製、１．３９ｍｍｏｌ）を用いた以外、同様の操作を行い、含フッ素アンモニウム塩（２１）１．００ｇを無色蝋状物として取得した。 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)

The same procedure as in Example 1 was repeated 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.

Example 15
Evaluation of Water Solubility of Fluorine-Containing Ammonium Salt The fluorine-containing ammonium salt (4) obtained in Example 1 and pure water were mixed in a predetermined ratio in a 20 mL screw tube bottle, and the mixture was stirred at 400 rpm for 30 minutes at room temperature using a magnetic stirrer, and the appearance of the mixture was then visually confirmed to evaluate the 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.

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

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.

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.

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

The results in Table 1 show that in Examples 15 to 28, the fluorine-containing ammonium salts exhibit excellent water solubility. 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 as 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.

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.

Water and oil repellency evaluation A stainless steel plate (material: SUS304, 30 mm x 15 mm x 2 mm thick, surface 2B polished finish) was degreased by immersing in a solution consisting of 5 wt% sodium hydroxide, 47.5 wt% pure water, and 47.5 wt% ethanol for 1 hour, and washed with pure water. Thereafter, the plate was 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. Thereafter, the contact angles of water and hexadecane were measured using a contact angle meter DMs-401 manufactured by Kyowa Interface Science. The droplet volume in the measurement was 2 μL, and the θ/2 method was used to analyze the contact angle.

Examples 30 to 42
Stainless steel sheets were treated in the same manner as in Example 21, except that the fluorine-containing ammonium salt (4) was replaced with each of the fluorine-containing ammonium salts (5) to (17), and the water and oil repellency were evaluated in the same manner. The results are shown in Table 2.

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.

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 thereto 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 aqueous solution was used as a surface modifier, and the water and oil repellency was evaluated in the same manner as in Example 29. The results are shown in Table 2.

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.

Example 46
The same operation as in Example 44 was carried out 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.

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.

The results in Table 2 show that the surface modifier made of the fluorine-containing ammonium salt aqueous composition of the present invention provides excellent water and oil repellency to the substrate. Therefore, it is 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, etc.

The fluorine-containing ammonium salt of the present invention and the aqueous composition using the same can be used as a surface modifier that exhibits 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 (6)

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),
^Rf1 is a perfluoroalkyl group having 1 to 6 carbon atoms;
^Rf2 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, and M ¹ and M ² are not simultaneously a hydrogen atom.) 2. The fluorine-containing ammonium salt according to claim 1, wherein Rf ¹ is a linear perfluoroalkyl group having 4 to 6 carbon atoms, and Rf ² is a linear perfluoroalkylene group having 4 to 6 carbon atoms. An aqueous composition comprising the fluorine-containing ammonium salt according to claim 1 or 2 and water as a solvent. The aqueous composition according to claim 3, characterized in that the water content in the solvent is 50% by weight or more. The aqueous composition according to claim 3, characterized in that the water content in the solvent is 90% by weight or more. A surface modifier comprising the aqueous composition according to any one of claims 3 to 5.