JP2004130306A - Fluorosurfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorosurfactant which is used mainly for various coating materials and molding materials such as a printing material, a photosensitive material, photographic material, a paint, a cleaning material, an optical material, a mold release matrial, which is used adequately as an additive for enhancing penetration, wettability, a leveling property, a surface functional property or the like, and which cpmprises a short chain compound in which the carbon number of a perfluoroalkyl group in the compound is 6 or less. <P>SOLUTION: The fluorosurfactant contains F (CF<SB>2</SB>)<SB>2m</SB>(CH<SB>2</SB>)<SB>n</SB>SO<SB>2</SB>- of 1-3 in one molecule as a functional group having fluorine (wherein m is 2 or 3 and n is an integer of 0-2), F(CF<SB>2</SB>)<SB>2m</SB>(CH<SB>2</SB>)<SB>2</SB>- of 1-3 (wherein m is 2 or 3) and -COOM as a hydrophilic group (wherein M is hydrogen atom, ammonium or an alkali metal), and comprises a fluorocompound (A) in which the sum of two functional groups having fluorine is 2-4. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention is mainly soluble in various coating materials and molding materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, mold release agents, etc., easily penetrates and wets, leveling properties, The present invention relates to a fluorine-based surfactant which can be suitably used as an additive for enhancing surface functionality and the like.

Fluorosurfactants are additives that have a high surface tension lowering ability and achieve excellent penetration / wetting properties, leveling properties, surface functionality, etc. when mixed with coating compositions and molding compositions. There have been proposed various fluorine-based surfactants.

Generally, a fluorine-based surfactant has an affinity for a perfluoroalkyl (Rf) group for realizing a surface tension lowering function and various compositions such as a coating material and a molding material using the activator as an additive. It is composed of a compound having an amphiphilic group contributing to the property in the same molecule.

C ₈ F ₁₇ SO ₂ N (R) (CH ₂ ) _n COOM which is a conventional fluorine-based surfactant ( _where R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is 1 to 4) And M is a hydrogen atom, sodium, potassium, or lithium.) Is excellent in surface active effect and water solubility, and is widely used for plating and various coating applications (for example, see Patent Document 1). . However, recently, a fluorinated compound having a perfluoroalkyl group having 7 or more carbon atoms causes inhibition of intercellular communication which is considered to contribute to carcinogenicity in an in vitro test using a cell line. In addition, this inhibition is determined not by the functional group but by the length of the fluorinated carbon chain, and it is found that the longer the fluorinated carbon chain, the higher the inhibitory power (see, for example, Non-Patent Document 1). The use of such fluorine-based surfactants has been shunned. On the other hand, in general, a fluorine-based surfactant comprising a compound having a small number of carbon atoms in a perfluoroalkyl group does not have a sufficient surface-active effect. Therefore, a fluorine-based compound having a surface active effect equal to or higher than that of a conventionally used fluorine-based surfactant and comprising a compound having a short carbon number of a perfluoroalkyl group which is generally recognized as having high safety. There is a strong need for surfactants.

U.S. Pat. No. 2,809,990 (pages 1-3) "International Journal of Cancer" (USA) 1998, vol.78, p.491-495 (pages 1-3, FIG. 5)

In view of the above circumstances, the object of the present invention is mainly used for various coating materials and molding materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, release agents, Fluorinated surfactant which can be suitably used as an additive for enhancing permeation / wetting property, leveling property, surface functionality, etc., and which is composed of a short compound having 6 or less carbon atoms in a perfluoroalkyl group in the compound Is to provide.

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a fluorine-based compound having the following specific structure has a perfluoroalkyl group having a short carbon number of 6 or less, The present inventors have found that a fluorine-based surfactant as an effective surfactant does not impair the surfactant effect of a conventional fluorine-based surfactant, and have completed the present invention.

That is, in the present invention, 1 to 3 F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — (where m is 2 or 3; An integer of 0 to 2) and 1 to 3 F (CF ₂ ) _2m (CH ₂ ) _2- (where m is 2 or 3); and -COOM (wherein m is 2 or 3) as a hydrophilic group. , M is a hydrogen atom, ammonium or an alkali metal.) And a fluorine-based surfactant comprising a fluorine-based compound in which the total number of two fluorine-containing functional groups is 2 to 4. It is.

According to the present invention, mainly used for printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, compositions of various coating materials and molding materials such as release agents, penetration and wettability, It is possible to provide a fluorine-based surfactant which can be suitably used as an additive for enhancing the leveling property, the surface functionality, and the like, and is composed of a short compound having a perfluoroalkyl group having 6 or less carbon atoms.

Hereinafter, the present invention will be described in detail.
The surfactant effect according to the present invention includes various surfactant effects, for example, wettability, permeability, anti-repellent property, leveling property, uniformity / homogeneity of a coating film, and surface modification in coating and molding applications. And the like.

The fluorine-based surfactant of the present invention has 1 to 3 F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — as a functional group having fluorine in one molecule, wherein m is 2 or 3. , N is an integer of 0 to 2) and 1 to 3 F (CF ₂ ) _2m (CH ₂ ) _2- (where m is 2 or 3), and -COOM as a hydrophilic group. (Wherein, M is a hydrogen atom, ammonium or an alkali metal), and a fluorine-based compound (A) having a total number of 2 to 4 fluorine-containing functional groups is 2 to 4 as an active ingredient. The structure of the fluorine compound (A) is not particularly limited as long as it is a fluorine surfactant.

F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ -and F (CF ₂ ) _2m (CH ₂ ) _{2-in the} fluorine compound (A) are indispensable for obtaining an excellent surface active effect. A fluorine-based surfactant composed of a compound having only one of them in one molecule is insufficient in the surface-active effect, and a fluorine-based surfactant composed of a compound having five or more of these groups in total is a segment. In the case of a surfactant, when it is used as a surfactant, the compatibility with a composition such as a coating material or a molding material is deteriorated, and practicality is reduced. Therefore, 1 to 3 F (CF ₂ ) _2m (CH ₂ ) It is essential that the compound has _n SO ₂ -and 1 to 3 F (CF ₂ ) _2m (CH ₂ ) _2- and a total of 2 to 4 compounds. The chain length of both groups depends on the use when used as a surfactant, the composition of a composition such as a coating material or a molding material, which is mixed as an additive, the level of a desired surface active effect, and the like. Although it is appropriately selected, when m is 1, the surface active effect of the obtained fluorine-based compound is insufficient, and when m is 4 or more, there is concern about safety. It is mandatory. Further, in any case, if n is 3 or more, a practical surface activity effect cannot be obtained, and therefore, it is essential that n is an integer of 0 to 2.

In the fluorine-based compound (A), —COOM (where M is a hydrogen atom, ammonium or an alkali metal) is a hydrophilic group, and M in the group is a hydrogen atom of a carboxylic acid, is indicative of an alkali metal ammonium or alkali metal carboxylates of amine salts, e.g., -COOH as the hydrophilic _{group, -COONH 4, -COOLi, -COONa,} -COOK , and the like.

（式中、ｍは２または３であり、ｎは０〜２の整数であり、Ｒ_２は炭素数１〜１０のアルキレン鎖であり、Ｒ_３は直接結合または炭素数１〜１０のアルキレン鎖であり、Ｍは水素原子、アンモニウムまたはアルカリ金属である。）
で示されるものが挙げられる。 As the fluorine-based compound (A), F (CF ₂ ) _2m (CH ₂ ) _n SO _{2 is} contained in one molecule because it is easy to produce and the obtained fluorine-based compound has a good balance between the surfactant effect and the water solubility. -And one F (CF ₂ ) _2m (CH ₂ ) _2- are preferable, and for example, the following general formulas (1) to (3)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } {F (CF ₂ ) _2m (CH ₂ ) ₂ } NR ₁ COOM (1)
(In the formula, m is 2 or 3, n is an integer of 0 to 2, R ₁ is an alkylene chain having 1 to 10 carbon atoms, and M is a hydrogen atom, ammonium or an alkali metal.)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } {F (CF ₂ ) _2m (CH ₂ ) ₂ } CHCOOM (2)
(In the formula, m is 2 or 3, n is an integer of 0 to 2, and M is a hydrogen atom, ammonium or an alkali metal.)

(Wherein m is 2 or 3, n is an integer of 0 to 2, R ₂ is an alkylene chain having 1 to 10 carbon atoms, and R ₃ is a direct bond or an alkylene chain having 1 to 10 carbon atoms. And M is a hydrogen atom, ammonium or an alkali metal.)
Are shown.

Among them, n in the general formulas (1) to (3) is 0 or 2 because a fluorine-based compound having a practical surface active effect is obtained and the production is easy. Is preferred. The fluorine-based compounds represented by the general formulas (1) to (3) may be used alone or as a mixture of two or more kinds having the same or different structures. M, n and M in the formulas representing the compounds may be the same or different.

Further, R ₁ in the general formula (1) is an alkylene chain having 1 to 5 carbon atoms since a fluorine-based compound having excellent surfactant effect and affinity with various compositions to be added can be obtained. It is particularly preferable that the alkylene chain has 1 to 3 carbon atoms. Further, R ₂ in the general formula (3) is an alkylene chain having 1 to 6 carbon atoms since a fluorine-based compound having excellent surface active effect and affinity with various compositions to be added can be obtained. Is preferably an alkylene chain having 1 to 4 carbon atoms, and R ₃ is preferably a direct bond or an alkylene chain having 1 to 6 carbon atoms, and is preferably a direct bond or an alkylene chain having 1 to 4 carbon atoms. Is particularly preferred.

In the general formulas (1) to (3), -COOM (where M represents a hydrogen atom, ammonium or an alkali metal) is a hydrophilic group, and in the formula, M is, for example, ammonium as ammonium. , Diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine, propanolamine, toluidine, pyridine, etc. Derived ammonium is mentioned, and examples of the alkali metal include lithium, sodium, potassium, rubidium and the like. Among them, M in the formula is preferably NH ₄ , lithium, sodium, or potassium, and lithium, sodium, and potassium are preferable because a fluorine-based compound having a practical surfactant effect can be obtained and the production is easy. Is particularly preferred.

具体 Specific examples of the fluorine-based compound used for the fluorine-based surfactant of the present invention include the following compounds.

　尚、本発明がこれら具体例により、なんら限定されないことは勿論である。

The present invention is, of course, not limited by these specific examples.

The method for producing the fluorine-based compound represented by the general formulas (1) to (3) is not particularly limited. For example, the method for producing the fluorine-based compound represented by the general formula (1) is as follows. (I) to (III).

(I) The following general formula (9)
NH ₂ R ₁ COOH (9)
(In the formula, R ₁ is an alkylene chain having 1 to 10 carbon atoms.)
Or an aminocarboxylic acid represented by the following general formula (10)
NH ₂ R ₁ COOM ₂ (10)
(In the formula, R ₁ is an alkylene chain having 1 to 10 carbon atoms, and M ₂ is ammonium or an alkali metal.)
The aminocarboxylate represented by the general formula (4)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (4)
(In the formula, m is 2 or 3, n is an integer of 0 to 2, and X ₁ is a halogen atom.)
With a perfluoroalkylsulfonyl halide (B) represented by the general formula (11):
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NHR ₁ COOM (11)
(In the formula, m, n, R ₁ and M are the same as described above.)
After converting into a perfluoroalkylsulfonylaminocarboxylic acid or a salt thereof represented by the following formula (5),
F (CF ₂ ) _2m (CH ₂ ) ₂ I (5)
(In the formula, m is the same as described above.)
Wherein the perfluoroalkylethyl iodide (C) is reacted.

(II) The aminocarboxylic acid represented by the general formula (9) is reacted with a perfluoroalkylsulfonyl halide (B) represented by the general formula (4) (dehydrohalogenation reaction) to give the following general formula (12) )
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NHR ₁ COOH (12)
(In the formula, m, n, and R ₁ are the same as described above.)
And then reacted with a perfluoroalkylethyl iodide (C) represented by the general formula (5) to give a perfluoroalkylsulfonylaminocarboxylic acid represented by the following general formula (13)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } {F (CF ₂ ) _2m (CH ₂ ) _n } NR ₁ COOH (13)
(In the formula, m, n, and R ₁ are the same as described above.)
(Perfluoroalkylsulfonyl) (perfluoroalkyl) aminocarboxylic acid represented by the formula: and then neutralizing.

(III) The following general formula (14)
NH ₂ R ₁ COOR ₄ (14)
(In the formula, R ₁ is an alkylene chain having 1 to 10 carbon atoms, and R ₄ is an alkyl group.)
Is reacted with a perfluoroalkylsulfonyl halide (B) represented by the above general formula (4) (dehydrohalogenation reaction) to give an aminocarboxylic acid ester represented by the following general formula (15)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NHR ₁ COOR ₄ (15)
(In the formula, m, n, R ₁ and R ₄ are the same as described above.)
And then reacted with a perfluoroalkylethyl iodide (C) represented by the general formula (5) to obtain a perfluoroalkylsulfonylaminocarboxylic acid ester represented by the following general formula (16)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } {F (CF ₂ ) _2m (CH ₂ ) _n } NR ₁ COOR ₄ (16)
(Perfluoroalkylsulfonyl) (perfluoroalkyl) aminocarboxylic acid ester represented by the formula: and then saponified.

First, the manufacturing method (I) will be described in detail.
As the perfluoroalkylsulfonyl halide (B) represented by the general formula (4), a fluorine-based compound having an excellent surface active effect and having 6 or less carbon atoms in the perfluoroalkyl group is obtained. N is preferably 0 or 2, and specifically, 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride, 3,3,4,4,5 5,6,6,6-nonafluorohexanesulfonyl bromide, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanesulfonyl chloride, 3,3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanesulfonyl bromide, 1,1,2,2,3,3,4,4,4-nonafluoro Butane-1-sulfonyl fluoride, 1,1, , 2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride is preferred, and 3,3,4,4,5,5,6,6,6 6-nonafluorohexanesulfonyl chloride, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanesulfonyl chloride, 1,1,2,2,3 , 3,4,4,4-nonafluorobutane-1-sulfonyl fluoride, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane- 1-Sulfonyl fluoride is particularly preferred.

Further, as the aminocarboxylic acid represented by the general formula (9) or the aminocarboxylic acid salt represented by the general formula (10), fluorine having an excellent surface-active effect and an affinity with various added compositions is preferred. In order to obtain a system compound, R _{1 in} the formula is preferably an alkylene chain having 1 to 5 carbon atoms, and particularly preferably an alkylene chain having 1 to 3 carbon atoms.

ア ミ ノ Examples of the aminocarboxylic acid represented by the general formula (9) include aminoacetic acid, 2-aminopropionic acid, 3-amino-2-methylpropionic acid, and 3-aminobutylic acid.

Examples of the aminocarboxylate represented by the general formula (10) include, for example, ammonia, diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butylamine) as amine salts. A) amine salts derived from amines, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine, propanolamine, toluidine, pyridine and the like, and alkali metal salts such as lithium salt, sodium salt and potassium salt. Of these, amine salts, lithium salts, sodium salts, and potassium salts derived from ammonia are preferred because a fluorine-based compound having a practical surface-active effect can be obtained and the production is particularly easy.

Specifically, ammonium aminoacetate, ammonium 2-aminopropionate, ammonium 3-amino-2-methylpropionate, ammonium 3-aminobutyrate, lithium aminoacetate, lithium 2-aminopropionate Lithium 3-amino-2-methylpropionate, lithium 3-aminobutyrate, sodium aminoacetate, sodium 2-aminopropionate, sodium 3-amino-2-methylpropionate, 3-aminobutyl Acid sodium salt, potassium aminoacetate, potassium 2-aminopropionate, potassium 3-amino-2-methylpropionate, potassium 3-aminobutyrate, and the like.

In the synthesis of the perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (11) or a salt thereof, the amount of the perfluoroalkylsulfonyl halide (B) used is determined by the aminocarboxylic acid represented by the general formula (9) or the general formula (9). The amount is 0.5 to 7.0 mol, preferably 0.9 to 2.0 mol, per 1 mol of the aminocarboxylate represented by the formula (10). Since this reaction is a dehydrohalogenation reaction, it is preferable to use a base to remove by-product hydrogen halide. As the base, any of an inorganic base and an organic base can be used. . Examples of the inorganic base include potassium hydroxide, sodium hydroxide, lithium hydroxide and the like, and examples of the organic base include pyridine and triethylamine. The amount of the base to be used is 0.8 to 4.0 mol, preferably 0.9 to 2.0 mol, per 1 mol of the aminocarboxylic acid or aminocarboxylate used. This reaction can be carried out without a solvent or in an organic solvent, but a method in which the reaction is carried out in an organic solvent is preferred because the operation is easy and the safety of the operation is high.

The solvent is inert to the aminocarboxylic acid represented by the general formula (9) or the aminocarboxylic acid salt represented by the general formula (10), and the perfluoroalkylsulfonyl halide (B), and There is no particular limitation as long as both can be dissolved, but for example, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene. Chlorobenzene, orthodichlorobenzene, halogenated aromatic hydrocarbons such as paradichlorobenzene, n-pentane, n-hexane, n-octane, aliphatic hydrocarbons such as cyclohexane, tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether, Diethylene glycol Ethers such as ethyl ether, ethyl acetate, butyl acetate, esters such as propyl acetate. Among these, halogenated hydrocarbons, ethers, esters are preferable, ethers, esters are particularly preferred. These solvents may be used singly or as a mixture of two or more.

The reaction conditions for the reaction are not particularly limited, but since the reaction time is short and the removal of by-produced hydrogen halide is easy, the aminocarboxylic acid represented by the general formula (9) or the general formula It is preferable that perfluoroalkylsulfonyl halide (B) alone or a solution obtained by diluting perfluoroalkylsulfonyl halide (B) in the solvent is added dropwise to the solution obtained by diluting the aminocarboxylate represented by (10) in the solvent. The reaction temperature is not limited, but there is no problem if the dehydrohalogenation reaction occurs efficiently, and it is usually 5 to 80 ° C, preferably 10 to 50 ° C. The reaction time is not limited, and is usually 0.5 to 10 hours, preferably 1 to 5 hours. The reaction atmosphere is not limited, either. The aminocarboxylic acid represented by the general formula (9) or the aminocarboxylic acid salt represented by the general formula (10) and the product represented by the general formula (11) are used. In order to suppress oxidation of the perfluoroalkylsulfonylaminocarboxylic acid or a salt thereof, it is preferable to use an atmosphere of an inert gas such as nitrogen, helium, or argon.

Next, the reaction of the perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (11) or a salt thereof with perfluoroalkylethyl iodide (C) will be described.

In this reaction, a perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (11) is reacted with an amide hydrogen of a salt thereof and a base to form a salt with an alkali metal in the base. This is a reaction of reacting with ethyl iodide (C) to cause de-iodination alkali metal.

The amount of perfluoroalkylethyl iodide (C) used here is 0.5 to 7.0 mol, preferably 0.9 to 2.0 mol per mol of perfluoroalkylsulfonylaminocarboxylic acid or a salt thereof. Is a mole. Examples of the base include inorganic carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium methoxide, and sodium ethoxide. Bases are preferred. The amount of the base to be used is 0.8 mol to 4.0 mol, preferably 0.9 to 2.0 mol, per 1 mol of the perfluoroalkylsulfonylaminocarboxylic acid or a salt thereof used. This reaction can be carried out without a solvent or in an organic solvent, but a method in which the reaction is carried out in an organic solvent is preferable because the reaction operation is easy and the operation is highly safe.

The solvent is inert to perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (11) or a salt thereof, and perfluoroalkylethyl iodide (C), and can dissolve both. Although there is no particular limitation as long as it is present, for example, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, chlorobenzene, orthodichlorobenzene , Halogenated aromatic hydrocarbons such as paradichlorobenzene, aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane, cyclohexane, tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether. Ethers such as ter, esters such as ethyl acetate, butyl acetate and propyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and benzonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide and the like. Among these, ketones, nitriles, dimethylformamide, dimethylacetamide, and dimethylsulfoxide are preferred, and acetone, methylethylketone, acetonitrile, dimethylformamide, and dimethylsulfoxide are particularly preferred because of their good solubility. These solvents may be used singly or as a mixture of two or more. Further, these solvents can be used as a mixed solvent with water.

The reaction conditions are not particularly limited. However, since the reaction time is short and the by-product alkali metal iodide is easily removed, the perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (11) is used. Alternatively, a method is preferable in which perfluoroalkylethyl iodide (C) alone or a solution obtained by diluting the same in the solvent is dropped into a solution obtained by diluting the salt in the solvent. The reaction temperature is not limited, but is usually 5 ° C to 80 ° C, preferably 10 to 50 ° C. The reaction time is not limited, and is usually 0.5 to 10 hours, preferably 1 to 5 hours. Although the reaction atmosphere is not limited, it is preferable to use an atmosphere of an inert gas such as nitrogen, helium, or argon in order to suppress oxidation of the perfluoroalkylsulfonylaminocarboxylic acid or a salt thereof used and the product.

Next, the manufacturing method (II) will be described.
The method for obtaining the (perfluoroalkylsulfonyl) (perfluoroalkyl) aminocarboxylic acid represented by the general formula (13) is the same as the above-mentioned production method (I).

フ ッ 素 By neutralizing the (perfluoroalkylsulfonyl) (perfluoroalkyl) aminocarboxylic acid obtained by the above-mentioned method, the fluorine-based compound represented by the general formula (2) can be obtained.

中 和 As the neutralizing agent in the neutralization reaction, there may be mentioned alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and alkali metal halides such as potassium chloride and lithium chloride. The neutralizing agent is used in an amount of 1 to 5 mol, preferably 1 to 2.5 mol, per 1 mol of the compound before neutralization.

The reaction conditions are not particularly limited, but examples of the reaction solvent include water alone or a mixed solvent of water and an alcohol such as methanol, ethanol, and isopropanol. Further, the reaction temperature is preferably 5 to 50C, particularly preferably 10 to 30C.

Next, the manufacturing method (III) will be described.
The method for obtaining the perfluoroalkylsulfonylaminocarboxylic acid ester represented by the general formula (15) is a method other than using the aminocarboxylic acid ester instead of the aminocarboxylic acid or the aminocarboxylic acid salt in the above-mentioned production method (I). Is similar.

Examples of the aminocarboxylic acid ester represented by the general formula (14) used herein include esters of the aminocarboxylic acid represented by the general formula (9). Among them, R in the general formula (14) Is preferably an alkyl group having 1 to 7 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

Specifically, aminoacetic acid methyl ester, aminoacetic acid ethyl ester, 2-aminopropionic acid methyl ester, 2-aminopropionic acid ethyl ester, 3-aminopropionic acid methyl ester, 3-aminopropionic acid ethyl ester, 3-amino -2-methylpropionic acid methyl ester, 3-amino-2-methylpropionic acid ethyl ester, 3-aminobutyric acid methyl ester, 3-aminobutyric acid ethyl ester and the like. Among these, aminoacetic acid methyl ester, amino Preferred are ethyl acetate, methyl 3-aminopropionate, ethyl 3-aminopropionate, methyl 3-aminobutyrate, and ethyl 3-aminobutyrate. , 3-aminopropionic acid methyl ester, 3-aminopropionic acid ethyl ester is particularly preferred.

In the above method (I), the perfluoroalkylsulfonylaminocarboxylic acid ester represented by the general formula (15) is used instead of the perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (11) or a salt thereof. Is reacted with perfluoroalkylethyl iodide (C) in the same manner as (I) to obtain (perfluoroalkylsulfonyl) (perfluoroalkyl) aminocarboxylic acid ester represented by the general formula (16). After that, by further saponifying, the fluorine-based compound represented by the general formula (2) can be obtained.

ケ ン Examples of the saponifying agent used herein include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and alkali metal halides such as potassium chloride and lithium chloride. The saponifying agent is used in an amount of 1 to 5 mol, preferably 1 to 2.5 mol, per 1 mol of the compound before the saponification. The reaction conditions for the saponification reaction are not particularly limited, and examples of the reaction solvent include water alone or a mixed solvent of water and an alcohol such as methanol, ethanol, and isopropanol. Further, the reaction temperature is preferably from 10C to reflux temperature, particularly preferably from 40C to 90C.

The fluorine-based compound represented by the general formula (1) obtained by the above-mentioned production methods (I) to (III) can be used in an unpurified state depending on the use and purpose. It can also be purified by recrystallization, various types of chromatography, adsorbents and the like.

Among the above three production methods, aminocarboxylic acid or aminocarboxylic acid salt has low solubility in an organic solvent and low operability by reaction with perfluoroalkylsulfonyl halide (B). Is used, the amine salt or alkali metal halide formed by the hydrogen halide by-produced by the reaction with the perfluoroalkylsulfonyl halide (B) and the hydrogen halide catcher (base) is soluble in water, Since it is difficult to separate from a product having a relatively high property and the yield is reduced, a method using an aminocarboxylic acid ester of (III) is preferable as a method for efficiently obtaining a fluorine compound.

Next, a method for producing the fluorine-based compound represented by the general formula (2) will be described. The production method is not particularly limited, but examples include the following method.

The malonic acid diester is reacted with the perfluoroalkylsulfonyl halide (B) represented by the general formula (4) to obtain the following general formula (17)
_{F (CF 2) 2m (CH} 2) n SO 2 CH (COOR 5) 2 (17)
(In the formula, m is 2 or 3, n is an integer of 0 to 2, and R ₅ is an alkyl group.)
Is converted to a perfluoroalkylsulfonylmalonic acid diester represented by the general formula (5), and further reacted with a perfluoroalkylethyl iodide (C) represented by the general formula (5) to obtain the following general formula (18)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } {F (CF ₂ ) _2m (CH ₂ ) _n } C (COOR ₅ ) ₂ (18)
(In the formula, m, n, and R ₅ are the same as described above.)
(Perfluoroalkylsulfonyl) (perfluoroalkyl) malonic acid diester represented by the formula (1) and then saponifying.

The manufacturing method will be described in detail.
The perfluoroalkylsulfonyl halide (B) used here is the same as described above. Further, the malonic acid diester may have any structure that can be saponified, and examples thereof include dimethyl malonate and diethyl malonate.

This reaction is a method to which a malonate ester synthesis method is applied. By reacting the malonate diester with a base, a salt is formed by extracting methylene hydrogen of the malonate diester, and further, a perfluoroalkylsulfonyl halide (B) To produce a perfluoroalkylsulfonylmalonic acid diester represented by the general formula (17) via a dehalogenated salt, and then using perfluoroalkylethyl iodide (C) as a raw material in the same manner. By introducing a perfluoroalkyl group into the remaining methylene hydrogen bonding site, the (perfluoroalkylsulfonyl) (perfluoroalkyl) malonic acid diester represented by the general formula (18) can be obtained.

The base used herein is preferably an inorganic base, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, and the like. Potassium hydroxide, sodium hydroxide And lithium hydroxide are particularly preferred. The amount of the base to be used is 0.8 to 3.0 mol, preferably 0.9 to 1.5 mol, per 1 mol of the malonic diester used. This reaction can be carried out without a solvent or in an organic solvent, but a method in which the reaction is carried out in an organic solvent is preferable because the reaction operation is easy and the operation is highly safe.

The solvent is not particularly limited as long as it is inert to the perfluoroalkylsulfonyl halide (B) and the malonic diester and can dissolve both of them. In the method for producing a fluorine-based compound of the above), the organic solvent used in the reaction of the aminocarboxylic acid or a salt thereof with the perfluoroalkylsulfonyl halide (B) may be mentioned. These solvents may be used singly or as a mixture of two or more.

The reaction conditions for this reaction are not particularly limited, but since the reaction time is short, malonic diester and a base are reacted in the organic solvent to form a salt. The method of dropping the perfluoroalkylsulfonyl halide (B) alone represented by (4) or a dilution thereof in the solvent is preferable.

反 応 The reaction temperature during salt formation is not limited, but there is no problem as long as salt formation occurs efficiently, and it is usually 30 to 200 ° C, preferably 50 to 150 ° C. The reaction time for salt formation is not limited, and is usually 0.5 to 10 hours, preferably 1 to 5 hours. The reaction atmosphere for salt formation is not limited, but is preferably under an atmosphere of an inert gas such as nitrogen, helium, or argon to suppress the generation of peroxide.

The reaction temperature at the time of dropping the perfluoroalkylsulfonyl halide (B) is not limited, but there is no problem as long as the dehalogenated salt is efficiently generated, and it is usually 30 to 200 ° C, preferably 30 to 200 ° C. 50-150 ° C. The reaction time of the dropping reaction is not limited, and is usually 0.5 to 10 hours, preferably 1 to 5 hours. Although there is no limitation on the reaction atmosphere of the dropping reaction, it is preferable to use an atmosphere of an inert gas such as nitrogen, helium, or argon in order to suppress the generation of peroxide.

The perfluoroalkylsulfonylmalonic acid diester represented by the general formula (17) obtained by this reaction is reacted with a perfluoroalkylethyl iodide (C) using the same method as described above to obtain the compound represented by the general formula (17). After obtaining (perfluoroalkylsulfonyl) (perfluoroalkyl) malonic acid diester represented by (18), the same saponification method as described in the method for producing the fluorine-based compound represented by the general formula (1) is followed. By performing the saponification reaction using the technique, the fluorine-based compound represented by the general formula (2) is obtained.

The obtained fluorine-based compound represented by the general formula (2) can be used in an unpurified state depending on the use and purpose. However, distillation, washing with a solvent, recrystallization, various chromatography, adsorbent, etc. Purification is also possible.

Next, a method for producing the fluorine-based compound represented by the general formula (3) will be described. The production method is not particularly limited, and examples thereof include the following methods (IV) to (VI).

（式中、Ｒ_２、Ｒ_３は前記と同じである。）
で示されるカルボン酸（Ｄ）、または下記一般式（７）

（式中、Ｒ_２、Ｒ_３は前記と同じであり、Ｍ_１はアンモニウムまたはアルカリ金属である。）
で示されるカルボン酸塩（Ｅ）を反応（脱ハロゲン化水素反応）させ、更に下記一般式（５）
Ｆ(ＣＦ_２)_２ｍ(ＣＨ_２)₂Ｉ　　（５）
（式中、ｍは前記と同じである。）
で示されるパーフルオロアルキルエチルアイオダイド（Ｃ）を反応（脱ヨウ化水素反応）させる製造方法。 (IV) The following general formula (4)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (4)
(In the formula, m and n are the same as described above, and X ₁ is a halogen atom.)
A perfluoroalkylsulfonyl halide (B) represented by the following general formula (6)

(In the formula, R ₂ and R ₃ are the same as described above.)
A carboxylic acid (D) represented by the following general formula (7):

(In the formula, R ₂ and R ₃ are the same as described above, and M ₁ is ammonium or an alkali metal.)
Is reacted (dehydrohalogenation reaction), and further represented by the following general formula (5)
F (CF ₂ ) _2m (CH ₂ ) ₂ I (5)
(In the formula, m is the same as described above.)
Wherein the perfluoroalkylethyl iodide (C) is reacted (dehydroiodination reaction).

（式中、Ｒ_２、Ｒ_３は前記と同じである。）
で示されるカルボン酸（Ｄ）を反応（脱ハロゲン化水素反応）させ、更に下記一般式（５）
Ｆ(ＣＦ_２)_２ｍ(ＣＨ_２)₂Ｉ　　（５）
（式中、ｍは前記と同じである。）
で示されるパーフルオロアルキルエチルアイオダイド（Ｃ）を反応（脱ヨウ化水素反応）させた後、中和する製造方法。 (V) The following general formula (4)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (4)
(In the formula, m and n are the same as described above, and X ₁ is a halogen atom.)
A perfluoroalkylsulfonyl halide (B) represented by the following general formula (6)

(In the formula, R ₂ and R ₃ are the same as described above.)
Is reacted (dehydrohalogenation reaction), and further represented by the following general formula (5)
F (CF ₂ ) _2m (CH ₂ ) ₂ I (5)
(In the formula, m is the same as described above.)
A reaction method for reacting (dehydroiodination reaction) perfluoroalkylethyl iodide (C) represented by the formula (1), followed by neutralization.

（式中、Ｒ_２、Ｒ_３は前記と同じであり、Ｒ_４はアルキル基である。）
で示されるカルボン酸エステル（Ｆ）を反応（脱ハロゲン化水素反応）させ、更に下記一般式（５）
Ｆ(ＣＦ_２)_２ｍ(ＣＨ_２)₂Ｉ　　（５）
（式中、ｍは前記と同じである。）
で示されるパーフルオロアルキルエチルアイオダイド（Ｃ）を反応（脱ヨウ化水素反応）させた後、ケン化する製造方法。 (VI) The following general formula (4)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (4)
(In the formula, m and n are the same as described above, and X ₁ is a halogen atom.)
A perfluoroalkylsulfonyl halide (B) represented by the following general formula (8)

(In the formula, R ₂ and R ₃ are the same as described above, and R ₄ is an alkyl group.)
Is reacted (dehydrohalogenation reaction), and further represented by the following general formula (5)
F (CF ₂ ) _2m (CH ₂ ) ₂ I (5)
(In the formula, m is the same as described above.)
After reacting (dehydroiodination reaction) perfluoroalkylethyl iodide (C) represented by the formula (1), and then saponifying.

First, the manufacturing method (IV) will be described in detail.
The perfluoroalkylsulfonyl halide (B) represented by the general formula (4) is the same as that described in the description of the method for producing the fluorine-based compound represented by the general formula (1).

Further, as the carboxylic acid (C) represented by the general formula (5) or the carboxylate (D) represented by the general formula (6), the alkylene chain R ₂ in the formula is added to have a surfactant effect. Since a fluorine-based compound having excellent affinity for various compositions can be obtained, the compound is preferably a methylene chain having 1 to 6 carbon atoms, particularly preferably a methylene chain having 1 to 4 carbon atoms. The chain R ₃ is preferably a direct bond or a methylene chain having 1 to 6 carbon atoms, and particularly preferably a direct bond or a methylene chain having 1 to 4 carbon atoms.

Examples of the carboxylic acid (C) represented by the general formula (5) include diazidin-3-carboxylic acid, [1,3] azetidine-2-carboxylic acid, imidazolidine-2-carboxylic acid, and hexahydro-pyrimidine- 2-carboxylic acid, piperazine-2-carboxylic acid, [1,3] diazepan-2-carboxylic acid, diaziridin-3-yl-acetic acid, [1,3] diazetidin-2-yl-acetic acid, imidazolidine-2- Yl-acetic acid, (hexahydro-pyrimidin-2-yl) -acetic acid, piperazin-2-yl-acetic acid, diadiidine-3-carboxylic acid, [1,3] azetidine-2-carboxylic acid, imidazolidine-2 -Carboxylic acids, hexahydro-pyrimidine-2-carboxylic acids, piperazine-2-carboxylic acids are preferred.

The carboxylate (D) represented by the general formula (6) is preferably a salt of the carboxylic acid (C) represented by the general formula (5). For example, ammonia, diethylamine, triethylamine as an amine salt Amines derived from n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine, propanolamine, toluidine, pyridine and the like Salts, and examples of the alkali metal salts include lithium salts, sodium salts, and potassium salts. Among them, a fluorine-based compound having a practical surface-active effect can be obtained, and the production is particularly easy. , Amine salts derived from ammonia, lithi Arm salts, sodium salts, potassium salts are preferred.

Specifically, ammonium diaziidine-3-carboxylate, ammonium [1,3] azetidine-2-carboxylate, ammonium imidazolidine-2-carboxylate, ammonium hexahydro-pyrimidine-2-carboxylate, piperazine Ammonium 2-carboxylate, ammonium [1,3] diazepan-2-carboxylate, ammonium diaziridin-3-yl-acetate, ammonium [1,3] diazetidin-2-yl-acetate, imidazolidine- 2-yl-ammonium acetate, (hexahydro-pyrimidin-2-yl) -ammonium acetate, piperazin-2-yl-ammonium acetate, lithium diazidin-3-carboxylate, [1,3] azetidine-2- Lithium carboxylate, Lithium imidazolidine-2-carboxylate Salt, lithium hexahydro-pyrimidine-2-carboxylate, lithium piperazine-2-carboxylate, lithium [1,3] diazepan-2-carboxylate, lithium diaziridin-3-yl-acetate, [1,3 ] Diazetidin-2-yl-lithium acetate, lithium imidazolidine-2-yl-acetate, lithium (hexahydro-pyrimidin-2-yl) -acetate, lithium piperazin-2-yl-acetate, diazidin-3- Sodium carboxylate, [1,3] azetidine-2-carboxylic acid sodium salt, imidazolidine-2-carboxylic acid sodium salt, hexahydro-pyrimidine-2-carboxylic acid sodium salt, piperazine-2-carboxylic acid sodium salt, [ 1,3] diazepan-2-carboxylic acid sodium salt, diaziridin-3-yl-acetic acid Thorium salt, [1,3] diazetidin-2-yl-acetic acid sodium salt, imidazolidine-2-yl-acetic acid sodium salt, (hexahydro-pyrimidin-2-yl) -acetic acid sodium salt, piperazin-2-yl-acetic acid Sodium salt, diazidin-3-carboxylic acid potassium salt, [1,3] azetidine-2-carboxylic acid potassium salt, imidazolidine-2-carboxylic acid potassium salt, hexahydro-pyrimidine-2-carboxylic acid potassium salt, piperazine-2 -Potassium carboxylate, potassium [1,3] diazepan-2-carboxylate, potassium diaziridin-3-yl-acetate, potassium [1,3] diazetidin-2-yl-acetate, imidazolidine-2- Yl-potassium acetate, (hexahydro-pyrimidin-2-yl) -potassium acetate, piperazine-2 -Yl-acetic acid potassium salt.

Among these, ammonium diaziidine-3-carboxylate, ammonium [1,3] azetidine-2-carboxylate, ammonium imidazolidine-2-carboxylate, ammonium hexahydro-pyrimidine-2-carboxylate, piperazine- 2-carboxylate ammonium salt, diazidin-3-carboxylate lithium salt, [1,3] azetidine-2-carboxylate lithium salt, imidazolidine-2-carboxylate lithium salt, hexahydro-pyrimidine-2-carboxylate lithium salt , Lithium piperazine-2-carboxylate, sodium diaziidine-3-carboxylate, sodium [1,3] azetidine-2-carboxylate, sodium imidazolidine-2-carboxylate, hexahydro-pyrimidine-2-carboxylate Acid sodium salt, pipera Sodium 2-carboxylate, potassium diaziidine-3-carboxylate, potassium [1,3] azetidine-2-carboxylate, potassium imidazolidine-2-carboxylate, hexahydro-pyrimidine-2-carboxylic acid Particularly preferred are potassium salts and potassium piperazine-2-carboxylate.

The amount of the perfluoroalkylsulfonyl halide (B) used in this reaction is based on 1 mol of the carboxylic acid (D) represented by the general formula (6) or the carboxylic acid salt (E) represented by the general formula (7). It is 0.1 to 0.7 mol, preferably 0.4 to 0.6 mol. Further, since this reaction is a dehydrohalogenation reaction, it is preferable to use a base to remove by-product hydrogen halide, and as the base, an organic base is preferable, and examples thereof include pyridine and triethylamine. . The amount of the base to be used is 0.1 to 1.5 mol, preferably 0.2 to 0.8 mol, per 1 mol of the carboxylic acid (D) or aminocarboxylic acid salt (E) used. This reaction can be carried out without a solvent or in an organic solvent, but a method in which the reaction is carried out in an organic solvent is preferred because the operation is easy and the safety of the operation is high. Examples of the solvent include the organic solvents used in the reaction of the aminocarboxylic acid or a salt thereof with the perfluoroalkylsulfonyl halide (B) in the method (I) for producing the fluorine compound represented by the general formula (1). In addition, these solvents may be used alone or as a mixture of two or more. Other reaction conditions (preparation method, temperature, time, reaction atmosphere) are the same as those described in the method (I) for producing the fluorine-based compound represented by the general formula (1).

Next, the reaction between the product obtained by the above reaction and perfluoroethyl iodide (C) represented by the general formula (5) will be described.

The amount of perfluoroalkylethyl iodide (C) used in this reaction is based on 1 mol of the product obtained by the reaction of carboxylic acid (D) or carboxylate (E) with perfluoroalkylsulfonyl halide (B). The amount is 0.5 to 3.0 mol, preferably 0.9 to 2.0 mol. In addition, since this reaction is a dehydroiodination reaction, it is preferable to use a base to remove by-produced hydrogen iodide, and the base is preferably an organic base, such as pyridine and triethylamine. . The amount of the base used is 0.9 to 4.0 with respect to 1 mol of the product obtained by the reaction between the carboxylic acid (D) or aminocarboxylate (E) and the perfluoroalkylsulfonyl halide (B). Mole, preferably 1.0-3.0 mole. This reaction can be carried out without a solvent or in an organic solvent, but a method in which the reaction is carried out in an organic solvent is preferred because the operation is easy and the safety of the operation is high. Examples of the solvent include the organic solvent used in the reaction with perfluoroalkylethyl iodide (C) in the method (I) for producing the fluorine-based compound represented by the general formula (1). In addition, these solvents may be used alone or as a mixture of two or more. Other reaction conditions (preparation method, temperature, time, reaction atmosphere) are the same as those described in the method (I) for producing the fluorine-based compound represented by the general formula (1).

Next, the manufacturing method (V) will be described.
The method of reacting the perfluoroalkylsulfonyl halide (B) with the carboxylic acid (D) and further reacting with the perfluoroalkylethyl iodide (C) is the same as the method of the above (IV). The product obtained by this reaction is neutralized by the same method as the neutralization method described in the production method (II) of the fluorine-based compound represented by the general formula (1), thereby obtaining the compound represented by the general formula (3). Can be obtained.

Next, the manufacturing method of (VI) will be described.
The production method is the same as the above (IV) except that the carboxylic acid ester (F) represented by the general formula (8) is used instead of the carboxylic acid (D) or the carboxylate (E).

As R ₄ in the carboxylic acid ester (F) used here, an alkyl group having 1 to 7 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

Among them, esters of the carboxylic acid (D) represented by the general formula (6) are preferable, and examples thereof include methyl diazidin-3-carboxylate, methyl [1,3] azetidine-2-carboxylate, and imidazolidine-2. -Methyl carboxylate, methyl hexahydro-pyrimidine-2-carboxylate, methyl piperazine-2-carboxylate, [1,3] methyl diazepan-2-carboxylate, methyl diaziridin-3-yl-methyl acetate, [1,3] Diazetidin-2-yl-methyl acetate, imidazolidine-2-yl-methyl acetate, (hexahydro-pyrimidin-2-yl) -methyl acetate, piperazin-2-yl-methyl acetate, diazidin-3-carboxylate, [ Ethyl 1,3] azetidine-2-carboxylate, ethyl imidazolidine-2-carboxylate, hexahydro-pyri Ethyl gin-2-carboxylate, ethyl piperazine-2-carboxylate, [1,3] ethyl diazepan-2-carboxylate, ethyl diaziridin-3-yl-ethyl acetate, [1,3] diazetidin-2-yl-acetic acid Ethyl, imidazolidine-2-yl-ethyl acetate, (hexahydro-pyrimidin-2-yl) -ethyl acetate, piperazin-2-yl-ethyl acetate are preferred, and methyl diazidin-3-carboxylate, [1,3] azetidine Methyl-2-carboxylate, methyl imidazolidine-2-carboxylate, methyl hexahydro-pyrimidine-2-carboxylate, methyl piperazine-2-carboxylate, ethyl diaziidine-3-carboxylate, [1,3] azetidine-2 -Ethyl carboxylate, imidazolidine-2-ethyl carboxylate, hexahydro-pyrimidine-2-carbo Ethyl, piperazine-2-carboxylic acid ethyl are particularly preferred.

The product obtained by this reaction is saponified by the same method as the saponification method described in the method (III) for producing the fluorine-based compound represented by the general formula (1), thereby obtaining the compound represented by the general formula (3). Can be obtained.

The fluorine-based compound represented by the general formula (3) obtained by the above-mentioned production methods (IV) to (VI) can be used in an unpurified state depending on the use and purpose. Purification can also be performed by washing, recrystallization, various types of chromatography, adsorbents, and the like.

Among the production methods (IV) to (VI) described above, a method for efficiently obtaining a fluorine compound is the same as the reason described in the method for producing a fluorine compound represented by the general formula (1). Therefore, the method using the carboxylic acid ester (E) of (VI) is preferable.

The fluorosurfactant of the present invention has a shorter perfluoroalkyl group chain length than conventionally used fluorosurfactants, but has solubility in water and / or an organic solvent and a surfactant effect. Are almost the same, and are not particularly limited in use, and can be widely used. The fluorine-based surfactant of the present invention may be used alone, or two or more fluorine-based compounds (A) may be used simultaneously.

Examples of the composition using the fluorosurfactant of the present invention as an additive include, for example, various coating materials and molding materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, and release agents. And the like.

Examples of the form of the composition include, for example, a mixture of the fluorosurfactant in one or more solvents, the fluorosurfactant containing a solvent as an essential component, and a polymer as a solute. Examples thereof include a mixture of at least one compound such as a compound, a low-molecular organic compound, and an inorganic compound, and, if necessary, a compound composed of various additives described below.

Examples of the solvent include water and / or various organic solvents, for example, alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol. Hydrophilic ketones such as toluene, acetone and methyl ethyl ketone; polar solvents such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone; hydrophilic cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; ethylene glycol and propylene glycol. And hydrophilic ethers such as tetrahydrofuran and dioxane. These solvents may be one kind or a mixed solvent of two or more kinds. The solvent used herein as a dispersion medium in the system is also referred to as a solvent.

As the solute, those which dissolve or disperse in water and / or the organic solvent are preferable. For example, acrylic resins, urethane resins, epoxy resins, polyimide resins, polyamide resins, cellulose, chitin, natural polymers such as chitosan, and the like, Gelatin and the like can be mentioned. These solutes may be used alone or in combination of two or more.

Examples of the additive include coupling agents such as silane-based, titanium-based, and zircon-aluminate-based compounds, and fluorine atoms such as a fluorine atom-containing alkoxysilane compound, a fluorine atom-containing titanium acylate compound, and a fluorine atom-containing alkoxy zirconium compound. -Based coupling agents, inorganic powders and fillers such as silica, titanium oxide, zinc oxide, aluminum oxide, tin oxide, zirconium oxide, calcium oxide, calcium carbonate, glass filler, higher fatty acids, poly (vinylidene fluoride), poly ( Organic fine powders such as tetrafluoroethylene), polyethylene, acrylic beads, carbon, etc., photosensitizers, sensitizers, light resistance improvers, weather resistance improvers, heat resistance improvers, conductive agents, antioxidants, rust inhibitors, Various fillers such as rheology control agents, thickeners, anti-settling agents, defoamers and deodorants And the like. These additives may be used alone or in combination of two or more.

Further, as the fluorine-based surfactant of the present invention, various kinds of other fluorine-based surfactants, silicon-based surfactants, hydrocarbon-based surfactants and the like can be used as needed within a range that does not impair the effects of the present invention. These surfactants may be used in any combination in combination and applied to the various compositions described above. The mixing ratio is not particularly limited, and is appropriately selected depending on the level of the intended surface active effect, compatibility with the various compositions to be applied, and the like. As a weight ratio of the fluorine-based surfactant composed of the fluorine-based compound (A) to the other surfactant, (fluorine-based surfactant) / (other surfactant) is 1/99 to 99/1. The weight ratio is particularly preferably from 80/20 to 10/90, and most preferably from 50/50 to 20/80, from the viewpoint that a stable and sufficient surface active effect is obtained.

In general, a fluorine-based surfactant is used in combination with a hydrocarbon-based surfactant to form a material (for example, glass, steel plate, plastic film, or the like, when applied) in contact with the composition to which the surfactant is added. In this case, the function of lowering the interfacial tension with respect to the mold is increased, and this is also effective from an economic viewpoint.

The hydrocarbon-based surfactant comprises a hydrocarbon-based compound having a hydrophilic group and a lipophilic group in one molecule, and is usually an anion, a cation, a nonion, a betaine mainly due to the ionicity of the hydrophilic group. Classified into types. As the hydrocarbon-based surfactant that can be used in combination with the fluorine-based surfactant of the present invention, any type can be used without limitation. Representative anionic surfactants include sulfone salts, phosphate salts, carboxylate salts, and the like, and specific examples thereof include Emar series and Perex series manufactured by Kao Corporation. Examples of the cationic surfactant include oxonium salts, ammonium salts, and phosphonium salts, and specific examples thereof include acetamine series and coatamine series manufactured by Kao Corporation. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, sorbitan fatty acid ester and the like, and specific examples thereof include Emulgen series and Rheodol series manufactured by Kao Corporation. Examples of the betaine-based surfactant include amino acid salts and amine oxides, and specific examples include Amphitol series manufactured by Kao Corporation.

組成 The composition containing the above-mentioned fluorine-containing surfactant of the present invention can obtain excellent permeation / wetting property and leveling property by applying various processing methods. The processing method is not particularly limited. For example, coating such as gravure coater, knife coater, roll coater, comma coater, spin coater, bar coater, brush coating, dipping coating, spray coating, electrostatic coating, screen printing, etc. Method / Apparatus, Ink jet method, Injection, Extrusion, Hollow, Compression, Reaction, Vacuum, FRP, Heat, Roll sheet, Calendar, Biaxially stretched film, Lamination, Rotation, etc. Various molding methods, Various dies, Stampers Injection molding and the like can be mentioned.

There is no limitation on the use of the above-mentioned composition. For example, adhesives for industrial use and home use, scratch resistance, slipperiness, non-adhesion, water / oil repellency, gas barrier properties, heat resistance, light resistance Surface-functional protective film forming materials such as, weather resistance, physiological activity, water resistance, moisture resistance, antifouling properties, lubricity, etc., fabrics for clothing, furniture, shoes, sundries, etc., artificial leather, synthetic leather nonwoven fabric, etc. , Paper, film, various coating agents such as cards, automobiles, building materials, home appliances, medical materials, office automation equipment, electrical and electronic equipment, optical members, electric wires and wiring materials, molding materials for various industrial parts, grease, various seals Anti-blocking materials, release agents, anti-rust agents, anti-fog agents, anti-fog agents, anti-blocking agents, anti-static agents such as PS plates, photosensitive materials such as LCDs, LSIs, organic EL, and various photoresists for plasma display manufacturing , Anti-reflective coating agent for LSI manufacturing, LCD, Photographic materials such as SI, organic EL, detergents for plasma display manufacturing, etching agents, release agents, developers, emulsions, paints for automobiles, aircraft, ships, building materials, home appliances, etc., dyes, detergents, floor polish, foam It can be suitably used as a fire extinguishing agent, a plating bath mist inhibitor, an optical material such as a lens sheet and an optical fiber, or a dispersion medium for an organic chemical reaction.

Next, in order to explain the present invention in more detail, examples, test examples and comparative test examples are listed.

Example 1
i) Synthesis of monoperfluoro compound In a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser and a thermometer, 82.5 g (0.8 mol) of ethyl aminoacetate and 101.2 g of triethylamine were placed. (1 mol) and 800 g of ethyl acetate, and 302.1 g (1 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was further added to the dropping tube. Was put. In a nitrogen atmosphere, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added dropwise over 30 minutes while stirring at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 3 hours. After completion of the stirring, 500 g of a 10% by weight aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was continued, and 285 g of nonafluorobutane-1-sulfonylaminoacetic acid ethyl ester [monoperfluoro compound (1-i)] was obtained as a fraction. Got.

ii) Synthesis of diperfluoro compound 200 g (0.52 mol) of the monoperfluoro compound (1-i) obtained in i) was placed in a 2-liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer. 33.5 g (0.62 mol) of sodium methoxide and 400 g of methanol were added, and 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane 221. 7 g (0.62 mol) were charged. After stirring for 2 hours while maintaining the inside of the flask at 60 ° C. under a nitrogen atmosphere, 600 g of ethyl acetate was further added to the reaction solution, followed by stirring at the same temperature for 5 minutes. After completion of the stirring, 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane was added dropwise over 30 minutes at the same temperature under a nitrogen atmosphere. After the addition, the mixture was further stirred at the same temperature for 2 hours. After completion of the stirring, the reaction solution was cooled to room temperature, 1 kg of saturated saline was added to the reaction solution, and the mixture was stirred at room temperature for 10 minutes. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was further continued to obtain [(nonafluorobutane-1-sulfonyl) (3,3,4,4,5,5,5) as a fraction. 6,6,6-Nonafluorohexyl)] aminoacetic acid ethyl ester [diperfluoro compound (1-ii)] was obtained in an amount of 315.9 g.

iii) Saponification reaction In a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 284 g (0.45 mol) of the diperfluoro compound (1-ii) obtained in ii), lithium hydroxide After adding 18.9 g (0.45 mol) of monohydrate, 600 g of isopropanol and 400 g of ion-exchanged water, the mixture was stirred at 60 ° C. for 2 hours to perform a saponification reaction. After completion of the stirring, the solvent was distilled off under reduced pressure, and the remaining solid was dried to obtain the desired fluorine compound (1-iii) [(nonafluorobutane-1-sulfonyl) (3,3,4,4). to give 5,5,6,6,6- nonafluorohexyl)] aminoacetic acid lithium salt _{[(C 4 F 9 SO 2} ) (C 4 F 9 CH 2 CH 2) NCH 2 COOLi] 268.5g.

Example 2
i) Sulfonamidation reaction In Example 1-i, instead of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride 302.1 g (1 mol), , 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonylfluoride, except that 402.1 g (1 mol) was used. In the same manner as in Example 1, 376.6 g of ethyl (tridecafluorohexane-1-sulfonyl) aminoacetate [monoperfluoro compound (2-i)] was obtained.

ii) Diperfluoro compound In Example 1-ii, 252.3 g (0.52 mol) of monoperfluoro compound (2-i) was used instead of 200 g (0.52 mol) of monoperfluoro compound (1-i). Used, and 1,1,1,2,2,3,4,4-nonafluoro-6-iodo-hexane 221.7 g (0.62 mol) was replaced with 1,1,1,2,2 The procedure of Example 1 was repeated, except that 283.7 g (0.62 mol) of 2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodo-octane was used. (Tridecafluorohexane-1-sulfonyl) (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)] aminoacetic acid ethyl ester [diperfluoro compound (2-ii)] 425.6 g was obtained.

iii) Saponification reaction Except that in Example 1-iii, 374.1 g (0.45 mol) of diperfluoro compound (2-ii) was used instead of 300 g (0.45 mol) of diperfluoro compound (1-ii) In the same manner as in Example 1, the target fluorine compound [(tridecafluorohexane-1-sulfonyl) (3,3,4,4,5,5,6,6,7,7,8,8,8 8-tridecafluorooctyl)] aminoacetic acid lithium salt _{[(C 6 F 13 SO 2} ) (C 6 F 13 CH 2 CH 2) to give the NCH 2 COOLi] 363.8g.

Example 3
i) Synthesis of monoperfluoro compound In Example 1-i, 302.1 g (1 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was used. Instead of using 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride (330.2 g (1 mol)) in the same manner as in Example 1, (3,3 3,4,4,5,5,6,6,6-Nonafluorohexane-1-sulfonyl) aminoacetic acid ethyl ester [monoperfluoro compound (3-i)] 320.5 g was obtained.

ii) Bisperfluoro compound In Example 1-ii, instead of 200 g (0.52 mol) of monoperfluoro compound (1-i), 214.9 g (0.52 mol) of monoperfluoro compound (3-i) ) Except that [(3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) (3,3,4,4) was used. , 5,5,6,6,6-Nonafluorohexyl)] aminoacetic acid ethyl ester [diperfluoro compound (3-ii)] 335.7 g was obtained.

iii) Saponification reaction Except that in Example 1-iii, 294.3 g (0.45 mol) of diperfluoro compound (3-ii) was used instead of 300 g (0.45 mol) of diperfluoro compound (1-ii) In the same manner as in Example 1, the desired fluorine compound [(3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) (3,3,4,4) , 5,5,6,6,6- nonafluorohexyl)] aminoacetic acid lithium salt _{[(C 4 F 9 CH 2} CH 2 SO 2) (C 4 F 9 CH 2 CH 2) NCH 2 COOLi] 284.3g Got.

Example 4
i) Synthesis of monoperfluoro compound In a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser and a thermometer, 128.1 g (0.8 mol) of diethyl malonate, sodium methoxide 51. 3 g (0.95 mol) and 100 g of methanol are charged, and 302.1 g (1 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride is further added to a dropping tube. Was put. After stirring the flask in a nitrogen atmosphere at 60 ° C. for 2 hours, 200 g of ethyl acetate was added to the reaction solution, and the mixture was stirred at the same temperature for 5 minutes. After completion of the stirring, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added dropwise over 30 minutes at the same temperature under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 2 hours. After completion of the stirring, the reaction solution was cooled to room temperature, 300 g of saturated saline was added to the reaction solution, and the mixture was stirred at room temperature for 10 minutes. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was further continued to give 2- (nonafluorobutane-1-sulfonyl) -malonic acid diethyl ester [monoperfluoro compound (4- i)] 341.5 g were obtained.

ii) Synthesis of bisperfluoro compound In a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 230 g (0.52 mol) of the monoperfluoro compound (4-i) obtained in i) was added. ), 33.5 g (0.62 mol) of sodium methoxide and 500 g of methanol, and further, 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane was added to the dropping tube. 221.7 g (0.62 mol) were charged. After stirring in a flask at 60 ° C. for 2 hours under a nitrogen atmosphere, 600 g of ethyl acetate was added to the reaction solution, followed by stirring at the same temperature for 5 minutes. After completion of the stirring, 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane was added dropwise over 30 minutes at the same temperature under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 2 hours. After completion of the stirring, the reaction solution was cooled to room temperature, 1 kg of saturated saline was added to the reaction solution, and the mixture was stirred at room temperature for 10 minutes. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was further continued to give 2- (nonafluorobutane-1-sulfonyl) -2- (3,3,4,4,5,5 , 5,6,6,6-Nonafluorohexyl) -malonic acid diethyl ester [diperfluoro compound (4-ii)] 340.7 g was obtained.

iii) Saponification reaction In a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 309.7 g (0.45 mol) of the diperfluoro compound (4-ii) obtained in ii), water After adding 18.9 g (0.45 mol) of lithium oxide monohydrate, 600 g of isopropanol and 400 g of ion-exchanged water, the flask was kept at 60 ° C. and stirred for 2 hours to carry out a saponification reaction. After completion of the stirring, the solvent is distilled off under reduced pressure, and the remaining solid is dried to obtain the desired fluorine compound (4-iii) 5,5,6,6,7,7,8,8,8-. 267.4 g of nonafluoro-2- (nonafluorobutane-1-sulfonyl) -octanoic acid lithium salt [(C ₄ F ₉ SO ₂ ) (C ₄ F ₉ CH ₂ CH ₂ ) CHCOOLi] was obtained.

Example 5
i) Synthesis of sulfonyl compound In Example 4-i, instead of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (302.1 g (1 mol)) , 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride 402.1 g (1 mol) was used. In the same manner as in Example 4, 2- (tridecafluorohexane-1-sulfonyl) -malonic acid diethyl ester [monoperfluoro body (5-i)] (642.7 g) was obtained.

ii) Bisperfluoro compound In Example 4-ii, instead of 230 g (0.52 mol) of monoperfluoro compound (4-i), 428.6 g (0.52 mol) of monoperfluoro compound (5-i) ) And 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane in place of 221.7 g (0.62 mol) of 1,1,1,2,3 , 2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodo-octane except that 283.7 g (0.62 mol) was used. 2- (tridecafluorohexane-1-sulfonyl) -2- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) -malonic acid 455.9 g of diethyl ester [diperfluoro compound (5-ii)] was obtained.

iii) Saponification reaction Except that in Example 4-iii, 399.7 g (0.45 mol) of diperfluoro compound (5-ii) was used instead of 300 g (0.45 mol) of diperfluoro compound (4-ii) In the same manner as in Example 4, the target fluorine compound (5-iii) 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-2 - was obtained (tridecafluoro-hexane-1-sulfonyl) lithium octanoate _{[(C 6 F 13 SO 2} ) (C 6 F 13 CH 2 CH 2) CHCOOLi] 312.4g.

Example 6
i) Synthesis of monoperfluoro compound In Example 4-i, 302.1 g (1 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was used. Instead of using 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride (330.2 g (1 mol)), the procedure of Example 4 was repeated, except that 2- (3 , 3,4,4,5,5,6,6,6-Nonafluorohexane-1-sulfonylamino) -malonic acid diethyl ester [monoperfluoro compound (6-i)] 354.4 g was obtained.

ii) Diperfluoro compound In Example 4-ii, instead of 230 g (0.52 mol) of the monoperfluoro compound (4-i), 244.6 g (0.52 mol) of the monoperfluoro compound (6-i) was used. Except for using, the same procedures as in Example 4 were carried out to obtain 2- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) -2- (3,3,4 , 4,5,5,6,6,6-Nonafluorohexyl) -malonic acid diethyl ester [diperfluoro compound (6-ii)] 376.9 g was obtained.

iii) Saponification reaction Example 4 was repeated except that 335 g (0.45 mol) of the diperfluoro compound (6-ii) was used instead of 300 g (0.45 mol) of the diperfluoro compound (4-ii). In the same manner as described above, the desired fluorine compound (6-iii) 5,5,6,6,7,7,8,8,8-nonafluoro-2- (3,3,4,4,5,5, 292.6 g of lithium 6,6,6-nonafluorohexane-1-sulfonyl) -octoate [[(C ₄ F ₉ CH ₂ CH ₂ SO ₂ ) (C ₄ F ₉ CH ₂ CH ₂ ) CHCOOLi] was obtained. .

Example 7
i) Synthesis of sulfonyl compound In a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser, and a thermometer, 126.6 g (0.8 mol) of ethyl piperazine-2-carboxylate and triethylamine 91 were added. .1 g (0.9 mol) and 500 g of ethyl acetate were charged, and 241.7 g of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added to a dropping tube. 0.8 mol). In a nitrogen atmosphere, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added dropwise over 1 hour while stirring at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours. After completion of the stirring, 500 g of a 10% by weight aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was further continued to give a fraction as 1- (nonafluorobutane-1-sulfonyl) -piperazine-3-carboxylic acid ethyl ester [mono] 348.9 g of perfluoro compound (7-i)] was obtained.

ii) Synthesis of diperfluoro compound In a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser and a thermometer, 220.2 g of the monoperfluoro compound (7-i) obtained in i) was added. 5.5 mol), 60.7 g (0.6 mol) of triethylamine and 500 g of ethyl acetate, and further, 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo- was added to the dropping tube. Hexane (214.6 g, 0.6 mol) was charged. Under a nitrogen atmosphere, 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane was added dropwise over 1 hour while stirring at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours. After completion of the stirring, 500 g of a 10% by weight aqueous hydrochloric acid solution was added to the reaction solution, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was further continued to obtain [1- (nonafluorobutane-1-sulfonyl) -4- (3,3,4,4). 4,5,5,6,6,6-Nonafluorohexyl)]-piperazine-3-carboxylic acid ethyl ester [diperfluoro compound (7-ii)] 343.2 g was obtained.

iii) Saponification reaction In a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 308.9 g (0.45 mol) of the diperfluoro compound (7-ii) obtained in ii), water 18.9 g (0.45 mol) of lithium oxide monohydrate, 600 g of isopropanol and 400 g of ion-exchanged water were charged and stirred at 60 ° C. for 1 hour to perform a saponification reaction. After completion of the stirring, the solvent was distilled off under reduced pressure, and the remaining solid was dried to obtain a fluorine-based compound (7-iii) [1- (nonafluorobutane-1-) represented by the structural formula (3-1). 298.9 g of lithium salt of sulfonyl) -4- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)]-piperazine-3-carboxylic acid was obtained.

Example 8
Same as Example 7 except that in Example 7-iii, 25.2 g (0.45 mol) of potassium hydroxide was used instead of 18.9 g (0.45 mol) of lithium hydroxide monohydrate. To a fluorine-based compound (8-iii) [1- (nonafluorobutane-1-sulfonyl) -4- (3,3,4,4,5,5,6) represented by the structural formula (3-3) , 6,6-Nonafluorohexane-1-sulfonyl)]-piperazine-3-carboxylic acid potassium salt, 313.4 g, was obtained.

Example 9
i) Synthesis of monoperfluoro compound In a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser, and a thermometer, 104.1 g (0.8 mol) of piperazine-2-carboxylic acid, triethylamine 91 were added. .1 g (0.9 mol), 400 g of acetone, 400 g of ethyl acetate and 400 g of ion-exchanged water, and 1,1,2,2,3,3,4,4,4-nonafluorobutane-1 was added to the dropping tube. -241.7 g (0.8 mol) of sulfonyl fluoride were charged. In a nitrogen atmosphere, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added dropwise over 1 hour while stirring at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 3 hours. After completion of the stirring, 400 g of a 10% by weight aqueous hydrochloric acid solution and 800 g of ethyl acetate were added to the reaction solution, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was further continued to obtain 1- (nonafluorobutane-1-sulfonyl) -piperazine-3-carboxylic acid [monoperfluoro] Compound (9-i)] 328.7 g was obtained.

ii) Synthesis of bisperfluoro compound 206.1 g of monoperfluoro compound (9-i) obtained in i) was placed in a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser, and a thermometer. (0.5 mol), 60.7 g (0.6 mol) of triethylamine, 500 g of acetone, 500 g of ethyl acetate and 500 g of ion-exchanged water, and 1,1,1,2,2,3,3,3 were added to the dropping tube. 214.6 g (0.6 mol) of 4,4-nonafluoro-6-iodo-hexane was added. Under a nitrogen atmosphere, 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane was added dropwise over 1 hour while stirring at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours. After completion of the stirring, 500 g of a 10% by weight aqueous hydrochloric acid solution and 1 kg of ethyl acetate were added to the reaction solution, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. After completion of the stirring, the organic layer was separated, the solvent was distilled off by distillation, and the distillation was further continued to obtain [1- (nonafluorobutane-1-sulfonyl) -4- (3,3,4,4). 4,5,5,6,6,6-Nonafluorohexyl)]-piperazine-3-carboxylic acid [diperfluoro compound (9-ii)] 326.6 g was obtained.

iii) 'Neutralization reaction In a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 296.2 g (0.45 mol) of the diperfluoro compound (9-ii) obtained in ii) was added. 18.9 g (0.45 mol) of lithium hydroxide monohydrate, 600 g of isopropanol and 400 g of ion-exchanged water were charged and stirred at 25 ° C. for 1 hour to carry out a neutralization reaction. After completion of the stirring, the solvent is distilled off under reduced pressure, and the remaining solid is dried to obtain a fluorine-based compound (9-iii) [1- (nonafluorobutane-1-) represented by the structural formula (3-1). 298.5 g of lithium salt of sulfonyl) -4- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)]-piperazine-3-carboxylic acid was obtained.

Example 10
i) Synthesis of monoperfluoro compound In a 2 L four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser, and a thermometer, 108.8 g (0.8 mol) of lithium piperazine-2-carboxylate, triethylamine 91.1 g (0.9 mol), 400 g of acetone, 400 g of ethyl acetate and 400 g of ion-exchanged water were charged, and 1,1,2,2,3,3,4,4,4-nonafluorobutane- was added to the dropping tube. 241.7 g (0.8 mol) of 1-sulfonyl fluoride was added. In a nitrogen atmosphere, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added dropwise over 1 hour while stirring at 25 ° C. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. After completion of the stirring, 400 g of ion-exchanged water and 400 g of ethyl acetate were added to the reaction solution, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. After completion of the stirring, the aqueous layer was separated, washed with water and dried to give lithium 1- (nonafluorobutane-1-sulfonyl) -piperazine-3-carboxylate [monoperfluoro form (10-i)] 330. 0.7 g was obtained.

ii) Synthesis of diperfluoro compound 209.1 g (0-i) of the monoperfluoro compound (10-i) obtained in i) was placed in a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser and a thermometer. 0.5 mol), 60.7 g (0.6 mol) of triethylamine, 400 g of acetone, 500 g of ethyl acetate and 400 g of ion-exchanged water, and 1,1,1,2,2,3,3,4,4 were added to the dropping tube. 214.6 g (0.6 mol) of 4-nonafluoro-6-iodo-hexane was charged. Under a nitrogen atmosphere, 1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane was added dropwise over 1 hour while stirring at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 2 hours. After completion of the stirring, 400 g of ion-exchanged water and 400 g of ethyl acetate were added to the reaction solution, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. After completion of the stirring, the aqueous layer was separated, washed with water and dried to obtain a fluorine-based compound (10-ii) [1- (nonafluorobutane-1-sulfonyl) -4 represented by the structural formula (3-1). -(3,3,4,4,5,5,6,6,6-nonafluorohexyl)]-piperazine-3-carboxylic acid lithium salt 332.1 was obtained.

Example 11
i) Synthesis of monoperfluoro compound In Example 7-i, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride 241.7 g (0.8 mol ) Instead of 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride 321.7 g (0.8 mol) In the same manner as in Example 7 except for using, ethyl 1- (tridecafluorohexane-1-sulfonyl) -piperazine-3-carboxylate [monoperfluoro compound (11-i)] (430.5 g) was obtained. Was.

ii) Synthesis of diperfluoro compound In Example 7-ii, instead of 220.2 g (0.5 mol) of monoperfluoro compound (7-i), 270.2 g of monoperfluoro compound (11-i) (0. 5 mol) and 1,1,1,1,2,2,3,3,4,4-nonafluoro-6-iodo-hexane instead of 214.6 g (0.6 mol). 2,7,3,4,4,5,5,6,6-tridecafluoro-8-iodo-octane In the same manner as in Example 7 except that 274.6 g (0.6 mol) was used. , [1- (tridecafluorohexane-1-sulfonyl) -4- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorohexyl)] -Piperazine-3-carboxylic acid ethyl ester [diperfluoro compound (11-ii)] 436.7 g was obtained.

iii) Saponification reaction In Example 7-iii), instead of 325.1 g (0.45 mol) of diperfluoro compound (7-ii), 398.9 g (0.45 mol) of diperfluoro compound (11-ii) In the same manner as in Example 7 except that was used, the fluorine-based compound (11-iii) [1- (tridecafluorohexane-1-sulfonyl) -4- (3,3) represented by the structural formula (3-6) was used. 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorohexyl)]-piperazine-3-carboxylic acid lithium salt 388.5 g was obtained.

Example 12
i) Synthesis of monoperfluoro compound In Example 7-i, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride 241.7 g (0.8 mol ) Was replaced with 264.2 g (0.8 mol) of 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride in the same manner as in Example 7, except that 1- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) -piperazine-3-carboxylic acid ethyl ester [monoperfluoro compound (12-i)] 370 0.5 g was obtained.

ii) Synthesis of diperfluoro compound In Example 7-ii, instead of 220.2 g (0.5 mol) of the monoperfluoro compound (7-i), 234.2 g of a monoperfluoro compound (12-i) (0.5 mol) was used. [1- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) -4- (5-mol) 3,3,4,4,5,5,6,6,6-nonafluorohexyl)]-piperazine-3-carboxylic acid ethyl ester [diperfluoro compound 12-ii] 350.6 g was obtained.

iii) Saponification reaction In Example 7-iii, 321.5 g (0.45 mol) of the diperfluoro compound (12-ii) was used instead of 325.1 g (0.45 mol) of the diperfluoro compound (7-ii). Fluorine-based compound (12-iii) [1- (3,3,4,4,5,5,6,6,6,6) represented by Structural Formula (3-5), except that -Nonafluorohexane-1-sulfonyl) -4- (3,3,4,4,5,5,6,6,6-nonafluorohexyl)]-piperazine-3-carboxylic acid lithium salt 311.2 g was obtained. Was.

Test Examples 1 to 12, Comparative Test Example 1
The aqueous solubility and surface tension of the aqueous solution of the fluorine-based surfactant comprising the fluorine-based compound obtained in Examples 1 to 12 were measured by the following methods, and are shown in Table 1 as Test Examples 1 to 12.

Test Method Water Solubility: Stirred with ion-exchanged water at 25 ° C., and a clear state free from visual turbidity was defined as complete dissolution. (Unit: wt%)
Surface tension: The surface tension at each concentration (ion exchange aqueous solution) at 20 ° C. was measured by Wilhelmy platinum plate method using an automatic surface tensiometer CBPV-Z (manufactured by Kyowa Interface Chemical Co., Ltd.). (Unit: mN / m)

In Comparative Test Example 1, Dainippon Ink and Chemicals Megafac Co., Ltd. _{F-120 (C 8 F 17} SO 2 N (CH 2 CH 2 CH 3) CH 2 COOK) aqueous solubility and surface of an aqueous solution of The tension was measured. Table 1 shows the results.

In Test Examples 1 to 12 using the fluorine-based surfactant comprising the fluorine-based compound of the present invention, the carbon number of the perfluoro group in the compound was as short as 6 or less, but the conventionally used carbon number of 8 was used. It was confirmed that the solubility in water and the effect of lowering the surface tension were almost the same as those of the fluorine-based surfactant of Comparative Example 1 comprising a compound having a perfluoro group.

Test Examples 13 and 14, Comparative Test Examples 2 and 3
Methanol (Test Example 13, Comparative Test Example 2) and ion-exchanged water / methanol = 1/1 (weight) using the fluorine compound 1-iii obtained in Example 1 and Megafac F-120 as a conventional product. Ratio) Solubility in a mixed solvent (Test Example 14, Comparative Test Example 3) and surface tension were measured. Table 2 shows the results.

(4) It was confirmed that the fluorine surfactant comprising the fluorine-based compound of the present invention can exert almost the same surfactant effect as a conventional product on not only water but also a hydrophilic organic solvent.

Test Examples 15 and 16
Using the fluorine compound (1-iii) obtained in Example 1, the effect of using the compound with a hydrocarbon surfactant was confirmed. The surface tension in a 0.001% by weight aqueous solution of a mixture of a fluorine-based compound (1-iii) and a hydrocarbon-based surfactant (polyoxyethylene oleyl ether: Emulgen 430 manufactured by Kao Corporation) was measured. Table 3 shows the result as 16.

It was confirmed that the fluorine-based surfactant comprising the fluorine-based compound of the present invention exhibited an excellent surfactant effect even when used in combination with other surfactants.

Claims (9)

In one molecule, 1 to 3 F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — (where m is 2 or 3 and n is an integer of 0 to ₂ ) as a fluorine-containing functional group ) And 1-3 F (CF ₂ ) _2m (CH ₂ ) _2- (where m is 2 or 3) and -COOM as a hydrophilic group (where M is a hydrogen atom, And a fluorine-based compound (A) containing 2 to 4 fluorine-containing functional groups in total. The fluorine compound (A) has the following general formula (1)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } {F (CF ₂ ) _2m (CH ₂ ) ₂ } NR ₁ COOM (1)
(In the formula, m is 2 or 3, n is an integer of 0 to 2, R ₁ is an alkylene chain having 1 to 10 carbon atoms, and M is a hydrogen atom, ammonium or an alkali metal.)
A fluorine compound represented by the following general formula (2)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } {F (CF ₂ ) _2m (CH ₂ ) ₂ } CHCOOM (2)
(In the formula, m is 2 or 3, n is an integer of 0 to 2, and M is a hydrogen atom, ammonium or an alkali metal.)
And a fluorine compound represented by the following general formula (3)

(Wherein m is 2 or 3, n is an integer of 0 to 2, R ₂ is an alkylene chain having 1 to 10 carbon atoms, and R ₃ is a direct bond or an alkylene chain having 1 to 10 carbon atoms. And M is a hydrogen atom, ammonium or an alkali metal.)
The fluorine-based surfactant according to claim 1, which is at least one fluorine-based compound selected from the group consisting of fluorine-based compounds represented by the formula: The fluorine compound (A) has the following general formula (3)

(Wherein m is 2 or 3, n is an integer of 0 to 2, R ₂ is an alkylene chain having 1 to 10 carbon atoms, and R ₃ is a direct bond or an alkylene chain having 1 to 10 carbon atoms. And M is a hydrogen atom, ammonium or an alkali metal.)
The fluorine-based surfactant according to claim 1, which is a fluorine-based compound represented by the formula: The fluorine compound (A) has the following general formula (4)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (4)
(In the formula, m and n are the same as described above, and X ₁ is a halogen atom.)
A perfluoroalkylsulfonyl halide (B) represented by the following general formula (6)

(In the formula, R ₂ and R ₃ are the same as described above.)
A carboxylic acid (D) represented by the following general formula (7):

(In the formula, R ₂ and R ₃ are the same as described above, and M ₁ is ammonium or an alkali metal.)
Is reacted with a carboxylate (E) represented by the following general formula (5):
F (CF ₂ ) _2m (CH ₂ ) ₂ I (5)
(In the formula, m is the same as described above.)
The fluorine-based surfactant according to claim 3, which is a fluorine-based compound obtained by reacting a perfluoroalkylethyl iodide (C) represented by the following formula: The fluorine compound (A) has the following general formula (4)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (4)
(In the formula, m and n are the same as described above, and X ₁ is a halogen atom.)
A perfluoroalkylsulfonyl halide (B) represented by the following general formula (8)

(In the formula, R ₂ and R ₃ are the same as described above, and R ₄ is an alkyl group.)
And a carboxylic acid ester (F) represented by the following general formula (5):
F (CF ₂ ) _2m (CH ₂ ) ₂ I (5)
(In the formula, m is the same as described above.)
The fluorine-based surfactant according to claim 3, which is a fluorine-based compound obtained by reacting a perfluoroalkylethyl iodide (C) represented by the following formula and saponifying the reaction. R ₁ in the general formula (1) is an alkylene chain having 1 to 5 carbon atoms, R ₂ in the general formula (3) is an alkylene chain having 1 to 6 carbon atoms, and R ₃ is a direct bond or is an alkylene chain of 1 to 6 carbon atoms, the general formula (1) M is a hydrogen atom in the ~ _(3), NH 4, fluorine-based surface active agent according to claim 2 wherein the lithium, sodium or potassium. In the general formula (3), R ₂ is an alkylene chain having 1 to 6 carbon atoms, R ₃ is a direct bond or an alkylene chain having 1 to 6 carbon atoms, and M is a hydrogen atom, NH ₄ , lithium, or sodium. 4. The fluorine-containing surfactant according to claim 3, which is potassium. R ₂ in the general formula (6) is an alkylene chain having 1 to 6 carbon atoms, R ₃ is a direct bond or an alkylene chain having 1 to 6 carbon atoms, and M ₁ in the general formula (7) is The fluorinated surfactant according to claim 4, which is NH ₄ , lithium, sodium or potassium. Wherein R ₂ in the general formula (8) is an alkylene chain of 1 to 6 carbon atoms, a fluorine-based surface active agent according to claim 5, wherein R ₃ is a direct bond or an alkylene chain of 1 to 6 carbon atoms.