JP2004131488A - Fluorine-based surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-based surfactant used mainly as various coating materials or molding materials of a printing material, a photosensitive material, a photographic material, a paint, a detergent, an optical material, a releasing agent, etc., and suitably as an additive for increasing penetrating property, wetting property, leveling property, surface function, etc., and consisting of a short chain compound having ≤6C perfluoroalkyl group in the compound. <P>SOLUTION: This fluorine-based surfactant is characterized by consisting of a fluorine-based compound having the same or different 2-4: F(CF<SB>2</SB>)<SB>2m</SB>(CH<SB>2</SB>)<SB>n</SB>SO<SB>2</SB>- [wherein, (m) is 2 or 3; and (n) is 0-2 integer] and -COOM (wherein M is H, ammonium or an alkali metal) groups. <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 (see, for example, 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 penetration / wetting properties, leveling properties, surface functionality, etc., and which comprises a short compound having a perfluoroalkyl group having 6 or less carbon atoms in the compound. Is to provide.

The present inventors have conducted intensive studies 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, the present invention provides 2 to 4 identical or different F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — (wherein m is 2 or 3 and n is 0 to ₂ ) in one molecule. An integer.) And -COOM (wherein M is a hydrogen atom, ammonium or an alkali metal).

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 2 to 4 identical or different F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — (where m is 2 or 3 and n is 0 A fluorine-containing surfactant having a fluorine-containing compound (A) having -COOM (where M is a hydrogen atom, ammonium or an alkali metal) as an effective surfactant. The structure of the fluorine-based compound (A) is not particularly limited.

F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — in the fluorine-based compound (A) is an indispensable segment for obtaining an excellent surfactant effect, and the number of the groups in one molecule is When the number is one, the surfactant effect is insufficient, and when the number is five or more, the compatibility with a composition such as a coating material or a molding material when used as a surfactant deteriorates, and the practicality is reduced. It must be four. The chain length of the group is appropriately selected depending 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 with the surfactant as an additive, the intended level of performance, and the like. However, when m is 1, the resulting fluorine-based compound has insufficient surface active effect, and when m is 4 or more, the number of fluorinated carbons in the perfluoroalkyl group becomes 8 or more, which is safe. It is necessary to be 2 or 3 because it is concerned about gender. When n is 3 or more, a practical surface active effect cannot be obtained, and therefore it is essential that n is an integer of 0 to 2.

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

Although the structure of the fluorine-based compound (A) is not particularly limited, it is easy to produce and has a good balance between the surfactant activity and the water solubility of the obtained fluorine-based compound. It is preferable that the compound has _two F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — groups, for example, the following general formulas (1) to (3)
{F (CF ₂ ) _2m (CH ₂ ) _n SO 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 } 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.)

（式中、ｍは２又は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。

(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 singly or as a mixture of two or more kinds having the same or different structures. m, n, and M 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 examples of the ammonium include ammonia, diethylamine, Derived from triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine, propanolamine, toluidine, pyridine, etc. Ammonium is mentioned, and as the alkali metal salt, lithium salt, sodium salt, potassium salt, rubidium salt and the like are mentioned. 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 (8)
NH ₂ R ₁ COOH (8)
(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 (9)
NH ₂ R ₁ COOM ₂ (9)
(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.)
(B) is reacted (dehydrohalogenation reaction) to give a perfluoroalkylsulfonyl halide (B) represented by the following general formula (10)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NHR ₁ COOM (10)
(In the formula, m, n, R ₁ and M are the same as described above.)
And then a perfluoroalkylsulfonylaminocarboxylic acid or a salt thereof, and a perfluoroalkylsulfonyl halide (B) represented by the general formula (4), which is the same as or different from that used in the previous reaction, is further reacted. (Dehydrohalogenation reaction).

(II) The aminocarboxylic acid represented by the general formula (8) is reacted with a perfluoroalkylsulfonyl halide (B) represented by the general formula (4) (dehydrohalogenation reaction) to give a compound represented by the following general formula (11) )
_{F (CF 2) 2m (CH} 2) n SO 2 NHR 1 COOH (11)
(In the formula, m, n, and R ₁ are the same as described above.)
, And further reacted with a perfluoroalkylsulfonylaminocarboxylic acid (B) represented by the above general formula (4), which is the same as or different from that used in the previous reaction (dehalogenation). Hydrogenation reaction) to give the following general formula (12)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } ₂ NR ₁ COOH (12)
(In the formula, m, n, and R ₁ are the same as described above.)
And then neutralizing the diperfluoroalkylsulfonylaminocarboxylic acid represented by the formula (1).

(III) The following general formula (13)
NH ₂ R ₁ COOR ₄ (13)
(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 general formula (4) (dehydrohalogenation reaction) to give an aminocarboxylic acid ester represented by the following general formula (14)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NHR ₁ COOR ₄ (14)
(In the formula, m, n, R ₁ and R ₄ are the same as described above.)
After the perfluoroalkylsulfonylaminocarboxylic acid ester represented by the general formula (4), a perfluoroalkylsulfonyl halide (B) represented by the general formula (4), which is the same as or different from that used in the previous reaction, is further reacted (removed). Hydrogen halide reaction) to give the following general formula (15)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } ₂ NR ₁ COOR ₄ (15)
(In the formula, m, n, R ₁ and R ₄ are the same as described above.)
A diperfluoroalkylsulfonylaminocarboxylic acid ester represented by the formula (1), followed by saponification.

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 a short carbon number in the perfluoroalkyl group can be obtained. Is preferably 0 or 2, and specifically, 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride, 3,3,4,4,5,5,5 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-nonafluorobutane 1-sulfonyl fluoride, 1,1,2,2 , 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- 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 (8) or the aminocarboxylic acid salt represented by the general formula (9), fluorine having excellent surface active effect and affinity with various added compositions is used. 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 (8) include aminoacetic acid, 2-aminopropionic acid, 3-amino-2-methylpropionic acid, and 3-aminobutylic acid.

Examples of the aminocarboxylate represented by the general formula (9) include, for example, ammonia, diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, and di (n-butyl) 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.

The amount of the perfluoroalkylsulfonyl halide (B) used in the synthesis of the perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (10) or a salt thereof is determined based on the amount of the aminocarboxylic acid represented by the general formula (8) or the general formula (8). 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 (9). 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 (8) or the aminocarboxylic acid salt represented by the general formula (9), 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 di Ethers such as Chirueteru, 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 (8) or the general formula It is preferable that perfluoroalkylsulfonyl halide (B) alone or a solution obtained by diluting perfluoroalkylsulfonyl halide (B) is dropped into a solution obtained by diluting the aminocarboxylate represented by (9) 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, but the aminocarboxylic acid represented by the general formula (8) or the aminocarboxylic acid salt represented by the general formula (9) and the product represented by the general formula (10) 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 (10) or a salt thereof with the perfluoroalkylsulfonyl halide (B) will be described.

This reaction is the same as that described above except that the perfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (10) obtained by the reaction or the salt thereof is used instead of the aminocarboxylic acid or the aminocarboxylic acid salt. Same as the reaction.

Next, the manufacturing method (II) will be described.
The method for obtaining the diperfluoroalkylsulfonylaminocarboxylic acid represented by the general formula (12) is the same as the above-mentioned method (I).

フ ッ 素 By neutralizing the diperfluoroalkylsulfonylaminocarboxylic acid obtained by the method described above, the fluorine-based compound represented by the general formula (1) 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 neutralizer is preferably 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, and examples of the reaction solvent include water alone or a mixed solvent of water and an alcohol such as methanol, ethanol, or isopropanol. Further, the reaction temperature is preferably 5 to 50C, particularly preferably 10 to 30C.

Next, the manufacturing method (III) will be described.
A method for obtaining the diperfluoroalkylsulfonylaminocarboxylic acid ester represented by the general formula (15) is to use an aminocarboxylic acid ester instead of the aminocarboxylic acid or the aminocarboxylic acid salt in the above-mentioned production method (I). Other than that is the same.

Examples of the aminocarboxylic acid ester represented by the general formula (13) used herein include esters of the aminocarboxylic acid. Among them, R in the general formula (13) has 1 to 7 carbon atoms. An alkyl group is preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

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.

ケ ン By saponifying the perfluoroalkylsulfonylaminocarboxylic acid ester represented by the general formula (15), the fluorine-based compound represented by the general formula (1) 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 preferably 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 the fluorine-based compound (A) having a relatively high property and the yield is reduced, a method using an aminocarboxylic acid ester (III) is preferable as a method for efficiently obtaining the fluorine-based 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 (16)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ CH (COOR ₅ ) ₂ (16)
(In the formula, m is 2 or 3, n is an integer of 0 to 2, and R ₅ is an alkyl group.)
And then reacted with a perfluoroalkylsulfonyl halide (B) represented by the general formula (4), which is the same or different from that used in the previous reaction, , The following general formula (17)
{F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ } ₂ C (COOR ₅ ) ₂ (17)
(In the formula, m, n, and R ₅ are the same as described above.)
And then saponifying the diperfluoroalkylsulfonylmalonic acid diester.

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 above general formula (16) via a dehalogenated salt, and then a perfluoroalkylsulfonyl group is added to the bonding site of the remaining methylene hydrogen by the same method. To obtain a diperfluoroalkylsulfonylmalonic acid diester represented by the general formula (17).

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, and potassium hydroxide, sodium hydroxide, Lithium hydroxide is more 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. The organic solvent used in the method for producing a fluorine-based compound of the above (1) is exemplified. 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 above-mentioned organic solvent to form a salt, and then the salt is added with the above-mentioned general formula ( A method is preferred in which the perfluoroalkylsulfonyl halide (B) represented by 4) alone or a solution obtained by diluting the same in the solvent is dropped.

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 same or different perfluoroalkylsulfonyl halide (B) as used in the previous reaction is further added to the perfluoroalkylsulfonylmalonic acid diester represented by the general formula (16) obtained by this reaction, as described above. After obtaining diperfluoroalkylsulfonylmalonic acid diester represented by the general formula (17) by reacting using a technique, the method is then described in the method for producing a fluorine-based compound represented by the general formula (1). By performing the saponification reaction using the same method as the saponification method, 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. Although the production method is not particularly limited, for example, as a method for obtaining a fluorine-based compound having two identical F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ -groups in one molecule, The following methods (IV) and (VI) are exemplified.

（式中、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る。）
で示されるカルボン酸（Ｃ）、または下記一般式（６）

（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（Ｄ）を反応（脱ハロゲン化水素反応）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 is 2 or 3, n is an integer of 0 to 2, and X ₁ is a halogen atom.)
The perfluoroalkylsulfonyl halide (B) represented by the following formula (5)

(In the formula, 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.)
Or a carboxylic acid (C) represented by the following general formula (6):

(In the formula, R ₂ and R ₃ are the same as described above, and M ₁ is ammonium or an alkali metal.)
A production method of reacting a carboxylate (D) (dehydrohalogenation 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（Ｃ）を反応（脱ハロゲン化水素反応）させ、更に中和する製造方法。 (V) The following general formula (4)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (4)
(In the formula, m, n, and X ₁ are the same as described above.)
In the perfluoroalkylsulfonyl halide (B) represented by
The following general formula (5)

(In the formula, R ₂ and R ₃ are the same as described above.)
Wherein the carboxylic acid (C) is reacted (dehydrohalogenation reaction) and further neutralized.

（式中、Ｒ_２、Ｒ_３、Ｒは前記と同じである。）
で示されるカルボン酸エステル（Ｅ）を反応（脱ハロゲン化水素反応）させ、更に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, n, and X ₁ are the same as described above.)
In the perfluoroalkylsulfonyl halide (B) represented by
The following general formula (7)

(In the formula, R ₂ , R ₃ , and R are the same as described above.)
(E) a carboxylic acid ester (hydrogen halide reaction), followed by saponification.

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 production method, the carboxylic acid (C) or the carboxylic acid salt (in place of the aminocarboxylic acid or the aminocarboxylic acid salt in the method (I) for producing the fluorine-based compound represented by the general formula (1) described above) is used. It is the same except that D) was used.

As the carboxylic acid (C) represented by the general formula (5) or the carboxylate (D) represented by the general formula (6) used herein, the alkylene chain R ₂ in the formula has a surfactant effect and an addition effect. Since a fluorine-based compound excellent in affinity with various compositions to be obtained is obtained, a methylene chain having 1 to 6 carbon atoms is preferable, and a methylene chain having 1 to 4 carbon atoms is particularly preferable. The alkylene 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, imidazolidine-2-yl-acetic acid sodium salt, (hexahydro-pyrimidin-2-yl) -acetic acid sodium salt, piperazin-2-yl-acetic acid sodium salt Diadiidine-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-carboxylic acid Acid potassium salt, [1,3] diazepan-2-carboxylic acid potassium salt, diaziridin-3-yl-acetic acid potassium salt, [1,3] diazetidin-2-yl-acetic acid potassium salt, imidazolidine-2-yl- Potassium acetate, (hexahydro-pyrimidin-2-yl) -acetic acid potassium salt, piperazin-2-yl-acetic acid And potassium salts.

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.

Next, the manufacturing method (V) will be described.
The production method is the same as that of the above-described general formula (II) except that the carboxylic acid (C) is used in place of the aminocarboxylic acid in the production method (II) of the fluorine-based compound represented by the general formula (1). The fluorine compound represented by (2) can be obtained.

Next, the manufacturing method (VI) will be described.
The production method is the same as that of the above-mentioned production method (III) of the fluorine compound represented by the general formula (1) except that the carboxylic acid ester (E) is used instead of the aminocarboxylic acid ester. The fluorine compound represented by the general formula (2) can be obtained.

Ｒ As R in the carboxylic acid ester (E) represented by the general formula (7) used herein, 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 these, esters of the carboxylic acid (C) represented by the general formula (5) 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.

Further, among the fluorine compounds represented by the general formula (3), a method for obtaining a fluorine compound having two different F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ — groups in one molecule is as follows. For example, the following method can be mentioned.

First, one kind of the perfluoroalkylsulfonyl halide (B) represented by the general formula (4) is added to 1 mol of the carboxylic acid (C), the carboxylate (D), or the carboxylic ester (E) to be reacted therewith. On the other hand, using 0.1 to 0.7 mol, preferably 0.4 to 0.6 mol, and reacting in the same manner as in the above-mentioned method, one F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ -Group is introduced, and a different perfluoroalkylsulfonyl halide (B) different from that used in the previous reaction is reacted in the same manner, and a second F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ The fluorinated compound represented by the general formula (3) is obtained by introducing a group and performing a neutralization reaction and a saponification reaction as necessary.

The fluorine-based compound represented by the general formula (3) obtained by the above-mentioned production method can be used in an unpurified state depending on the use and purpose. However, distillation, washing with a solvent, recrystallization, and various types of chromatography can be used. It is also possible to purify with an adsorbent or the like.

Among the above-mentioned production methods, as a method for efficiently obtaining a fluorine-based compound, for the same reason as described in the above-mentioned method for producing the fluorine-based compound represented by the general formula (1), the carboxylic acid of (VI) A method using an ester (E) is preferred.

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.

The composition is a solvent, a solution or the like. In the case of a solution, the solvent contains a solvent as an essential component, and as a solute, a high molecular compound, a low molecular organic compound, at least one compound selected from inorganic compounds, and, if necessary, And 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 solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrophilic cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol, propylene glycol And hydrophilic ethers such as tetrahydrofuran and dioxane. These solvents may be a single solvent or a mixed solvent of two or more solvents. In addition, the solvent used here as a dispersion medium in the system is also referred to as a solvent.

As the solute, those dissolved or dispersed in water and / or the organic solvent are preferable. For example, acrylic polymers, 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. I put it. 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 further continued. As a fraction, 285 g of nonafluorobutane-1-sulfonylaminoacetic acid ethyl ester [monoperfluoro compound (1-i)] was obtained. Got.

ii) Synthesis of bisperfluoro compound In a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser and a thermometer, 200 g of the monoperfluoro compound (1-i) obtained in i) was added. 0.52 mol), 33.5 g (0.62 mol) of sodium methoxide and 400 g of methanol, and further, 1,1,2,2,3,3,4,4,4-nonafluorobutane- 187.3 g (0.62 mol) of 1-sulfonyl fluoride 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, 1,1,2,2,3,3,4,4,4-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 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. As a fraction, ethyl [bis- (nonafluorobutane-1-sulfonyl) -amino] acetic acid [bisperfluoro compound] (1-ii)] 340 g were obtained.

iii) Saponification reaction In a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 300 g (0.45 mol) of the bisperfluoro compound (1-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 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 lithium compound (1-iii) [bis- (nonafluorobutane-1-sulfonyl) -amino] acetate lithium salt 290 g of [(C ₄ F ₉ SO ₂ ) ₂ NCH ₂ COOLi] was obtained.

Example 2
i) Synthesis of monoperfluoro compound In the reaction of i) of Example 1, 302.1 g of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (1 Mol), 402.1 g (1 mol) of 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride Except for the use, as in Example 1, tridecafluorohexane-1-sulfonylaminoacetic acid ethyl ester [monoperfluoro compound (2-i)] 379 g was obtained.

ii) Synthesis of bisperfluoro compound In the synthesis of the bisperfluoro compound of Example 1-ii), the monoperfluoro compound (2-i) was used instead of the monoperfluoro compound (1-i) 200 g (0.52 mol). i) 252.3 g (0.52 mol) was used, and further, 187.3 g (0.62 mol) of 1,1,2,2,3,3,4,4,4-nonafluoro-butane-1-sulfonyl fluoride was used. Mol) instead of 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonylfluoride (249.3 g, 0.62 mol) ) Was used in the same manner as in Example 1 to obtain 445 g of [bis- (tridecafluorohexane-1-sulfonyl) -amino] acetic acid ethyl ester [bisperfluoro compound (2-ii)].

iii) Saponification reaction In the saponification reaction of Example 1-iii), instead of 300 g (0.45 mol) of bisperfluoro compound (1-ii), 390.3 g of bisperfluoro compound (2-ii) ( 0.45 mol) in the same manner as in Example 1 except that the intended fluorine-based compound (2-iii) [bis- (tridecafluorohexane-1-sulfonyl) -amino] acetic acid lithium salt [(C to obtain a _{6 F 9 SO 2) 2 NCH} 2 COOLi] 379g.

Example 3
i) Synthesis of monoperfluoro compound Example 1-i) 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride 302 in synthesis of monoperfluoro compound In the same manner as in Example 1 except that 330.2 g (1 mol) of 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride was used instead of 0.1 g (1 mol). Then, 320.5 g of ethyl (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonylamino) acetic acid [monoperfluoro compound (3-i)] was obtained. Was.

ii) Bisperfluoro body In the synthesis of the bisperfluoro body of Example 1-ii, monoperfluoro body (3-i) 214 was used in place of 200 g (0.52 mol) of monoperfluoro body (1-i). 1.9 g (0.52 mol), and 187.3 g (0.62 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride. Instead of using 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride, 204.7 g (0.62 mol) of [bis] -(3,3,4,4,5,5,6,6,6-Nonafluorohexane-1-sulfonylamino)] acetic acid ethyl ester [367.2 g of bisperfluoro compound (3-ii) was obtained.

iii) Saponification reaction In the saponification reaction of Example 1-iii), instead of 300 g (0.45 mol) of bisperfluoro compound (1-ii), 323.1 g of bisperfluoro compound (3-ii) ( In the same manner as in Example 1 except that 0.45 mol) was used, the target fluorine compound (3-iii) [bis- (3,3,4,4,5,5,6,6,6-) 313.1 g of lithium salt of nonafluorohexane-1-sulfonylamino) acetic acid [(C ₄ F ₉ CH ₂ CH ₂ SO ₂ ) ₂ NCH ₂ COOLi] was obtained.

Example 4
ii) Synthesis of 'diperfluoro form) In the reaction of Example 1-ii), 1,7.3,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride 187.3 g (0. 62 mol) instead of 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride 204.7 g (0.62 mol) in the same manner as in Example 1. , [(Nonafluorobutane-1-sulfonyl)-(3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) -amino] -acetic acid ethyl ester [diperfluoro compound ( 4-ii ')] 355.7 g.

iii) Saponification Reaction In the saponification reaction of Example 1-iii), 312.9 g of diperfluoro compound (4-ii ') was used instead of 300 g (0.45 mol) of bisperfluoro compound (1-ii). In the same manner as in Example 1 except that 45 mol) was used, the target fluorine compound (4-iii) [(nonafluorobutane-1-sulfonyl)-(3,3,4,4,5,5,5). 6,6,6-Nonafluorohexane-1-sulfonyl) -amino] -acetic acid lithium salt [(C ₄ F ₉ SO ₂ ) (C ₄ F ₉ CH ₂ CH ₂ SO ₂ ) NCH ₂ CO ₂ Li] 303 g Obtained.

Example 5
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 were charged, and 1,2.1,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added to a dropping tube at 302.1 g (1 mol). ) 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, distillation was further continued, and 2- (nonafluorobutane-1-sulfonyl) malonic acid diethyl ester [monoperfluoro compound (5-i )] 341.5 g.

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 (5-i) obtained in i) was added. ), 33.5 g (0.62 mol) of sodium methoxide and 500 g of methanol, and further, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl was added to the dropping tube. 187.3 g (0.62 mol) of fluoride were added. 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, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added dropwise over 30 minutes at the same temperature under a nitrogen atmosphere. After 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. As a fraction, [bis- (nonafluorobutane-1-sulfonyl)] malonic acid dityl ester [bisperfluoro compound (5- ii)] 340 g were obtained.

iii) Saponification reaction In a 2 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 300 g (0.45 mol) of the bisperfluoro compound (5-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 inside of 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 was distilled off under reduced pressure, and the remaining solid was dried to dry the desired fluorine-based compound (5-iii) bis- (nonafluorobutane-1-sulfonyl) acetic acid lithium salt [(C ₄ F ₉ SO ₂ ) ₂ CHCOOLi] 290 g.

Example 6
i) Synthesis of monoperfluoro compound Example 5-i) In synthesis of monoperfluoro compound, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride 302 Instead of 0.1 g (1 mole), 402.1 g of 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride ( In the same manner as in Example 5 except that 1 mol) was used, 64-2.7 g of 2- (tridecafluorohexane-1-sulfonyl) malonic acid diethyl ester [monoperfluoro compound (6-i)] was obtained.

ii) Synthesis of bisperfluoro compound In Example 5, instead of 230 g (0.52 mol) of monoperfluoro compound (5-i), 428.6 g (0.52 mol) of monoperfluoro compound (6-i) ) And 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride (187.3 g (0.62 mol) instead of 1,1,1) Example 5 was repeated except that 249.3 g (0.62 mol) of 2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride was used. In a similar manner, 470.5 g of [bis- (tridecafluorohexane-1-sulfonyl)] malonic acid diethyl ester [bisperfluoro compound (6-ii)] was obtained.

iii) Saponification reaction Example 5-iii) In the saponification reaction, instead of 300 g (0.45 mol) of the bisperfluoro compound (5-ii), 415.9 g of the bisperfluoro compound (6-ii) (0 .45 mol) in the same manner as in Example 5, except that the intended fluorine-based compound (6-iii) [bis- (tridecafluorohexane-1-sulfonyl)] lithium acetate [(C ₆ F ₁₃ SO ₂ ) ₂ CHCOOLi] was obtained.

Example 7
i) Synthesis of monoperfluoro compound Example 5-i) In synthesis of monoperfluoro compound, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride 302 Example 1 was repeated except that 330.2 g (1 mol) of 3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl chloride was used instead of 0.1 g (1 mol). Similarly to 5, 2- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) malonic acid diethyl ester [monoperfluoro compound (7-i)] 354.4 g were obtained.

ii) Bisperfluoro compound In Example 5, monoperfluoro compound (7-i) g (0.52 mol) was used in place of 230 g (0.52 mol) of monoperfluoro compound (5-i). Further, instead of 187.3 g (0.62 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride, 3,3,4,4, [Bis-2- (3,3,4,5) was obtained in the same manner as in Example 5 except that 5,5,6,6,6-nonafluorohexane-1-sulfonyl chloride g (0.62 mol) was used. 4,5,5,6,6,6-Nonafluorohexane-1-sulfonyl)] malonic acid diethyl ester [bisperfluoro compound (7-ii)] (400.3 g) was obtained.

iii) Saponification reaction Except for using bisperfluoro compound (7-ii) g (0.45 mol) instead of 300 g (0.45 mol) of bisperfluoro compound (5-ii) in Example 5. In the same manner as in Example 5, the objective fluorine compound (7-iii) bis-2- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) 308.7 g of lithium acetate salt [(C ₄ F ₉ CH ₂ CH ₂ SO ₂ ) ₂ CHCOOLi] was obtained.

Example 8
ii) Synthesis of 'diperfluoro form) In Example 5, instead of 187.3 g (0.62 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride In the same manner as in Example 5, except that 3,4.7,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride was used in an amount of 204.7 g (0.62 mol). Nonafluorobutane-1-sulfonyl) -2- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) malonic acid dityl ester [bisperfluoro compound (8- ii)] 376.8 g were obtained.

iii) Saponification reaction In the same manner as in Example 5-iii) except that the diperfluoro compound (8-ii) was used instead of the bisperfluoro compound (5-iii), the target fluorine-based compound (8-iii) Lithium (nonafluorobutane-1-sulfonyl)-(3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) acetate [(C ₄ F ₉ SO ₂ ) (C ₄ F ₉ CH ₂ CH ₂ SO ₂ ) CHCOOLi] was obtained.

Example 9
ii) Synthesis of bisperfluoro 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 was added. 182.2 g (1.8 mol) of triethylamine and 800 g of ethyl acetate were charged, and 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added to a dropping tube. 6 g (1.7 mol) were charged. Under 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 the completion of the dropwise addition, the mixture was further stirred 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 further continued to obtain 1,4-bis- (nonafluorobutane-1-sulfonyl) -piperazine-2-carboxylic acid as a fraction. 570.3 g of ethyl ester [bisperfluoro compound (9-ii)] was obtained.

iii) Saponification reaction In a 2-liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 325.1 g (0.45 mol) of the bisperfluoro compound (9-ii) obtained in ii) was added. Then, 18.9 g (0.45 mol) of lithium hydroxide monohydrate, 600 g of isopropanol and 400 g of ion-exchanged water were added, followed by stirring at 60 ° C. 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 a fluorine-based compound (9-iii) 1,4-bis- (nonafluorobutane) represented by the following structural formula (3-1). 315.1 g of lithium-1-sulfonyl) -piperazine-2-carboxylate was obtained.

Example 10
Example 9-iii The procedure was carried out except that in the saponification reaction, 25.2 g (0.45 mol) of potassium hydroxide was used instead of 18.9 g (0.45 mol) of lithium hydroxide monohydrate. Fluorinated compound (8-iii) 1,4-bis- (nonafluorobutane-1-sulfonyl) -piperazine-2-carboxylic acid potassium salt represented by the following structural formula (3-3) in the same manner as in Example 9 328.8 g were obtained.

Example 11
ii) Synthesis of bisperfluoro 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 and triethylamine 182 were added. .2 g (1.8 mol) and 800 g of ethyl acetate were charged, and 513.6 g of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was further added to a dropping tube. (1.7 mol). In a nitrogen atmosphere, 1,1,2,2,3,3,4,4,4-nonafluoro-butane-1-sulfonyl fluoride was added dropwise over 30 minutes 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, 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 a fraction as 1,4-bis- (nonafluorobutane-1-sulfonyl) -piperazine-2-carboxylic acid [ 552.5 g of bisperfluoro compound (11-ii)] was obtained.

iii) Neutralization reaction 312.4 g (0.45 mol) of the bisperfluoro compound (11-ii) obtained in ii) was placed in a 2-liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer. After adding 18.9 g (0.45 mol) of lithium hydroxide monohydrate, 600 g of isopropanol and 400 g of ion-exchanged water, the inside of the flask was kept at 60 ° C. and stirred for 2 hours 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 (11-iii) 1,4-bis- (nonafluoro) represented by the structural formula (3-1). 315.1 g of lithium butane-1-sulfonyl) -piperazine-2-carboxylate was obtained.

Example 12
In a 2 liter four-necked flask equipped with a stirrer, a dropping tube, a reflux condenser and a thermometer, 108.9 g (0.8 mol) of lithium piperazine-2-carboxylate and 151.2 g (1 2.8 mol), 300 g of isopropanol and 200 g of ion-exchanged water, and further, 513.6 g of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride in a dropping tube. (1.7 mol). 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 the completion of the dropwise addition, the mixture was further stirred for 3 hours. After completion of the stirring, the reaction solution was concentrated to dryness. The obtained solid is washed with 200 g of ion-exchanged water and then dried to obtain a fluorine-based compound (12-iii) 1,4-bis- (nonafluorobutane-1) represented by the structural formula (3-1). -Sulfonyl) -piperazine-2-carboxylic acid lithium salt 560.2 g was obtained.

Example 13
ii) Synthesis of bisperfluoro compound In Example 9, 513.6 g (1.7 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was used. Instead, 683.6 g (1.7 mol) of 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride was used. 72,9 g of 1,4-bis- (tridecafluorohexane-1-sulfonyl) -piperazine-2-carboxylic acid ethyl ester [bisperfluoro compound (13-ii)] Got.

iii) Saponification reaction In Example 9, 415.1 g (0.45 mol) of bisperfluoro compound (13-ii) was used instead of 325.1 g (0.45 mol) of bisperfluoro compound (9-ii). Except for using, in the same manner as in Example 9, a fluorine-based compound (13-iii) represented by the following structural formula (3-5) 1,4-bis- (tridecafluorohexane-1-sulfonyl) -piperazine- 405.1 g of lithium 2-carboxylate was obtained.

Example 14
ii) Synthesis of bisperfluoro compound In Example 9, 513.6 g (1.7 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was used. Instead of using 1,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride (561.3 g (1.7 mol)) in the same manner as in Example 9, 4-bis- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) -piperazine-2-carboxylic acid ethyl ester [bisperfluoro compound (14-ii) ] 620.7 g were obtained.

iii) Saponification reaction In Example 9, 350.3 g (0.45 mol) of bisperfluoro compound (14-ii) was used instead of 325.1 g (0.45 mol) of bisperfluoro compound (9-ii). Except for using, in the same manner as in Example 9, the target fluorine-containing compound (14-iii) 1,4-bis- (3,3,4,4,5,5) represented by the following structural formula (3-8) 340.3 g of lithium 5,6,6,6-nonafluorohexane-1-sulfonyl) -piperazine-2-carboxylate was obtained.

Example 15
ii) Synthesis of bisperfluoro compound In the synthesis of ii) bisperfluoro compound of Example 9, instead of 126.6 g (0.8 mol) of piperazine-2-carboxylic acid ethyl ester, [1,3] diazetidine- was used. 1,3-bis- (nonafluorobutane-1-sulfonyl)-[1,3] diazetidine in the same manner as in Example 9 except that 104.1 g (0.8 mol) of 2-carboxylic acid ethyl ester was used. 550.5 g of -2-carboxylic acid ethyl ester [bisperfluoro compound (15-ii)] was obtained.

iii) Saponification reaction In the saponification reaction of Example 9-iii, instead of 325.1 g (0.45 mol) of bisperfluoro compound (9-ii), 312.4 g of bisperfluoro compound (15-ii) was used. (0.45 mol) in the same manner as in Example 9 except that the target fluorine-based compound (15-iii) 1,3-bis- (nonafluorobutane) represented by the following general formula (3-7) was used. -1-Sulfonyl)-[1,3] diazetidine-2-carboxylic acid lithium salt (302.5 g) was obtained.

Example 16
i) Synthesis of monoperfluoro compound In Example 9, 513.6 g (1.7 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was used. In the same manner as in Example 9 except that 1,0.8 g (0.4 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was used instead. There were obtained 345.6 g of 1- (nonafluorobutane-1-sulfonyl) -piperazine-3-carboxylic acid ethyl ester [monoperfluoro compound (16-i)].

ii) Synthesis of 'diperfluoro form) 264.2 g of the monoperfluoro form (16-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. 0.6 mol), 40.5 g (0.4 mol) of triethylamine and 800 g of ethyl acetate, and 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride was added to the dropping tube. 99.1 g (0.3 mol) were charged. Under a nitrogen atmosphere, 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride was added dropwise over 30 minutes 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, 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 4- (nonafluorobutane-1-sulfonyl) -1- (3,3,4,4 , 5,5,6,6,6-Nonafluorohexane-1-sulfonyl) -piperazine-2-carboxylic acid ethyl ester [diperfluoro compound (16-ii ')] (450.2 g) was obtained.

iii) Saponification reaction In the saponification reaction of Example 9, 337.7 g (0.45 mol) of the diperfluoro compound (16-ii ') was used instead of 325.1 g (0.45 mol) of the bisperfluoro compound (9-ii). Mol)), except that fluorinated compound (16-iii) 4- (nonafluorobutane-1-sulfonyl) -1- (3) represented by the following structural formula (3-9) was used in the same manner as in Example 9. , 3,4,4,5,5,6,6,6-Nonafluorohexane-1-sulfonyl) -piperazine-2-carboxylic acid lithium salt 327.7 g was obtained.

Test Examples 1 to 16 and Comparative Test Example 1
The water solubility and surface tension of the fluorine-based surfactant comprising the fluorine-based compound obtained in Examples 1 to 16 were measured by the following methods, and are shown in Table 1 as Test Examples 1 to 16.

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 16 using the fluorine-based surfactant comprising the fluorine-based compound of the present invention, the carbon number of the perfluoroalkyl group in the compound is as short as 6 or less, but the carbon number conventionally used is 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 perfluoroalkyl group of 8.

Test Examples 17 and 18, Comparative Test Examples 2 and 3
Methanol (Test Example 17, Comparative Test Example 2) and ion-exchanged water / methanol = 1/1 (weight) using the fluorine-based compound 1-iii obtained in Example 1 and Megafac F-120 as a conventional product. Ratio) Solubility in a mixed solvent (Test Example 18, 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 19 and 20
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 of a mixture of the fluorine compound (1-iii) and a hydrocarbon surfactant (polyoxyethylene oleyl ether: Emulgen 430 manufactured by Kao Corporation) in a 0.001% by weight aqueous solution was measured. Table 3 shows the results as 20.

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)

2 to 4 F (CF ₂ ) _2m (CH ₂ ) _n SO _2- (where m is 2 or 3 and n is an integer of 0 to ₂ ) identical or different in one molecule. , -COOM (wherein M is a hydrogen atom, ammonium or an alkali metal), comprising a fluorine-containing compound (A). The fluorine compound (A) has the following general formula (1)
{F (CF ₂ ) _2m (CH ₂ ) _n SO 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 } 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)

(In the formula, 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)

(In the formula, 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.)
The perfluoroalkylsulfonyl halide (B) represented by the following formula (5)

(In the formula, R ₂ and R ₃ are the same as described above.)
Or a carboxylic acid (C) represented by the following general formula (6):

(In the formula, R ₂ and R ₃ are the same as described above, and M ₁ is ammonium or an alkali metal.)
The fluorine-based surfactant according to claim 3, which is a fluorine-based compound obtained by reacting a carboxylate (D) 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 (7)

(In the formula, R ₂ and R ₃ are the same as described above, and R is an alkyl group.)
The fluorinated surfactant according to claim 3, which is a fluorinated compound obtained by reacting a carboxylic acid ester (E) represented by the following formula and further saponifying the carboxylic acid ester. 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 formulas (5) and (6) is an alkylene chain having 1 to 6; R ₃ is a direct bond or an alkylene chain having 1 to 6 carbon atoms; The fluorosurfactant according to claim ₄ , wherein ₁ is NH4, lithium, sodium or potassium. Formula (7) is an alkylene chain of R ₂ is 1 to 6 in a fluorocarbon surfactant of claim 5, wherein R ₃ is a direct bond or an alkylene chain of 1 to 6 carbon atoms.