JP2006104240A - Fluorine-containing compound, surfactant and composition of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing surfactant excellent in surface tension-decreasing capacity even on its single use, especially exhibiting a sufficient surface tension-decreasing capacity even at a lower concentration than usual surfactant concentration, and also having a dynamic surface tension-decreasing capacity, a composition containing the surfactant and a new fluorine-containing compound useful as the surfactant. <P>SOLUTION: This surfactant consists of a straight chain perfluoropolyether amide expressed by formula: R<SP>F</SP>-Z [wherein, R<SP>F</SP>is a 6-15C perfluoropolyether group expressed by formula: R<SP>F1</SP>O(R<SP>F2</SP>O)<SB>k</SB>CF<SB>2</SB>-; and Z is a nitrogen-containing group having affinity with its medium, selected from a halogen salt of a quaternary ammonium, betaine and an amineoxide, and one of groups bonding to the nitrogen is a straight chain or branched 2-6C alkylene bonding to the R<SP>F</SP>through an amide bond, and one of the rest of the straight chain alkyl may be an alkylene group bonding to the amide nitrogen]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

    The present invention relates to a fluorine-containing surfactant, a composition thereof, and a fluorine-containing compound.

When the surfactant is blended as a composition, it gathers at the interface to reduce the surface tension, thereby improving the ease of spreading and penetrability of the composition.
Conventionally, it is known that the surface tension reducing ability of a fluorosurfactant is superior to a hydrocarbon surfactant or a silicone surfactant having a corresponding structure. For this reason, fluorinated surfactants have been used in a wide range of fields, and so far, fluorine-containing compounds having various structures useful for surfactants have been proposed.

  Fluorosurfactant has a structure in which a fluorinated alkyl skeleton is attached with an amphiphilic group. The surface tension reducing ability depends on the fluorination rate of the fluorinated alkyl skeleton, and the higher the fluorination rate, the lower the surface tension reducing ability. Is high and perfluorination is desirable. As a method for forming a perfluoroalkyl skeleton, an electrolytic fluorination method, a telomerization method, an oligomerization method, and the like are known.

As a compound having a perfluoro skeleton, for example, as an emulsifier for fluoroelastomer emulsion polymerization, R ^F O — (— CF ₂ CF ₂ O—) _n —CF ₂ —COOM (R ^F is a C 1-6 perfluoroalkyl group) , N is an integer including 0, M is Na or NH ₄ ) (see Patent Documents 1 to 3, etc.), and R ^F O — (— OCF ₂ CF ₂ —) _n — (OCF ₂ — ) _m -COOZ ^{(R F} is a linear, branched or cyclic perfluoroalkyl group, n and m are 4 or less in total, independently integers of 0 to 3, Z is a linear H or _{C 1 to 4} or A carboxylic acid or ester represented by (branched alkyl) has been proposed (see Patent Document 4). A compound represented by each formula when n or m in these formulas is an integer of 1 or more is a carboxylic acid of a perfluoropolyether skeleton, or a salt or ester derivative thereof.

As described above, the fluorosurfactant is excellent in surface tension lowering ability, but it is desired that it is effective even at a lower concentration, that is, the amount of the surfactant used can be reduced. Further, the effectiveness as a surfactant is required not only to reduce the static surface tension with respect to the static interface but also to reduce the dynamic surface tension when the interface is disturbed by stirring or the like. As described above, the surfactant has been used for various applications in anticipation of the effect of reducing the static or dynamic surface tension, but in the actual application field, a higher capacity is required. .
In order to respond to such a request, it has been proposed to mix a fluorine-containing compound and a hydrocarbon surfactant (see Patent Document 5), but it is costly to use a plurality of compounds as in this method. Causes high.
JP 61-223007 A JP 2002-317003 A JP 2003-119204 A US Pat. No. 5,118,494 Special table 2003-535950 gazette

  The present invention has excellent surface tension reducing ability even when used alone, and can exhibit sufficient surface tension reducing ability even at a concentration lower than the normal surfactant concentration. An object of the present invention is to provide a fluorine-containing surfactant having a lowering ability, a composition containing the surfactant, and a novel fluorine-containing compound useful as a surfactant.

In the present invention, the above-described object is achieved by using a perfluoropolyether skeleton that does not contain a long-chain repeating unit and an amphiphilic group bonded via an amide-bonded alkylene (in the present specification, alkanediyl). This is achieved by a surfactant comprising a fluorine-containing compound having a specific structure composed of a nitrogen-containing group. That is, the surfactant of the present invention comprises a linear perfluoropolyether amide represented by the following formula (1).
R ^F -Z (1)
In the formula, R ^F is R ^F1 O — (— R ^F2 O—) _k —CF ₂ — [wherein R ^F1 is a linear perfluoroalkyl group having 1 to 8 carbon atoms, k is an integer of 2 to 6 And the two or more (—R ^F2 O—) units are the same or different linear oxyalkylene units having 1 to 6 carbon atoms. And a straight-chain perfluoropolyether group having 6 to 15 carbon atoms in total,
Z is a nitrogen-containing amphiphilic group selected from a halogen salt of quaternary ammonium, betaine, and amine oxide, and one of the groups bonded to the nitrogen is 2 carbon atoms bonded to R ^F through an amide bond. -6 linear or branched alkylene group, the remaining group is independently a linear alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and one of the remaining linear alkyl groups is bonded to the amide nitrogen. It may be a bonded alkylene group.

In the formula (1), R ^F is preferably represented by the following formula (A).
R ^F1 O (CF ₂ CF ₂ O) _k CF ₂ − (A)
However, R < ^F1 > here is a C1-C7 linear perfluoroalkyl group, and k is an integer of 2-5.

Preferred examples of R ^F group represented by the above (A), include the following.
_{CF 3 CF 2 O (CF 2} CF 2 O) 2 CF 2 - (A22)
_{F (CF 2) 4 O (} CF 2 CF 2 O) 2 CF 2 - (A42)
_{F (CF 2) 6 O (} CF 2 CF 2 O) 2 CF 2 - (A62)
Surfactants of the present invention where R ^F group is the above-mentioned formula (A22) ~ (A62) is represented by the following formula.
_{CF 3 CF 2 O (CF 2} CF 2 O) 2 CF 2 -Z (A22-Z)
_{F (CF 2) 4 O (} CF 2 CF 2 O) 2 CF 2 -Z (A42-Z)
_{F (CF 2) 6 O (} CF 2 CF 2 O) 2 CF 2 -Z (A62-Z)
Z is the same as described in (1).

  In the above formula (1), examples of the amphiphilic group Z include groups represented by the following formulas (Za) to (Zc).

However, ^{R 1} is hydrogen atom, ^{R 3} is either a linear alkyl group having 1 to 4 carbon atoms, or ^{R 1} and ^{R 3,} is an alkylene group having 1 to 4 carbon atoms by binding each other, R ² is a linear or branched alkylene group having 2 to 6 carbon atoms, R ⁴ is a linear alkyl group or linear hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁵ is a carbon number having 1 to 4 carbon atoms. A straight-chain alkyl group, X is a chlorine atom, a bromine atom or an iodine atom, and n is 1 or 2;

The amphiphilic group Z represented by the above formulas (Za) to (Zc) is more specifically represented by the following formulas (Za1) to (Zc1).

  In the present invention, as a more specific example in the case where the amphiphilic group Z is the above formula (Za1) to (Zc1), any one of the compounds represented by the following formulas (A-Za1) to (A-Zc1) is used. And a surfactant.

Ｒ^Ｆは、式（１）の説明と同様である。

R ^F is the same as in the description of formula (1).

The surfactant of the present invention exerts its effect even when used alone, but is not limited to single use, and may be used by mixing with other surfactants as necessary. it can.
The present invention also provides an aqueous surfactant composition comprising the surfactant as described above and an aqueous medium. The aqueous medium is water or a mixture of at least one of methanol, ethanol, or isopropyl alcohol and water.
The aqueous surfactant composition of the preferable aspect of this invention contains 0.0001-5 mass% of surfactant of this invention in the composition total amount.

  In the present invention, among the compounds represented by the above formula (1), the compounds represented by the formulas (A22-Za1) to (A62-Zc1) described later are provided as novel compounds. These compounds are useful as surfactants.

  Since the compound of the present invention has an excellent ability to lower the dynamic surface tension, it can exhibit an excellent effect even in a system in which the interface state changes quickly. In addition, a composition containing a surfactant as described above has recently been composed of an aqueous medium mainly composed of water in view of ease of handling in work, safety, and environmental problems. However, the surfactant of the present invention works particularly effectively in such an aqueous medium. In particular, since the compound according to the present invention is stable against an acid or a base due to the structure defined above, it can be effectively used as a surfactant for a solution in a wide pH range. Polyethylene oxide type surfactants are likely to precipitate at high temperatures, and the solubility decreases when the temperature is raised, whereas the composition according to the present invention hardly precipitates even at high temperatures and is soluble even when the temperature is raised. There is no decline. As with ordinary compounds, improvement in solubility due to an increase in solution temperature can be expected.

In the present specification, the compound represented by the formula (1) is also referred to as the compound (1), and the group represented by the formula (A) is also referred to as the group (A). The same applies to compounds and groups represented by other formulas. Moreover, what is displayed by% in this specification represents the mass% unless there is particular notice.
In the present invention, the fluorine-containing compound provided as a surfactant is composed of a perfluoropolyether skeleton that does not contain a long-chain repeating unit, and an amphiphilic nitrogen-containing group that is bonded to the skeleton via alkylene bonded with an amide. A linear perfluoropolyether amide having a specific structure represented by the following formula (1):
R ^F -Z (1)

In the formula, R ^F is a linear perfluoropolyether group having 6 to 15 carbon atoms and represented by R ^F1 O — (— R ^F2 O—) _k —CF ₂ —.
R ^F1 is a linear perfluoroalkyl group having 1 to 8, preferably 1 to 7, and more preferably 1 to 6 carbon atoms.
k is an integer of 2 to 6, preferably 2 to 5, more preferably 2 to 4, and 2 or 3 is particularly preferable. Two or more (—R ^F2 O—) units are linear or oxyalkylene units having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, and particularly preferably 2 oxyethanediyl. Unit.
The total number of R ^F chains contains 3 to 7 ether bonds in total, but this number is preferably 3 to 5, particularly preferably 3 or 4.

A preferred embodiment of the R ^F group can be represented by the following formula (A).
R ^F1 O (CF ₂ CF ₂ O) _k CF _2- (A)
R ^F1 is a linear perfluoroalkyl group having 1 to 7 carbon atoms. R ^F1 preferably has 1 to 6 carbon atoms from the viewpoint of solubility in water, and particularly preferably has an even number of carbon atoms.
k is an integer of 2 to 5, 2 to 4 are preferable, and 2 or 3 is particularly preferable.

More specific examples of the group (A) include the following groups.
CF ₃ O (CF ₂ CF ₂ O) ₃ CF _2- (A13)
CF ₃ O (CF ₂ CF ₂ O) ₄ CF _2- (A14)
CF ₃ O (CF ₂ CF ₂ O) ₅ CF _2- (A15)
CF ₃ O (CF ₂ CF ₂ O) ₆ CF _2- (A16)
_{C 2 F 5 O (CF 2} CF 2 O) 2 CF 2 - (A22)
_{C 2 F 5 O (CF 2} CF 2 O) 3 CF 2 - (A23)
_{C 2 F 5 O (CF 2} CF 2 O) 4 CF 2 - (A24)
_{C 2 F 5 O (CF 2} CF 2 O) 5 CF 2 - (A25)
_{C 2 F 5 O (CF 2} CF 2 O) 6 CF 2 - (A26)
F (CF ₂ ) ₃ O (CF ₂ CF ₂ O) ₂ CF _2- (A32)
F (CF ₂ ) ₃ O (CF ₂ CF ₂ O) ₃ CF _2- (A33)
F (CF ₂ ) ₃ O (CF ₂ CF ₂ O) ₄ CF _2- (A34)
F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF _2- (A42)
F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₃ CF _2- (A43)
F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₄ CF _2- (A44)
F (CF ₂ ) ₅ O (CF ₂ CF ₂ O) ₂ CF _2- (A52)
F (CF ₂ ) ₅ O (CF ₂ CF ₂ O) ₃ CF _2- (A53)
F (CF ₂ ) ₆ O (CF ₂ CF ₂ O) ₂ CF _2- (A62)
F (CF ₂ ) ₆ O (CF ₂ CF ₂ O) ₃ CF _2- (A63)
F (CF ₂ ) ₇ O (CF ₂ CF ₂ O) ₂ CF _2- (A72)
F (CF ₂ ) ₈ O (CF ₂ CF ₂ O) ₂ CF _2- (A82)

Among the above, the following are mentioned as a particularly preferable R ^F group.
_{CF 3 CF 2 O (CF 2} CF 2 O) 2 CF 2 - (A22)
_{F (CF 2) 4 O (} CF 2 CF 2 O) 2 CF 2 - (A42)
_{F (CF 2) 6 O (} CF 2 CF 2 O) 2 CF 2 - (A62)

Z in the compound (1) is a nitrogen-containing amphiphilic group selected from a halogen salt of quaternary ammonium, betaine and amine oxide. These quaternary ammonium halogen salts, betaines, and amine oxides are groups that impart an amphiphilic, preferably hydrophilic group, to the compound (1), that is, groups corresponding to a cationic group, a zwitterionic group, and a nonionic group, respectively. Yes, as long as they constitute these amphiphilic groups via nitrogen bonds contained therein. However, one of the groups attached to Shin'nakadachimoto nitrogen is a linear or branched alkylene (alkanediyl) group having 2 to 6 carbon atoms that binds to R ^F via an amide bond. The remaining group is independently a linear alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and one of the remaining linear alkyl groups may be an alkylene group bonded to the amide nitrogen. The betaine may be carboxybetaine or sulfobetaine.

Specific examples of such an amphiphilic group Z include groups represented by the following formulas (Za) to (Zc).

However, R ¹ is a hydrogen atom, R ³ is from 1 to 4 carbon atoms or preferably a straight chain alkyl group having 1 to 4 carbon atoms is a methyl or ethyl group, or R ¹ and R ³ by binding to each other An alkylene group.
R ² is a linear or branched alkylene group having 2 to 6 carbon atoms, preferably an alkylene group containing a linear portion having 2 to 3 carbon atoms.
R ⁴ is a straight-chain alkyl group or straight-chain hydroxyalkyl group having 1 to ⁴ carbon atoms, preferably a methyl group or an ethyl group, or a straight-chain hydroxyalkyl group having 2 to 3 carbon atoms.
R ⁵ is a linear alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.
X is a chlorine atom, a bromine atom, or an iodine atom, and n is 1 or 2.

The amphiphilic group Z represented by the above formulas (Za) to (Zc) is more specifically represented by the following formulas (Za1) to (Zc1).

  In the present invention, as a more specific example in the case where the amphiphilic group Z is the above formula (Za1) to (Zc1), any one of the compounds represented by the following formulas (A-Za1) to (A-Zc1) is used. And a surfactant.

Ｒ^Ｆは、式（１）の説明と同様である。

R ^F is the same as in the description of formula (1).

  Furthermore, the compound shown by the following formula (A22-Za1)-(A62-Zc1) can be mentioned as a more specific example of the said compounds (A-Za1)-(A-Zc1). In the present invention, any one of these groups of compounds (A22-Za1) to (A62-Zc1) is provided as a novel compound useful as a surfactant.

As described above, the compound (1), which is the surfactant according to the present invention, has a linear perfluoropolyether skeleton containing a plurality of ether bonds as a part that causes the ability to lower the surface tension, and has a philic group. As a compound having a specific structure having a nitrogen-containing amphiphilic group bonded to the skeleton via an amide bond. The surfactant of the present invention, which is an amide derivative of such a linear perfluoropolyether, is preferably produced as a by-product in the production process of the linear perfluoropolyether skeleton in order to avoid a decrease in surface tension reducing ability. It is desirable not to mix a compound having a branched perfluoroalkyl skeleton.
In addition, the surfactant of the present invention may be a single kind of compound (1) or may be composed of two or more compounds represented by formula (1) as necessary, but is a mixture of two or more. In view of the ability to lower the surface tension, it is desirable that at least the linear perfluoropolyether skeleton has a single length.

The surfactant of the present invention exhibits an excellent effect as a surfactant only with the compound (1), and thus is useful alone as a surfactant, but with other surfactants as necessary. It does not prevent you from using it together. Other surfactants can be used in combination with fluorine-based, silicone-based or hydrocarbon-based surfactants, and the content ratio thereof can be appropriately set according to the purpose.
Although there is no restriction | limiting in particular in the aqueous medium at the time of using a compound (1) as surfactant, As an example, water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, ethyl acetate, etc. are mentioned. The aqueous medium may be a mixed solvent of two or more types including water.

The compound (1) according to the present invention is not particularly limited as long as it has the structure specified above, and is produced by applying a known organic chemical reaction or a known facility according to the purpose. be able to. The agent for providing the linear perfluoropolyether group R ^F and the philic group Z is not particularly limited, and may be appropriately selected and used.

For example, a linear perfluoropolyether group R ^F is, can be obtained by appropriately applying a known perfluoroalkyl group forming methods. However, the perfluoroalkyl group produced by the electrolytic fluorination method tends to produce a branched perfluoroalkyl group as a by-product, and tends to yield a compound in which a linear and by-product branched perfluoroalkyl group is mixed. . In addition, a perfluoroalkyl group-containing compound obtained by the telomerization method is a mixture of a plurality of chain lengths due to the nature of the reaction, and thus it is difficult to obtain a compound having a single chain length. Moreover, since the perfluoroalkyl group synthesized by the oligomerization method has a branch, it is difficult to obtain a compound having only a linear perfluoroalkyl group.

In the present invention, as a method for fluorinating a polyether to obtain a single-length linear perfluoropolyether group, fluorination by a method described in the corresponding WO2000 / 56694, and fluorination sequentially by a fluorine gas. The method to do is selected.
The amide conjugate of the perfluoropolyether skeleton R ^F and the amphiphilic group Z can be obtained using, for example, perfluoropolyether carboxylic acid R ^F —COOH obtained by these fluorination methods as a starting material.
There are amidation of perfluoropolyether carboxylic acid with diamine or amidation of perfluoropolyether ester and diamine, and the reaction can be carried out in the presence or absence of water or water-soluble solvent, but preferably May be a reaction in the presence of a solvent that dissolves both the perfluoro compound and the diamine, or in the absence of a solvent. The same applies to the reaction for perfusing perfluoroalkylamine.

  The temperature and temperature of the amidation reaction are not particularly limited, but are preferably 0 ° C to 150 ° C, particularly preferably 10 ° C to 80 ° C. The pressure is not particularly limited, and is preferably from atmospheric pressure to 1 MPa, particularly preferably atmospheric pressure.

The surfactant comprising the compound (1) of the present invention exhibits the ability to lower the surface tension even in an aqueous medium. Accordingly, the present invention also provides an aqueous surfactant composition comprising compound (1) and an aqueous medium.
The aqueous surfactant composition of the present invention exhibits an excellent effect when it contains a single compound (1) as a surfactant, but it does not prevent other surfactants from being included as necessary. Absent. Other surfactants can include fluorine-based, silicone-based or hydrocarbon-based surfactants, and the content ratio can be appropriately set according to the purpose.
Moreover, as long as the objective of this invention is not impaired, two or more types of compounds (1) may be contained.

  The aqueous medium is not particularly limited, and examples thereof include water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, and ethyl acetate. The aqueous medium may be a mixed solvent of two or more types including water.

  The surfactant concentration in the aqueous surfactant composition is appropriately set depending on the purpose and use conditions, but the compound (1) is contained in an amount of 0.0001 to 5% in the total amount of the composition. Is preferred. This concentration is more preferably 0.005 to 1%. If it is less than 0.0001%, it is difficult to exhibit sufficient surface tension reducing ability, and if it exceeds 5%, the functionality of the main material may be canceled. The aqueous surfactant composition of the present invention exhibits an excellent surface tension lowering effect even at an extremely low concentration of the compound (1) of 0.001% (10 ppm), as will be shown in the examples described later. ing.

As described above, the compound (1) containing fluorine can reduce static and dynamic surface tension even if used alone, and has excellent surface active properties. Since it has, leveling agents such as wax, foaming aids, additives for the purpose of stable foam generation for foam extinguishing and fire extinguishing performance, cleaning agents, mold release agents, emulsifiers, rust preventives, latex stabilizers , Anti-fogging agent for agricultural film, pigment dispersant, wettability / penetration improvement of ink, paint, resist, etc., imparting water / oil repellency to curable resin, antifouling agent, etc. Yes, it can be applied to a wide range of uses such as cleaning and gravure printing.
The use of the surfactant of the present invention is not limited to the examples given here, and can be applied to a wide range of uses as long as the action thereof is not hindered.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Example 1 Quaternary ammonium salt: F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ —C (O) NH— (CH ₂ ) ₃ —N ⁺ (CH ₃ ) ₃ I ⁻ ( Synthesis Example of A42-Za1) <Synthesis of (A42-COF)>
In a method for obtaining perfluoroalkyl acid fluoride (R ^1F COF, where R ^1F is a perfluorooxyalkyl group corresponding to R ¹ of the raw material alcohol) from alcohol (R ¹ CH ₂ OH) disclosed in WO2000 / 56694 Accordingly, F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ COF (A42-COF) was obtained. The outline of the reaction process is shown in the following (1) to (3).
(1) Esterification R ¹ CH ₂ OH → R ¹ CH ₂ OCOR ^F
(2) Total fluorination in liquid phase (fluorinated solvent) R ¹ CH ₂ OCOR ^F → R ^1F CH ₂ OCOR ^F
(3) Ester decomposition R ^1F CH ₂ OCOR ^F → R ^1F COF
Each of the above steps can be performed with reference to details such as reaction conditions described in WO2000 / 56694. In addition, it is assumed that the description is given in this specification by citing the description described therein.

<Synthesis of (A42-COOH)>
F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ COF (2 g) obtained in Synthesis Example 1 and ion-exchanged water (30 mL) were added to a 100 mL flask. The mixture was stirred for 3 hours while removing generated HF by nitrogen blowing. Although the reaction system was separated into two layers at the beginning of the reaction, it became one layer as time passed. The reaction was terminated when it became more layers. Next, water and HF were distilled off under reduced pressure to obtain F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ COOH (A42-COOH) as a viscous liquid.

<Esterification>
In a 300 mL glass flask, F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ COOH (109.2 g, 0.20 mol) obtained above, isopropyl alcohol (27.3 g), Cyclohexane (19.1 g) and 98% sulfuric acid (1.1 g) were charged, and the mixture was heated to reflux at 75 ° C. The reaction was continued for 4 hours while water produced as a by-product by azeotropic dehydration with cyclohexane was distilled out of the reaction system. After cooling, the mixture was neutralized with an aqueous sodium carbonate solution, and the organic layer was recovered. The collected organic layer was washed with water to obtain a crude liquid containing cyclohexane, isopropyl alcohol, and F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ COOCH (CH ₃ ) ₂ . The crude liquid was distilled under reduced pressure (100 ° C./2.67×10 ³ Pa) to obtain F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ COOCH (CH ₃ ) ₂ (93.6 g). . As a result of analysis using gas chromatography, the purity was 99.1% and the yield was 79.6%.

<Amidation>
Next, in a 100 mL glass flask, F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ COOCH (CH ₃ ) ₂ (79.1 g, 0.135 mol), H ₂ N (CH ₂ ) _{When 3} N (CH ₃ ) ₂ (14.3 g, 0.140 mol) was charged and mixed at room temperature for 10 minutes, F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (92.1 g) was obtained. The yield was 98.1%.

<Hydrophilicity>
In a 100 mL glass flask, F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ (35 g, 0.0556 mol), isopropyl alcohol (35 g) ), Water (7.5 g), and CH ₃ I (8.3 g, 0.0584 mol) were aged at 40 ° C. for 6 hours to obtain compound (A42-Za1).

The NMR spectrum data of the compound (A42-Za1) is shown below.
¹ HNMR (300 MHz, solvent: CD ₃ OD, standard substance: hexamethyldisiloxane) δ (ppm): 2.02 (2H, m), 3.16 (9H, s), 3.35 (4H, m) .
¹⁹ FNMR (300 MHz, solvent: CD ₃ OD, standard substance: R-11 (CCl ₃ F)) δ (ppm): −77.9, −80.9, −83.1, −88.3, −126 .1

＜親水化＞
１００ｍＬのガラス製フラスコに、実施例１の＜アミド化＞で得られたアミドＦ（ＣＦ_２）_４Ｏ（ＣＦ_２ＣＦ_２Ｏ）_２ＣＦ_２ＣＯＮＨ（ＣＨ_２）_３Ｎ（ＣＨ_３）_２（３５ｇ、０.０５５６ｍｏｌ）、イソプロピルアルコ-ル（１５ｇ）、水（１５ｇ）、および３０％過酸化水素水（８.５６ｇ）を仕込み、６５℃で７時間撹拌し、化合物（Ａ４２-Ｚｃ1）を７２.３ｇ得た。収率は９８.３％であった。
化合物（Ａ４２-Ｚｃ1）のＮＭＲスペクトルデ-タを以下に記す。
^１ＨＮＭＲ（３００ＭＨｚ、溶媒：ＣＤ_３ＯＤ、標準物質：ヘキサメチルジシロキサン）δ（ｐｐｍ）２.０８（２Ｈ、ｍ）、３.３９（４Ｈ、ｍ）、３.２１（６Ｈ、ｓ）。
^１９ＦＮＭＲ（３００ＭＨｚ、溶媒：ＣＤ_３ＯＤ、標準物質：Ｒ-１１（ＣＣｌ_３Ｆ））δ（ｐｐｍ）：−７７.９、−８０.９、−８３.０、−８８.２、−１２６.０ Example 2 Synthesis Example of Amine Oxide (A42-Zc1)

<Hydrophilicity>
In a 100 mL glass flask, the amide F (CF ₂ ) ₄ O (CF ₂ CF ₂ O) ₂ CF ₂ CONH (CH ₂ ) ₃ N (CH ₃ ) ₂ ( 35 g, 0.0556 mol), isopropyl alcohol (15 g), water (15 g), and 30% aqueous hydrogen peroxide (8.56 g) were added, and the mixture was stirred at 65 ° C. for 7 hours to give compound (A42-Zc1). 72.3 g was obtained. The yield was 98.3%.
The NMR spectrum data of the compound (A42-Zc1) is shown below.
¹ HNMR (300 MHz, solvent: CD ₃ OD, standard substance: hexamethyldisiloxane) δ (ppm) 2.08 (2H, m), 3.39 (4H, m), 3.21 (6H, s).
¹⁹ FNMR (300 MHz, solvent: CD ₃ OD, standard substance: R-11 (CCl ₃ F)) δ (ppm): −77.9, −80.9, −83.0, −88.2, −126 0.0

＜アミド化＞
１００ｍＬのガラス製フラスコに、Ｒ^１長さが異なる原料アルコール（Ｒ^１ＣＨ_２ＯＨ）を用いて実施例１と同様に調製したエステルＣＦ_３ＣＦ_２Ｏ（ＣＦ_２ＣＦ_２Ｏ）_２ＣＦ_２ＣＯＯＣ_３Ｈ_７（４６.２ｇ、０.１ｍｏｌ）、ジメチルアミノプロピルアミンＨ_２Ｎ（ＣＨ_２）_３Ｎ（ＣＨ_３）_２（１０.７ｇ、０.１０５ｍｏｌ）を仕込み、室温で２０分間撹拌し、目的アミドとイソプロピルアルコールとを含む反応粗液５５.９ｇを得た。
＜親水化＞
上記で得られた反応粗液のうちの１６.９２ｇに、イソプロピルアルコール８.８ｇ、水７.６ｇ、３０％Ｈ_２Ｏ_２４.２ｇを添加し、６５℃で１５時間反応させ、目的物（Ａ２２-Ｚｃ1）のアミンオキシドを得た。 Example 3 Synthesis Example of Amine Oxide (A22-Zc1)

<Amidation>
Esters CF ₃ CF ₂ O (CF ₂ CF ₂ O) ₂ CF ₂ COOC prepared in the same manner as in Example 1 using raw alcohol (R ¹ CH ₂ OH) having different R ¹ lengths in a 100 mL glass flask ₃ H ₇ (46.2 g, 0.1 mol), dimethylaminopropylamine H ₂ N (CH ₂ ) ₃ N (CH ₃ ) ₂ (10.7 g, 0.105 mol) were charged and stirred at room temperature for 20 minutes. 55.9 g of a crude reaction solution containing the desired amide and isopropyl alcohol was obtained.
<Hydrophilicity>
To 16.92 g of the reaction crude liquid obtained above, 8.8 g of isopropyl alcohol, 7.6 g of water, and 4.2 g of 30% H ₂ O ₂ were added, and reacted at 65 ° C. for 15 hours. An amine oxide of (A22-Zc1) was obtained.

The NMR spectrum data of the compound (A22-Zc1) is shown below.
¹ HNMR (300 MHz, solvent: CD ₃ OD, standard substance: hexamethyldisiloxane) δ (ppm): 2.04 (m), 3.23 (m), 3.35 (m).
¹⁹ FNMR (300 MHz, solvent: CD ₃ OD, standard substance: R-11 (CCl ₃ F)) δ (ppm): −76.8, −78.0, −86.7, −87.9, −88 .1, -88.3
It should be noted that integrated values could not be measured for both ¹ H- and ¹⁹ F-NMR.

１００ｍＬのガラス製フラスコに、実施例３と同様に調製したエステルＣＦ_３ＣＦ_２Ｏ（ＣＦ_２ＣＦ_２Ｏ）_２ＣＦ_２ＣＯＯＣ_３Ｈ_７（１５.１２ｇ、０.０３０ｍｏｌ）、ヒドロキシエチルピペラジン（４.０ｇ、０.０３１ｍｏｌ）を仕込み、室温で２時間撹拌した。
その後、イソプロピルアルコール１５.４ｇを加え、４０℃に昇温後、ＩＣＨ_２ＣＯＯＨ５.８６ｇ（０.０３２ｍｏｌ）を加え、さらに３時間後、３０％ＮａＯＨ４.０ｇを添加、４０℃で５時間保持した後、析出物をろ別し、イソプロピルアルコール・水混合溶液として目的物（Ａ２２-Ｚｂ２）を３６.６ｇ回収した。収率は９０.９％であった。 (Example 4) Synthesis example of betaine (A22-Zb2)

In a 100 mL glass flask, ester CF ₃ CF ₂ O (CF ₂ CF ₂ O) ₂ CF ₂ COOC ₃ H ₇ (15.12 g, 0.030 mol), hydroxyethylpiperazine (4 0.0 g, 0.031 mol), and stirred at room temperature for 2 hours.
Thereafter, 15.4 g of isopropyl alcohol was added, the temperature was raised to 40 ° C., 5.86 g (0.032 mol) of ICH ₂ COOH was added, and after another 3 hours, 4.0 g of 30% NaOH was added and held at 40 ° C. for 5 hours. Thereafter, the precipitate was filtered off, and 36.6 g of the target product (A22-Zb2) was recovered as a mixed solution of isopropyl alcohol and water. The yield was 90.9%.

The NMR spectrum data of the compound (A22-Zb2) is shown below.
¹ HNMR (300 MHz, solvent: CD ₃ OD, standard substance: hexamethyldisiloxane), δ (ppm): 3.86 (m), 3.76 (t), 3.41 (d), 3.28 ( d) 3.04 (t).
¹⁹ FNMR (300 MHz, solvent: CD ₃ OD, standard substance: R-11 (CCl ₃ F)) δ (ppm): −71.3, −76.9, −86.8, −87.9, −88 .2, -88.3
It should be noted that integrated values could not be measured for both ¹ H- and ¹⁹ F-NMR.

(Example 5) quaternary ammonium _{salts: CF 3 CF 2 O (CF} 2 CF 2 O) 2 CF 2 -C (O) NH- (CH 2) 3 -N + (CH 3) 3 I - (A22- Synthesis Example of Za1) Using the reaction crude liquid containing the amide synthesized in Example 3, the same <hydrophilization> step of Example 1 was performed to obtain the target compound (A22-Za1).

(Comparative Example 1)
Using H (CH ₂ ) ₄ OCH ₂ CH ₂ OCH ₂ —CH ₂ OH as the raw material alcohol, H (CF ₂ ) ₄ OCF ₂ CF ₂ OCF ₂ —C (O) according to each step of Example 1 ^{_{NH- (CH 2) 3 -N +}} (CH 3) 3 I - I was synthesized. This compound has a general formula showing the compound of the present invention, and the number of repetitions represented by k is 1 (that is, not repeated), and the oxyfluoroalkylene unit (CF ₂ CF ₂ ) is more than the compound of Example 5 (A22-Za1). O) is one shorter (total carbon number is equal).

(Test Example 1) Measurement of static surface tension Compound (A42-Za1) synthesized in Example 1, Compound (A42-Zc1) synthesized in Example 2, Compound (A22-Zc1) synthesized in Example 3, The compound synthesized in Example 4 (A22-Zb1), the compound synthesized in Example 5 (A22-Za1), and the compound synthesized in Comparative Example 1 were diluted with water, and 0.01% by mass and 0.001 respectively. An aqueous surfactant composition was obtained by preparing a mass% aqueous solution.
Static surface tension was measured for these aqueous surfactant compositions. The static surface tension is measured by using an automatic surface tension meter CBVP-A3 type apparatus manufactured by Kyowa Interface Chemical Co., Ltd., and standing at 25 ° C. for 30 minutes by the Wilhelmy method (hanging plate method). It was measured. The results are shown in Table 1.

(Comparative Example 2)
A well-known fluorine-containing surfactant (DuPont, trade name: ZONYL-FSO) is diluted in the same manner as in Example 1 to prepare an aqueous surfactant composition. Tension was measured. The results are shown in Table 1.
The structural formula of ZONYL-FSO described in the catalog of Surface DuPont is as follows.
_{CF 3 CF 2 (CF 2 CF} 2) n -CH 2 CH 2 O (CH 2 CH 2 O) x H
(Where n is an integer of 2 to 4, x is an integer)

(Test Example 2) Measurement of dynamic surface tension The compounds of Examples 1, 3 and Comparative Example 2 were each diluted with water to prepare 0.05% by mass aqueous solutions as aqueous surfactant compositions. . The dynamic surface tension was measured for these aqueous surfactant compositions. The dynamic surface tension was measured by using a BP-D2 type apparatus manufactured by Kyowa Interface Chemical Co., Ltd. and measuring the dynamic surface tension at a frequency at 25 ° C. by the bubble pressure method. The results are shown in Table 2.

As shown in each of the above tables, the surfactant of the present invention has an excellent surface tension reducing ability, and an excellent surface even at an extremely low concentration of about 0.001% (10 ppm), in particular, compared to known surfactants. It can be seen that the tension lowering ability is shown. In addition, the surfactant of the present invention has an excellent decrease in dynamic surface tension as the bubbling frequency increases and the interface becomes more turbulent in relative evaluation of dynamic surface tension in comparison with known surfactants. It was also confirmed to show ability.
Even if it is a compound other than the compound shown in the said Example, if it is a compound contained in this invention, it is excellent in the ability to reduce surface tension similarly.

Claims (5)

Surfactant comprising a linear perfluoropolyether amide represented by the following formula (1):
R ^F -Z (1)
In the formula, R ^F is R ^F1 O — (— R ^F2 O—) _k —CF ₂ — [wherein R ^F1 is a linear perfluoroalkyl group having 1 to 8 carbon atoms, k is an integer of 2 to 6 And the two or more (—R ^F2 O—) units are the same or different linear oxyalkylene units having 1 to 6 carbon atoms. And a straight-chain perfluoropolyether group having 6 to 15 carbon atoms in total,
Z is a nitrogen-containing amphiphilic group selected from a halogen salt of quaternary ammonium, betaine, and amine oxide, and one of the groups bonded to the nitrogen is 2 carbon atoms bonded to R ^F through an amide bond. -6 linear or branched alkylene group, the remaining group is independently a linear alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and one of the remaining linear alkyl groups is bonded to the amide nitrogen. It may be a bonded alkylene group. The surfactant according to claim 1, wherein Z is selected from the groups represented by the following formulas (Za) to (Zc):

However, ^{R 1} is hydrogen atom, ^{R 3} is either a linear alkyl group having 1 to 4 carbon atoms, or ^{R 1} and ^{R 3,} is an alkylene group having 1 to 4 carbon atoms by binding each other, R ² is a linear or branched alkylene group having 2 to 6 carbon atoms, R ⁴ is a linear alkyl group or linear hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁵ is a carbon number having 1 to 4 carbon atoms. A straight-chain alkyl group, X is a chlorine atom, a bromine atom or an iodine atom, and n is 1 or 2; The surfactant according to claim 1 or 2, wherein R ^F is a group represented by the following formula (A):
R ^F1 O (CF ₂ CF ₂ O) _k CF _2- (A)
However, R < ^F1 > here is a C1-C7 linear perfluoroalkyl group, and k is an integer of 2-5.   An aqueous surfactant composition comprising the surfactant according to any one of claims 1 to 3 and an aqueous medium. Any compound selected from the group consisting of compounds represented by the following formulas (A22-Za1) to (A62-Zc1).