JP5214945B2 - Fluorine-containing compound and surfactant composition - Google Patents

Description

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

  Surfactants gather at the interface of the added liquid and reduce the surface tension of the liquid, so that they are widely used, for example, for the purpose of improving permeability. In particular, a surfactant having a fluorine-containing alkyl group as a hydrophobic group exhibits excellent penetrability, wettability, and leveling properties when added to a coating composition or the like. Therefore, surfactant compositions containing fluorine-containing compounds having various structures have been shown so far.

For example, as a fluorine-containing compound contained in a surfactant composition used as a leveling agent, a penetrating agent, or the like, a fluorine-containing compound having an amine oxide is disclosed (Patent Document 1).
However, in the above applications, since it is required to develop high performance with a smaller amount of use, a surfactant composition exhibiting excellent surface tension reducing ability at a lower concentration is desired.
JP 2003-183242 A

The present invention relates to a fluorine-containing compound effective as a surfactant exhibiting excellent surface tension reducing ability even at a low concentration, a surfactant composition containing the fluorine-containing compound, and a composition containing the fluorine-containing compound. Provide a method.
The present invention also provides a fluorine-containing compound effective as a raw material for a fluorine-containing compound particularly effective as the surfactant.

ただし、式（Ｉ）中、Ｒｆ ^１１ およびＲｆ ^２１ がＣ _６ Ｆ _１３ であり、Ａ ^１ およびＢ ^１ が水酸基を有する炭素原子数２〜４のアルキレン基であり、Ｒ ^１１ が炭素原子数２または３のアルキレン基であり、Ｒ ^２１ およびＲ ^３１ が炭素原子数１〜４のアルキル基である。 The present invention provides a fluorine-containing compound represented by the following formula (I).

In the formula (I), ^{Rf 11} and ^{Rf 21} is the _C 6 _{F 13,} an alkylene group having 2 to 4 carbon atoms with ^{A 1} and ^{B 1} is hydroxyl ^{group, R 11} is the number 2 or carbon atom 3 and R ²¹ and R ³¹ are each an alkyl group having 1 to 4 carbon atoms.

ただし、式（Ｉａ）及び式（Ｉｂ）中の記号は前記式（Ｉ）における記号と同じ意味を示す。 The surfactant composition of the present invention contains any of the fluorine-containing compounds represented by the formula (I).
The surfactant composition of the present invention may further contain a fluorine-containing compound represented by the following formula (Ia) and a fluorine-containing compound represented by the following formula (Ib).

However, the symbols in the formulas (Ia) and (Ib) have the same meaning as the symbols in the formula (I).

ただし、式（ＩＩ）、Ｒｆ ^３ がＣ _６ Ｆ _１３ であり、Ｘ ^１ が水酸基を有する炭素原子数２〜４のアルキレン基である。Ｒ^１１、Ｒ^２１、Ｒ^３１ は前記式（Ｉ）における記号と同じ意味を示す。 Moreover, the surfactant composition of the present invention may further contain a fluorine-containing compound represented by the following formula (II).

However, formula (II), Rf ³ is a _C 6 _{F 13,} ^{X 1} is an alkylene group having 2 to 4 carbon atoms having a hydroxyl group. R ¹¹ , R ²¹ and R ³¹ have the same meaning as the symbols in the formula (I).

According to the fluorine-containing compound and the surfactant composition containing the fluorine-containing compound of the present invention, excellent surface tension reducing ability can be obtained even at a low concentration.
Moreover, according to the manufacturing method of this invention, the composition containing the fluorine-containing compound which shows the outstanding surface tension reduction ability even if it is a low density | concentration is obtained.
In addition, when a fluorine-containing compound effective particularly as a raw material of the present invention is used, a fluorine-containing compound exhibiting excellent surface tension reducing ability can be easily obtained even at a low concentration.

[Fluorine-containing compound (I)]
Hereinafter, the compound represented by the following formula (I) which is the fluorine-containing compound of the present invention (hereinafter referred to as fluorine-containing compound (I)) will be described.

Rf ¹¹ in the fluorine-containing compound (I) is a perfluoroalkyl group or a perfluoroether group having 1 to 14 carbon atoms.
The perfluoroalkyl group means a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.
When Rf ¹¹ is a perfluoroalkyl group, the number of carbon atoms is preferably 4 to 6, and particularly preferably 6 (C ₆ F ₁₃ ). The perfluoroalkyl group may be linear or branched, and is preferably linear.

A perfluoroether group means a group in which an etheric oxygen atom is inserted between one or more carbon-carbon atoms in a perfluoroalkyl group.
If Rf ¹¹ is a perfluoroalkyl ether group, more preferably the number of carbon atoms is 4 to 6, particularly preferably 6. Further, the perfluoroether group may be linear or branched, and is preferably linear.
Specific examples of the case where Rf ¹¹ is a perfluoroether group include C ₄ F ₉ OC ₂ F ₄ .
Rf ²¹ may be the same as Rf ^11, and the preferred embodiment is also the same.
Rf ¹¹ and Rf ²¹ may be the same or different from each other, and are preferably the same.

A ¹ is a divalent linking group.
Examples of the divalent linking group include —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, —NH—, —N (R ⁴ ) — (R ⁴ ). Is an alkyl group having 1 to 3 carbon atoms), a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of these, and the like. May be. Examples of the substituent include a halogen atom and a hydroxyl group, and a hydroxyl group is preferable. The divalent aliphatic hydrocarbon group may be linear or branched. The carbon atom in the divalent aliphatic hydrocarbon group may be substituted with an etheric oxygen atom, a thioetheric sulfur atom, an ester bond, a carbonyl group, or the like.

As preferable divalent linking groups, an alkylene group having 1 to 12 carbon atoms which may have a substituent, —CO—, —NH—, —N (R ⁴ ) —, —CH (OH) — , —CH (CH ₂ OH) —, —O—, —S—, or a combination thereof. The alkylene group may be linear or branched.
Among them, A ¹ may have a substituent, and is more preferably an alkylene group having 1 to 6 carbon atoms in which a carbon atom in the group may be substituted with an etheric oxygen atom, Particularly preferred is an alkylene group having 2 to 4 carbon atoms having a hydroxyl group as a substituent.

B ¹ is a divalent linking group, and examples thereof include the same as A ^1, and preferred embodiments are also the same.
A ¹ and B ¹ may be the same or different from each other, and are preferably the same.
Rf ¹¹ -A ¹ and Rf ²¹ -B ¹ may be the same or different from each other, and are preferably the same.

R ¹¹ is an alkylene group having 2 to 6 carbon atoms and may have a substituent.
Examples of the substituent, the same thing can be mentioned those mentioned in A ^1, it is preferably a hydroxyl group R ¹¹ may be a branched be linear, and is preferably linear.
The number of carbon atoms of R ¹¹ is particularly preferably 2 or 3.

R ²¹ and R ³¹ are each independently an alkyl group having 1 to 6 carbon atoms, and may have a substituent.
Examples of the substituent, the same thing can be mentioned those mentioned in A ^1, it is preferably a hydroxyl group.
R ²¹ and R ³¹ may each be linear or branched, and are preferably linear.
R ²¹ and R ³¹ are each preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R ²¹ and R ³¹ are preferably the same as each other.

A ring having 4 to 12 carbon atoms may be formed by R ²¹ and R ³¹ . The carbon atoms forming the ring may be substituted with a nitrogen atom or an oxygen atom to which either a hydrogen atom or an alkyl group is bonded. Specific examples of the ring structure include a piperidine ring, a morpholine ring, and an N-alkyl piperazine ring.

The fluorine-containing compound (I) is not particularly limited, but specific examples include those exemplified in Table 1.

Further, examples of the fluorine-containing compound (I) in which a ring having 4 to 12 carbon atoms is formed by R ²¹ and R ³¹ include those represented by the following formula.

Among them, in the fluorine-containing compound (I), Rf ¹¹ and Rf ²¹ are perfluoroalkyl groups having 4 to 6 carbon atoms, and A ¹ and B ¹ may have a substituent. It is preferable that it is a C1-C6 alkylene group by which the carbon atom may be substituted by the etheric oxygen atom (for example, I-1 to I-13 of Table 1).
Particularly preferred fluorine-containing compound (I) is that Rf ¹¹ and Rf ²¹ are C ₆ F ₁₃ , R ¹¹ is an alkylene group having 2 or 3 carbon atoms, and A ¹ and B ¹ are hydroxyl groups as substituents. And a fluorine-containing compound in which R ²¹ and R ³¹ are alkyl groups having 1 to 4 carbon atoms (for example, I-3 to I-8 in Table 1). .

[Surfactant composition]
The surfactant composition of the present invention is a composition containing the fluorine-containing compound (I). Only 1 type may be sufficient as the fluorine-containing compound (I) contained, and 2 or more types may be sufficient as it.
The content of the fluorine-containing compound (I) in the surfactant composition is preferably 0.0001 to 10% by mass with respect to the total mass (100% by mass) of the surfactant composition. More preferably, it is .0005 to 5% by mass.
When the content of the fluorine-containing compound (I) is 0.0001% by mass or more, the effect of lowering the surface tension, the effect of lowering the interfacial tension between water / organic solvent, and the like are sufficiently obtained. If content of a fluorine-containing compound (I) is 10 mass% or less, it will be easy to suppress inhibiting the effect which the other component contained in surfactant composition has.

  However, the said content means content at the time of use of surfactant composition. That is, when the surfactant composition (product) containing 10% by mass of the fluorine-containing compound (I) is diluted 10 times and used, the content is 1% by mass. When using 2 or more types of fluorine-containing compounds (I), it is preferable that the total amount is in the said range.

ただし、式（Ｉａ）および式（Ｉｂ）中の記号は式（Ｉ）における記号と同じものを意味する。 The surfactant composition of the present invention comprises a fluorine-containing compound represented by the following formula (Ia) (hereinafter referred to as fluorine-containing compound (Ia)) and a fluorine-containing compound represented by the following formula (Ib) (hereinafter referred to as “fluorine-containing compound”). , Fluorine-containing compound (Ib)) may be further contained.

However, the symbols in formula (Ia) and formula (Ib) mean the same symbols as in formula (I).

When the surfactant composition contains the fluorinated compound (I), the fluorinated compound (Ia), and the fluorinated compound (Ib), the mixing ratio thereof is not particularly limited. The total content of the fluorine-containing compounds (I) to (Ib) in the surfactant composition is 0.0001 to 10 with respect to the total mass (100% by mass) of the surfactant composition. It is preferable that it is mass%, and it is more preferable that it is 0.0005-5 mass%.
However, the said content means content at the time of use of surfactant composition. That is, when the surfactant composition (product) containing 10% by mass of the fluorine-containing compound (I), the fluorine-containing compound (Ia), and the fluorine-containing compound (Ib) is diluted 10 times, The content is 1% by mass. When using two or more of fluorine-containing compound (I), fluorine-containing compound (Ia), and fluorine-containing compound (Ib) (for example, one fluorine-containing compound (I) and two kinds of fluorine-containing compounds) The total amount of compound (Ia) and one fluorine-containing compound (Ib) is preferably within the above range.

ただし、式（ＩＩ）中の記号は以下の意味を示す。
Ｒｆ^３は、炭素原子数１〜１４の、パーフルオロアルキル基またはパーフルオロエーテル基である。Ｘ^１は２価の連結基である。また、Ｒ^１１、Ｒ^２１、およびＲ^３１は、前記式（Ｉ）における記号と同じである。
Ｒｆ^３は、Ｒｆ^１１と同じものが挙げられ、好ましい態様も同じである。Ｘ^１はＡ^１で挙げたものと同じものが挙げられ、好ましい態様も同じである。
Ｒｆ^３−Ｘ^１は、Ｒｆ^１１−Ａ^１またはＲｆ^２１−Ｂ^１と同じであることが好ましい。 In addition to the fluorine-containing compounds (I) to (Ib), the surfactant composition of the present invention further includes a fluorine-containing compound represented by the following formula (II) (hereinafter referred to as fluorine-containing compound (II)). ) May be contained.

However, the symbols in formula (II) have the following meanings.
Rf ³ is a perfluoroalkyl group or a perfluoroether group having 1 to 14 carbon atoms. X ¹ is a divalent linking group. R ¹¹ , R ²¹ , and R ³¹ are the same as the symbols in the formula (I).
Rf ³ may be the same as Rf ¹¹ and the preferred embodiment is also the same. X ¹ may be the same as mentioned for A ¹ , and the preferred embodiment is also the same.
Rf ³ -X ¹ is preferably the same as Rf ¹¹ -A ¹ or Rf ²¹ -B ¹ .

When the surfactant composition contains the fluorine-containing compound (II), the fluorine-containing compound (I) (substance amount: M _I ), the fluorine-containing compound (Ia) (substance amount: M _Ia ), and the fluorine-containing compound (Ib) (Substance amount: M _Ib ) The total amount of each substance [M _I + M _Ia + M _Ib ] and the molar ratio of the fluorine-containing compound (II) substance amount M _II is [M _I + M _Ia + M _Ib ]: M _II = 10: 90 to 95: 5 is preferable, and 15:85 to 90:10 is more preferable.
When the total amount of the fluorine-containing compounds (I), (Ia) and (Ib) is larger than the molar ratio ([M _I + M _Ia + M _Ib ]: M _II = 10: 90), sufficient surface tension reducing ability Easy to get.

The surfactant composition of the present invention may contain a solvent, other additives and the like in addition to the fluorine-containing compound.
Examples of the solvent include water and organic solvents.
Examples of the organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and t-butanol; esters such as ethyl acetate, methyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and N-methylpyrrolidone; glycol ethers such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; glycols such as ethylene glycol and propylene glycol; diethyl ether , Ethers such as tetrahydrofuran and dioxane; nitrogen-containing solvents such as pyridine and piperazine; paraffins such as hexane, octane, decane and isohexane; Toluene, xylene and the like aromatic hydrocarbons; 2,2,3,3-tetrafluoropropanol, a fluorine-containing solvents such as m- xylene hexafluoride and the like.
A solvent may be used individually by 1 type and may use 2 or more types together.
There is no limitation in particular as another additive, What is necessary is just to select suitably according to the use etc. of the said surfactant composition.

By adding the surfactant composition of the present invention to various liquids, the surface tension of the liquid can be lowered without being limited by the solvent composition. Moreover, functions, such as leveling property, permeability, foaming property, washing | cleaning property, emulsifying property, can be provided to the added liquid by the surface tension decreasing ability. Moreover, since the surfactant composition of the present invention can exhibit a sufficient surface tension reducing ability even at a low concentration, it can be suitably used for various applications.
Applications of the surfactant composition of the present invention include, for example, penetrants, wettability improvers, leveling agents, paint / pigment additives, emulsifiers, fire extinguishing agents, floor waxes, cleaning agents, foaming agents, antifoaming agents. , Lubricants, oil fields, rust inhibitors, antistatic agents, water repellents, flotation agents, smoothing agents, deinking agents and the like.

[Fluorine-containing compound (III)]
Next, the fluorine-containing compound represented by the following formula (III) (hereinafter referred to as fluorine-containing compound (III)) will be described. The fluorine-containing compound (III) is particularly useful as a raw material for the fluorine-containing compound (I).

Rf ¹² and Rf ²² in the fluorine-containing compound (III) are a perfluoroalkyl group or a perfluoroether group having 1 to 14 carbon atoms. Rf ¹² and Rf ²² may be the same as those described for Rf ¹¹ , and preferred embodiments are also the same. Rf ¹² and Rf ²² may be the same or different from each other, and are preferably the same.
A ² and B ² are divalent linking groups, and the same examples as those described for A ¹ can be mentioned, and preferred embodiments are also the same. A ² and B ² may be the same or different from each other, and are preferably the same.
Rf ¹² -A ² and Rf ²² -B ² may be the same as or different from each other, and are preferably the same.

R ¹² is an alkylene group having 2 to 6 carbon atoms, and may have a substituent. ^{Further, R 12} is ^the same thing can be mentioned as ^{R 11,} and their preferred embodiments are also the same.
R ²² and R ³² are each independently an alkyl group having 1 to 6 carbon atoms and may have a substituent. R ²² and R ³² are the same as R ²¹ and R ^31, and preferred embodiments are also the same.

The fluorine-containing compound (III) is not particularly limited, but specific examples include those exemplified in Table 2.

A ring having 4 to 12 carbon atoms may be formed by R ²² and R ³² . Examples of the fluorine-containing compound (III) in which a ring having 4 to 12 carbon atoms is formed by R ²² and R ³² include those represented by the following formula.

In the fluorine-containing compound (III), A ² and B ² may have a substituent, and a carbon atom in the group may be substituted with an etheric oxygen atom. R ¹² is preferably an alkylene group having 2 to 6 carbon atoms, and R ²² and R ³² are preferably alkyl groups having 1 to 6 carbon atoms.
Rf ¹² and Rf ²² are a perfluoroalkyl group or a perfluoroether group having 4 to 6 carbon atoms, A ² and B ² may have a substituent, and the carbon atom in the group is An alkylene group having 1 to 6 carbon atoms which may be substituted with an etheric oxygen atom is preferable (for example, III-1 to III-13 in Table 2).
Particularly preferred fluorine-containing compound (III) is that Rf ¹² and Rf ²² are a perfluoroalkyl group or a perfluoroether group having 4 to 6 carbon atoms, and A ² and B ² have a substituent. Well, the carbon atom in the group is an alkylene group having 1 to 6 carbon atoms which may be substituted with an etheric oxygen atom, R ¹² is an alkylene group having 2 to 6 carbon atoms, R ²² and R ³² is a fluorine-containing compound in which ³² is an alkyl group having 1 to 6 carbon atoms (for example, III-1 to III-8 in Table 2).

When the fluorine-containing compound (I) is produced using the fluorine-containing compound (III) as a raw material, Rf ¹¹ , Rf ²¹ , A ¹ , B ¹ , R ¹¹ , R ²¹ , R ³¹ of the fluorine-containing compound (I) are These are the same as Rf ¹² , Rf ²² , A ² , B ² , R ¹² , R ²² , R ^{32 in the} fluorine-containing compound (III), respectively.

[Production method]
The production method of the fluorine-containing compound (I) of the present invention comprises a fluorine-containing compound represented by the formula (IV) (hereinafter referred to as fluorine-containing compound (IV)) and a formula (V) as shown in the following formula: And a fluorine-containing compound represented by the following formula (VI) (hereinafter referred to as a fluorine-containing compound (VI)). And a step (step (b)) of reacting a compound having an —O—O— bond with the obtained mixture. Thereby, the composition containing fluorine-containing compound (I), (Ia), (Ib), and (II) is obtained.

Rf ⁴ in the fluorine-containing compound (IV) is a perfluoroalkyl group or a perfluoroether group having 1 to 14 carbon atoms. Rf ⁴ may be the same as Rf ¹¹ in the fluorine-containing compound (I), and the preferred embodiment is also the same.
M ¹ is a divalent linking group or a single bond. Examples of the divalent linking group include an alkylene group, —O—, —S—, —SO—, —SO ₂ —, —CO—, —CO ₂ —, —NH—, —N (R ⁵ ) — (R ⁵ is an alkyl group having 1 to 3 carbon atoms), or a combination thereof, and may have a substituent. The alkylene group may be linear or branched. Examples of the substituent include the same as those listed in A ^1.
Z ¹ is a reactive group. However, the reactive group possessed by the fluorine-containing compound (IV) in the present invention is a group for reacting the fluorine-containing compound (IV) with the primary amine moiety of the compound (V).
Examples of Z ¹ include halogen atoms such as chlorine atom, bromine atom and iodine atom, acyl halide groups such as acyl chloride group, acyl fluoride group, acyl bromide group and acyl iodide group, carboxyl group and carboxylic acid Examples include ester groups and epoxy groups (Table 3).
^{R 12,} R ^{22, R 32} in the compound (V) show respectively the same meaning as ^{R 12,} R ^{22, R 32} in the formula (III).

In the present invention, in step (a), by causing the fluorinated compound (IV) and of compounds and (V) is reacted, the fluorine-containing compound (III) and fluorine-containing compound (VI) is obtained.
Rf ⁴ in the fluorine-containing compound (IV) becomes Rf ¹² and Rf ^{22 of} the fluorine-containing compound (III) and Rf ^{3 of the} fluorine-containing compound (VI) by the reaction in the step (a).
M ¹ -Z ¹ in the fluorine-containing compound (IV) becomes A ² and B ^{2 of} the fluorine-containing compound (III) and X ^{1 of the} fluorine-containing compound (VI) by the reaction in the step (a).

M ¹ -Z ¹ is the case where Z ¹ is eliminated after the reaction in step (a) and only M ¹ becomes A ² , B ² , and X ¹ , and M ¹ and Z ^{1 represent} A ² , B ² , and X ¹ may be derived.
Examples of the case where only M ¹ is A ² , B ² and X ¹ include M ¹ -Z ¹ where M ¹ is an alkylene group and Z ¹ is a halogen atom (III- in Table 2). 10, synthesis of III-11).
Further, as a case where the divalent linking group is derived from ^{M 1} and ^{Z 1} Prefecture, for example, ^{M 1} is an alkylene group, ^{Z 1} can be cited ^M 1 -Z ¹ and the like is an epoxy group (Table 2 III-1 to III-9 and III-12 to III-13). Further, ^{M 1} is a single bond, ^M 1 -Z ¹ and the like ^{Z 1} is acyl halide group (Synthesis of Table 2 III-14~III-16).

Fluorine-containing compound (IV) and of compound (V) may be used alone individually or as a combination of two or more thereof.
When the fluorine-containing compound (IV) is one kind, Rf ¹² -A ² and Rf ²² -B ^{2 of} the fluorine-containing compound (III) and Rf ³ -X ^{1 of the} fluorine-containing compound (VI) are the same. .
When the fluorine-containing compound (IV) is 2 or more, the reaction activity of each of the fluorine-containing compound (IV), varies depending mixing ratio, the fluorine-containing compound ^{(III), Rf} 12 -A ² and ^{Rf 22} - A mixture of the same and different B ² is used, and the fluorine-containing compound (VI) is a mixture of two or more of Rf ³ -X ¹ .

ただし、式（ＩＩＩ−Ａ）、（ＩＶ−Ａ）、（ＶＩ−Ａ）中の記号は前記式（ＩＩＩ）、（ＩＶ）、（ＶＩ）における記号と同じ意味を示す。 As described above, in the step (a), a mixture of the fluorine-containing compound (III) and the fluorine-containing compound (VI) is obtained by reacting the fluorine-containing compound (IV) with the compound (V).
As a specific example, for example, by reacting a fluorine-containing compound represented by the following formula (IV-A), in which M ¹ is methylene and Z ¹ is an epoxy group, with compound (V), A mixture of the fluorine-containing compound represented by the formula (III-A) and the fluorine-containing compound represented by the following formula (VI-A) is obtained.

However, the symbols in formulas (III-A), (IV-A), and (VI-A) have the same meanings as the symbols in formulas (III), (IV), and (VI).

The reaction of the fluorine-containing compound (IV) (substance amount: M _IV ) and the compound (V) (substance amount: M _V ) is carried out using a molar ratio of M _IV : M _V = 1.1: 1.0 to 2.0 : 1.0, and it is more preferable to carry out as M _IV : M _V = 1.15: 1.0 to 1.8: 1.0.
By setting the amount of the fluorine-containing compound (IV) to 1.1 mol or more per 1 mol of the compound (V), a sufficient amount of the fluorine-containing compound (III) can be obtained. In addition, by controlling the amount of the fluorine-containing compound (IV) to 1 mol or less relative to 1 mol of the compound (V), the occurrence of side reactions such as dimerization of the fluorine-containing compounds (IV) is suppressed. It's easy to do.

In the step (b), a compound having an —O—O— bond is reacted with the mixture of the obtained fluorine-containing compound (III) and fluorine-containing compound (VI). Thereby, the composition containing fluorine-containing compound (I) can be manufactured. Further, in the step (b), the fluorine-containing compound (Ia) and the fluorine-containing compound (Ib) are also produced simultaneously by reacting the fluorine-containing compound (III) with a compound having an —O—O— bond.
The fluorine-containing compound (II) is inevitably produced by the reaction of the fluorine-containing compound (VI) with a compound having an —O—O— bond.
In the production method of the present invention, Rf ¹¹ , Rf ²¹ , A ¹ , B ¹ , R ¹¹ , R ²¹ , and R ³¹ in the fluorine-containing compounds (I), (Ia), and (Ib) are each a fluorine-containing compound ( It is the same as Rf ¹² , Rf ²² , A ² , B ² , R ¹² , R ²² , R ^{32 in} III). Further, Rf ³ , X ¹ , R ¹² , R ²² , R ³² of the fluorine-containing compound (VI) are the same as Rf ³ , X ¹ , R ¹¹ , R ²¹ , R ^{31 in the} fluorine-containing compound (II), respectively. Become.

  The compound having a —O—O— bond is not particularly limited, and examples thereof include hydrogen peroxide, peracetic acid, performic acid, perbenzoic acid, perphthalic acid, and the by-product after the reaction is water. For this reason, hydrogen peroxide is preferred.

The amount of the compound having —O—O— bond used is that of the nitrogen atom of the tertiary amine contained in the fluorine-containing compound (III) or the mixture of the fluorine-containing compound (III) and the fluorine-containing compound (VI). It is preferable to set it as 1.0-5.0 mol% on the basis of the number of moles, and it is more preferable to set it as 1.0-4.0 mol%.
However, the number of moles of the nitrogen atom of the tertiary amine is 2 moles per mole of the fluorine-containing compound (III) in the case of the fluorine-containing compound (III), and in the case of the fluorine-containing compound (VI), the fluorine-containing compound. (VI) 1 mol per 1 mol.

The reaction of the fluorine-containing compound (III) and the fluorine-containing compound (VI) with the compound having an —O—O— bond is carried out in the following solvent.
Examples of the solvent include water and organic solvents.
Examples of the organic solvent include poorly water-soluble organic solvents such as ethyl acetate and methylene chloride, and water-soluble organic solvents such as 2-propanol (IPA) and t-butanol, and a water-soluble organic solvent is used. It is preferable.
The reaction temperature is preferably between room temperature and the boiling point of the reaction solvent, and varies depending on the reaction solvent, but when the boiling point of the reaction solvent exceeds 100 ° C., the reaction temperature is preferably 100 ° C. or less, and preferably 20 to 90 ° C. More preferably, it is ° C.
The pressure during the reaction is preferably normal pressure.

The surfactant composition containing the fluorine-containing compound (I) and the fluorine-containing compound (I) described above can be suitably used in various fields because it exhibits excellent surface tension reducing ability. Further, the surfactant composition of the present invention exhibits excellent surface tension reducing ability even in the state containing the fluorine-containing compounds (I), (Ia), (Ib) and (II).
Moreover, according to the manufacturing method of this invention, the composition containing fluorine-containing compound (Ia), (Ib), and (II) other than fluorine-containing compound (I) can be manufactured easily.
Moreover, it is thought that the surfactant composition containing the fluorine-containing compound (I) obtained by the production method of the present invention can impart water and oil repellency to the surface after coating.

EXAMPLES Hereinafter, an Example and a comparative example are shown and this invention is demonstrated in detail. However, the present invention is not limited by the following description.
[Capacity method]
In this example, the solid content concentration of the obtained reaction liquid (liquid) was measured by the volume method shown below.
The solid content concentration (%) was measured from the ratio between the total amount (g) of the reaction solution obtained and the dry residue (g) obtained by removing the solvent from the reaction solution.

[Example 1]
(Synthesis of Compound III-4)
Hereinafter, the synthesis of Compound III-4 (Table 2) represented by the formula will be described.

N, N-diethylpropanediamine (19.5 g) was added to a 200 mL four-necked flask and heated to 60 ° C. Next, 3-perfluorohexyl-1,2-epoxypropane (95.5%, 88.6 g) was added dropwise thereto over 2 hours, and then aged at 60 ° C. for 27 hours. 9 g of reaction solution A was obtained. The purity of the compound III-4 in the reaction solution A in the gas chromatography analysis was 39.8%, and the compound VI-4 represented by the following formula (VI-4) was also included in 46.9%.

The NMR spectrum data of the obtained reaction solution A is shown below.
¹ HNMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 1.02 (6H, t), 1.66 (2H, m), 2.50 (14H, m) 4.12 (1.5 H, m).
¹³ C NMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 9.9, 11.4, 24.0, 27.1, 35.8, 35.9, 36. 0, 45.8, 46.7, 48.1, 51.0, 53.0, 55.0, 60.6, 61.9, 63.0, 63.9.

(Synthesis of Compound I-4)
Hereinafter, the synthesis of the compound I-4 (Table 1) represented by the following formula will be described.

  The reaction solution A (35.0 g) and 2-propanol (hereinafter referred to as IPA) (10 g) were added to a 200 mL four-necked flask and heated to 65 ° C. Next, 30% hydrogen peroxide solution (7.26 g) was dropped into the solution over 2 hours, and the reaction was continued at 65 ° C. until 30% hydrogen peroxide solution was added to 9.44 g as needed. The reaction was performed for 15 hours. Then, it cooled to room temperature and collect | recovered reaction liquid B 75.95g. The solid content concentration in the reaction solution B was measured by the volumetric method and found to be 43.7%.

The NMR spectrum data of the solid content is shown below.
¹ HNMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 1.01 (0.4H, m), 1.28 (6H, t), 2.16 (4H, m), 2.70 (4H, m), 3.28 (6H, m), 4.10 (1.5H, m), 6.22 (2H, br).
¹³ C NMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 8.1, 8.2, 8.3, 20.7, 21.4, 22.1, 35. 8, 45.8, 46.3, 52.3, 54.3, 58.4, 59.0, 61.8, 63.5, 64.2.

As a solid content in the obtained reaction solution B by NMR measurement and gas chromatography analysis, in addition to the compound I-4, compounds Ia-4 and Ib-4 represented by the following formula are included. It is also considered that compound VI-4 and compound II-4 represented by the following formula are included.

[Example 2]
As shown below, Compound III-4 was synthesized by changing the ratio of raw materials used.
N, N-diethylpropanediamine (6.5 g) was added to a 50 mL three-necked flask and heated to 60 ° C. Subsequently, 3-perfluorohexyl-1,2-epoxypropane (96%, 34.3 g) was added dropwise thereto over 2 hours, and then aged at 60 ° C. for 24 hours, which was cooled to 39.4 g of Reaction liquid C was obtained. The purity of the compound III-4 in the reaction solution C in gas chromatography analysis was 60.8%, and 26.4% of the compound VI-4 represented by the following formula (VI-4) was also contained.

The NMR spectrum data of the obtained reaction solution C is shown below.
¹ HNMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 1.02 (6H, m), 1.65 (2H, m), 2.55 (14.8H, m), 4.14 (1.7H, m).
¹³ C NMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 9.9, 11.3, 23.6, 27.1, 35.9, 45.8, 46. 7, 48.1, 51.0, 53.0, 55.0, 60.7, 61.9, 63.0, 63.9.

  Subsequently, the said reaction liquid C (10.0g) and IPA (10.0) were added to a 50 mL three necked flask, and it heated at 65 degreeC. Next, 30% hydrogen peroxide solution (2.15 g) was dropped into the solution over 2 hours, and the reaction was continued at 65 ° C. until 30% hydrogen peroxide solution was added to 6.45 g as needed. The reaction was carried out for 23 hours. Then, it cooled to room temperature and 23.12g of reaction liquid D was collect | recovered. When the solid content concentration in the reaction solution D was measured by the volumetric method, it was 41.4%.

The NMR spectrum data of the solid content is shown below.
¹ HNMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 1.01 (3H, m), 1.27 (6H, t), 2.50 (18H, m) 3.25 (6H, m), 4.1 (2H, br), 5.4 (2.7H, br).
¹³ C NMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 8.2, 8.3, 8.4, 9.7, 20.7, 21.6, 35. 7, 45.8, 46.3, 52.2, 54.6, 58.4, 59.2, 61.0, 61.9, 63.8, 64.3.

  As a solid content in the obtained reaction liquid D by NMR measurement and gas chromatography analysis, in addition to compound I-4, compounds Ia-4 and Ib-4 are included, and compound VI-4 And Compound II-4 is also considered to be included.

[Comparative Example 1]
(Synthesis of Compound VI-4)
N, N-diethylpropanediamine (13.0 g) was added to a 50 mL three-necked flask and heated to 60 ° C. Subsequently, 3-perfluorohexyl-1,2-epoxypropane (99%, 18.8 g) was added dropwise thereto over 2 hours, and then aged at 60 ° C. for 18 hours. Reaction liquid E was obtained. The purity of the compound VI-4 in the reaction solution E in the gas chromatography analysis was 92.7%, and the main impurities were the above-mentioned two kinds of raw materials.

(Synthesis of Compound II-4)
The reaction solution E (5.46 g), IPA (5.46 g) and water (2.73 g) were added to a 50 mL three-necked flask and heated to 65 ° C. Next, 30% hydrogen peroxide solution (1.2 g) was dropped into the solution over 2 hours, and the reaction was continued at 65 ° C. until 30% hydrogen peroxide solution was added to 2.0 g as needed. The reaction was carried out for 16 hours. Then, it cooled to room temperature and 14.3g of reaction liquid F was collect | recovered. The solid content concentration in the reaction solution F was measured by the volumetric method and found to be 31.5%.

The NMR spectrum data of the solid content is shown below.
¹ HNMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 1.23 (8H, m), 2.51 (8H, m), 3.20 (4H, m) 4.20 (1H, m).
¹³ C NMR (300 MHz, solvent: CDCl ₃ , standard substance: hexamethyldisiloxane), σ (ppm): 8.5, 10.9, 22.4, 36.1, 46.5, 54.6, 59. 3, 62.5.

  According to NMR measurement and gas chromatography analysis, the solid content in the obtained reaction solution F is considered to contain the compound VI-4 as a raw material in addition to the compound II-4.

[Measurement of static surface tension]
The reaction liquids B, D and F containing the fluorine-containing compounds obtained in Examples and Comparative Examples were diluted with water to obtain a surfactant composition having a solid content concentration of 0.001% by mass, and static surface tension. (MN / m) was measured.
The static surface tension was a value after standing at 25 ° C. for 30 minutes in the Wilhelmy method (hanging plate method) using an automatic surface tension meter CBVP-A3 type apparatus manufactured by Kyowa Interface Science Co., Ltd. Table 4 shows the measurement results.

  In the reaction solution B obtained in Example 1, the static surface tension was low (23.5 mN / m) even when used at a low concentration of 0.001% by mass, and excellent surface tension reducing ability was exhibited. Similarly, the reaction solution D obtained in Example 2 also showed a low value (22.5 mN / m) for the static surface tension and an excellent surface tension reducing ability.

  On the other hand, in the reaction solution F obtained in Comparative Example 1, the value of the static surface tension at the same concentration is as high as 38.5 mN / m, which is higher than that of the reaction solution B of Example 1 and the reaction solution D of Example 2. The tension reducing ability was inferior.

Claims (4)

A fluorine-containing compound represented by the following formula (I).

In the formula (I), ^{Rf 11} and ^{Rf 21} is the _C 6 _{F 13,} an alkylene group having 2 to 4 carbon atoms with ^{A 1} and ^{B 1} is hydroxyl ^{group, R 11} is the number 2 or carbon atom 3 and R ²¹ and R ³¹ are each an alkyl group having 1 to 4 carbon atoms. A surfactant composition comprising the fluorine-containing compound according to claim 1 . The surfactant composition according to claim 2 , further comprising a fluorine-containing compound represented by the following formula (Ia) and a fluorine-containing compound represented by the following formula (Ib).

However, the symbols in the formulas (Ia) and (Ib) have the same meaning as the symbols in the formula (I). The surfactant composition according to claim 3 , further comprising a fluorine-containing compound represented by the following formula (II).

In the formula (II), Rf ³ is a _C 6 _{F 13,} ^{X 1} is an alkylene group having 2 to 4 carbon atoms having a hydroxyl group. R ¹¹ , R ²¹ and R ³¹ are the same as the symbols in the formula (I).