JP4349056B2 - Fluorosurfactant - Google Patents

Description

  The present invention mainly dissolves in various coating materials and molding materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, release agents, etc., penetrating / wetting properties, leveling properties, The present invention relates to a fluorosurfactant that can be suitably used as an additive for enhancing surface functionality and the like.

  Fluorosurfactant has a high surface tension reducing ability, and is an additive that achieves excellent penetration / wetting, leveling, surface functionality, etc. by mixing with a coating composition or molding composition. In the past, various fluorosurfactants have been proposed.

  In general, a fluorosurfactant has a perfluoroalkyl (Rf) group for realizing a surface tension reducing function and an affinity for various compositions such as coatings and molding materials using the activator as an additive. It consists of a compound having an amphiphilic group contributing to the properties in the same molecule.

C ₈ F ₁₇ SO ₂ N (R) (CH ₂ ) _n COOM, which is a conventional fluorosurfactant, wherein R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is 1 to 4 M is a hydrogen atom, sodium, potassium, or lithium.) Is excellent in surface activity and water solubility, and is widely used for plating and various coating applications (see, for example, Patent Document 1). . However, in recent years, fluorinated compounds having a perfluoroalkyl group with 7 or more carbon atoms cause inhibition of intercellular communication, which is thought to contribute to carcinogenicity in in vitro tests using cell lines. In addition, this inhibition is determined not by the functional group but by the length of the fluorinated carbon chain, and it can be seen that the longer the inhibition, the higher the inhibition (see, for example, Non-Patent Document 1). The use of fluorinated surfactants has been avoided. On the other hand, a fluorosurfactant composed of a compound having a small number of carbon atoms in a perfluoroalkyl group generally does not have a sufficient surface active effect. Therefore, a fluorine-based compound composed of a compound having a short carbon number of a perfluoroalkyl group that has a surface active effect equivalent to or higher than that of a conventionally used fluorine-based surfactant and generally recognized as high safety. There is a strong need for surfactants.

US Pat. No. 2,809,990 (page 1-3) "International Journal of Cancer" (USA) 1998, vol. 78, p.491-495, (page 1-3, Fig. 5)

  In view of the above situation, the subject of the present invention is mainly used for various coating materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, release agents, molding materials, etc. Fluorosurfactant comprising a short compound having a perfluoroalkyl group in the compound having a carbon number of 6 or less, which can be suitably used as an additive for enhancing the penetration / wetting property, leveling property, surface functionality, etc. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a fluorine-based compound having the following specific structure has a perfluoroalkyl group as short as 6 or less carbon atoms, The present inventors have found that a fluorosurfactant as an effective surfactant component does not impair the surfactant effect of conventional fluorosurfactants.

That is, the present invention comprises a fluorine compound (A) obtained by reacting sorbic acid or sorbate with perfluoroalkylthiol (B) represented by the following general formula (2). A surfactant is provided. Furthermore, the perfluoroalkylthiol (B) represented by the following general formula (2) is reacted with sorbic acid or sorbate and then neutralized, or the general formula (A), or the general formula A fluorosurfactant comprising a fluorochemical compound (A) obtained by reacting a sorbic acid ester with the perfluoroalkylthiol (B) represented by (2) and then saponifying it. It is.
F (CF ₂ ) _2m (CH ₂ ) _n SH (2)
(In the formula, m is 2 or 3, and n is an integer of 0 to 2.)

  According to the present invention, it is mainly used for compositions such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, mold release agents, and other coating materials and molding materials. A fluorosurfactant that can be suitably used as an additive for improving leveling properties, surface functionality, and the like and that is made of a short compound having a perfluoroalkyl group having 6 or less carbon atoms can be provided.

Hereinafter, the present invention will be described in detail.
Examples of the surface active effect according to the present invention include various surface active effects such as wettability, permeability, anti-repellency, leveling, coating uniformity / homogeneity, and surface modification of the composition in coating and molding applications. Qualities and the like.

The fluorosurfactant of the present invention comprises , as an active ingredient, a fluorochemical compound (A) obtained by reacting perfluoroalkylthiol (B) represented by the following general formula (2) with sorbic acid or sorbate. It is a fluorinated surfactant . Furthermore, the perfluoroalkylthiol (B) represented by the following general formula (2) is reacted with sorbic acid or sorbate and then neutralized, or the general formula (A), or the general formula A fluorinated surfactant containing, as an active ingredient, a fluorinated compound (A) obtained by reacting a sorbic acid ester with the perfluoroalkylthiol (B) represented by (2) and then saponifying it.
F (CF ₂ ) _2m (CH ₂ ) _n SH (2)
(In the formula, m is 2 or 3, and n is an integer of 0 to 2.)

The fluorine-based compound (A) has shown the F segment by perfluoroalkyl thiols _{(B) (CF 2) 2m} (CH 2) n S- at that material which is the general formula (2), which Is an indispensable segment for obtaining an excellent surface-active effect, and a fluorosurfactant composed of a compound having only one in one molecule lacks the surface-active effect, and more than 5 In the case of a fluorosurfactant composed of a compound having two or more of the same or different two or four, the compatibility with a composition such as a coating material or a molding material when used as a surfactant is deteriorated and it is put to practical use. It is essential that the compound has F (CF ₂ ) _2m (CH ₂ ) _n S-. The chain length of the group is appropriately determined depending on the use when used as a surfactant, the composition of a composition such as a coating material or a molding material mixed with this as an additive, the level of the desired surface active effect, etc. However, if m is 1, the surface-active effect of the obtained fluorine-based compound is insufficient, and if m is 4 or more, there is a concern about safety, so that it is 2 or 3. Required. Moreover, since practical surface-active effect is not acquired as n is three or more, it is essential that it is an integer of 0-2.

In addition , the fluorine-based compound (A) uses sorbic acid or sorbate as a raw material, or sorbic acid ester as the raw material, and saponifies after the reaction, whereby -COOM (in the formula , M is a hydrogen atom, ammonium or an alkali metal . -COOM is a hydrophilic group, and M in the group represents a hydrogen atom of a carboxylic acid, an ammonium of a carboxylic acid amine salt or an alkali metal of a carboxylic acid alkali metal salt, for example, -COOH as a hydrophilic group, -COONH4, -COOLi, -COONa, -COOK, etc.

The fluorine-based compound (A) is easy to produce and has a good balance between the surface-active effect of the resulting fluorine-based compound and water solubility, so that the same or different F (CF ₂ ) _2m (CH ₂ ) in one molecule. is preferably _{one n} S- and having two, for example, those represented by the following general formula (1).

（式中、ｍは２又は３であり、ｎは０〜２の整数であり、同一でも異なっていても良く、ｐは１又は２であり、ｑは０〜２の整数であり、ｒは０又は１であり、且つｐ＋ｑ＋ｒ＝３であり、Ｍは水素原子、アンモニウム又はアルカリ金属である。）

(In the formula, m is 2 or 3, n is an integer of 0 to 2, which may be the same or different, p is 1 or 2, q is an integer of 0 to 2, and r is 0 or 1 and p + q + r = 3, and M is a hydrogen atom, ammonium or an alkali metal.)

  The fluorine compound represented by the general formula (1) may be used alone or as a mixture of two or more.

  Among these, n in the general formula (1) is preferably 2 because a fluorine-based compound having a practical surface-active effect can be obtained and the production is easy.

In the general formula (1), -COOM (wherein M represents a hydrogen atom, ammonium or an alkali metal) is a hydrophilic group, and in the formula, M is, for example, ammonium, ammonia, diethylamine, triethylamine. , Ammonium derived from n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine, propanolamine, toluidine, pyridine, etc. Examples of the alkali metal include lithium, sodium, potassium, rubidium and the like. Among these, it is preferable that M in the formula is NH ₄ , lithium, sodium, potassium because lithium-containing compounds having a practical surface-active effect are obtained and easy to produce, and lithium, sodium, potassium It is particularly preferred that

  Specific examples of the fluorine compound used in the fluorine surfactant of the present invention include compounds represented by the following structural formulas (1-1) to (1-16).

  Although the manufacturing method of the fluorine-type compound shown by the said General formula (1) is not specifically limited, For example, the method of the following (I)-(III) is mentioned.

(I) The following general formula (2)
F (CF ₂ ) _2m (CH ₂ ) _n SH (2)
(In the formula, m is 2 or 3, and n is an integer of 0 to 2.)
The manufacturing method which makes sorbic acid or sorbate react with perfluoroalkylthiol (B) shown by these.

(II) The following general formula (2)
F (CF ₂ ) _2m (CH ₂ ) _n SH (2)
(In the formula, m is 2 or 3, and n is an integer of 0 to 2.)
The manufacturing method which neutralizes, after making sorbic acid or sorbate react with perfluoroalkylthiol (B) shown by these.

(III) The following general formula (2)
F (CF ₂ ) _2m (CH ₂ ) _n SH (2)
(In the formula, m is 2 or 3, and n is an integer of 0 to 2.)
The manufacturing method which saponifies after making sorbic acid ester react with perfluoroalkyl thiol (B) shown by these.

First, the production method (I) will be described in detail.
The perfluoroalkylthiol (B) represented by the general formula (2) is preferably one in which n in the general formula (2) is 2 in terms of obtaining a compound having a high surface-active effect. 3,4,4,5,5,6,6,6-nonafluorohexylthiol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro Examples include octyl thiol.

  The sorbic acid used here is represented by the following structural formula.

  Examples of the sorbate include ammonia, diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, Examples include amine salts derived from monoethanolamine, diethanolamine, propanolamine, toluidine, pyridine, etc., and alkali metal salts include lithium salts, sodium salts, and potassium salts. An amine salt, a lithium salt, a sodium salt, or a potassium salt derived from ammonia is preferable because a fluorine-based compound having a hydrogen atom can be obtained and can be produced easily.

  Specific examples include those represented by the following structural formulas (4-1) to (4-4).

  The amount of perfluoroalkylthiol (B) used in this reaction is 1.5 to 7.0 mol, preferably 1.9 to 4.0 mol, per 1 mol of sorbic acid or sorbate. In order to accelerate this reaction, it is preferable to use a base. Examples of the base include sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, potassium hydroxide, sodium hydroxide, water Inorganic bases such as lithium oxide, sodium methoxide, sodium ethoxide and the like can be mentioned. The amount of the base used is 1.1 to 3.0 mol, preferably 1.1 to 2.0 mol, based on 1 mol of sorbic acid when sorbic acid is used, and when sorbate is used, It is 0.1-1.0 mol with respect to 1 mol of sorbates, Preferably it is 0.1-0.5 mol. This reaction can be carried out without a solvent or in an organic solvent, but a reaction method in an organic solvent is preferable because the reaction operation is easy and the safety of the operation is high.

  The solvent is not particularly limited as long as it is inactive with respect to sorbic acid or sorbate and perfluoroalkylthiol (B) and can dissolve both. For example, dichloromethane, chloroform, Halogenated hydrocarbons such as 1,2-dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, halogenated aromatic hydrocarbons such as chlorobenzene, orthodichlorobenzene and paradichlorobenzene, n-pentane , N-hexane, n-octane, cyclohexane and other aliphatic hydrocarbons, tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and other ethers, ethyl acetate, butyl acetate, propyl acetate, and other esters Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether and diethylene glycol diethyl ether, nitriles such as acetonitrile and benzonitrile, dimethylformamide, dimethylacetamide and dimethyl sulfoxide Among these, ketones, nitriles, dimethylformamide, dimethylacetamide, and dimethylsulfoxide are preferable because of good solubility, and acetone, methylethylketone, acetonitrile, dimethylformamide, and dimethylsulfoxide are particularly preferable. These solvents may be used alone or in combination of two or more. Furthermore, these solvents can also be used as a mixed solvent with water.

  The reaction conditions for this reaction are not particularly limited, but from the point that the reaction proceeds promptly, sorbic acid or sorbate alone, or a solution obtained by diluting it with the solvent, perfluoroalkylthiol (B) and the above Preference is given to a method in which a mixture of bases or a mixture of this mixture diluted in the solvent is added dropwise. Although there is no restriction | limiting in reaction temperature, Usually, it is 5-120 degreeC, and can be suitably selected according to the kind of solvent to be used. There is no restriction | limiting in reaction time, It is 0.5 to 10 hours normally, Preferably, it is 1 to 5 hours. Although there is no restriction | limiting in reaction atmosphere, In order to suppress the oxidation of sorbic acid or sorbate, and a product, inert gas atmosphere, such as nitrogen, helium, and argon, is preferable.

Next, the manufacturing method (II) will be described.
The method for reacting perfluoroalkylthiol (B) with sorbic acid or sorbate is the same as the method for producing (I) described above. By neutralizing the product obtained by this reaction, the fluorine-based compound represented by the general formula (1) can be obtained.

  Examples of the neutralizing agent used in the neutralization reaction include alkali metal hydroxides such as lithium hydroxide, alkali metal halides such as lithium chloride, and amines such as ammonia, trimethylamine, triethylamine, and pyridine. The amount of these neutralizing agents used is 1 to 5 mol, preferably 1 to 2.5 mol, relative to 1 mol of the compound before neutralization.

  The reaction conditions for the neutralization reaction are not particularly limited. Examples of the reaction solvent include water alone or a mixed solvent of water and alcohols such as methanol, ethanol, and isopropanol. . The reaction temperature is preferably 5 to 50 ° C, particularly 10 to 30 ° C. Although there is no restriction | limiting in reaction atmosphere, In order to suppress the oxidation of a product, inert gas atmosphere, such as nitrogen, helium, argon, is preferable.

Next, the manufacturing method of (III) is described.
In (I), when sorbic acid ester is used instead of sorbic acid or sorbic acid salt and a base is used for promoting the reaction, 0.1 mol of base is added to 1 mol of sorbic acid ester. The product is obtained in the same manner as in the method (I) except that it is used in the same manner as in the method (I) except that 0.1 to 0.5 mol, preferably 0.1 to 0.5 mol is used. This is a method for obtaining a fluorine compound.

  The ester group of the sorbic acid ester used here is preferably an alkyl group having 1 to 7 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. For example, the following structural formula (5-1) What is shown by-(5-7) is mentioned.

  Examples of the saponifying agent for the saponification reaction include alkali metal hydroxides such as lithium hydroxide, alkali metal halides such as lithium chloride, amines such as ammonia, trimethylamine, triethylamine, and pyridine. The amount of these saponifying agents to be used is 1 to 5 mol, preferably 1 to 2.5 mol, relative to 1 mol of the compound before saponification.

  The reaction conditions for the saponification reaction are not particularly limited. Examples of the reaction solvent include water alone or a mixed solvent of water and alcohols such as methanol, ethanol, and isopropanol. The reaction temperature is preferably 10 ° C. to reflux temperature, particularly 40 to 90 ° C. Although there is no restriction | limiting in reaction atmosphere, In order to suppress the oxidation of a product, inert gas atmosphere, such as nitrogen, helium, argon, is preferable.

In addition, as a method for producing the compound represented by the general formula (1) having _two different types of F (CF ₂ ) _2m (CH ₂ ) _n S— groups in one molecule, perfluoroalkylthiol (B) A method of using a mixture of two or more in advance and reacting in the same manner as in any of the methods (I) to (III) described above.

  The fluorine-based compound represented by the general formula (1) obtained by the above-described production methods (I) to (III) can be used unpurified depending on applications and purposes, but is distilled or washed with a solvent. Purification by recrystallization, various types of chromatography, adsorbents and the like is also possible.

  Of the above-mentioned three production methods, sorbic acid or sorbate has low solubility in organic solvents and low operability due to reaction with perfluoroalkylthiol, resulting in a decrease in yield. As a method for obtaining, a method using the sorbic acid ester of (III) is preferable.

  The fluorosurfactant of the present invention has a perfluoroalkyl group chain length shorter than that of conventionally used fluorosurfactants, but is soluble in water and / or an organic solvent and has a surfactant effect. Are substantially the same, and are not particularly limited in use, and can be widely used. In addition, as the fluorine-based surfactant of the present invention, the above-mentioned fluorine-based compounds may be used alone, or two or more kinds of fluorine-based compounds may be used simultaneously.

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

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

  Examples of the solvent include water and / or various organic solvents. For example, alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol and the like. , Hydrophilic ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, hydrophilic cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethylene glycol, propylene glycol And hydrophilic glycols such as water and ethers such as tetrahydrofuran and dioxane. These solvents may be one kind or a mixed solvent system of two or more kinds. As used herein, the term “solvent” refers to a solvent that functions as a dispersion medium in the system.

  The solute is preferably dissolved or dispersed in water and / or the organic solvent, for example, an acrylic resin, urethane resin, epoxy resin, polyimide resin, polyamide resin, natural polymer such as cellulose, chitin, chitosan, etc. Examples include gelatin. These solutes may be used alone or in combination of two or more.

  Examples of the additive include coupling agents such as silane, titanium, and zirco-aluminate, and fluorine such as fluorine atom-containing alkoxysilane compounds, fluorine atom-containing titanium acyl compounds, and fluorine atom-containing alkoxyzirconium compounds. 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 ( Tetrafluoroethylene), polyethylene, acrylic beads, carbon fine powder, photosensitizer, sensitizer, light resistance improver, weather resistance improver, heat resistance improver, conductive agent, antioxidant, rust preventive, Various fillers such as rheology control agent, thickener, anti-settling agent, antifoaming agent, deodorant And the like. These additives may be used alone or in combination of two or more.

  In addition, as the fluorosurfactant of the present invention, various other fluorosurfactants, silicon-based surfactants, hydrocarbon-based surfactants, and the like are necessary as long as the effects of the present invention are not impaired. These surfactants can be used in the above-mentioned various compositions in combination. The mixing ratio is not particularly limited, and is appropriately selected according to the level of the desired surface-active effect, compatibility with the above-described various compositions to be applied, etc. As a weight ratio of the fluorine-based surfactant made of the fluorine-based compound (A) and the other surfactant, (fluorine-based surfactant) / (other surfactant) is 1/99 to 99/1. The weight ratio is particularly preferably 80/20 to 10/90, and most preferably 50/50 to 20/80, from the viewpoint of obtaining a stable and sufficient surface active effect.

  In general, a fluorosurfactant is used in combination with a hydrocarbon surfactant to form a material that comes into contact with the composition to which the surfactant is added (for example, when applied, glass, steel plate, plastic film, or the like). In some cases, the function of lowering the interfacial tension with respect to the mold) is increased, and it is also effective from an economical viewpoint.

  The hydrocarbon surfactant is composed of a hydrocarbon compound having a hydrophilic group and a lipophilic group in one molecule, and is usually anion, cation, nonion, betaine mainly depending on the ionicity of the hydrophilic group. Classified into types. Any type of hydrocarbon surfactant that can be used in combination with the fluorosurfactant of the present invention can be used without limitation. Typical anionic surfactants include sulfone salts, phosphates, carboxylates, and the like, and specific examples include the Emar series and Pelex series manufactured by Kao Corporation. Examples of the cationic surfactant include oxonium salts, ammonium salts, and phosphonium salts, and specific examples thereof include an acetamine series and a coatamine series manufactured by Kao Corporation. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, sorbitan fatty acid esters, and the like, and specific examples include the Emulgen series and Rheodor series manufactured by Kao Corporation. Examples of betaine surfactants include amino acid salts, amine oxides, and the like, and specific examples include Amphital series manufactured by Kao Corporation.

  The composition containing the above-described fluorosurfactant of the present invention can obtain excellent penetration / wetting properties, leveling properties and the like by applying various processing methods. The processing method is not particularly limited. For example, gravure coater, knife coater, roll coater, comma coater, spin coater, bar coater, brush coating, dipping coating, spray coating, electrostatic coating, screen printing, etc. Method / Equipment, Inkjet Method, Injection, Extrusion, Hollow, Compression, Reaction, Vacuum, FRP, Heat, Roll Sheet, Calendar, Biaxially Stretched Film, Lamination, Rotation, etc. Various Molding Methods, Various Molds, Stampers Examples include injection molding.

  Further, there is no limitation on the use of the above-mentioned composition, for example, industrial and household adhesives, scratch resistance, slipperiness, non-tackiness, water and oil repellency, gas barrier properties, heat resistance, and light resistance. , Surface functional protective film forming materials such as weather resistance, physiological activity, water resistance, moisture resistance, antifouling property, lubricity, treatment agents for textiles such as clothing, furniture, shoes, miscellaneous goods, artificial leather, synthetic leather nonwoven fabric, etc. Various coating agents such as paper, film, card, automobiles, building materials, home appliances, medical materials, OA equipment, electrical / electronic equipment, optical members, electric wires / wiring materials, molding materials for various industrial parts, grease, various seals Photosensitive materials such as anti-static agents such as stoppers, mold release agents, anti-rust agents, anti-fogging agents, anti-fogging agents, anti-blocking agents, PS plates, LCDs, LSIs, organic ELs, and various photoresists for plasma display manufacturing , Anti-reflective coating for LSI manufacturing, LCD, L I, Organic EL, Plasma display manufacturing detergents, Etching agents, Release agents, Developers, Emulsion and other photographic materials, Automobiles, aircraft, ships, building materials, home appliances, paints, dyes, cleaning agents, floor polish, foam It can be used suitably for fire extinguishing agents, plating bath mist prevention agents, lens sheets, optical materials such as optical fibers, or organic chemical reaction dispersion media.

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

Example 1
i) Synthesis of bisperfluoro compound 3,3,4,4,5,5,6,6,6-nonafluorohexanethiol 35 in a 200 ml flask equipped with a stirrer, dropping tube, calcium chloride tube and thermometer 0.0 g, 30 ml of dimethylformamide and 1.0 g of sodium methoxide were charged, and a solution obtained by dissolving 6.3 g of sorbic acid methyl ester in 10 g of dimethylformamide in advance was placed in a dropping tube. The flask was kept at 25 ° C. and stirred for 10 minutes, and then a dimethylformamide solution of sorbic acid methyl ester was added dropwise over 20 minutes. After further stirring at 25 ° C. for 4 hours, 50 ml of saturated ammonium chloride was added. The reaction solution was extracted twice using ethyl acetate, and then the organic layer was dried using anhydrous magnesium sulfate. After the solid content was filtered off, the solvent was distilled off under reduced pressure, and the distillation under reduced pressure was continued, and bis (3,3,4,4,5,5,6,6,6-nonafluorohexylsulfanyl was obtained as a fraction. ) 28.9 g of hexanoic acid methyl ester [bisperfluoro product (1-i)] was obtained.

ii) Saponification reaction Into a 200 ml flask equipped with a reflux condenser and a thermometer, 28.9 g of the bisperfluoro product (1-i) obtained in i), 2.1 g of lithium hydroxide monohydrate and Saponification reaction was performed by charging 60 ml of ion-exchanged water and stirring the flask for 4 hours while maintaining the temperature at 85 ° C. After completion of the stirring, 40 g of isopropanol was added to the reaction solution, and the mixture was further heated under reflux for 30 minutes. After the solvent was distilled off by distillation, the remaining solid was dried with a blow dryer to obtain the fluorine-based compound (a1) [bis 26.0 g of (3,3,4,4,5,5,6,6,6-nonafluorohexylsulfanyl) hexanoic acid lithium salt] was obtained.

Example 2
In Example 1-ii, in the same manner as in Example 1 except that 2.0 g of sodium hydroxide was used instead of 2.1 g of lithium hydroxide monohydrate, the fluorine-based compound (a2) [bis (3 , 3,4,4,5,5,6,6,6-nonafluorohexylsulfanyl) hexanoic acid sodium salt] was obtained.

Example 3
i) Synthesis of bisperfluoro compound 3,3,4,4,5,5,6,6,6-nonafluorohexanethiol in a 200 ml flask equipped with a reflux condenser, dropping tube, thermometer and calcium chloride tube 35.0 g, 30 ml of dimethylformamide and 1.0 g of sodium methoxide were charged, and a solution obtained by dissolving 6.7 g of sodium sorbate in 10 g of dimethylformamide in advance was put in a dropping tube. The inside of the flask was kept at 25 ° C. and stirred for 10 minutes. To this was added dropwise a dimethylformamide solution of sodium sorbate over 20 minutes, and the mixture was further heated at 25 ° C. for 1 hour, further heated to 80 ° C. and stirred for 3 hours. After completion, the mixture was cooled to 25 ° C., 150 ml of 2N hydrochloric acid was added, the reaction solution was extracted twice with ethyl acetate, and then the organic layer was dried with anhydrous magnesium sulfate. After filtering off the solid content, the solvent was distilled off under reduced pressure, and bis (3,3,4,4,5,5,6,6,6-nonafluorohexylsulfanyl) hexanoic acid [bisperfluoro Body (3-i)] 36.0 g was obtained.

ii) 'Neutralization reaction In a 200 ml flask equipped with a stirrer, a reflux condenser and a thermometer, 27.0 g of the bisperfluoro product (3-i) obtained in i), 4.5 g of potassium hydroxide, isopropanol 40 g and 60 ml of ion-exchanged water were charged, and a neutralization reaction was performed by stirring at 25 ° C. for 1 hour. After completion of the stirring, the solvent was distilled off under reduced pressure, and the remaining solid was forcibly dried to obtain a fluorine-based compound (a3) [bis (3,3,4,4,5,5,6,6,6- Nonafluorooctylsulfanyl) hexanoic acid potassium salt] was obtained.

Example 4
i) Synthesis of bisperfluoro compound 3,3,4,4 instead of 35.0 g of 3,3,4,4,5,5,6,6,6-nonafluorohexanethiol in Example 1-i , 5,5,6,6,7,7,8,8,8-tridecafluorooctylthiol in the same manner as in Example 1-i, except that bis (3,3,4, 3,5.4 g of 4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfanyl) hexanoic acid methyl ester [bisperfluoro product (4-i)] was obtained.

ii) Saponification reaction Example 1-ii was the same as Example 1-ii except that 35.4 g of bisperfluoro product (4-i) was used instead of 28.9 g of bisperfluoro product (1-i). Similarly, fluorine compound (a4) [bis (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylsulfanyl) hexanoic acid lithium Salt] 35.0 g was obtained.

Example 5
In Example 1-ii, 35.4 g of bisperfluoro product (4-i) was used instead of 28.9 g of bisperfluoro product (1-i), and 2.1 g of lithium hydroxide monohydrate was used. Fluorine compound (a5) [bis (3,3,4,4,5,5,6,6,7,7,8) in the same manner as in Example 1 except that 2.0 g of sodium hydroxide was used. , 8,8-Tridecafluorooctylsulfanyl) hexanoic acid sodium salt] was obtained.

Example 6
i) Synthesis of bisperfluoro compound 3,3,4,4,5,5,6,6,7,7,8,8 in a 200 ml flask equipped with a stirrer, dropping tube, calcium chloride tube and thermometer , 8-tridecafluorooctylthiol, 35.0 g of dimethylformamide and 5.0 g of sodium methylate were charged, and 5.6 g of sorbic acid was placed in the dropping tube. The flask was maintained at 25 ° C. and stirred for 10 minutes, sorbic acid was added dropwise over 20 minutes, and the mixture was further stirred at 25 ° C. for 1 hour and at 80 ° C. for 3 hours. After completion of stirring, the mixture was cooled to room temperature and 150 ml of 2N hydrochloric acid was added. The reaction solution was extracted twice using ethyl acetate, and then the organic layer was dried using anhydrous magnesium sulfate. After the solid content was filtered off, the solvent was distilled off under reduced pressure, and the distillation under reduced pressure was continued, and bis (3,3,4,4,5,5,6,6,7,7,8, 2,8-Tridecafluorooctylsulfanyl) hexanoic acid [bisperfluoro product (6-i)] 27.0 g was obtained.

ii) 'Neutralization reaction In a 200 ml flask equipped with a stirrer, a reflux condenser and a thermometer, 27.0 g of the bisperfluoro product (6-i) obtained in i, 4.5 g of potassium hydroxide, 40 g of isopropanol And 60 ml of ion-exchanged water was charged, and the neutralization reaction was performed by stirring at 25 ° C. for 1 hour. After completion of the stirring, the solvent was distilled off under reduced pressure, and the remaining solid was forcibly dried to obtain a fluorine-based compound (a6) [bis (3,3,4,4,5,5,6,6,7, 7,8,8,8-tridecafluorooctylsulfanyl) hexanoic acid potassium salt] was obtained.

Test Examples 1-6 and Comparative Test Example 1
The surface tension (ion exchange aqueous solution) of the fluorinated surfactants comprising the fluorinated compounds (a1) to (a6) obtained in Examples 1 to 6 was measured by the following method and shown in Table 1 as Test Examples 1 to 6. Show.

Test method Surface tension: Using an automatic surface tension meter CBPV-Z (manufactured by Kyowa Interface Chemical Co., Ltd.), the surface tension at each concentration (ion exchange aqueous solution, weight%) at 20 ° C. is measured by the Wilhelmy platinum plate method. did. (Unit: mN / m)

Further, as Comparative Test Example 1, the surface tension of Megafac F-120 [C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₂ CH ₃ ) CH ₂ COOK] manufactured by Dainippon Ink & Chemicals, Inc. was measured. The results are shown in Table 1.

  In Test Examples 1 to 6 using the fluorosurfactant composed of the fluorochemical 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 that has been conventionally used It was confirmed that the surface tension lowering effect was almost the same as that of the fluorosurfactant of Comparative Example 1 comprising a compound having 8 perfluoroalkyl groups.

Test Examples 7-8 and Comparative Test Examples 2-3
Using the fluorine-based compound (a1) obtained in Example 1 and the conventional Megafac F-120, methanol (Test Example 7, Comparative Test Example 2) and ion-exchanged water / methanol = 1/1 (weight) Ratio) The surface tension of the mixed solvent (Test Example 8, Comparative Test Example 3) was measured. These results are shown in Table 2.

  It was confirmed that the fluorosurfactant comprising the fluorochemical compound of the present invention can exhibit the same surface-active effect as that of the conventional product not only with water but also with a hydrophilic organic solvent.

Test Examples 9 and 10
Using the fluorine-based compound (a1) obtained in Example 1, the combined use effect with the hydrocarbon-based surfactant was confirmed. The surface tension in a 0.001% by weight aqueous solution of a mixture of the fluorine compound (a1) and a hydrocarbon surfactant (polyoxyethylene oleyl ether: Emulgen 430 manufactured by Kao Corporation) was measured. The results are shown in Table 3.

It has been confirmed that the fluorosurfactant comprising the fluorochemical compound of the present invention exhibits an excellent surfactant effect even in combination with other surfactants.

Claims (3)

A fluorine-based surfactant comprising a fluorine-based compound (A) obtained by reacting sorbic acid or sorbate with perfluoroalkylthiol (B) represented by the following general formula (2).
F (CF ₂ ) _2m (CH ₂ ) _n SH (2)
(In the formula, m is 2 or 3, and n is an integer of 0 to 2.) Fluorine compound (A) obtained by reacting sorbic acid or sorbate with perfluoroalkylthiol (B) represented by the following general formula (2), or the general formula (2) A fluorosurfactant comprising a fluorochemical compound (A) obtained by reacting a sorbate with the perfluoroalkylthiol (B) represented by
F (CF ₂ ) _2m (CH ₂ ) _n SH (2)
(In the formula, m and n are the same as described above.) The fluorosurfactant according to claim 1 or 2, wherein n in the general formula (2) is 2.