JP4411515B2 - 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.

Rf—A—O—B—SO ₃ M which is a conventional fluorosurfactant (wherein Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, and A is an alkylene chain having 1 to 10 carbon atoms) And B is an alkylene chain having 3 to 4 carbon atoms, and M is a hydrogen atom, ammonium or metal.) Is excellent in surface tension reducing ability and is widely used for plating, various coating applications and the like (for example, , See Patent Document 1). However, the surface tension reducing ability of the fluorosurfactant is not satisfactory.

JP 55-4309 (page 1-4)

  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. An object of the present invention is to provide a fluorosurfactant that can be suitably used as an additive for improving the penetration / wetting property, leveling property, surface functionality and the like.

  As a result of intensive studies to solve the above problems, the present inventors have found that a fluorosurfactant containing a fluorochemical compound having the following specific structure as an effective surfactant is a conventional fluorosurfactant. As a result, the present invention was completed.

That is, the present invention relates to the general formula (1)
_{F (CF 2) 2m (CH} 2) n S- (CH 2 CH 2 O) p (CH 2) q -SO 3 M (1)
Wherein m and n are the same or different integers of 1 to 12, p is an integer of 1 to 40, q is 3 or 4, and M is a hydrogen atom, ammonium or an alkali metal. )
The fluorine-type surfactant characterized by comprising the fluorine-type compound (A) represented by these is provided.

  According to the present invention, it is mainly used for various coating materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, mold release agents, molding materials, etc., penetrating / wetting properties, leveling properties, A fluorine-based surfactant that can be suitably used as an additive for enhancing surface functionality and the like 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.

F (CF ₂ ) _2m (CH ₂ ) _n S— (wherein m and n are the same or different integers from 1 to 12) in the fluorine-based compound (A) is an excellent surface-active effect. Is an indispensable segment. The chain length of the group is appropriately selected according to the application 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 surfactant effect, etc. However, in order to obtain a practical surface active effect, it is essential that m and n in the formula are the same or different integers of 1 to 12, and a compound having an excellent surface active effect is obtained. From the point obtained, m in the formula is preferably 2 or more, particularly 3 or more, and m in the formula is 6 or less, particularly 4 or less from the point that a compound having excellent affinity for the composition to be added is obtained. It is preferable that Therefore, m is preferably an integer of 2 to 6, and particularly preferably 3 or 4, in order to achieve both the surfactant effect and the affinity. In addition, since a compound having a practical surface active effect and an affinity with the added composition can be obtained and the production is easy, n in the group general formula is an integer of 2 to 4. preferable.

In the fluorine-based compound (A), —SO ₃ M (wherein M is a hydrogen atom, ammonium or an alkali metal) is a hydrophilic group, and M in the group is a hydrogen atom of sulfonic acid, Ammonium salt of sulfonic acid amine or alkali metal of sulfonic acid alkali metal salt is shown, for example, as —SO ₃ H, —SO ₃ NH ₄ , —SO ₃ Li, —SO ₃ Na, —SO ₃ as a hydrophilic group. K etc. are mentioned.

The fluorine-based compound (A) has one F (CF ₂ ) _2m (CH ₂ ) _n S- in one molecule because it is easy to produce and the surface-active effect of the resulting fluorine-based compound is good. For example, the following general formula (1)
F (CF ₂ ) _{2 m} (CH ₂ ) _n SXSO ₃ M (1)
(In the formula, m and n are the same or different integers of 1 to 12, X is a divalent linking group, and M is a hydrogen atom, ammonium or an alkali metal.)
The fluorine-type compound represented by these is mentioned.

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

  M in the general formula (1) is preferably 3 or 4 from the viewpoint of excellent balance between the surface-active effect of the obtained fluorine-based compound and the affinity for the composition, and n is a practical interface. It is preferable that it is an integer of 2-4 from the point from which the fluorine-type compound which has an active effect is obtained.

Furthermore, p in the general formula (1) is an integer of 1 to 40, and q is 3 or 4. In view of obtaining a fluorine-based compound having a practical surface-active effect, p in the general formula ( 1 ) is preferably an integer of 1 to 25, and particularly preferably an integer of 1 to 15. Further, q in the general formula ( 1 ) is preferably 4 from the viewpoint of easy industrial acquisition and handling of raw materials and high safety during production.

The fluorine-based surfactant composed of a fluorine-based compound in which p in the general formula ( 1 ) is 0 is preferably used in applications where hydrophobicity is required, and is composed of a compound where p is an integer of 1 to 40. Fluorosurfactants are preferably used in applications where hydrophilicity is required. Depending on the required level of hydrophobicity and hydrophilicity, these compounds can be used properly, or compounds of different lengths can be mixed and used. It is possible.

In the general formula (1), —SO ₃ M (wherein M is a hydrogen atom, ammonium or an alkali metal) is a hydrophilic group, and M in the formula is, for example, ammonium or ammonia. , Diethylamine, triethylamine, 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, and rubidium. 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

  The following compounds are mentioned as a specific example of the fluorine-type compound used for the fluorine-type surfactant of this invention.

尚、本発明がこれら具体例により、なんら限定されないことは勿論である。

Needless to say, the present invention is not limited to these specific examples.

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

The following general formula (3)
F (CF ₂ ) _2m (CH ₂ ) _n SY (3)
[Wherein, m and n are the same or different integers of 1 to 12, and Y is (CH ₂ CH ₂ O) _p H (wherein p is an integer of 0 to 40). ]
After reacting the sultone compound with the compound (B) represented by
_{F (CF 2) 2m (CH} 2) n S (CH 2 CH 2 O) p (CH 2) q SO 3 M (4)
(In the formula, m, n, and p are the same as described above, q is 3 or 4, and M is a hydrogen atom, ammonium, or an alkali metal.)
The manufacturing method of the fluorine-type compound represented by these.

  The manufacturing method can be classified into two types when (I) p is 0 and (II) p is 1 to 40. Hereinafter, the production method will be described in detail.

First, (I) a manufacturing method when p is 0 will be described.
When p is 0, the general formula (4) is represented by the following general formula (5)
_{F (CF 2) 2m (CH} 2) n S (CH 2) q SO 3 M (5)
(In the formula, m, n, q and M are the same as described above.)
It can be obtained by reacting a sultone compound with a thiol represented by formula (3) where Y is a hydrogen atom, and then neutralizing.

  Specific examples of the thiols include 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-decane-1. -Thiol, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoro-undecan-1-thiol, 5,5 , 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluoro-dodecane-1-thiol, 3,3,4,4,5 , 5,6,6,7,7,8,8,8-tridecafluoro-octane-1-thiol, 4,4,5,5,6,6,7,7,8,8,9,9 , 9-tridecafluoro-nonane-1-thiol, 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-decane-1-thiol 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-decane- 1-thiol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octane-1-thiol is preferred.

  Examples of the sultone compound include 1,3-propane sultone and 1,4-butane sultone, and 1,4-butane sultone is preferably used from the viewpoint of good handling safety.

  The reaction conditions, operations, and equipment in the production of the compound represented by the general formula (5) are not particularly limited, but the reaction temperature is selected according to the type of thiol or sultone compound used. Usually, it is 30-200 degreeC, Preferably it is 50-180 degreeC, Most preferably, it is 100-150 degreeC. As a molar ratio of the reaction, a sultone compound is usually used in an amount of 0.9 to 3 mol, preferably 1 to 2 mol, particularly preferably 1 to 1.5 mol, relative to 1 mol of thiols. The reaction time is usually 0.5 to 20 hours, preferably 1 to 10 hours, particularly preferably 2 to 5 hours. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen, helium or argon in order to suppress the oxidation reaction of thiols as raw materials.

  This reaction is usually performed in the absence of a solvent, but can also be performed in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is inert to the thiols, sultone compounds and products of the raw material and can dissolve both, but for example, dichloromethane, chloroform, 1, Halogenated hydrocarbons such as 2-dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, halogenated aromatic hydrocarbons such as chlorobenzene, orthodichlorobenzene and paradichlorobenzene, n-pentane, n- Aliphatic hydrocarbons such as hexane, n-octane and cyclohexane, ethers such as tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether and diethylene glycol diethyl ether, esters such as ethyl acetate, butyl acetate and propyl acetate, methanol, ethanol And alcohols such as isopropanol, acetonitrile, nitriles such as benzonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and the like. Among these, ethers, esters, alcohols, nitriles, dimethylformamide, Dimethylacetamide, dimethylsulfoxide and the like are preferable, and alcohols, dimethylformamide and dimethylsulfoxide are particularly preferable. These solvents may be used alone or in combination of two or more.

  The compound represented by the general formula (5) is obtained by neutralizing the sulfonic acid obtained by the above reaction. The method of the neutralization reaction is not particularly limited, and examples thereof include a method of adding an aqueous base solution into the sulfonic acid. The base is not particularly limited, and examples thereof include potassium hydroxide, sodium hydroxide, lithium hydroxide, and aqueous ammonia. Although it does not specifically limit as this reaction temperature, Usually, 5-100 degreeC, Preferably it is 10-80 degreeC, Most preferably, it is 20-50 degreeC. The number of moles of the base used is usually 0.9 to 2 moles, preferably 1 to 1.5 moles, particularly preferably 1 to 1.2 moles per mole of sulfonic acid which is the compound before neutralization. is there. The reaction atmosphere is not particularly limited, and can be either an air atmosphere or an inert gas atmosphere.

  The fluorine-based compound represented by the general formula (5) obtained by the production method can be used unpurified depending on the use and purpose, but is distilled, washed with a solvent, recrystallization, various chromatography, adsorption. It can also be purified by an agent or the like.

Next, the manufacturing method in the case of (II) p is 1-40 is demonstrated.
This compound is represented by the following general formula (6) to thiols in which Y in the general formula (3) is a hydrogen atom.
Z (CH ₂ CH ₂ O) _pH (6)
(In the formula, Z is a halogen atom, and p is an integer of 1 to 40.)
Is reacted with a halogenated polyoxyethylene represented by the following general formula (7):
F (CF ₂ ) _2m (CH ₂ ) _n S (CH ₂ CH ₂ O) _pH (7)
(In the formula, m, n and p are the same as above.)
It can obtain by making it react with a sultone compound, and then neutralizing.

The thiols are the same as those described in (I).
Examples of the halogenated polyoxyethylene represented by the general formula (6) include a chlorine atom, a bromine atom and an iodine atom as Z in the formula. From the viewpoint of reactivity and stability, a chlorine atom and a bromine atom In addition, p in the formula can be appropriately selected according to the level of hydrophobicity and hydrophilicity required for the obtained fluorine-based compound.

  Conditions, operations, and apparatuses in the reaction of the thiols with the halogenated polyoxyethylene are not particularly limited. The reaction temperature is selected according to the types of thiols and halogenated polyoxyethylene, but is usually 20 to 150 ° C, preferably 30 to 120 ° C, particularly preferably 40 to 90 ° C. The molar ratio of the reaction is generally 0.9 to 3 mol, preferably 1 to 2 mol, particularly preferably 1 to 1.5 mol of halogenated polyoxyethylene with respect to 1 mol of thiols as raw materials. There is no restriction | limiting in particular also about reaction time, Usually, 0.5 to 20 hours, Preferably it is 1 to 15 hours, Most preferably, it is 2 to 10 hours. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen, helium or argon in order to suppress the oxidation reaction of thiols as raw materials.

  This reaction is usually performed in the absence of a solvent, but can also be performed in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is inactive with respect to the raw material thiols, halogenated polyoxyethylene and the product, and can dissolve both, but 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 Aliphatic hydrocarbons such as n-hexane, n-octane and cyclohexane, ethers such as tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether and diethylene glycol diethyl ether, esters such as ethyl acetate, butyl acetate and propyl acetate, Examples include alcohols such as diol, ethanol, isopropanol, nitriles such as acetonitrile and benzonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. Among these, ethers, esters, alcohols, nitriles, dimethylformamide Dimethylacetamide, dimethylsulfoxide and the like are preferable, and ethers, esters, dimethylformamide, dimethylsulfoxide are particularly preferable. These solvents may be used alone or in combination of two or more.

  Although hydrogen halide is by-produced in this reaction, it is preferable to remove this hydrogen halide in order to carry out the reaction efficiently and safely. Although there is no restriction | limiting in particular as a removal method, For example, the method of adding a hydrogen halide catcher to a system is mentioned. As the hydrogen halide catcher, a base is usually used. As the base, either an organic base or an inorganic base can be used. Examples of the organic base include triethylamine and pyridine, and examples of the inorganic base include potassium carbonate, sodium carbonate, lithium carbonate, sodium bicarbonate, and potassium bicarbonate. Hydroxides such as potassium hydroxide and sodium hydroxide, which are a kind of inorganic base, are not preferred because they may oxidize thiols as raw materials. The amount of the base to be used is generally 1 to 3.5 mol, preferably 1.1 to 3 mol, particularly preferably 1.1 to 1.8 mol, per 1 mol of thiols as a raw material.

  Next, the reaction of the obtained compound represented by the general formula (7) with the sultone compound will be described. This reaction is the same except that the compound represented by the general formula (7) is used in place of the starting thiols in the reaction method in which p in (I) is 0.

  The fluorine-based compound represented by the general formula (5) obtained by the production method can be used unpurified depending on the use and purpose, but distillation, washing with a solvent, recrystallization, various chromatography, It is also possible to purify with an adsorbent or the like.

  The fluorosurfactant of the present invention has almost the same solubility in water and / or organic solvent as the use of conventionally used fluorosurfactants, and has a high surfactant effect. There is no restriction in particular and it can be used widely.

  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 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, natural polymers such as acrylic resin, urethane resin, epoxy resin, polyimide resin, polyamide resin, 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.

  Also, the use of the above-mentioned composition is not limited, for example, industrial and household adhesives, scratch resistance, slipperiness, non-tackiness, water and oil repellency, gas barrier properties, heat resistance, light resistance , Surface functional protective film forming materials such as weather resistance, physiological activity, water resistance, moisture resistance, antifouling property, lubricity, treatment agents such as clothing, furniture, shoes, miscellaneous fibers, 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 suitably used 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.

Comparative Example 1
To a 3 liter four-necked flask equipped with a stirrer, reflux condenser and thermometer, add 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10 , 10,10-heptadecafluoro-decane-1-thiol 480.2 g (1 mol) and 1,4-butane sultone 149.8 g (1.1 mol) were added, and the mixture was stirred at 120 ° C. for 4 hours under a nitrogen atmosphere. Thereafter, the mixture was cooled to 25 ° C., and 460 g of a 10 wt% lithium hydroxide aqueous solution was added to the reaction solution. After stirring at 25 ° C. for 30 minutes, water was distilled off under reduced pressure. By recrystallizing the obtained compound from methanol, the fluorine-based compound (i) [4- (3,3,4,4,5,5,6,6,7,7,8,8,9,9 , 10,10,10-heptadecafluorodecanesulfanyl) -butane-1-sulfonic acid lithium] 529g.

Comparative Example 2
In Comparative Example 1, the fluorine-based compound (ii) [4- (3, 3] was used in the same manner as in Example 1 except that 440 g of 10 wt% aqueous sodium hydroxide solution was used instead of 460 g of 10 wt% lithium hydroxide aqueous solution. , 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanesulfanyl) -butane-1-sulfonic acid sodium] 574.6 g Obtained.

Comparative Example 3
In Comparative Example 1, the fluorine-based compound (iii) [4- (3, 3] was used in the same manner as in Example 1 except that 617 g of 10 wt% aqueous potassium hydroxide solution was used instead of 460 g of 10 wt% lithium hydroxide aqueous solution. , 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanesulfanyl) -butane-1-sulfonate potassium] 576g .

Comparative Example 4
In Comparative Example 1, the fluorine-based compound (iv) [4] was used in the same manner as in Example 1 except that 74.8 g of 25 wt% aqueous ammonia solution and 400 g of ion-exchanged water were used instead of 460 g of 10 wt% lithium hydroxide aqueous solution. -(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanesulfanyl) -butane-1-sulfonate ammonium 570 g was obtained.

Comparative Example 5
In Comparative Example 1, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-decane-1-thiol 480. Instead of 2 g (1 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octane-1-thiol 380.2 g (1 mol) Fluorine-based compound (v) [4- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro] except in the same manner as in Example 1. 550 g of (octanesulfanyl) -butane-1-sulfonic acid lithium] was obtained.

Comparative Example 6
In Comparative Example 1, a fluorine-based compound was obtained in the same manner as in Example 1 except that 134.4 g (1.1 mol) of 1,3-propane sultone was used instead of 149.8 g (1.1 mol) of 1,4-butane sultone. Compound (vi) [3- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecanesulfanyl) -propane 5-1 g of lithium -1-sulfonate was obtained.

Example 1
To a 3 liter four-necked flask equipped with a stirrer, reflux condenser and thermometer, add 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10 , 10,10-heptadecafluoro-decane-1-thiol 480.2 g (1 mol) and 524.7 g of chloropolyoxyethylene (addition moles of ethylene oxide: 10 mol on average) were added, and at 80 ° C. in a nitrogen atmosphere. Stir for 8 hours. Thereafter, 149.8 g (1.1 mol) of 1,4-butane sultone was added, followed by stirring at 120 ° C. for 4 hours in a nitrogen atmosphere. After cooling to 25 ° C., 460 g of a 10 wt% aqueous lithium hydroxide solution was added to the reaction solution. After stirring at 25 ° C. for 30 minutes, water was distilled off under reduced pressure. By recrystallizing the obtained compound from methanol, the fluorine-based compound (vii) [4-{(3,3,4,4,5,5,6,6,7,7,8,8,9, 9,10,10,10-heptadecafluorodecanesulfanyl) -polyoxyethylene} -butane-1-sulfonate lithium] 903 g was obtained.

Example 2
In Example 1 , 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-decane-1-thiol 480. Instead of 2 g (1 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octane-1-thiol 380.2 g (1 mol) The fluorine-containing compound (viii) [4-{(3,3,4,4,5,5,6,6,7,7,8,8,8-trideca] is used in the same manner as in Example 1 except that it is used. 870 g of lithium fluorooctanesulfanyl) -polyoxyethylene} -butane-1-sulfonate] was obtained.

Example 3
In Example 1 , 766.9 g of chloropolyoxyethylene (added mole number of ethylene oxide: average 15 moles) was used instead of 524.7 g of chloropolyoxyethylene (addition mole number of ethylene oxide: average 10 moles). In the same manner as in Example 1 , the fluorine-based compound (ix) [4-{(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 1,134 g of lithium 10,10-heptadecafluorodecanesulfanyl) -polyoxyethylene} -butane-1-sulfonate] was obtained.

Example 4
In Example 1 , 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-decane-1-thiol 480. Instead of 2 g (1 mol), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octane-1-thiol 380.2 g (1 mol) Furthermore, except that 526.9 g of chloropolyoxyethylene (addition mole number of ethylene oxide: average 10 moles) 524.7 g is used, except that 766.9 g of chloropolyoxyethylene (addition mole number of ethylene oxide: average 15 moles) is used In the same manner as in Example 1 , fluorine compound (x) [4-{(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanesulfanyl ) -Polyoxyethylene} -butane-1-sulfonic acid lithium] 989 g.

Test Examples 1 to 3 and Comparative Test Examples 1 to 7
The surface tension in the aqueous solution of the fluorine-based surfactant composed of the fluorine-based compounds obtained in Examples 1 to 3 and Comparative Examples 1 to 6 was measured by the following method, and the results are shown in Table 1 as 3 and Comparative 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)

As Comparative Test Example 7 , 3- (3,3,4,4,5,5,6,6,7,7,8) described in JP-A-55-4309 (page 4) , 8,9,9,10,10,10-heptadecafluorodecanoxy) -sodium propane-1-sulfonate in aqueous solution is shown.

In Test Examples 1 to 4 using the fluorine-based surfactant composed of the fluorine-based compound of the present invention, the surface tension reducing effect is lower than that of the fluorine-based surfactant used in Comparative Test Example 7 which is a conventional compound. It was confirmed that it was excellent.

Test Examples 5 and 6
Using the fluorine-based compound (vii) obtained in Example 1 , the combined use effect with the hydrocarbon-based surfactant was confirmed. Fluorine compounds (vii) and hydrocarbon surfactant: surface tension was measured at 0.001 wt% aqueous solution of a mixture of (polyoxyethylene oleyl ether Kao Corp. Emulgen 430), Test Example 5 and 6 The results are shown in Table 2.

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 (5)

General formula (1)
_{F (CF 2) 2m (CH} 2) n S- (CH 2 CH 2 O) p (CH 2) q -SO 3 M (1)
Wherein m and n are the same or different integers of 1 to 12, p is an integer of 1 to 40, q is 3 or 4, and M is a hydrogen atom, ammonium or an alkali metal. )
The fluorine-type surfactant characterized by comprising the fluorine-type compound (A) represented by these . In the general formula (1), m is 3 or 4, n is an integer of 2 to 4, and M is NH. ₄ The fluorosurfactant according to claim 1, which is lithium, sodium or potassium. The fluorine-based surfactant according to claim 1, wherein p in the general formula (1) is an integer of 1 to 15. The fluorine-based compound (A) is represented by the following general formula (3)
F (CF ₂ ) _2m (CH ₂ ) _n SY (3)
[Wherein, m and n are the same as defined above, and Y is (CH ₂ CH ₂ O) _p H (wherein p is the same as defined above). ]
The following general formula (4) obtained by reacting the sultone compound with the compound (B) represented by
_{F (CF 2) 2m (CH} 2) n S (CH 2 CH 2 O) p (CH 2) q SO 3 M (4)
(In the formula, m, n, p, q and M are the same as described above.)
The fluorine-based surfactant according to claim 1 , which is a fluorine-based compound represented by the formula: In the general formula (4), m is 3 or 4, n is an integer of 2 to 4, p is an integer of 1 to 15, and M is NH. ₄ The fluorosurfactant according to claim 4, which is lithium, sodium or potassium.