JP2011184333A - Fluorine-containing organosilicon compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing organosilicon compound that exhibits high surface tension-reducing performances and excellent dissolvability in various solvents, and a fluorine-containing surfactant. <P>SOLUTION: The compound is represented by general formula (1) (wherein Rf is a monovalent perfluoroalkyl group or the like; Z is a bivalent organic group; Q is a polyether group; R<SP>1</SP>'s are each independently a hydrogen atom or a hydrocarbon group; R<SP>2</SP>is a hydrogen atom or a hydroxy group; a is 1-2; b is 1-3; and c is 0-2). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel fluorine-containing organosilicon compound and a method for producing the same, and more particularly to a fluorine-containing organosilicon compound that can significantly reduce the surface tension when used as a surfactant.

  Conventionally, as a fluorine-containing surfactant, for example, perfluoroalkylsulfonic acid (PFOS) or perfluorooctanoic acid (PFOA) in which a polyether group is bonded via an amide group or an ester group is known. However, concerns have been pointed out that the fluorine-containing surfactants cause environmental pollution, and legal or voluntary regulations regarding the use thereof are being strengthened.

（式中、Ｒｆは独立に炭素原子数４〜１４のパーフルオロアルキル基又は炭素原子数５〜１４のパーフルオロポリエーテル基であり、Ｑは独立にエチレン基及び／又はプロピレン基がエーテル結合で繰り返し結合されてなるポリエーテル基であり、Ｒは独立に水素原子、アリル基、炭素原子数１〜４のアルキル基及び炭素原子数２〜３のアシル基からなる群から選ばれる１価の炭化水素基又は原子であり、Ｌ及びｍはそれぞれ独立に０又は１であり、ｎは独立に１又は２、ｘは２又は３であり、Ｍｅはメチル基である） A fluorine-containing organosilicon compound represented by the following formula and a method for producing the same are disclosed as a fluorine-containing organosilicon compound that can significantly reduce the surface tension when added to an organic solvent or the like (Patent Document 1).

(In the formula, Rf is independently a perfluoroalkyl group having 4 to 14 carbon atoms or a perfluoropolyether group having 5 to 14 carbon atoms, and Q is independently an ether bond of an ethylene group and / or a propylene group. A polyether group formed by repeated bonding, R is independently a monovalent carbon selected from the group consisting of a hydrogen atom, an allyl group, an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 3 carbon atoms. A hydrogen group or an atom, L and m are each independently 0 or 1, n is independently 1 or 2, x is 2 or 3, and Me is a methyl group)

JP 9-241381

  However, the above-mentioned compound has a large molecular weight of the main chain silicone chain and has two perfluoropolyether groups in the molecule. Therefore, the molecular weight of the whole molecule is large and the solubility in an organic solvent or the like is not sufficient. . Therefore, the present invention provides a fluorine-containing organic compound having a high surface tension reducing ability equal to or higher than that of the fluorine-containing organic silicon compound disclosed in JP-A-9-241181 and having excellent solubility in various solvents. An object is to provide a silicon compound and a fluorine-containing surfactant.

  As a result of intensive studies to solve the above problems, the present inventor has developed a novel siloxane having a low molecular weight main chain by sequentially introducing a fluorine-containing organic group and a polyether group into a cyclic tetrasiloxane or a cyclic pentasiloxane. The present inventors have found that a fluorine-containing organic silicon compound can be provided, and that the fluorine-containing organic silicon compound has a high surface tension reducing ability and an excellent solubility in various solvents.

（式中、Ｒｆは互いに独立に、１価のパーフルオロアルキル基又はパーフルオロポリエーテル基であり、Ｚは単結合、又は酸素原子、ケイ素原子及び／又は窒素原子を含んでいてよい炭素原子数１〜２０の２価の有機基であり、Ｑは互いに独立に、エチレン基及び／又はプロピレン基がエーテル結合で繰り返し結合されてなるポリエーテル基であり、Ｒ^１は互いに独立に、水素原子又は、アリル基、炭素原子数１〜４のアルキル基、及び炭素原子数２〜３のアシル基から選ばれる１価の炭化水素基であり、Ｒ^２は水素原子または水酸基であり、ａは１〜２、ｂは１〜３、ｃは０〜２であり、但しａ＋ｂ＋ｃの合計が４または５であり、ｘは１又は２である）
で表される含フッ素有機ケイ素化合物及び、該含フッ素有機ケイ素化合物の製造方法並びに該含フッ素有機ケイ素化合物より成る界面活性剤を提供する。 That is, the present invention provides the following general formula (1):

(In the formula, Rf independently of each other is a monovalent perfluoroalkyl group or a perfluoropolyether group, and Z is a single bond, or the number of carbon atoms that may contain an oxygen atom, a silicon atom and / or a nitrogen atom) 1 to 20 divalent organic groups, Q is independently a polyether group in which an ethylene group and / or a propylene group are repeatedly bonded by an ether bond, and R ¹ is independently a hydrogen atom or , An allyl group, an alkyl group having 1 to 4 carbon atoms, and a monovalent hydrocarbon group selected from an acyl group having 2 to 3 carbon atoms, R ² is a hydrogen atom or a hydroxyl group, and a is 1 to 1 2, b is 1-3, c is 0-2, provided that the sum of a + b + c is 4 or 5, and x is 1 or 2)
And a method for producing the fluorine-containing organic silicon compound, and a surfactant comprising the fluorine-containing organic silicon compound.

  The fluorine-containing organosilicon compound of the present invention is useful as a fluorine-containing surfactant because it has a low molecular weight of siloxane as the main chain, has excellent solubility in various solvents, and can significantly reduce the surface tension of the solvent. It is.

1 is a ¹ H-NMR chart of a compound produced in Example 1. 2 is an IR spectrum of the compound produced in Example 1.

Fluorine-containing organosilicon compound The fluorine-containing organosilicon compound of the present invention is represented by the general formula (1). The fluorine-containing organic silicon compound of the present invention is a compound having hydrophobicity due to a fluorine-containing organic group and hydrophilicity due to a polyether group. In the above formula (1), Rf, independently of each other, is a monovalent perfluoroalkyl group or a perfluoropolyether group, and has 4 to 14, preferably 4 to 10, more preferably 6 to 9 carbon atoms. It may be a fluoroalkyl group or a perfluoropolyether group having 5 to 18 carbon atoms, preferably 8 to 11 carbon atoms. By introducing such a fluorine-containing organic group, hydrophobicity can be imparted to the organosilicon compound. When the number of carbon atoms is larger than the upper limit, the total molecular weight increases when used as a surfactant, so that the solubility in a solvent is lowered, which is not preferable. On the other hand, if the number of carbon atoms is less than the lower limit, the characteristics of the fluorine group are not sufficiently exhibited, and high surface activity cannot be obtained.

（式中、ｋは４〜１４の整数、好ましくは４〜１０の整数、より好ましくは６〜９の整数である） Examples of the perfluoroalkyl group include the groups shown below. The perfluoroalkyl group of the present invention may have a branch in the molecular chain.

(Wherein, k is an integer of 4 to 14, preferably an integer of 4 to 10, more preferably an integer of 6 to 9)

  Specifically, nonafluorobutyl group, undecafluoropentyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, nonadecafluorononyl group, heneicosafluorodecyl group, 7-tricyl Examples thereof include a fluoromethylhexadecafluorooctyl group and a 5-trifluoromethyldodecafluorohexyl group, and a nonafluorobutyl group, an undecafluoropentyl group, and a tridecafluorohexyl group are preferable.

（式中、ｙは１〜５の整数である） Examples of the perfluoropolyether group include the following groups.

(Wherein y is an integer of 1 to 5)

Among them, the following groups are preferable.

Z is a single bond or a divalent organic group having 1 to 20, preferably 1 to 14, more preferably 1 to 10 carbon atoms which may contain an oxygen atom, a silicon atom and / or a nitrogen atom (ie, oxygen , A divalent linking group that may contain at least one heteroatom selected from silicon and nitrogen atoms. For example, groups having an amide, ether, ester bond, dimethylsilylene group and the like can be mentioned, and a group having a cyclic structure, an aliphatic and / or aromatic unsaturated bond may be used. Among them, the following groups are preferable.

When Rf is a perfluoroalkyl group, Z preferably does not contain an ether bond. In this case, the group represented by — (CH ₂ ) x —CH ₂ —Z—Rf includes 3,3,4,4,5,5,6,6,7,7,8,8,8-tri Examples include decafluorooctyl group, 3,3,4,4,5,5,6,6,6-nanofluorohexyl group.

Examples of the group represented by — (CH ₂ ) x —CH ₂ —Z—Rf in which Rf is a perfluoropolyether group include 6-trifluoromethyl-6,8,8,9,9,10,10,10. -Octafluoro-4,7-dioxadecyl group, 6,9-bis (trifluoromethyl) -6,8,8,9,11,11,12,12,13,13,13-undecafluoro-4, 7,10-trioxatridecyl group, 6,9,12-tris (trifluoromethyl) -6,8,8,9,11,11,12,14,14,15,15,16,16,16 -Tetradecafluoro-4,7,10,13-tetraoxadecyl group etc. are mentioned.

  In the general formula (1), Q is a polyether group in which an ethylene group and / or a propylene group are repeatedly bonded by an ether bond independently of each other. Thereby, hydrophilicity is imparted to the fluorine-containing organosilicon compound of the present invention. The polyether group may be a homopolymer chain of ethylene glycol, a homopolymer chain of propylene glycol, or a copolymer (chain polymerization, random polymerization) chain of both, and is appropriately selected according to the use of the fluorine-containing organosilicon compound. Is done.

  The degree of polymerization of the polyether group may be usually determined in consideration of the balance with the fluorine-containing organic group. When ethylene glycol is used as a homopolymer chain, the degree of polymerization is preferably 3 to 20, more preferably 3 ~ 12. When propylene glycol having a lower hydrophilicity than ethylene glycol is used as a homopolymer chain, one having a high polymerization degree is preferable, and one having a polymerization degree of 100 to 200 is more preferable. In the case of a copolymer chain of propylene glycol and ethylene glycol, the degree of polymerization is 10 to 100, more preferably 10 to 50, and the content of propylene glycol in the entire polyether group is 0 to 50 mol%. It is preferable to polymerize the polymer in an amount of 2 to 10 mol%.

（式中、ｎは３〜２０の整数、ｍは１００〜２００の整数である。）

（式中、ｓ及びｔは、ｓ＋ｔが１０〜１００となる整数。） Examples of Q include the following groups.

(In the formula, n is an integer of 3 to 20, and m is an integer of 100 to 200.)

(In the formula, s and t are integers such that s + t is 10 to 100.)

In general formula (1), R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group selected from an allyl group, an alkyl group having 1 to 4 carbon atoms, and an acyl group having 2 to 3 carbon atoms. And preferably a hydrogen atom, a methyl group or a butyl group. R ² is a hydrogen atom or a hydroxyl group.

The following can be illustrated as a fluorine-containing organosilicon compound of this invention. In addition, the repeating number of each siloxane unit in the following exemplary formula is an average value.

（式中、Ｒｆ、Ｚ、ｘは前記と同じ意味である）
及び下記式（３）で示されるオレフィン化合物（以下、「オレフィン化合物」と称する）

（式中、Ｑ、Ｒ^１は前記と同じ意味である）
を順次付加反応させることにより製造することができる。 Method for Producing Fluorine-Containing Organosilicon Compound The fluorine-containing organosilicon compound of the present invention is obtained by adding 2,4,6,8-tetramethylcyclotetrasiloxane or 2,4,6,8,10-pentamethylcyclopentasiloxane to the following: An olefin compound represented by the formula (2) (hereinafter referred to as “fluorinated olefin compound”),

(Wherein Rf, Z, and x have the same meanings as described above)
And an olefin compound represented by the following formula (3) (hereinafter referred to as “olefin compound”)

(Wherein Q and R ¹ have the same meaning as described above)
Can be produced by sequential addition reaction.

(I) Addition reaction of fluorine-containing olefin compound 2,4,6,8-tetramethylcyclotetrasiloxane represented by the following formula (4) or 2,4,6,8,10 represented by the following formula (5) -Pentamethylcyclopentasiloxane and the fluorine-containing olefin compound of the above formula (2) are subjected to an addition reaction in the presence of an addition reaction catalyst such as a platinum-based catalyst. The fluorine-containing olefin compound is preferably 0.2 to 2.0 moles per mole of 2,4,6,8-tetramethylcyclotetrasiloxane or 2,4,6,8,10-pentamethylcyclopentasiloxane. Is preferably added in an amount of 0.2 to 1.0 mol, more preferably 0.2 to 0.5 mol.

（式中、ｄは１または２、ｅは２〜４の数、但しｄ＋ｅは４または５である。Ｘ、Ｚ、Ｒｆは前述の通り。） As the platinum-based catalyst, a conventionally known catalyst used for hydrosilylation can be used, and examples thereof include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum / vinylsiloxane complex, platinum black, and a complex of chloroplatinic acid and olefin or aldehyde. It is done. Of these, chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum / vinylsiloxane complexes are preferred because of their high activity. The usage-amount of a platinum-type catalyst may be normally 1-100 ppm (platinum weight conversion) with respect to the whole reaction liquid. The reaction temperature is 60 ° C to 140 ° C, preferably 80 ° C to 120 ° C. The reaction time is 1 to 20 hours, preferably 2 to 6 hours. After completion of the reaction, unreacted 2,4,6,8-tetramethylcyclotetrasiloxane or 2,4,6,8,10-pentamethylcyclopentasiloxane is removed by distillation, which is represented by the following formula (6). Can be obtained.

(In the formula, d is 1 or 2, e is a number of 2 to 4, where d + e is 4 or 5. X, Z, and Rf are as described above.)

  In the above reaction, a solvent may be used as necessary. The solvent is not particularly limited as long as it does not react with the solute. For example, hydrocarbons such as benzene, toluene, xylene, hexane, heptane, octane and cyclohexane; ethers such as diisopropyl ether and dibutyl ether; Examples thereof include siloxanes such as siloxane.

(Ii) Addition reaction with olefin compound Next, the compound of the above formula (6) and the olefin compound of the above formula (3) are subjected to an addition reaction in the presence of an addition reaction catalyst such as a platinum-based catalyst. The olefin compound is reacted in an amount of 1.0 to 2.5 equivalents, preferably 1.1 to 1.7 equivalents, based on 1 equivalent of Si—H groups determined from the hydrogen gas generation amount of the compound of formula (6). It is good to let them. The reaction can be performed, for example, by adding the compound of formula (6) to a platinum-based catalyst and an olefin compound that have been mixed in advance. The same platinum catalyst can be used as described above.

  The reaction temperature is 60 ° C to 140 ° C, preferably 80 ° C to 120 ° C. The reaction time is 1 to 20 hours, preferably 2 to 6 hours. The resulting product is brownish and may be treated with an adsorbent such as activated carbon to decolorize. By the said method, the fluorine-containing organosilicon compound of the said General formula (1) can be obtained.

  Further, the fluorine-containing organosilicon compound produced by the above method may be converted to Si—OH by hydrolyzing the Si—H group remaining in the molecule. Hydrolysis is performed by adding water to the mixture after the addition reaction and reacting at 20 to 40 ° C. for 1 to 20 hours. At this time, the platinum-based catalyst used in the addition reaction serves as a hydrolysis catalyst, but a catalyst may be further added to accelerate the reaction. As the catalyst to be added, palladium or platinum supported on carbon, alumina or the like, and alkylhydroxylamine such as diethylhydroxylamine are preferable.

  The fluorine-containing organosilicon compound of the present invention can be used as a surfactant by adding it to various solvents, particularly organic solvents. In this case, examples of the organic solvent include isopropyl alcohol, ethyl lactate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, N-methyl-2-pyrrolidone, and γ-butyrolactone. At this time, the concentration of the fluorine-containing organosilicon compound is preferably 0.01 to 10% by mass.

  The fluorine-containing organosilicon compound of the present invention can remarkably lower the surface tension of an organic solvent and is useful as a fluorine-containing surfactant. When used as a fluorine-containing surfactant, the fluorine-containing organosilicon compound represented by the general formula (1) may be used singly or in appropriate combination of two or more.

  The fluorine-containing surfactant of the present invention, when added to various liquids, particularly organic solvents, wettability, permeability, spreadability, foam stability, fluidity, emulsification, dispersibility, water repellency. The following uses are expected because of its excellent ability to impart or improve oiliness. That is, an emulsifier for polymerization in the plastic and rubber industry, a stabilizer for latex, a preparation aid for powdered fluorocarbon polymer aggregates, a foaming additive for controlling spread or coating unevenness, and a grease for imparting water and oil repellency. Additives, polyolefin internal antistatic agent and anti-adhesive agent; additive for improving fluidity when recovering heavy oil from oil storage equipment in the petroleum industry, additive for improving wear resistance of lubricating oil, Additive for preventing freezing in gasoline vaporizer, Gasoline by film formation, Evaporation inhibitor for jet fuel; Additive for improving fluidity to improve melting prevention process in textile industry, 20 Carbonization aid for wool , Additive for lowering surface tension of synthetic sizing agent PVA aqueous solution in spinning sizing process, mercerization assistant, dyeing finish assistant; dye and pigment industry Aids for improving pigment colorability and dispersibility in pigments, flowability and anti-dentation imparting agents for correcting paint defects, regulators for the evaporation rate of solvents in paints; Additives, additives for metal etching, additives for solder flux, corrosion inhibitors, plating mist prevention agents; penetration improvers for fungicides in the pharmaceutical and agrochemical fields, wettability improvers for promoters and insecticides, emulsification , Dispersion and spreadability improvers; additives to cleaner products in the field of household goods, leveling improvers to polishes, additives for cosmetics, antistatic agents; fluidity and flow of ink in the field of photography and printing Examples thereof include additives for imparting properties, leveling agents for photographic emulsions, antistatic agents for films, and film drying aids.

  Furthermore, since the fluorine-containing organosilicon compound of the present invention does not use alkali metal salts in the production process and has a low content of alkali metals, it is used for applications that dislike alkali metal contamination, particularly semiconductors, liquid crystal displays, electronic devices, etc. It is useful as a leveling agent for resist compositions used in the manufacturing process.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. In addition, the repeating number of each siloxane unit in following formula (8), (9) is an average value.

で示される２，４，６，８−テトラメチルシクロテトラシロキサン１９５ｇを仕込み、９５℃まで昇温した。
次に、下記式（８）

で示される含フッ素オレフィン化合物１４０ｇと、白金／ビニルシロキサン錯体のトルエン溶液（白金金属０．５％含有）０．８ｇとの混合溶液を調製した。該混合溶液を上記フラスコ中に３０分間かけて滴下し、１０５℃で６時間保持した後、２５℃まで冷却した。反応後溶液を、ロータリーエバポレーターを用い９０℃下５ｍｍＨｇにて濃縮し、下記式（９）で示される化合物１８７ｇを得た。

[Example 1]
In a four-necked flask with an internal volume of 500 mL equipped with a condenser and a thermometer, the following formula (7)

Was charged with 195 g of 2,4,6,8-tetramethylcyclotetrasiloxane, and the temperature was raised to 95 ° C.
Next, the following formula (8)

A mixed solution of 140 g of the fluorine-containing olefin compound represented by the above and 0.8 g of a toluene solution of platinum / vinylsiloxane complex (containing 0.5% platinum metal) was prepared. The mixed solution was dropped into the flask over 30 minutes, held at 105 ° C. for 6 hours, and then cooled to 25 ° C. The solution after the reaction was concentrated at 5 mmHg at 90 ° C. using a rotary evaporator to obtain 187 g of a compound represented by the following formula (9).

Next, 100 g of the compound of the above formula (9) (Si—H group content: 2.93 × 10 ⁻³ mol / g) was charged into a 500 ml flask and heated to 95 ° C. And 83 g of polyethylene oxide (average degree of polymerization 3) in which each end of the molecular chain is sealed with an allyl group and a methyl group, 0.7 g of a toluene solution of platinum / vinylsiloxane complex (containing 0.5% platinum metal), A mixture of was prepared. This mixture was dropped into a 500 ml flask over 30 minutes and then held at a temperature of 105 ° C. for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, 2 g of powdered activated carbon was added and stirred, and then filtered to recover 172 g of a light brown transparent oily product.

As a result of analyzing the product by ¹ H-NMR and IR, it was found that the product had a structure represented by the following formula (10).

¹ H-NMR and IR used the following apparatuses. The results are shown in FIGS.
¹ H-NMR: JNMLA300WB (manufactured by JEOL)
IR: Spectrum 100 FT-IR (manufactured by Perkin Elmer)
In FIG. 1, ¹ H-NMR chemical shifts are as follows: Si—CH ₃ : 0.0 to 0.10 ppm, Si—CH ₂ —: 0.43 ppm, —CH ₂ —: 1.52 ppm, O—CH ₃ : 3.30 ppm, O—CH ₂ −: 3.30 to 3.70 ppm.
In FIG. 2, IR characteristic absorption is as follows: —CF ₂ —CF (CF ₃ ) —: 991.7 cm ⁻¹ , C—F: 1000 to 1100 cm ⁻¹ , Si—O: 1000 to 1100 cm ⁻¹ , —CF _2. −: 1200.1 cm ⁻¹ , Si—CH ₃ : 1239.5 cm ⁻¹ , —CF ₃ : 1302.7 to 1350.1 cm ⁻¹ , C—H: 2870.3 cm ⁻¹ .

[Comparative Example 1]
A fluorine-containing organosilicon compound disclosed in JP-A-9-241382 was used as a comparative example.

で表される化合物１００ｇ、及びトルエン１００ｇを仕込み、内温９５℃まで昇温した。次に、分子鎖の各末端がアリル基及びメチル基で封止されたポリエチレンオキシド（平均重合度３）７９ｇと、白金／ビニルシロキサン錯体のトルエン溶液（白金として０．５％含有）０．８ｇとの混合物を調製した。該混合物を上記式（１１）のトルエン溶液に３０分間かけて滴下し、１０５℃で１５時間保持した後、４０℃まで冷却した。 In a four-necked flask with an internal volume of 500 mL equipped with a cooling pipe and a thermometer, the following formula (11)

100 g of the compound represented by the formula (1) and 100 g of toluene were charged, and the temperature was raised to an internal temperature of 95 ° C. Next, 79 g of polyethylene oxide (average polymerization degree 3) in which each end of the molecular chain is sealed with an allyl group and a methyl group, and a toluene solution of platinum / vinylsiloxane complex (containing 0.5% as platinum) 0.8 g A mixture with was prepared. The mixture was added dropwise to the toluene solution of the above formula (11) over 30 minutes, kept at 105 ° C. for 15 hours, and then cooled to 40 ° C.

Next, the obtained reaction mixture was heated to 45 ° C., 3 ml of 1 mol / L sodium hydroxide aqueous solution was added and stirred for 1 hour, and 3.3 ml of 1 mol / L hydrochloric acid was added. The organic layer was taken out and the volatile components were distilled off at 105 ° C./10 mmHg to obtain a brown oily liquid. 1.7 g of powdered activated carbon was added and stirred and filtered to recover 161 g of a light brown transparent oily product. As a result of analyzing the product by ¹ H-NMR and IR, it was found that the product had a structure represented by the following formula (12).

[Measurement of surface tension]
A 0.1% by mass solution and a 1.0% by mass solution of propylene glycol monomethyl ether acetate (PGMEA) of the compounds obtained in the examples and comparative examples were prepared. With respect to these solutions, the surface tension was measured by a Wilhelmy type surface tension meter A3 (manufactured by Kyowa Interface Science). The results are shown in Table 1.

[Evaluation of solubility]
The compounds obtained in Examples and Comparative Examples were added to each organic solvent shown in Table 2 in an amount that would be a 1% by mass solution, and after mixing well, the uniformity of the solution was visually evaluated. The results are shown in Table 2.
The evaluation criteria of solubility are as follows.
○: The solution is transparent.
X: The solution is turbid.

  From Table 1, the fluorinated organosilicon compound of the present invention has an excellent surface tension reducing ability equivalent to that of the fluorinated organosilicon compound disclosed in JP-A-9-241381. From Table 2, it can be seen that the fluorine-containing organosilicon compound of the present invention exhibits superior solubility in various organic solvents as compared with the fluorine-containing organosilicon compound disclosed in JP-A-9-241382.

  The fluorine-containing surfactant of the present invention has high solubility in various solvents and is excellent in ability to lower the surface tension of various solvents. Therefore, it is useful as a fluorine-containing surfactant in the fields of plastic and rubber industry, petroleum industry, dye and pigment industry, metal and machinery industry, pharmaceutical and agricultural chemicals, household goods, photography and printing.

Claims (7)

The following general formula (1):

(In the formula, Rf independently of each other is a monovalent perfluoroalkyl group or a perfluoropolyether group, and Z is a single bond, or the number of carbon atoms that may contain an oxygen atom, a silicon atom and / or a nitrogen atom) 1 to 20 divalent organic groups, Q is independently a polyether group in which an ethylene group and / or a propylene group are repeatedly bonded by an ether bond, and R ¹ is independently a hydrogen atom or , An allyl group, an alkyl group having 1 to 4 carbon atoms, and a monovalent hydrocarbon group selected from an acyl group having 2 to 3 carbon atoms, R ² is a hydrogen atom or a hydroxyl group, and a is 1 to 1 2, b is 1-3, c is 0-2, provided that the sum of a + b + c is 4 or 5, and x is 1 or 2)
The fluorine-containing organosilicon compound represented by these.   The fluorine-containing organosilicon compound according to claim 1, wherein Rf is independently a perfluoroalkyl group having 4 to 14 carbon atoms or a perfluoropolyether group having 5 to 18 carbon atoms. The fluorine-containing organosilicon compound according to claim 1 or 2, wherein Z is any group shown below.

2,4,6,8-tetramethylcyclotetrasiloxane or 2,4,6,8,10-pentamethylcyclopentasiloxane and the following formula (2)

(In the formula, Rf independently of each other is a monovalent perfluoroalkyl group or a perfluoropolyether group, and Z is a single bond, or the number of carbon atoms that may contain an oxygen atom, a silicon atom and / or a nitrogen atom) 1 to 20 divalent organic group, x is 1 or 2)
And an addition reaction of the olefin compound represented by the following formula (3):

(Q is a polyether group in which an ethylene group and / or a propylene group are repeatedly bonded by an ether bond independently of each other, and R ¹ is a hydrogen atom, an allyl group, or a carbon atom number 1 to 4 independently of each other. (It is a group selected from an alkyl group and an acyl group having 2 to 3 carbon atoms)
A process for producing the fluorine-containing organosilicon compound according to claim 1 by addition reaction of the olefin compound represented by formula (1).   The method for producing a fluorinated organosilicon compound according to claim 4, wherein Rf is independently a perfluoroalkyl group having 4 to 14 carbon atoms or a perfluoropolyether group having 5 to 18 carbon atoms. The method for producing a fluorine-containing organosilicon compound according to claim 4 or 5, wherein Z is any group shown below.

  A fluorine-containing surfactant comprising the fluorine-containing organosilicon compound according to any one of claims 1 to 3.

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