Emulsion and method for producing the same

Abstract

To provide an emulsion of perfluoropolyether phosphate ester.SOLUTION: An emulsion comprises (A) a perfluoropolyether phosphate ester compound represented by a formula (I), (B) a fluorine-based anionic surfactant with a counter cation, (C) alcohol, and (D) water [where Rf is a C1-4 perfluoroalkyl group. X is a fluoro group or a trifluoromethyl group. Y is a C1-10 divalent group. m is 5-60. n is 1 or 2].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an emulsion and a method for producing the same. [Background technology]

[0002] Although high molecular weight perfluoropolyether compounds (e.g., weight average molecular weight of 2000 or more) are generally soluble in fluorine-based solvents, their solubility in water and other organic solvents is very low. Therefore, when preparing a composition containing a perfluoropolyether compound, a fluorine-based solvent is usually used. However, since fluorine-based solvents are expensive and have an environmental impact, an aqueous composition has been desired.

[0003] Techniques for preparing an emulsion containing perfluoropolyether oil are known, such as those described in Patent Documents 1 and 2, but both require an ultrasonic homogenizer or a high-pressure homogenizer and cannot be considered simple methods. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 1995 / 18194 [Patent Document 2] JP 2020-158600 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an emulsion of a perfluoropolyether phosphate ester. [Means for solving the problem]

[0006] In order to solve the above problems, the present inventors conducted extensive research and found that an emulsion of a perfluoropolyether phosphate ester can be prepared by using a perfluoropolyether phosphate ester, a fluorine-based anionic surfactant having a counter cation, an alcohol, and water.

[0007] The present invention has been completed based on these findings, and includes the following broad aspects. [Section 1] (A) a perfluoropolyether phosphate ester compound represented by the following formula (I), (B) a fluorine-containing anionic surfactant having a counter cation; (C) alcohol; (D)Water An emulsion comprising [ka] [In the formula, Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group having 1 to 10 carbon atoms. m is 5 to 60. n is 1 or 2.] [Section 2] Item 2. The emulsion according to item 1, wherein the perfluoropolyether phosphate ester compound (A) has a weight average molecular weight in the range of 2,000 to 20,000. [Section 3] Item 3. The emulsion according to item 1 or 2, wherein the alcohol (C) is a water-soluble alcohol having 1 to 10 carbon atoms. [Section 4] 4. The emulsion according to any one of items 1 to 3, wherein the content of the fluorine-based anionic surfactant (B) is 10 to 40 parts by mass based on 100 parts by mass of the perfluoropolyether phosphate ester compound (A). [Section 5] 5. The emulsion according to any one of items 1 to 4, wherein the content of the alcohol (C) is 10 to 100 parts by mass based on 100 parts by mass of the perfluoropolyether phosphate ester compound (A). [Section 6] Item 6. A water / oil repellent comprising the emulsion according to any one of items 1 to 5. [Section 7] Item 6. A fiber treatment agent comprising the emulsion according to any one of items 1 to 5. [Section 8] Item 6. A release agent comprising the emulsion according to any one of items 1 to 5. [Section 9] preparing a dispersion containing the perfluoropolyether phosphate ester compound (A), the fluorine-based anionic surfactant (B), and the alcohol (C); and A step of mixing the dispersion with the water (D). 6. A method for producing the emulsion according to any one of items 1 to 5, comprising: [Section 10] Item 10. The method according to item 9, wherein the amount of the water (D) mixed is 100 to 10,000 parts by mass per 100 parts by mass of the dispersion. Effect of the Invention

[0008] According to the present invention, an emulsion of a perfluoropolyether phosphate ester can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <Emulsion> The emulsion according to the present invention contains the following (A) to (D). (A) A perfluoropolyether phosphate compound represented by the following formula (I): [ka] [In the formula, Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group having 1 to 10 carbon atoms. m is 5 to 60. n is 1 or 2.] (B) A fluorine-containing anionic surfactant having a counter cation. (C) Alcohol. (D) Water.

[0010] Each component will be described in detail below.

[0011] (A) Perfluoropolyether phosphate ester compound represented by formula (I)

[0012] [ka]

[0013] Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group having 1 to 4 carbon atoms include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

[0014] X is a fluoro group or a trifluoromethyl group, preferably a trifluoromethyl group.

[0015] The divalent group having 1 to 10 carbon atoms represented by Y may contain a heteroatom and may be an aromatic group, a heteroaromatic group, a heterocyclic group, an aliphatic group, or an alicyclic group. Specific examples include the following groups.

[0016] -(CH2) N1 - (N1=1~10) -A-(CH2) N2 - (N2=1~5) -B-(CH2) N3 - (N3=1~5) -CH2CH2(OCH2CH2) N4 - (N4=1~4) -BCO(OCH2CH2) N5 - (N5=1~4) (In the formula, A represents -O-CO-, -CO-O-, -CONH- or -NHCO-. B represents phenylene which may have 1 to 3 substituents selected from the group consisting of an alkyl group having 1 to 3 carbon atoms (methyl, ethyl, propyl), an alkoxy group having 1 to 4 carbon atoms (methoxy, ethoxy, propoxy, butoxy, etc.), and a halogen atom (F, Cl, Br, I).)

[0017] Preferred divalent groups having 1 to 10 carbon atoms represented by Y include divalent groups having the following structures.

[0018] -(CH2) N1 - (N1=1~10) -CONH-(CH2) N2 - (N2=1~5) -CO-O-(CH2) N2 - (N2=1~5)

[0019] m is 5-60, preferably 10-50, and more preferably 15-35. n is 1 or 2.

[0020] In the emulsion of the present invention, the perfluoropolyether phosphate compound (A) represented by the above formula (I) may be used alone or in combination of two or more. Also, as the perfluoropolyether phosphate compound (A), a compound in which n in formula (I) is 1 and a compound in which n is 2 may be mixed and used.

[0021] The weight average molecular weight of the perfluoropolyether phosphate compound (A) is preferably 2,000 or more, more preferably 2,500 or more, and particularly preferably 3,000 or more. The weight average molecular weight is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 12,000 or less, even more preferably 10,000 or less, particularly preferably 8,000 or less, and most preferably 5,000 or less. The weight average molecular weight can be measured by a conventionally known method such as gel filtration chromatography.

[0022] In addition, the above-mentioned perfluoropolyether phosphate compound (A) can form metal salts, amine salts, ammonium salts, etc. by reacting with basic metal compounds, amine compounds, ammonia, etc., and these salts also have the same usefulness as the above-mentioned perfluoropolyether phosphate compound (A). The types of metal salts include alkali metal salts, alkaline earth metal salts, transition metal salts, etc. Specific examples of metal atoms forming metal salts include Li, Na, K, Ca, Mg, Cu, Co, Ni, Zn, Mn, Fe, Pb, Hg, Zr, etc. Examples of amine compounds or ammonia forming amine salts or ammonium salts include ammonia, trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, pyridine, etc.

[0023] The perfluoropolyether phosphate ester compound (A) may be used alone or in combination of two or more kinds.

[0024] Specific examples of the perfluoropolyether phosphate ester compound (A) include, but are not limited to, the following:

[0025] [ka]

[0026] [In the formula, m is 5 to 60.]

[0027] [ka]

[0028] [In the formula, m is 5 to 60.]

[0029] [ka]

[0030] [In the formula, m is 5 to 60.]

[0031] [ka]

[0032] [In the formula, m is 5 to 60.]

[0033] [ka]

[0034] [In the formula, m is 5 to 60.]

[0035] [ka]

[0036] [In the formula, m is 5 to 60.]

[0037] The perfluoropolyether phosphate compound (A) can be obtained as a commercial product or can be produced by a known method, for example, by phosphorylating the hydroxyl group of a perfluoropolyether monool represented by the following formula (II).

[0038] [ka]

[0039] [In the formula, Rf is a perfluoroalkyl group having 1 to 4 carbon atoms, X is a fluoro group or a trifluoromethyl group, Y is a divalent group having 1 to 10 carbon atoms, and m is 5 to 60.]

[0040] In the above formula (II), Rf, X, Y and m are the same as those in the above formula (I).

[0041] The perfluoropolyether monool represented by the above formula (II) has a weight average molecular weight of preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, particularly preferably 2,500 or more, and most preferably 3,000 or more. The weight average molecular weight is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 12,000 or less, even more preferably 10,000 or less, particularly preferably 8,000 or less, and most preferably 5,000 or less. The weight average molecular weight can be measured by a conventionally known method such as gel filtration chromatography.

[0042] The perfluoropolyether monool represented by the above formula (II) can be obtained as a commercial product, or can be produced by a known method. The perfluoropolyether monool represented by the formula (II) can be synthesized according to the method disclosed in, for example, U.S. Patent Publication No. 3,293,306.

[0043] The hydroxyl group of the perfluoropolyether monool represented by formula (II) can be converted into a phosphoric acid ester by a known method, for example, by using diphosphorus pentoxide (P2O5).

[0044] From the viewpoint of emulsion stability, the content of the perfluoropolyether phosphate ester compound (A) in the emulsion of the present invention is preferably 0.2 to 40 mass%, more preferably 0.4 to 30 mass%, even more preferably 1 to 25 mass%, particularly preferably 2 to 20 mass%, and most preferably 5 to 15 mass%, relative to 100 mass% of the total amount of the emulsion.

[0045] (B) Fluorine-containing anionic surfactant having a counter cation The fluorine-based anionic surfactant (B) having a counter cation is preferably a fluorocarbon-based surfactant, such as a surfactant having a perfluoroalkyl group or a perfluoroalkenyl group. Examples of the surfactant (B) include the following (i) to (iv). Among these, carboxylates (i) and sulfonates (ii) are preferred. These may be used alone or in combination of two or more.

[0046] (i) A carboxylate represented by the following formula: Rf1COOM1 (In the formula, Rf1 represents a fluoroorganic group. M1 represents an alkali metal, an amine base, or an ammonium base.)

[0047] (ii) a sulfonic acid salt represented by the following formula: Rf2SO3M2 (In the formula, Rf2 represents a fluoroorganic group. M2 represents an alkali metal, an amine base, or an ammonium base.)

[0048] (iii) a phosphonate represented by the following formula: Rf3PO(OM3)(OM4) (In the formula, Rf3 represents a fluoroorganic group. M3 represents a hydrogen atom, an alkali metal, an amine base, or an ammonium base. M4 represents an alkali metal, an amine base, or an ammonium base.)

[0049] (iv) a phosphate salt represented by the following formula: Rf4OPO(OM5)(OM6) (In the formula, Rf4 represents a fluoroorganic group. M5 represents a hydrogen atom, an alkali metal, an amine base, or an ammonium base. M6 represents an alkali metal, an amine base, or an ammonium base.)

[0050] The fluoroorganic group represented by Rf1 to Rf4 is preferably a substituted or unsubstituted fluorohydrocarbon group having 3 to 20 carbon atoms (preferably having 5 to 20 carbon atoms, more preferably having 10 to 20 carbon atoms).

[0051] Examples of the substituted or unsubstituted fluorohydrocarbon group having 3 to 20 carbon atoms include a substituted or unsubstituted fluoroalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted fluoroalkenyl group having 3 to 20 carbon atoms, a substituted or unsubstituted fluorocycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted fluoroaryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted fluoroaralkyl group having 7 to 20 carbon atoms. Among these, a substituted or unsubstituted fluoroalkyl group having 3 to 20 carbon atoms or a substituted or unsubstituted fluoroalkenyl group having 3 to 20 carbon atoms is preferred, and a substituted or unsubstituted perfluoroalkyl group having 3 to 20 carbon atoms or a substituted or unsubstituted perfluoroalkenyl group having 3 to 20 carbon atoms is more preferred.

[0052] Examples of the substituent include a halogen atom, C1 to C4 alkoxy, aryloxy, aralkyloxy, C1 to C4 alkyl, C2 to C4 alkenyl, NO, NO2, NH2, CN, OH, SH, COOH, CONH2, NHCOCH3, monoalkylamino, dialkylamino, monoalkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, and aryloxycarbonyl.

[0053] In addition, in Rf1 to Rf4, the fluorohydrocarbon group may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The number of heteroatoms may be preferably 1 to 10, more preferably 1 to 6. When the fluorohydrocarbon group is substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the fluorohydrocarbon group has at least one of groups such as -O-, -N<, -S-, -SO2-, -(C=O)-, -(C=O)O-, -O(C=O)-, -NH(C=O)-, -(C=O)NH-, -NH(C=O)O-, or -O(C=O)NH-, and the fluorohydrocarbon chain is interrupted by these groups. In Rf1 to Rf4, the fluorohydrocarbon group may be substituted with a heteroatom, so that Rf1 to Rf4 may have a structure having a heterocycle.

[0054] When the fluoroorganic groups represented by Rf1 to Rf4 are substituted fluorohydrocarbon groups having 3 to 20 carbon atoms, they preferably have one or more ether bonds (-O-).

[0055] Examples of the alkali metal in M1 to M6 include lithium, sodium, potassium, etc. Examples of the amine base include trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, pyridine, etc. Note that the counter cation consisting of an alkali metal, an amine base, or an ammonium base may be introduced (formed a salt) by neutralizing an acid compound (free acid) in which all of M1 to M6 are hydrogen atoms.

[0056] Examples of the fluorine-based anionic surfactant (B) include Ftergent 100, Ftergent 110, Ftergent 150 (all manufactured by Neos Corporation), Surflon S-211 (manufactured by AGC Seiko Chemical Co., Ltd.), Zonyl TBS (manufactured by DuPont), Megafac F-410, Megafac F-510 (all manufactured by DIC Corporation), PF-136A, PF-156A (all manufactured by OMNOVA), and the like.

[0057] From the viewpoint of emulsion stability, the content of the fluorine-based anionic surfactant (B) in the emulsion of the present invention is preferably 0.04 to 15 mass%, more preferably 0.1 to 12 mass%, even more preferably 0.2 to 10 mass%, particularly preferably 0.5 to 8 mass%, and most preferably 1 to 5 mass%, relative to 100 mass% of the total amount of the emulsion.

[0058] From the viewpoint of emulsion stability, the content of the fluorine-based anionic surfactant (B) in the emulsion of the present invention is preferably 10 to 40 parts by mass, more preferably 12 to 35 parts by mass, particularly preferably 15 to 30 parts by mass, and most preferably 15 to 25 parts by mass, per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

[0059] (C) Alcohol The alcohol (C) used in the emulsion of the present invention is preferably a water-soluble alcohol having 1 to 10 carbon atoms, more preferably a water-soluble alcohol having 1 to 8 carbon atoms, and particularly preferably a water-soluble alcohol having 1 to 6 carbon atoms.

[0060] Examples of such alcohols include lower alcohols and polyhydric alcohols, such as lower alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, and 2-methyl-2-butanol; ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,3-butanol. Examples of the alcohols include dihydric alcohols such as hexanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,2-pentanediol, and 2-methyl-2,4-pentanediol; trihydric alcohols such as glycerin, trimethylolpropane, 1,2,4-butanetriol, 1,2,5-pentanetriol, and 1,2,6-hexanetriol; tetrahydric alcohols such as pentahydric alcohols such as xylitol; and hexahydric alcohols such as sorbitol and mannitol. Among these, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, glycerin, and 2-methyl-2,4-pentanediol (hexylene glycol) are preferred. These may be used alone or in combination of two or more.

[0061] From the viewpoint of emulsion stability, the content of the alcohol (C) in the emulsion of the present invention is preferably 0.05 to 25 mass%, more preferably 0.1 to 20 mass%, even more preferably 0.2 to 18 mass%, particularly preferably 0.5 to 15 mass%, and most preferably 1 to 12 mass%, relative to 100 mass% of the total amount of the emulsion.

[0062] From the viewpoint of emulsion stability, the content of the alcohol (C) in the emulsion of the present invention is preferably 10 to 100 parts by mass, more preferably 12 to 90 parts by mass, particularly preferably 15 to 80 parts by mass, and most preferably 15 to 70 parts by mass, relative to 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

[0063] (D)Water From the viewpoint of emulsion stability, the content of water (D) in the emulsion of the present invention is preferably 50 to 99 mass%, more preferably 60 to 97 mass%, even more preferably 65 to 95 mass%, particularly preferably 70 to 92 mass%, and most preferably 75 to 90 mass%, relative to 100 mass% of the total amount of the emulsion.

[0064] (Other additives) The emulsion of the present invention may be appropriately blended with organic solvents other than the alcohol (C), rust inhibitors, catalysts, antibacterial agents, flame retardants, surfactants, defoamers, thickeners, viscosity regulators, leveling agents, UV absorbers, preservatives, antifreeze agents, wetting agents, pH adjusters, stabilizers, light resistance stabilizers, weather resistance stabilizers, neutralizers, matting agents, drying accelerators, foaming agents, non-adhesive agents, deterioration inhibitors, etc., within the range that does not impair the object of the present invention. These may be used alone or in combination of two or more. Each of these additives may be used within the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the perfluoropolyether phosphate compound (A), the fluorine-based anionic surfactant (B), and the alcohol (C).

[0065] <Emulsion manufacturing method> The emulsion of the present invention can be produced by a method including the following (Step 1) and (Step 2). (Step 1) A step of preparing a dispersion containing a perfluoropolyether phosphate ester compound (A), a fluorine-based anionic surfactant (B), and an alcohol (C). (Step 2) A step of mixing the dispersion with water (D).

[0066] In (step 1), the mixing order in the dispersion is not particularly limited, and the perfluoropolyether phosphate ester compound (A) may be mixed with the fluorine-based anionic surfactant (B) and the alcohol (C), or other mixing orders may be used. In addition, various additives and the like may be mixed as necessary. It is preferable to mix these components and sufficiently stir them to make each component uniformly dispersed.

[0067] The amount of the fluorine-based anionic surfactant (B) mixed in the dispersion liquid is preferably 10 to 40 parts by mass, more preferably 12 to 35 parts by mass, particularly preferably 15 to 30 parts by mass, and most preferably 15 to 25 parts by mass, per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

[0068] The amount of the alcohol (C) mixed in the dispersion is preferably 10 to 100 parts by mass, more preferably 12 to 90 parts by mass, particularly preferably 15 to 80 parts by mass, and most preferably 15 to 70 parts by mass, per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

[0069] In (Step 2), the method of mixing the dispersion and water (D) is preferably to gradually add water (D) while stirring the dispersion obtained in Step 1. By gradually mixing water (D) into the dispersion, it becomes easy to uniformly disperse each component.

[0070] The amount of water (D) mixed in (Step 2) is preferably 100 to 10,000 parts by mass, more preferably 150 to 3,500 parts by mass, even more preferably 200 to 2,000 parts by mass, particularly preferably 250 to 1,500 parts by mass, and most preferably 300 to 900 parts by mass, relative to 100 parts by mass of the dispersion.

[0071] To the emulsion thus obtained, various additives and the like can be mixed, if necessary.

[0072] <Uses of emulsion> The coating film obtained from the emulsion of the present invention has excellent releasability, liquid repellency and continuous releasability, and therefore the emulsion of the present invention can be suitably used as a release agent, a water / oil repellent, a fiber treatment agent, etc.

[0073] The molding material or resin material that can be released by using the emulsion of the present invention is not particularly limited, and examples thereof include rubbers such as urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR, urethane foam, epoxy resin, polyimide resin, polyamide resin, melamine resin, urea resin, polyurethane, silicone resin, alkyd resin, phenol resin, unsaturated polyester resin, vinyl ester resin, and thermosetting resins such as FRP (glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), aramid fiber reinforced plastic (AFRP)), PP (polypropylene), PE (polyethylene), PVC (polyvinyl chloride), PS (polystyrene), PA (polyamide), polyester, polycarbonate, ABS resin, poly(meth)acrylic acid, polyacetal, polyvinylidene fluoride, polyphenylene sulfide, polyetherimide, polyether ether ketone, Examples of suitable materials include thermoplastic resins such as FRTP (glass fiber reinforced thermoplastic resin (GFRTP), carbon fiber reinforced thermoplastic resin (CFRTP), and aramid fiber reinforced thermoplastic resin (AFRTP)). In particular, it is useful as a mold release agent for molds for resins such as polyurethane and epoxy resins.

[0074] Furthermore, materials to which the emulsion of the present invention is applied include, but are not limited to, metals such as aluminum, SUS, iron, etc., resins such as PP, PE, epoxy, etc., rubber, FRP (fiber reinforced plastic), gypsum substrates, wooden substrates, fibers, glass, composite materials, etc. The emulsion of the present invention can impart high water repellency and oil repellency to these materials.

[0075] In one embodiment, the emulsion of the present invention can be used as a fiber treatment agent. The fibers treated with the emulsion of the present invention may be in any form, such as short fibers, linters, rovings, slivers, yarns, woven fabrics, knitted fabrics, nonwoven fabrics, etc. Examples of fiber materials include cellulose fibers such as cotton, flax, jute, hemp, ramie, regenerated cellulose fiber, and rayon, and polyvinyl alcohol-based synthetic fibers.

[0076] The emulsion of the present invention can be used by applying it to the part to be treated with the emulsion and drying it. When applying, the emulsion may be diluted with water or the like as necessary. The concentration after dilution is appropriately selected according to the application method and viscosity, and is not particularly limited, but can be prepared so that the solid content concentration is, for example, 0.1 to 5 mass %. The application method is not particularly limited, and examples thereof include spray application, brush application, roll coater application, and dipping application. The drying method includes a method in which the solvent is evaporated by air drying or heating to form a film. The dry thickness of the film containing the emulsion of the present invention is usually 0.01 to 15 μm, preferably 0.1 to 5.0 μm. EXAMPLES

[0077] The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

[0078] (Materials used) PFPE phosphate ester 1: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 4000, m is about 24.) PFPE phosphate ester 2: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 3000, m is about 16.) PFPE phosphate ester 3: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 5000, m is about 30.) FEOH-4000: Perfluoropolyether monool (manufactured by Sanmei Co., Ltd.) CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OH (weight average molecular weight 4000) FT-100: Futergent 100 (fluorine-based anionic surfactant, sodium sulfonate, manufactured by Neos Co., Ltd.) FT-150: Futergent 150 (fluorine-based anionic surfactant, sodium sulfonate, manufactured by Neos Co., Ltd.) F-140A Et3N salt: Obtained by neutralizing F-140 with an equimolar amount of triethylamine. (Fluorine-based anionic surfactant, phosphonic acid triethylamine salt) F-140A: F-140 (fluorine-based anionic surfactant, free phosphonic acid, manufactured by NEOS Co., Ltd.) FT-212M: Futergent 212M (nonionic surfactant, manufactured by Neos Co., Ltd.) IPA: 2-propanol GL: Glycerin

[0079] <Example 1> PFPE phosphate ester 1 (10.0 g), FT-150 (2.0 g), and IPA (2.0 g) were placed in a 200 ml beaker containing a stirring bar. The mixture was stirred with a magnetic stirrer for 10 minutes to produce a dispersion. Distilled water (86.0 g) was gradually added dropwise while stirring the dispersion. An emulsion with a PFPE phosphate ester concentration of 10 wt% was produced. The appearance of the resulting emulsion after emulsification was checked. The emulsion was diluted with distilled water to a concentration of 1 wt% of the active ingredient to prepare a coating sample. SPCC-SB was used as the coating substrate. The coating substrate was degreased with acetone, heated to 170°C, and 50 g / m of the coating sample was applied using a spray gun. 2 After coating, the sample was heated at 170°C for 1 minute to prepare an evaluation sample. The obtained evaluation sample was subjected to contact angle, surface free energy, and tape peeling tests. The results are shown in Tables 1 and 3.

[0080] (Appearance evaluation of emulsion) The emulsified liquid was visually inspected. 〇: Beautifully emulsified and stable. △: Emulsifies, but has poor stability and gradually settles. ×: Unable to emulsify, layer separation occurred.

[0081] (Contact angle measurement) The contact angles of the evaluation samples with water, diiodomethane (DI), and hexadecane (HD) were measured using DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.).

[0082] (Surface Free Energy) The contact angle was calculated using the Kaelble-Uy formula from the contact angle measured as above.

[0083] (Tape peeling test) For the evaluation sample, 7.5 cm of polyester adhesive tape No. 31B manufactured by Nitto Denko Corporation was applied. 2The load applied when the tape was peeled off at a 90° angle was measured with a push-pull gauge. The tape was also applied to the same location and the peeling test was repeated 10 times.

[0084] <Examples 2 to 7 and Comparative Examples 1 to 5> Except for changing the composition as shown in Tables 1 and 2, emulsions were prepared in the same manner as in Example 1. Thereafter, the appearance, contact angle, surface free energy, and tape peeling test of the emulsified liquid were evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0085] [Table 1]

[0086] [Table 2]

[0087] [Table 3]

[0088] In Examples 1 to 7, a stable emulsion was obtained by stirring perfluoropolyether phosphate in the presence of a fluorine-based anionic surfactant having a counter cation and alcohol, and then adding water dropwise after preparing a dispersion. Example 1 and Comparative Example 1 revealed that a stable emulsion could not be obtained when perfluoropolyether phosphate was replaced with perfluoropolyether monool. Example 3 and Comparative Examples 2 and 3 revealed that a stable emulsion could not be obtained when a free acid surfactant or a nonionic surfactant was used as the fluorine-based surfactant. Furthermore, no emulsion was obtained when no alcohol was added (Comparative Example 4) or no fluorine-based surfactant was added (Comparative Example 5).

[0089] In the coating evaluation, the surface free energy was a sufficiently low value of less than 16 mN / m in both Examples 1 and 5. In the tape peeling test, the surface free energy was less than 3 N even after 10 repetitions, confirming that the performance could be maintained even after repetition.

Claims

1. (A) a perfluoropolyether phosphate compound represented by the following formula (I), (B) a fluorine-containing anionic surfactant having a counter cation; (C) an alcohol; (D) Water An emulsion comprising 【Chemistry 1】 [In the formula, Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group having 1 to 10 carbon atoms. m is 5 to 60. n is 1 or 2.]

2. 2. The emulsion according to claim 1, wherein the perfluoropolyether phosphate ester compound (A) has a weight average molecular weight in the range of 2,000 to 20,000.

3. The emulsion according to claim 1, wherein the alcohol (C) is a water-soluble alcohol having 1 to 10 carbon atoms.

4. 2. The emulsion according to claim 1, wherein the content of the fluorine-based anionic surfactant (B) is 10 to 40 parts by mass per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

5. 2. The emulsion according to claim 1, wherein the content of the alcohol (C) is 10 to 100 parts by mass based on 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

6. A water / oil repellent comprising the emulsion according to claim 1.

7. A textile treatment agent comprising the emulsion of claim 1.

8. A mold release agent comprising the emulsion of claim 1.

9. A step of preparing a dispersion containing the perfluoropolyether phosphate ester compound (A), the fluorine-based anionic surfactant (B), and the alcohol (C); and A step of mixing the dispersion with the water (D). A method for producing the emulsion of claim 1, comprising:

10. The method according to claim 9, wherein the amount of the water (D) mixed with respect to 100 parts by mass of the dispersion is 100 to 10,000 parts by mass.

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