Emulsion and method for producing 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) a water-soluble thickener, (D) alcohol, and (E) 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] High-molecular-weight perfluoropolyether compounds (e.g., those with a weight-average molecular weight of 2000 or more) generally dissolve in fluorine-based solvents, but have very low solubility in water and other organic solvents. Therefore, when preparing compositions containing perfluoropolyether compounds, fluorine-based solvents are usually used. However, fluorine-based solvents are expensive and have an environmental impact, so aqueous compositions have been desired.

[0003] Techniques for preparing emulsions containing perfluoropolyether oils are known, such as those disclosed in Patent Documents 1 and 2, but both require an ultrasonic homogenizer or a high-pressure homogenizer, and are therefore hardly simple methods. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 1995 / 18194 [Patent Document 2] Japanese Patent Application Publication No. 2020-158600 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 have conducted extensive research and have 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, a water-soluble thickener, 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) a water-soluble thickener; (D) alcohol; (E)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, and 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 (D) 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 per 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 water-soluble thickener (C) is 0.3 to 40 parts by mass per 100 parts by mass of the perfluoropolyether phosphate ester compound (A). [Section 6] 6. The emulsion according to any one of items 1 to 5, wherein the content of the alcohol (D) is 10 to 100 parts by mass per 100 parts by mass of the perfluoropolyether phosphate ester compound (A). [Section 7] Item 6. A water and oil repellent agent comprising the emulsion according to any one of items 1 to 5. [Section 8] Item 6. A fiber treatment agent comprising the emulsion according to any one of items 1 to 5. [Section 9] Item 6. A release agent comprising the emulsion according to any one of Items 1 to 5. [Section 10] preparing a dispersion containing the perfluoropolyether phosphate ester compound (A), the fluorine-based anionic surfactant (B), the water-soluble thickener (C), and the alcohol (D); and a step of mixing the dispersion with the water (E) Item 6. A method for producing the emulsion according to any one of Items 1 to 5, comprising: [Section 11] Item 11. The method according to Item 10, wherein the amount of water (E) mixed is 100 to 10,000 parts by mass per 100 parts by mass of the dispersion. [Effects of the Invention]

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

[0009] <Emulsion> The emulsion according to the present invention contains the following (A) to (E): (A) A perfluoropolyether phosphate ester 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, and n is 1 or 2.] (B) A fluorine-containing anionic surfactant having a counter cation. (C) Water-soluble thickener. (D) Alcohol. (E) 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 alkyl groups having 1 to 3 carbon atoms (methyl, ethyl, propyl), alkoxy groups having 1 to 4 carbon atoms (methoxy, ethoxy, propoxy, butoxy, etc.), and halogen atoms (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 to 60, preferably 10 to 50, and more preferably 15 to 35. n is 1 or 2.

[0020] In the emulsion of the present invention, the perfluoropolyether phosphate ester compound (A) represented by the above formula (I) may be used alone or in combination of two or more. Also, as the perfluoropolyether phosphate ester 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 perfluoropolyether phosphate ester compound (A) preferably has a weight-average molecular weight of 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 conventional method such as gel filtration chromatography.

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

[0023] Specific examples of the perfluoropolyether phosphate ester compound (A) include, but are not limited to, the following:

[0024] [ka]

[0025] [In the formula, m is 5 to 60.]

[0026] [ka]

[0027] [In the formula, m is 5 to 60.]

[0028] [ka]

[0029] [In the formula, m is 5 to 60.]

[0030] [ka]

[0031] [In the formula, m is 5 to 60.]

[0032] [ka]

[0033] [In the formula, m is 5 to 60.]

[0034] [ka]

[0035] [In the formula, m is 5 to 60.]

[0036] The perfluoropolyether phosphate ester compound (A) can be commercially available or can be produced by a known method, for example, by phosphate esterification of the hydroxyl groups of a perfluoropolyether monool represented by the following formula (II):

[0037] [ka]

[0038] [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.]

[0039] In the above formula (II), Rf, X, Y, and m are the same as those in the above formula (I).

[0040] The perfluoropolyether monool represented by the above formula (II) preferably has a weight-average molecular weight of 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 conventional method such as gel filtration chromatography.

[0041] The perfluoropolyether monool represented by the formula (II) can be commercially available 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.

[0042] The hydroxyl groups of the perfluoropolyether monool represented by formula (II) can be converted into phosphoric acid esters by known methods, such as by using diphosphorus pentoxide (PO).

[0043] 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.

[0044] (B) Fluorine-containing anionic surfactant with a counter cation The fluorine-based anionic surfactant (B) having a counter cation is preferably a fluorocarbon surfactant, such as a surfactant having a perfluoroalkyl group or a perfluoroalkenyl group. Examples of surfactant (B) include the following (i) to (iv). Among these, carboxylate (i) or sulfonate (ii) is preferred. These may be used alone or in combination of two or more.

[0045] (i) a carboxylic acid salt represented by the following formula: Rf1COOM1 (In the formula, Rf1 represents a fluoroorganic group, and M1 represents an alkali metal, an amine base, or an ammonium base.)

[0046] (ii) a sulfonate represented by the following formula: Rf2SO3M2 (In the formula, Rf2 represents a fluoroorganic group, and M2 represents an alkali metal, an amine base, or an ammonium base.)

[0047] (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.)

[0048] (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.)

[0049] The fluoroorganic groups represented by Rf1 to Rf4 are preferably substituted or unsubstituted fluorohydrocarbon groups having 3 to 20 carbon atoms (preferably 5 to 20 carbon atoms, more preferably 10 to 20 carbon atoms).

[0050] 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.

[0051] 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.

[0052] 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 is preferably 1 to 10, and 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 group 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 this group. In Rf1 to Rf4, the fluorohydrocarbon group may be substituted with a heteroatom, so that Rf1 to Rf4 may have a heterocyclic structure.

[0053] 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—).

[0054] Examples of alkali metals in M1 to M6 include lithium, sodium, potassium, etc. Examples of amine bases include trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, pyridine, etc. Note that counter cations consisting of alkali metals, amine bases, or ammonium bases may be introduced (salt formation) by neutralizing an acid compound (free acid) in which all of M1 to M6 are hydrogen atoms.

[0055] 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 Sei 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.

[0056] 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% by mass, more preferably 0.1 to 12% by mass, even more preferably 0.2 to 10% by mass, particularly preferably 0.5 to 8% by mass, and most preferably 1 to 5% by mass, relative to 100% by mass of the total amount of the emulsion.

[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 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).

[0058] (C) Water-soluble thickener The inclusion of the water-soluble thickener (C) in the emulsion of the present invention can further improve the stability of the emulsion, which is thought to be because the inclusion of the water-soluble thickener increases the viscosity of the emulsion, making it more susceptible to shear.

[0059] Examples of the water-soluble thickener (C) include chitin-based polymers such as chitin, carboxymethylchitin, chitosan, and hydroxypropylchitosan; plant-based polymers such as gum arabic, tragacanth gum, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, and algae colloid (brown algae extract); microbial polymers such as dextran, succinoglucan, pullulan, and xanthan gum; animal-based polymers such as collagen, casein, albumin, and gelatin; methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, and hydroxypropylcellulose. Examples of suitable polymers include cellulose-based polymers such as cellulose, sodium carboxymethylcellulose, crystalline cellulose, and cellulose powder; alginic acid-based polymers such as sodium alginate and propylene glycol alginate; vinyl-based polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, and carboxyvinyl polymer (carbomer); polyoxyethylene-based polymers such as hydrophobically modified polyether urethane; acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide; and inorganic water-soluble polymers such as polyethyleneimine, cationic polymers, bentonite, magnesium aluminum silicate, laponite, hectorite, and silicic anhydride.

[0060] In one embodiment, the viscosity of the water-soluble thickener (C) in a 1 to 20% by mass aqueous solution at 25°C is preferably 50 to 3500 mPa·s, more preferably 50 to 1000 mPa·s. A viscosity within this range is preferable because it improves the emulsion stability and is easy to handle. Here, viscosity refers to the viscosity calculated from measurements taken with an E-type viscometer (E-type viscometer, TVE-25, manufactured by Toki Sangyo Co., Ltd., 10 rpm).

[0061] From the viewpoint of emulsion stability, the content of the water-soluble thickener (C) in the emulsion of the present invention is preferably 0.001 to 7 mass%, more preferably 0.005 to 5 mass%, even more preferably 0.01 to 4 mass%, particularly preferably 0.05 to 3 mass%, and most preferably 0.1 to 2 mass%, relative to 100 mass% of the total amount of the emulsion.

[0062] From the viewpoint of emulsion stability, the content of the water-soluble thickener (C) in the emulsion of the present invention is preferably 0.3 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, particularly preferably 0.7 to 20 parts by mass, and most preferably 1 to 15 parts by mass, per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

[0063] (D) Alcohol The alcohol (D) 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.

[0064] 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-butanediol. Examples of suitable 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 pentaerythritol; 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.

[0065] From the viewpoint of emulsion stability, the content of the alcohol (D) in the emulsion of the present invention is preferably 0.05 to 25% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.2 to 18% by mass, particularly preferably 0.5 to 15% by mass, and most preferably 1 to 12% by mass, relative to 100% by mass of the total amount of the emulsion.

[0066] From the viewpoint of emulsion stability, the content of the alcohol (D) 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, per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

[0067] (E)Water From the viewpoint of emulsion stability, the content of water (E) in the emulsion of the present invention is preferably 50 to 99% by mass, more preferably 60 to 97% by mass, even more preferably 65 to 95% by mass, particularly preferably 70 to 92% by mass, and most preferably 75 to 90% by mass, relative to 100% by mass of the total amount of the emulsion.

[0068] (Other additives) The emulsion of the present invention may contain, as appropriate, organic solvents other than the alcohol (D), rust inhibitors, catalysts, antibacterial agents, flame retardants, surfactants, antifoaming agents, thickeners, viscosity modifiers, leveling agents, UV absorbers, preservatives, antifreeze agents, wetting agents, pH adjusters, stabilizers, antifungal agents, light resistance stabilizers, weather resistance stabilizers, neutralizing agents, matting agents, drying accelerators, foaming agents, anti-tack agents, and anti-degradants, as long as the additives do not impair the objectives of the present invention. These additives may be used alone or in combination of two or more. Each of these additives may be used in an amount of 0.01 to 10 parts by mass per 100 parts by mass of the total of the perfluoropolyether phosphate ester compound (A), the fluorine-based anionic surfactant (B), the water-soluble thickener (C), and the alcohol (D).

[0069] <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), a water-soluble thickener (C), and an alcohol (D). (Step 2) A step of mixing the dispersion liquid with water (E).

[0070] In (Step 1), the order of mixing in the dispersion is not particularly limited, and the perfluoropolyether phosphate ester compound (A) may be mixed with the fluorine-based anionic surfactant (B), the water-soluble thickener (C), and the alcohol (D), or another mixing order may be used. The water-soluble thickener (C) may also be mixed as an aqueous solution. When preparing an aqueous solution of the water-soluble thickener, it is preferable to prepare it so that the viscosity is in the range of 50 to 1000 mPa·s. Furthermore, various additives may be added as necessary. It is preferable to mix these components and thoroughly stir them to ensure that each component is uniformly dispersed.

[0071] 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).

[0072] The amount of the water-soluble thickener (C) mixed in the dispersion is preferably 0.3 to 40 parts by mass, more preferably 0.5 to 30 parts by mass, particularly preferably 0.7 to 20 parts by mass, and most preferably 1 to 15 parts by mass, per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

[0073] The amount of alcohol (D) 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).

[0074] In (Step 2), the method for mixing the dispersion and water (E) is preferably to gradually add water (E) while stirring the dispersion obtained in Step 1. By gradually adding water (E) to the dispersion and mixing, it becomes easier to uniformly disperse each component.

[0075] The amount of water (E) 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.

[0076] Various additives can be mixed with the emulsion thus obtained, if necessary.

[0077] <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, water and oil repellent, fiber treatment agent, etc.

[0078] The molding material or resin material that can be released 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; thermosetting resins such as urethane foam, epoxy resin, polyimide resin, polyamide resin, melamine resin, urea resin, polyurethane, silicone resin, alkyd resin, phenolic resin, unsaturated polyester resin, vinyl ester resin, and 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 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)). It is particularly useful as a mold release agent for molds for resins such as polyurethane and epoxy resins.

[0079] Furthermore, materials to which the emulsion of the present invention can be applied include, but are not limited to, metals such as aluminum, SUS, and iron, resins such as PP, PE, and epoxy, rubber, FRP (fiber reinforced plastic), gypsum substrates, wooden substrates, fibers, glass, composite materials, etc. The emulsion of the present invention can impart high water and oil repellency to these materials.

[0080] In one embodiment, the emulsion of the present invention can be used as a fiber treatment agent. 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, and nonwoven fabrics. Examples of fiber materials include cellulose fibers such as cotton, flax, jute, hemp, ramie, regenerated cellulose, and rayon, and polyvinyl alcohol-based synthetic fibers.

[0081] The emulsion of the present invention can be used by applying it to the area to be treated with the emulsion and drying it. When applying, the emulsion may be diluted with water or the like as needed. The concentration after dilution is appropriately selected depending on the application method and viscosity, and is not particularly limited. For example, the emulsion can be prepared so that the solids concentration is 0.1 to 5% by mass. The application method is not particularly limited, and examples thereof include spray application, brush application, roll coater application, and dipping application. Drying methods include air drying or heating to evaporate the solvent to form a film. The dry thickness of a film containing the emulsion of the present invention is usually 0.01 to 15 μm, and preferably 0.1 to 5.0 μm. [Example]

[0082] The present invention will be further explained below with reference to examples, but the present invention is not limited thereto.

[0083] (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) 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.) FT-212M: Futergent 212M (nonionic surfactant, manufactured by Neos Co., Ltd.) PVP: Polyvinylpyrrolidone Chitin nanofiber: Chitin nanofiber (manufactured by Sugino Machine Co., Ltd., SFo-2002) HEX-G: Hexylene glycol

[0084] Example 1 PFPE phosphate ester 1 (10.0 g), FT-150 (2.0 g), 2% chitin nanofiber aqueous solution (10.0 g), and HEX-G (2.0 g) were placed in a 200 ml beaker equipped with a stir bar. The mixture was stirred for 10 minutes using a magnetic stirrer to produce a dispersion. While stirring, distilled water (76.0 g) was gradually added dropwise to the dispersion. An emulsion with a PFPE phosphate ester concentration of 10 wt% was produced. The viscosity of the 2% chitin nanofiber aqueous solution was measured using a Toki Sangyo TVE-25 E-type viscometer (rotation speed: 10 rpm). 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. After degreasing the coating substrate with acetone, it was heated to 170°C and a coating sample of 50 g / m was applied using a spray gun. 2 After application, 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.

[0085] (Evaluation of emulsion appearance) The emulsified liquid was visually inspected. 〇: Beautifully emulsified and stable. △: Emulsifies, but is unstable and gradually settles. ×: Unable to emulsify and separated into layers.

[0086] (Contact angle measurement) The contact angles of the evaluation sample with water, diiodomethane (DI), and hexadecane (HD) were measured using DMo-702 (manufactured by Kyowa Interface Science Co., Ltd.).

[0087] (surface free energy) The contact angle was calculated using the Kaelble-Uy formula from the values ​​measured above.

[0088] (Tape peel test) For the evaluation sample, Nitto Denko polyester adhesive tape No. 31B was applied to a 7.5cm 2 The 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.

[0089] <Examples 2 to 4, Comparative Examples 1 to 4> Emulsions were prepared in the same manner as in Example 1, except for the changes in composition shown in Tables 1 and 2. The viscosity of the 10% aqueous polyvinylpyrrolidone solution was measured using a Toki Sangyo E-type viscometer TVE-25 (rotation speed: 10 rpm). Thereafter, the appearance, contact angle, surface free energy, and tape peel test of the emulsified liquid were evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0090] [Table 1]

[0091] [Table 2]

[0092] [Table 3]

[0093] In Examples 1 to 4, a stable emulsion was obtained by stirring a perfluoropolyether phosphate ester in the presence of a fluorine-based anionic surfactant having a counter cation, a water-soluble thickener, and alcohol, and then adding water dropwise to the resulting dispersion. Example 1 and Comparative Example 1 revealed that a stable emulsion could not be obtained when the perfluoropolyether phosphate ester was replaced with a perfluoropolyether monool. Example 1 and Comparative Example 2 revealed that a stable emulsion could not be obtained when a nonionic surfactant was used as the fluorine-based surfactant. Furthermore, no emulsion was obtained when a fluorine-based anionic surfactant having a counter cation was not added (Comparative Example 3). Furthermore, it was also revealed that no emulsion was obtained when a water-soluble thickener and alcohol were not included (Comparative Example 4).

[0094] In the coating evaluation, the surface free energy was shown to be sufficiently low, less than 16 mN / m, in both Examples 1 and 3. In the tape peeling test, the surface free energy remained less than 3 N even after 10 repetitions, confirming that the performance could be maintained even after repeated use.

Claims

1. (A) a perfluoropolyether phosphate ester compound represented by the following formula (I), (B) a fluorine-containing anionic surfactant having a counter cation; (C) a water-soluble thickener; (D) an alcohol; (E) 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, and n is 1 or 2.]

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

3. 2. The emulsion according to claim 1, wherein the alcohol (D) 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 water-soluble thickener (C) is 0.3 to 40 parts by mass per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

6. 2. The emulsion according to claim 1, wherein the content of the alcohol (D) is 10 to 100 parts by mass per 100 parts by mass of the perfluoropolyether phosphate ester compound (A).

7. A water and oil repellent comprising the emulsion according to claim 1.

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

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

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

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

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