Emulsion and method for producing same

Abstract

Provided is a perfluoropolyether phosphate emulsion which can be prepared by a simple method. An emulsion containing (A) a perfluoropolyether phosphate compound represented by formula (I), (B) a basic compound, (C) an alcohol, and (D) water. [Rf-O-(C3F6O) m-CFX-Y-O] n-PO (OH) 3-n (I) (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).

Description

Technical Field

[0001] This invention relates to emulsions and methods for manufacturing the same. Background Technology

[0002] High molecular weight perfluoropolyether compounds (e.g., weight-average molecular weight above 2000) are generally soluble in fluorinated solvents, but have very low solubility relative to water, other organic solvents, etc. Therefore, fluorinated solvents are typically used when preparing compositions containing perfluoropolyether compounds. However, fluorinated solvents are not only expensive but also environmentally burdensome, thus requiring aqueous compositions.

[0003] Patent Document 1, Patent Document 2, etc. are known as techniques for preparing emulsions containing perfluoropolyether oil.

[0004] Existing technical documents Patent documents Patent Document 1: International Publication No. 1995 / 18194 Patent Document 2: Japanese Patent Application Publication No. 2020-158600 Summary of the Invention

[0005] The technical problem that the invention aims to solve However, the methods described in Patent Documents 1 and 2 both require ultrasonic homogenizers and high-pressure homogenizers, which can hardly be considered simple methods. The technical problem of the present invention is to provide an emulsion of perfluoropolyether phosphate that can be prepared by a simple method.

[0006] Technical solutions for solving technical problems In order to solve the above-mentioned technical problems, the inventors have repeatedly conducted in-depth research and found that an emulsion of perfluoropolyether phosphate can be easily prepared by using perfluoropolyether phosphate, an alkaline compound, an alcohol and water.

[0007] This invention is based on these insights and includes inventions in a wide range of ways as shown below.

[0008] [Item 1] An emulsion comprising: (A) The perfluoropolyether phosphate compound represented by formula (I) below, (B) Alkaline compounds, (C) alcohols, and (D) Water.

[0009] [Chemistry 1] [Rf-O-(C3F6O) m -CFX-YO] n -PO(OH) 3-n (I) (In the formula, Rf is a perfluoroalkyl group with 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group with 1 to 10 carbon atoms. m is 5 to 60. n is 1 or 2.) [Item 2] According to the emulsion of claim 1, wherein the weight-average molecular weight of the perfluoropolyether phosphate compound (A) is in the range of 2000 to 20000.

[0010] [Item 3] The emulsion according to item 1 or 2, wherein the alkaline compound (B) is an organic base.

[0011] [Item 4] The emulsion according to any one of items 1 to 3, wherein the alcohol (C) is a water-soluble alcohol having 1 to 10 carbon atoms.

[0012] [Item 5] The emulsion according to any one of items 1 to 4, wherein the content of the alkaline compound (B) is 0.5 to 50 parts by mass relative to 100 parts by mass of the perfluoropolyether phosphate compound (A).

[0013] [Item 6] The emulsion according to any one of items 1 to 5, wherein the molar ratio ((B) / (A)) of the basic compound (B) in the emulsion relative to the perfluoropolyether phosphate compound (A) is 0.2 to 10.

[0014] [Item 7] The emulsion according to any one of items 1 to 6, wherein the content of the alcohol (C) is 30 to 500 parts by mass relative to 100 parts by mass of the perfluoropolyether phosphate compound (A).

[0015] [Item 8] A water- and oil-repellent agent comprising the emulsion described in any one of items 1 to 7.

[0016] [Item 9] A fiber treatment agent comprising the emulsion described in any one of items 1 to 7.

[0017] [Item 10] A release agent comprising the emulsion described in any one of items 1 to 7.

[0018] [Item 11] The method for manufacturing the emulsion according to any one of items 1 to 7 comprises the following steps: The process of preparing a dispersion comprising the perfluoropolyether phosphate compound (A), the basic compound (B), and the alcohol (C); and The process of mixing the dispersion with the water (D).

[0019] [Item 12] According to the manufacturing method described in item 11, the mixing amount of water (D) is 100 to 10,000 parts by mass relative to 100 parts by mass of the dispersion.

[0020] Invention Effects According to the present invention, an emulsion of perfluoropolyether phosphate that can be prepared by a simple method can be provided. Detailed Implementation

[0021] <Emulsion> The emulsion involved in this invention comprises the following (A) to (D).

[0022] (A) The perfluoropolyether phosphate compound represented by formula (I) below.

[0023] [Chemistry 2] [Rf-O-(C3F6O) m -CFX-YO] n -PO(OH) 3-n (I) (In the formula, Rf is a perfluoroalkyl group with 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group with 1 to 10 carbon atoms. m is 5 to 60. n is 1 or 2.)

[0024] (B) Basic compounds.

[0025] (C) Alcohol.

[0026] (D) Water.

[0027] The following is a detailed description of each ingredient.

[0028] (A) The perfluoropolyether phosphate compound represented by formula (I) [Chemistry 3] [Rf-O-(C3F6O) m -CFX-YO] n -PO(OH) 3-n (I) Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of perfluoroalkyl groups having 1 to 4 carbon atoms include: trifluoromethyl, perfluoroethyl, perfluoron-propyl, perfluoroisopropyl, perfluoron-butyl, perfluoroisobutyl, perfluorosec-butyl, perfluorotert-butyl, etc.

[0029] In formula (I), -(C3F6O) n- Part of -C3F6- can be -CF2CF2CF2-, -CF(CF3)CF2-, or -CF2CF(CF3)-, preferably -CF2CF2CF2- or -CF(CF3)CF2-, more preferably -CF(CF3)CF2-.

[0030] X is a fluorinated group or a trifluoromethyl group, preferably a trifluoromethyl group.

[0031] The divalent group represented by Y, having 1 to 10 carbon atoms, is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms. Examples of substituted or unsubstituted divalent hydrocarbon groups having 1 to 10 carbon atoms include substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkylene groups having 4 to 10 carbon atoms, substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, or substituted or unsubstituted arylalkylene groups having 7 to 10 carbon atoms.

[0032] As the divalent group represented by Y with 1 to 10 carbon atoms, it is preferably a substituted or unsubstituted alkylene group with 1 to 8 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 8 carbon atoms, a substituted or unsubstituted cycloalkylene group with 4 to 8 carbon atoms, a substituted or unsubstituted arylene group with 6 to 8 carbon atoms, or a substituted or unsubstituted arylene group with 7 to 8 carbon atoms. More preferably, it is a substituted or unsubstituted alkylene group with 1 to 6 carbon atoms, a substituted or unsubstituted alkenyl group with 2 to 6 carbon atoms, a substituted or unsubstituted cycloalkylene group with 4 to 6 carbon atoms, or a substituted or unsubstituted arylene group with 6 carbon atoms. It is even more preferably a substituted or unsubstituted alkylene group with 1 to 6 carbon atoms, and particularly preferably an (unsubstituted) alkylene group with 1 to 6 carbon atoms.

[0033] When the hydrocarbon group has substituents, examples of substituents that replace hydrogen atoms in the hydrocarbon group include halogen atoms, hydroxyl groups, thiols, amide groups, guanidino groups, nitro groups, and cyano groups. When the hydrocarbon group has substituents, the number of substituents is preferably 1 to 5, more preferably 1 to 3. Furthermore, when there are multiple substituents, the substituents can be the same or different.

[0034] Furthermore, as a substituent hydrocarbon group, a divalent group containing at least one heteroatom such as oxygen, nitrogen, or sulfur can be inserted between the carbon-carbon groups of the hydrocarbon group. The number of heteroatoms is preferably 1 to 10, more preferably 1 to 6. Examples of divalent groups containing at least one heteroatom include: -O-, -N<, -S-, -SO2-, -(C=O)-, -(C=O)O-, -O(C=O)-, -NH(C=O)-, -(C=O)NH-, -NH(C=O)O-, -O(C=O)NH-, etc. When such a divalent group is inserted between the carbon-carbon groups of the hydrocarbon group, the hydrocarbon chain is interrupted by these groups. Furthermore, by inserting such a divalent group between the carbon-carbon groups of the hydrocarbon group, a structure with heterocyclic rings can also be formed.

[0035] In one embodiment, the divalent group with 1 to 10 carbon atoms represented by Y can be exemplified by the following groups.

[0036] -(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 a phenylene compound that may have 1 to 3 substituents selected from alkyl groups (methyl, ethyl, propyl) with 1 to 3 carbon atoms, alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.) with 1 to 4 carbon atoms, or halogen atoms (F, Cl, Br, I).) As preferred divalent groups with 1 to 10 carbon atoms as Y, examples of divalent groups with the following structures can be cited.

[0037] -(CH2) N1 -(N1=1~10) -CONH-(CH2) N2 - (N2 = 1~5) -CO-O-(CH2) N2 - (N2 = 1~5) m is 5 to 60, preferably 10 to 50, and more preferably 15 to 35.

[0038] n is 1 or 2.

[0039] In the emulsion of the present invention, the perfluoropolyether phosphate compound (A) shown in formula (I) above can be used alone or in combination of two or more. In addition, as the perfluoropolyether phosphate compound (A), compounds with n=1 and compounds with n=2 in formula (I) can also be used in combination.

[0040] The weight-average molecular weight of the aforementioned perfluoropolyether phosphate compound (A) is preferably 2000 or more, more preferably 2500 or more, and particularly preferably 3000 or more. Furthermore, the weight-average molecular weight is preferably 20000 or less, more preferably 15000 or less, further preferably 12000 or less, even more preferably 10000 or less, particularly preferably 8000 or less, and most preferably 5000 or less. It should be noted that the weight-average molecular weight can be determined by conventionally known methods such as gel filtration chromatography.

[0041] Specific examples of the aforementioned perfluoropolyether phosphate compound (A) include, but are not limited to, the following.

[0042] [Chemistry 4] C3F7-O-(C3F6O) m -CF(CF3)-CH2-O-PO(OH)2 [In the formula, m is 5 to 60.] [Chemistry 5] [C3F7-O-(C3F6O) m -CF(CF3)-CH2-O]2-PO(OH) [In the formula, m is 5 to 60.] [Chemistry 6] C3F7-O-(C3F6O) m -CF(CF3)-CONHCH2CH2-O-PO(OH)2 [In the formula, m is 5 to 60.] [Chemistry 7] [C3F7-O-(C3F6O) m -CF(CF3)-CONHCH2CH2-O]2-PO(OH) [In the formula, m is 5 to 60.] [Chemistry 8] C3F7-O-(C3F6O) m -CF(CF3)-COOCH2CH2-O-PO(OH)2 [In the formula, m is 5 to 60.] [Chemistry 9] [C3F7-O-(C3F6O) m-CF(CF3)-COOCH2CH2-O]2-PO(OH) [In the formula, m is 5 to 60.] Perfluoropolyether phosphate compound (A) is also available in commercially available form, and can also be manufactured by known methods. For example, it can be obtained by phosphorylating the hydroxyl groups of the perfluoropolyether monohydric alcohol shown in formula (II) below.

[0043] [Chemistry 10] Rf-O-(C3F6O) m -CFX-Y-OH (II) [In the formula, Rf is a perfluoroalkyl group with 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group with 1 to 10 carbon atoms. m is 5 to 60.] In equation (II) above, Rf, X, Y, and m use the same definitions as in equation (I) above.

[0044] The weight-average molecular weight of the perfluoropolyether monohydric alcohol represented by formula (II) above is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, particularly preferably 2500 or more, and most preferably 3000 or more. Furthermore, the weight-average molecular weight is preferably 20000 or less, more preferably 15000 or less, further preferably 12000 or less, even more preferably 10000 or less, particularly preferably 8000 or less, and most preferably 5000 or less. It should be noted that the weight-average molecular weight can be determined by conventionally known methods such as gel filtration chromatography.

[0045] The perfluoropolyether monohydric alcohol represented by formula (II) above can also be obtained in commercially available form, and can also be manufactured by known methods. The perfluoropolyether monohydric alcohol represented by formula (II) can be synthesized according to methods disclosed, for example, in U.S. Patent Publication No. 3293306.

[0046] Furthermore, regarding the method of phosphorylating the hydroxyl groups of the perfluoropolyether monohydric alcohol shown in formula (II), known methods can be used. For example, it can be obtained by using phosphorus pentoxide (P2O5) or the like.

[0047] From the viewpoint of emulsification stability, the content of perfluoropolyether phosphate compound (A) in the emulsion of the present invention is preferably 0.2 to 40% by mass, more preferably 0.4 to 30% by mass, further preferably 1 to 25% by mass, particularly preferably 2 to 20% by mass, and most preferably 5 to 15% by mass, relative to 100% by mass of the total emulsion.

[0048] (B) Basic compounds The basic compound (B) can be an organic base or an inorganic base, but is preferably an organic base. Among the organic bases, amines are preferred. Examples of amines that can be used as basic compounds (B) include: aliphatic amines (aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines), alicyclic amines (alicyclic secondary amines, alicyclic tertiary amines), aromatic amines, heterocyclic amines, etc.

[0049] Examples of aliphatic primary amines include: methylamine, ethylamine, propylamine, butylamine, pentamine, hexamine, cyclohexylamine, ethylenediamine, etc.

[0050] Examples of aliphatic secondary amines include: dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, etc.

[0051] Examples of aliphatic tertiary amines include trimethylamine, triethylamine, diisopropylethylamine, triethanolamine, N,N-diisopropylethylamine, and N,N,N′,N′-tetramethylethylenediamine.

[0052] Examples of alicyclic secondary amines include piperidine, piperazine, pyrrolidine, and morpholine. Examples of alicyclic tertiary amines include N-methylpiperazine, N-methylpyrrolidine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and 1,4-diazabicyclo[2.2.2]octane.

[0053] Examples of aromatic amines include aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, N-methylaniline, 2,3-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, N,N-dimethylaniline, halogenated aniline, nitroaniline, etc.

[0054] Examples of heterocyclic amines include pyridine, pyrimidine, piperazine, quinoline, and imidazole.

[0055] Preferably, the amine is an aliphatic tertiary amine or an alicyclic tertiary amine, and more preferably, triethylamine, trimethylamine, triethanolamine, N,N-diisopropylethylamine, tetramethylethylenediamine, diazabicycloundecene (DBU), or diazabicyclononene (DBN).

[0056] The above-mentioned amines can be used alone or in combination of two or more.

[0057] From the viewpoint of emulsification stability, the content of the above-mentioned alkaline compound (B) in the emulsion of the present invention is preferably 0.01 to 15% by mass relative to 100% of the total emulsion volume, more preferably 0.05 to 10% by mass, further preferably 0.1 to 8% by mass, particularly preferably 0.2 to 5% by mass, and most preferably 0.3 to 3% by mass.

[0058] Furthermore, from the viewpoint of emulsion stability, the content of the alkaline compound (B) in the emulsion of the present invention is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of the perfluoropolyether phosphate compound (A), more preferably 1 to 30 parts by mass, particularly preferably 2 to 20 parts by mass, and most preferably 3 to 15 parts by mass.

[0059] The molar ratio ((B) / (A)) of the alkaline compound (B) to the perfluoropolyether phosphate compound (A) in the emulsion of the present invention is preferably 0.2 to 10, more preferably 0.5 to 8, and particularly preferably 1 to 5.

[0060] (C) alcohol The alcohol (C) used in the emulsion of the present invention is preferably a water-soluble alcohol with 1 to 10 carbon atoms, more preferably a water-soluble alcohol with 1 to 7 carbon atoms, particularly preferably a water-soluble alcohol with 1 to 4 carbon atoms, and most preferably a water-soluble alcohol with 2 or 3 carbon atoms.

[0061] Examples of such alcohols include lower alcohols and polyols, such as: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, etc.; diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, etc.; triols such as glycerol, trimethylolpropane, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, etc.; tetraols such as pentaerythritol; pentaols such as xylitol; and hexaols such as sorbitol and mannitol, etc. Ethanol, 1-propanol, and 2-propanol are preferred. They can be used alone or in combination of two or more.

[0062] From the viewpoint of emulsification stability, the alcohol (C) content in the emulsion of the present invention is preferably 0.1 to 45% by mass relative to 100% of the total emulsion volume, more preferably 0.5 to 40% by mass, further preferably 1 to 35% by mass, particularly preferably 2 to 30% by mass, and most preferably 3 to 25% by mass.

[0063] Furthermore, from the viewpoint of emulsion stability, the content of alcohol (C) in the emulsion of the present invention is preferably 30 to 500 parts by mass relative to 100 parts by mass of the above-mentioned perfluoropolyether phosphate compound (A), more preferably 35 to 400 parts by mass, particularly preferably 40 to 300 parts by mass, and most preferably 45 to 250 parts by mass.

[0064] (D) Water From the viewpoint of emulsification stability, the water (D) content in the emulsion of the present invention is preferably 50 to 99% by mass relative to 100% of the total emulsion volume, more preferably 55 to 95% by mass, and particularly preferably 60 to 90% by mass.

[0065] (Other additives) The emulsion of the present invention, without hindering the purpose of the present invention, may be appropriately combined with organic solvents other than alcohol (C), rust inhibitors, catalysts, antibacterial agents, flame retardants, surfactants, defoamers, thickeners, viscosity modifiers, leveling agents, ultraviolet absorbers, preservatives, antifreeze agents, wetting agents, pH adjusters, stabilizers, light stabilizers, weather stabilizers, neutralizers, matting agents, drying enhancers, foaming agents, non-adhesive agents, anti-deterioration agents, etc. These additives can be used individually or in combination of two or more. Relative to a total of 100 parts by weight of the perfluoropolyether phosphate compound (A), the basic compound (B), and the alcohol (C), each of these additives can be used in the range of 0.01 to 10 parts by weight.

[0066] <Methods for manufacturing emulsions> The emulsion of the present invention can be manufactured by a method comprising the following steps (1) and (2).

[0067] (Step 1) The step of preparing a dispersion containing a perfluoropolyether phosphate compound (A), an alkaline compound (B) and an alcohol (C).

[0068] (Step 2) The step of mixing the dispersion and water (D).

[0069] In step 1, the mixing order in the dispersion is not particularly limited. It can be that the alkaline compound (B) and the alcohol (C) are mixed relative to the perfluoropolyether phosphate compound (A), or other mixing orders are possible. Furthermore, various additives can be mixed as needed. It is preferable to achieve a uniformly dispersed state by mixing and thoroughly stirring these components.

[0070] The amount of alkaline compound (B) in the dispersion is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of perfluoropolyether phosphate compound (A), more preferably 1 to 30 parts by mass, particularly preferably 2 to 20 parts by mass, and most preferably 3 to 15 parts by mass.

[0071] The amount of alcohol (C) in the dispersion is preferably 30 to 500 parts by mass relative to 100 parts by mass of the perfluoropolyether phosphate compound (A), more preferably 35 to 400 parts by mass, particularly preferably 40 to 300 parts by mass, and most preferably 45 to 250 parts by mass.

[0072] In step 2, as a method for mixing the dispersion and water (D), it is preferable to slowly add water (D) while stirring the dispersion obtained in step 1. By slowly mixing water (D) into the dispersion, it is easy to make the components uniformly dispersed. With this method, emulsions can be prepared even without using an ultrasonic homogenizer or a high-pressure homogenizer.

[0073] The amount of water (D) mixed in (step 2) is preferably 100 to 10,000 parts by mass relative to 100 parts by mass of dispersion, more preferably 120 to 5,000 parts by mass, further preferably 150 to 2,000 parts by mass, particularly preferably 170 to 1,000 parts by mass, and most preferably 200 to 600 parts by mass.

[0074] The emulsion obtained in the above manner can be mixed with various additives as needed.

[0075] <Uses of Emulsion> The coating film obtained from the emulsion of the present invention has excellent release properties, liquid repellency, and continuous release properties. Therefore, the emulsion of the present invention can be suitable for use as a release agent, water and oil repellent, fiber treatment agent, etc.

[0076] The molding material or resin material used for demolding using the emulsion of the present invention is not particularly limited, and examples include: polyurethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR rubbers; polyurethane foam, epoxy resin, polyimide resin, polyamide resin, melamine resin, urea-formaldehyde resin, polyurethane, silicone resin, alkyd resin, phenolic resin, unsaturated polyester resin, vinyl ester resin and FRP (glass fiber reinforced plastic (GFRP) and carbon fiber reinforced plastic (CFRP)). Thermosetting resins such as RP (polypropylene), aramid fiber reinforced plastic (AFRP), etc.; thermoplastic resins such as 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, polyetheretherketone, FRTP (glass fiber reinforced thermoplastic resin (GFRTP), carbon fiber reinforced thermoplastic resin (CFRTP), aramid fiber reinforced thermoplastic resin (AFRTP)), etc. It is particularly useful as a mold release agent for molds made of polyurethane, epoxy resin, and other resins.

[0077] Furthermore, the materials used to coat the emulsion of the present invention are not particularly limited, and examples include: metals such as aluminum, SUS, and iron; resins such as PP, PE, and epoxy resin; rubber; FRP (fiber-reinforced plastic); gypsum substrates; wood substrates; fibers; glass; and composite materials. The emulsion of the present invention can impart high water and oil repellency to these materials.

[0078] In one embodiment, the emulsion of the present invention can be used as a fiber treatment agent. The fiber treated with the emulsion of the present invention can be any form, such as staple fiber, cotton linter, roving, sliver, yarn, fabric, woven fabric, or nonwoven fabric. Examples of raw materials for the fiber include: cotton, flax, jute, hemp, ramie, regenerated cellulose fibers, rayon, and other cellulose fibers, as well as polyvinyl alcohol-based synthetic fibers.

[0079] The emulsion of the present invention can be used by coating it onto the portion to be treated with the emulsion and then drying it. It should be noted that the emulsion can be diluted with water or the like as needed during coating. The concentration after dilution is appropriately selected according to the coating method and viscosity, and is not particularly limited; for example, it can be prepared with a solid content concentration of 0.1 to 5% by mass. As for the coating method, there are no particular limitations; examples include spraying, brushing, roller coating, dip coating, etc. As for the drying method, methods such as air drying or heating to evaporate the solvent and form a film can be included. The dried thickness of the film containing the emulsion of the present invention is typically 0.01 to 15 mm. m m, preferably 0.1 to 5.0 m m.

[0080] Example The present invention will be further illustrated below by way of examples, but the present invention is not limited thereto.

[0081] (Materials used) • PFPE phosphate ester 1: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 2000, m = 10.) • PFPE phosphate ester 2: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 2500, m=13.) • PFPE phosphate ester 3: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OPO(OH)2 (weight-average molecular weight 3500, m=19.) • PFPE phosphate ester 4: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 4000, m=22.) • DOL-4000: Perfluorinated polyether monohydric alcohol CF3CF2CF2O-[CF(CF3)CF2O] m -CF(CF3)CH2OH (weight average molecular weight 4000) Et3N: Triethylamine • TEA: Triethanolamine • DBU: 1,8-diazabicyclo[5.4.0]-7-undecene IPA: 2-Propanol <Example 1> Add 10.0 g of PFPE phosphate ester 1, 0.6 g of Et3N, and 10.0 g of IPA to a 200 ml beaker equipped with a stir bar. Stir the mixture with a magnetic stirrer for 10 minutes to prepare a dispersion. While stirring the dispersion, slowly add 79.4 g of distilled water dropwise. Prepare an emulsion with a PFPE phosphate ester concentration of 10 wt%.

[0082] For the obtained emulsion, confirm the appearance of the emulsified liquid.

[0083] In addition, the emulsion was diluted with distilled water to a concentration of 1 wt% of the active ingredient to prepare a coating sample. Cold-rolled steel sheet SPCC-SB was used as the coating substrate. After degreasing the coating substrate with acetone, it was heated to 170°C, and 50 g / m² of the coating sample was applied using a spray gun. 2 The amount of coating was determined. After coating, the sample was heated at 170°C for 1 minute to prepare an evaluation sample. A tape peel test was performed on the obtained evaluation sample. The results are shown in Tables 1 and 3.

[0084] (Appearance evaluation of the emulsion) Visually confirm the emulsified liquid.

[0085] 〇: Completely emulsified and stable.

[0086] △: Emulsifies, but has poor stability and settles slowly.

[0087] ×: Cannot emulsify, will separate into layers.

[0088] (Tape peel test) The evaluation sample was pasted 7.5cm. 2 The load on the polyester adhesive tape No. 31B manufactured by Nitto Denko Corporation was measured using a push-pull force gauge when peeling the tape at 90°. Additionally, the tape was applied to the same location and peel tests were repeated 10 times.

[0089] <Examples 2-8, Comparative Examples 1-3> The composition was changed to that described in Tables 1 and 2, except that it was the same as in Example 1, and an emulsion was prepared. Then, the appearance 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 1-8, perfluoropolyether phosphate was stirred in the presence of an alkaline compound and an alcohol to prepare a dispersion, and then water was added dropwise to obtain a stable emulsion. As can be seen from Examples 1 and Comparative Example 1, a stable emulsion could not be obtained when the perfluoropolyether phosphate was replaced with a perfluoropolyether monohydric alcohol. Furthermore, an emulsion could not be obtained without the addition of an alcohol (Comparative Example 2) or without the addition of an alkaline compound (Comparative Example 3).

[0094] In the tape peel test, the number of times after 10 repetitions in Examples 1 and 3 was less than 3N, which confirms the performance maintenance during repetition.

Claims

1. An emulsion characterized in that, Comprising: (A) a perfluoropolyether phosphate compound represented by the following formula (I), (B) a basic compound, (C) an alcohol, and (D) water, [Rf-O-(C3F6O) m -CFX-Y-O] n -PO(OH) 3-n (I) in formula (1), Rf is a perfluoroalkyl group having 1 to 4 carbon atoms, X is a fluorine 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. The emulsion of claim 1, wherein, The weight average molecular weight of the perfluoropolyether phosphate compound (A) is in the range of 2000 to 20000.

3. The emulsion of claim 1, wherein, The basic compound (B) is an organic base.

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

5. The emulsion of claim 1, wherein, The content of the basic compound (B) is 0.5 to 50 parts by mass relative to 100 parts by mass of the perfluoropolyether phosphate compound (A).

6. The emulsion of claim 1, wherein, The molar ratio of the basic compound (B) to the perfluoropolyether phosphate compound (A) in the emulsion, that is, (B) / (A), is 0.2 to 10.

7. The emulsion of claim 1, wherein, The content of the alcohol (C) is 30 to 500 parts by mass relative to 100 parts by mass of the perfluoropolyether phosphate compound (A).

8. A water and oil repellent agent characterized by comprising: An emulsion comprising the perfluoropolyether phosphate compound (A) of claim 1.

9. A fiber treatment agent characterized by comprising: An emulsion comprising the perfluoropolyether phosphate compound (A) of claim 1.

10. A mold release agent characterized by comprising: An emulsion comprising the perfluoropolyether phosphate compound (A) of claim 1.

11. The method of producing the emulsion according to claim 1, characterized by, Comprising the following steps: a step of preparing a dispersion liquid containing the perfluoropolyether phosphate compound (A), the basic compound (B), and the alcohol (C); and a step of mixing the dispersion liquid with the water (D).

12. The manufacturing method according to claim 11, wherein, The mixing amount of the water (D) is 100 to 10000 parts by mass relative to 100 parts by mass of the dispersion liquid.

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