Emulsion and method for producing same

Abstract

Provided is an emulsion of perfluoropolyether carboxylic acid that can be prepared by a simple method. [Solution] An emulsion containing (A) a perfluoropolyether oil represented by the following formula (I), (B) a perfluoropolyether carboxylate represented by the following formula (II), (C) a water-soluble organic solvent, and (D) water, wherein the mass average value of the water / octanol partition coefficient (logP) of the water-soluble organic solvent (C) is in the range of -0.33 to 0. (In formulas (I) and (II), Rf and Rf' are the same or different and each is a perfluoroalkyl group having 1 to 3 carbon atoms. p, q, and r each independently represent an integer of 0 or greater, and p + q + r = 3 to 120.) JPEG0007821856000026.jpg9169 JPEG0007821856000027.jpg8169

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 from Patent Documents 1 and 2, for example. [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] However, the methods described in Patent Documents 1 and 2 require an ultrasonic homogenizer or a high-pressure homogenizer, and are therefore hardly simple methods. An object of the present invention is to provide an emulsion of perfluoropolyether oil that can be prepared by a simple method. [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 perfluoropolyether oil can be easily prepared by using a perfluoropolyether oil, a perfluoropolyether carboxylate, an aqueous organic solvent having a mass average value of a water / octanol partition coefficient within a specific range, and water.

[0007] The present invention has been completed based on these findings and includes the following broad aspects.

[0008] [Section 1] (A) a perfluoropolyether oil represented by the following formula (I), (B) a perfluoropolyether carboxylate represented by the following formula (II), (C) a water-soluble organic solvent; (D)Water An emulsion comprising: The emulsion has a mass average value of the water / octanol partition coefficient (logP) of the water-soluble organic solvent (C) in the range of -0.33 to 0. [ka] (In the formula, Rf and Rf' are the same or different and are perfluoroalkyl groups having 1 to 3 carbon atoms. p, q, and r each independently represent an integer of 0 or more, and p+q+r=3 to 120. The C3F6O group, C2F4O group, and CFO group may be bonded in any order.) [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 single bond or a divalent group having 1 to 10 carbon atoms. n is an integer of 7 to 20. M is an alkali metal, an ammonium base, or an organic amine base.) [Section 2] Item 2. The emulsion according to Item 1, wherein the perfluoropolyether oil (A) has a weight average molecular weight in the range of 1,000 to 20,000. [Section 3] Item 3. The emulsion according to Item 1 or 2, wherein the perfluoropolyether carboxylate (B) has a weight average molecular weight in the range of 1,800 to 3,000. [Section 4] 4. The emulsion according to any one of items 1 to 3, wherein the content of the perfluoropolyether carboxylate (B) is 1 to 20 parts by mass per 100 parts by mass of the perfluoropolyether oil (A). [Section 5] 5. The emulsion according to any one of items 1 to 4, wherein the content of the water-soluble organic solvent (C) is 5 to 100 parts by mass per 100 parts by mass of the perfluoropolyether oil (A). [Section 6] Item 6. A lubricant comprising the emulsion according to any one of Items 1 to 5. [Section 7] A step of preparing a dispersion containing the perfluoropolyether oil (A), the perfluoropolyether carboxylate (B), and the water-soluble organic solvent (C); and a step of mixing the dispersion with the water (D) Item 6. A method for producing the emulsion according to any one of Items 1 to 5, comprising: [Section 8] Item 8. The method according to Item 7, wherein the amount of water (D) mixed is 100 to 10,000 parts by mass per 100 parts by mass of the dispersion. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an emulsion of perfluoropolyether carboxylic oil that can be prepared by a simple method. DETAILED DESCRIPTION OF THE INVENTION

[0010] <Emulsion> The emulsion according to the present invention contains the following (A) to (D): (A) A perfluoropolyether oil represented by the following formula (I): [ka] (In the formula, Rf and Rf' are the same or different and are perfluoroalkyl groups having 1 to 3 carbon atoms. p, q, and r each independently represent an integer of 0 or more, and p+q+r=3 to 120. The C3F6O group, C2F4O group, and CFO group may be bonded in any order.) (B) A perfluoropolyether carboxylate represented by the following formula (II): [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 single bond or a divalent group having 1 to 10 carbon atoms. n is an integer of 7 to 20. M is an alkali metal, an ammonium base, or an organic amine base.) (C) Water-soluble organic solvents with mass-averaged water / octanol partition coefficients (logP) in the range of -0.33 to 0. (D) Water. Each component will be described in detail below.

[0011] (A) A perfluoropolyether oil represented by formula (I). [ka]

[0012] Rf and Rf' are the same or different and are perfluoroalkyl groups having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups having 1 to 3 carbon atoms include a trifluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, and a perfluoroisopropyl group.

[0013] p, q, and r each independently represent an integer of 0 or more, and p+q+r=3 to 120. p+q+r is preferably 5 to 100, and more preferably 10 to 80.

[0014] The C3F6O group, C2F4O group, and CFO group may be bonded in any order. Here, "the C3F6O group, C2F4O group, and CFO group are bonded in any order" means that the main chain of the perfluoropolyether oil (A) is configured with one or more repeating units of C3F6O groups, one or more repeating units of C2F4O groups, and one or more repeating units of CFO groups randomly arranged, and there is no regularity in the arrangement of the number of repeating units of C3F6O groups, the number of repeating units of C2F4O groups, and the number of repeating units of CFO groups along the main chain. Furthermore, the C3F6 group in formula (I) may be a CF2CF2CF2 group, a CF(CF3)CF2 group, or a CF2CF(CF3) group. The C2F4 group in formula (I) may be a CF2CF2 group or a CF(CF3) group.

[0015] Examples of such perfluoropolyether oils include those having structures represented by the following general formulas (Ia) to (Id). [ka] (In the formula, Rf and Rf′ are the same or different and each represents a perfluoroalkyl group having 1 to 3 carbon atoms, and p is 3 to 120.) [ka] (In the formula, Rf and Rf' are the same or different and are perfluoroalkyl groups having 1 to 3 carbon atoms. p+r=3 to 120. The CF(CF3)CF2O groups and CF2O groups may be bonded in any order.) [ka] (In the formula, Rf and Rf' are the same or different and are perfluoroalkyl groups having 1 to 3 carbon atoms. q+r=3 to 120. The CF2CF2O groups and CF2O groups may be bonded in any order.) [ka] (In the formula, Rf and Rf′ are the same or different and each represents a perfluoroalkyl group having 1 to 3 carbon atoms, and p is 3 to 120.)

[0016] In formula (Ia), p is 3 to 120, preferably 5 to 100, more preferably 10 to 80, and particularly preferably 15 to 50.

[0017] In formula (Ib), p:r is preferably in the range of 10:90 to 90:10. p+r is 3 to 120, preferably 5 to 100, and more preferably 10 to 80.

[0018] In formula (Ic), q:r is preferably in the range of 10:90 to 90:10. q+r is 3 to 120, preferably 5 to 100, and more preferably 10 to 80.

[0019] In formula (Id), p is 3-120, preferably 20-100, and more preferably 40-80.

[0020] Commercially available perfluoropolyether oils include, for example, the Krytox series (manufactured by DuPont), the Fomblin Y series (manufactured by Solvay Specialty Polymers Japan, Ltd.), the Fomblin M series (manufactured by Solvay Specialty Polymers Japan, Ltd.), the Fomblin W series (manufactured by Solvay Specialty Polymers Japan, Ltd.), the Fomblin Z series (manufactured by Solvay Specialty Polymers Japan, Ltd.), the Demnum S series (manufactured by Daikin Industries, Ltd.), and the RecaloFlosso PT series (manufactured by Nicca Chemical Co., Ltd.).

[0021] The weight-average molecular weight of the perfluoropolyether oil is preferably 1000 to 20000, more preferably 1500 to 15000, and particularly preferably 2000 to 10000. The weight-average molecular weight can be measured by a conventionally known method such as gel filtration chromatography.

[0022] In addition, perfluoropolyether oil has a kinematic viscosity of 15 to 600 mm at 40°C. 2 It is preferable to use a material in the range of 20 to 500 mm / s. 2 The kinematic viscosity can be measured according to the method of JIS Z8803.

[0023] In the emulsion of the present invention, the perfluoropolyether oil (A) represented by the above formula (I) may be used alone or in combination of two or more.

[0024] From the viewpoint of emulsion stability, the content of the perfluoropolyether oil (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.

[0025] (B) A perfluoropolyether carboxylate represented by the following formula (II): [ka]

[0026] 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 perfluoro-n-propyl group, a perfluoro-isopropyl group, a perfluoro-n-butyl group, a perfluoro-isobutyl group, a perfluoro-sec-butyl group, and a perfluoro-tert-butyl group.

[0027] The C3F6 group in formula (II) may be a CF2CF2CF2 group, a CF(CF3)CF2 group, or a CF2CF(CF3) group, with a CF2CF2CF2 group or a CF(CF3)CF2 group being preferred, and a CF(CF3)CF2 group being more preferred.

[0028] X is a fluoro group or a trifluoromethyl group, preferably a trifluoromethyl group.

[0029] Y is a single bond or a divalent group having 1 to 10 carbon atoms. The divalent group having 1 to 10 carbon atoms is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms include a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and a substituted or unsubstituted aralkylene group having 7 to 10 carbon atoms.

[0030] The divalent group having 1 to 10 carbon atoms is preferably a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 8 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 8 carbon atoms, a substituted or unsubstituted arylene group having 6 to 8 carbon atoms, or a substituted or unsubstituted aralkylene group having 7 to 8 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 6 carbon atoms, a substituted or unsubstituted cycloalkylene group having 4 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 6 carbon atoms, still more preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, and particularly preferably an (unsubstituted) alkylene group having 1 to 6 carbon atoms.

[0031] When the hydrocarbon group has a substituent, examples of the substituent that replaces a hydrogen atom in the hydrocarbon group include a halogen atom, a hydroxyl group, a thiol group, an amide group, a guanidide group, a nitro group, and a cyano group. When the hydrocarbon group has a substituent, the number of the substituents is preferably 1 to 5, and more preferably 1 to 3. When there are multiple substituents, the substituents may be the same or different.

[0032] The hydrocarbon group having a substituent may also contain a divalent group containing at least one heteroatom, such as an oxygen atom, nitrogen atom, or sulfur atom, between carbon atoms 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-, and -O(C=O)NH-. When such a divalent group is present between carbon atoms of the hydrocarbon group, the hydrocarbon chain is interrupted by the group. Furthermore, the presence of such a divalent group between carbon atoms of the hydrocarbon group may result in a heterocyclic structure.

[0033] In one embodiment, examples of the divalent group having 1 to 10 carbon atoms represented by Y include the following groups. -(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).)

[0034] Y is preferably a single bond or a divalent group of the following structure: -(CH2) N1 - (N1=1~10) -CONH-(CH2) N2 - (N2=1~5) -CO-O-(CH2) N2 - (N2=1~5) n is 7 to 20, preferably 9 to 18.

[0035] M is an alkali metal, an ammonium base, or an organic amine base. Examples of alkali metals include lithium, sodium, and potassium. Examples of amine bases include trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, and pyridine. 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 M is a hydrogen atom.

[0036] In the emulsion of the present invention, the perfluoropolyether carboxylate (B) represented by the above formula (II) may be used alone or in combination of two or more.

[0037] The perfluoropolyether carboxylate (B) preferably has a weight-average molecular weight of 1,700 or more, more preferably 1,800 or more, and preferably has a weight-average molecular weight of 3,500 or less, more preferably 3,000 or less. The weight-average molecular weight can be measured by a conventional method such as gel filtration chromatography.

[0038] Specific examples of the perfluoropolyether carboxylic acid compound that is a precursor of the perfluoropolyether carboxylic acid compound salt (B) include, but are not limited to, the following. [ka] (In the formula, n is 7 to 20.) [ka] (In the formula, n is 7 to 20.) [ka] (In the formula, n is 7 to 20.) [ka] (In the formula, n is 7 to 20.)

[0039] The perfluoropolyether carboxylate (B) can be produced by a known method, for example, by hydrolyzing a perfluoropolyether compound represented by the following formula (III). [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 single bond or a divalent group having 1 to 10 carbon atoms, R is a substituted or unsubstituted hydrocarbon group, and n is 7 to 25.)

[0040] Rf″, X, Y, and n in formula (III) are the same as defined in formula (II).

[0041] In formula (III), R is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms.

[0042] Examples of the unsubstituted hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, an allyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a phenyl group. Preferred are a methyl group, an ethyl group, a tert-butyl group, and a benzyl group, and particularly preferred is a methyl group.

[0043] In the case where the hydrocarbon group in R has a substituent, the substituents described above for Y in formula (II) can be used as the substituent without any particular limitation.

[0044] The perfluoropolyether compound represented by the formula (III) preferably has a weight-average molecular weight of 1,700 or more, more preferably 1,800 or more, and preferably 3,500 or less, more preferably 3,000 or less. The weight-average molecular weight can be measured by a conventional method such as gel filtration chromatography.

[0045] The perfluoropolyether compound represented by the formula (III) can be synthesized by anionic ring-opening polymerization of hexafluoropropylene oxide, for example, by referring to the method disclosed in Japanese Patent No. 5774470.

[0046] From the viewpoint of emulsion stability, the content of perfluoropolyether carboxylate (B) in the emulsion of the present invention is preferably 0.005 to 8 mass%, more preferably 0.01 to 6 mass%, even more preferably 0.02 to 5 mass%, particularly preferably 0.05 to 4 mass%, and most preferably 0.1 to 3 mass%, relative to 100 mass% of the total amount of the emulsion.

[0047] From the viewpoint of emulsion stability, the content of the perfluoropolyether carboxylate (B) in the emulsion of the present invention is preferably 1 to 20 parts by mass, more preferably 2 to 17 parts by mass, and particularly preferably 5 to 15 parts by mass, per 100 parts by mass of the perfluoropolyether oil (A).

[0048] (C) Water-soluble organic solvent The water-soluble organic solvent (C) has a mass average value of the water / octanol partition coefficient (logP) in the range of -0.33 to 0.

[0049] In this specification, the "mass average water / octanol partition coefficient (logP)" refers to a value obtained by multiplying the water / octanol partition coefficient of each component contained as a water-soluble organic solvent by its respective mass fraction (the mass of each water-soluble organic solvent divided by the sum of the masses of all water-soluble organic solvents) for each of all water-soluble organic solvents, and then summing these values. In other words, when a water-soluble organic solvent consists of only one component, the mass average water / octanol partition coefficient is the water / octanol partition coefficient of that water-soluble organic solvent itself, and when a water-soluble organic solvent is a mixture of two or more components, the mass average water / octanol partition coefficient is the sum of the water / octanol partition coefficients of those organic solvents multiplied by their respective mass fractions.

[0050] The mass average value of the water / octanol partition coefficient (logP) of the water-soluble organic solvent (C) is from −0.33 to 0, preferably from −0.30 to −0.10, from the viewpoint of emulsion stability.

[0051] In this specification, the term "water-soluble organic solvent" refers to an organic solvent that dissolves in 100 g of water at 25° C. in an amount of 10 g or more.

[0052] Examples of water-soluble organic solvents include alcohol-based solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, propylene glycol monomethyl ether, and glycerin; ketone-based solvents such as acetone; nitrile-based solvents such as acetonitrile; ether-based solvents such as tetrahydrofuran, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; dimethyl sulfoxide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone. By using these solvents alone or in combination of two or more, the mass average value of the water / octanol partition coefficient (logP) can be adjusted to the range of −0.33 to 0.

[0053] From the viewpoint of emulsion stability, the content of the water-soluble organic solvent (C) in the emulsion of the present invention is preferably 0.05 to 40 mass%, more preferably 0.1 to 20 mass%, and particularly preferably 0.5 to 10 mass%, relative to 100 mass% of the total amount of the emulsion.

[0054] From the viewpoint of emulsion stability, the content of the water-soluble organic solvent (C) in the emulsion of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 10 to 50 parts by mass, per 100 parts by mass of the perfluoropolyether oil (A).

[0055] (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 55 to 95 mass%, and particularly preferably 60 to 90 mass%, relative to 100 mass% of the total amount of the emulsion.

[0056] (Other additives) The emulsion of the present invention may contain, as appropriate, 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, 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 object 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 oil (A), perfluoropolyether carboxylate (B), and water-soluble organic solvent (C).

[0057] In one embodiment, the emulsion of the present invention preferably does not contain a thickener. When the emulsion of the present invention does not contain a thickener, it can be preferably used as a lubricant. In one embodiment, particularly as a lubricant, the emulsion of the present invention may contain additives (e.g., preservatives, antibacterial agents, rust inhibitors, etc.) as appropriate within the scope that does not impair the object of the present invention, but it is most preferable that the emulsion of the present invention does not contain any components other than the perfluoropolyether oil (A), the perfluoropolyether carboxylate (B), the water-soluble organic solvent (C), and water (D).

[0058] <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 oil (A), a perfluoropolyether carboxylate (B), and a water-soluble organic solvent (C). (Step 2) A step of mixing the dispersion liquid with water (D).

[0059] In (Step 1), the mixing order in the dispersion is not particularly limited, and the perfluoropolyether carboxylate (B) and the water-soluble organic solvent (C) may be mixed with the perfluoropolyether oil (A), or another mixing order may be used. Various additives may also be mixed as needed. It is preferable to mix these components and thoroughly stir them to make each component uniformly dispersed.

[0060] The amount of perfluoropolyether carboxylate (B) mixed in the dispersion is preferably 1 to 20 parts by mass, more preferably 2 to 17 parts by mass, and particularly preferably 5 to 15 parts by mass, per 100 parts by mass of perfluoropolyether oil (A).

[0061] The amount of the water-soluble organic solvent (C) mixed in the dispersion is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 10 to 50 parts by mass, per 100 parts by mass of the perfluoropolyether oil (A).

[0062] In (Step 2), the dispersion and water (D) are preferably mixed by gradually adding water (D) while stirring the dispersion obtained in Step 1. By gradually mixing water (D) into the dispersion, it becomes easier to uniformly disperse each component. By using such a method, an emulsion can be prepared without using an ultrasonic homogenizer or a high-pressure homogenizer.

[0063] The amount of water (D) mixed in (Step 2) is preferably 100 to 10,000 parts by mass, more preferably 120 to 5,000 parts by mass, even more 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, relative to 100 parts by mass of the dispersion.

[0064] Various additives can be mixed with the emulsion thus obtained, if necessary.

[0065] <Uses of emulsion> The emulsion of the present invention can be used for various purposes, and is particularly preferably used as a lubricant.As a lubricant, it can be used for, for example, home appliances, ships, railways, aircraft, machinery, structures, automobile repair, automobiles, construction, building materials, textiles, leather, stationery, woodworking, furniture, miscellaneous goods, steel plates, cans, electronic substrates, electronic components, printing, etc.Among these, it is particularly useful for automobiles and industrial machinery.

[0066] The emulsion of the present invention can also be used as a mold release agent, a water and oil repellent, a fiber treatment agent, and the like.

[0067] When the emulsion of the present invention is used as a mold release agent, the molding material or resin material to 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; 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.

[0068] Furthermore, when the emulsion of the present invention is used as a release agent or a water- and oil-repellent agent, the material to which the emulsion of the present invention is applied is not particularly limited, and examples thereof include 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.

[0069] When the emulsion of the present invention is used as a fiber treatment agent, the fibers to be treated using the emulsion of the present invention may be in any form, such as short fibers (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.

[0070] 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. Examples of 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]

[0071] The present invention will be further explained below with reference to examples, but the present invention is not limited thereto.

[0072] (Materials used) PFPE oil 1: Perfluoropolyether oil (RecaloFlosso PT82, manufactured by Nikka Chemical, weight average molecular weight 2800) RfO-(CFCF3CF2O) n -Rf' PFPE oil 2: Perfluoropolyether oil (RecaloFlosso PT05, manufactured by Nikka Chemical, weight average molecular weight 5000) RfO-(CFCF3CF2O) n -Rf' PFPE oil 3: Perfluoropolyether oil (RecaloFlosso PT57, manufactured by Nikka Chemical, weight average molecular weight 7500) RfO-(CFCF3CF2O) n -Rf' PFPE oil 4: Perfluoropolyether oil (Fomblin M07, manufactured by Solvay, weight average molecular weight 5400) CF3O-(CF2CF2O) q -(CF2O) r -CF3(q≒30, r≒30) PFPE carboxylic acid 1: Perfluoropolyether carboxylic acid CF3CF2CF2O-[CF(CF3)CF2O] n -CF(CF3)-CONHCH2-COOH·Et3N (weight average molecular weight 2000, n=10.) PFPE carboxylic acid 2: Perfluoropolyether carboxylic acid CF3CF2CF2O-[CF(CF3)CF2O] n -CF(CF3)-COOH·Et3N (weight average molecular weight 2000, n=10.) PFPE carboxylic acid 3: Perfluoropolyether carboxylic acid CF3CF2CF2O-[CF(CF3)CF2O] n -CF(CF3)-COOH·DBU (weight average molecular weight 2000, n=10.) PFPE carboxylic acid 4: Perfluoropolyether carboxylic acid CF3CF2CF2O-[CF(CF3)CF2O] n -CF(CF3)-CONHCH2-COOH·Et3N (weight average molecular weight 1800, n=9.) PFPE carboxylic acid 5: Perfluoropolyether carboxylic acid CF3CF2CF2O-[CF(CF3)CF2O] n -CF(CF3)-CONHCH2-COOH·Et3N (weight average molecular weight 3000, n=16.) MeOH: Methanol (water / octanol partition coefficient: -0.77) EtOH: Ethanol (water / octanol partition coefficient: -0.31) nPrOH: 1-propanol (water / octanol partition coefficient: 0.25) IPA: 2-propanol (water / octanol partition coefficient: 0.05) PGM: Propylene glycol monomethyl ether (water / octanol partition coefficient: -0.21) Acetone (water / octanol partition coefficient: -0.21) DME: Dimethoxyethane (water / octanol partition coefficient: -0.22)

[0073] Example 1 PFPE oil 1 (10.0 g), PFPE carboxylate 1 (1.0 g), and PGM (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 the dispersion, distilled water (87.0 g) was gradually added dropwise to produce an emulsion with a PFPE oil concentration of 10 wt%. The resulting emulsion was evaluated for appearance and measured for median diameter after emulsification. The results are shown in Table 1.

[0074] (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.

[0075] (Median diameter measurement) The sample was diluted with water to a measurable transmittance (80-90%) and measured using a particle size distribution analyzer, HORIBA LA-750.

[0076] <Examples 2 to 16 and Comparative Examples 1 to 6> Emulsions were prepared in the same manner as in Example 1, except that the compositions were changed as shown in Tables 1 to 4. Thereafter, the appearance of the emulsified liquid was evaluated and the median diameter was measured in the same manner as in Example 1. The results are shown in Tables 1 to 4.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3]

[0080] [Table 4]

[0081] In Examples 1 to 4 and Comparative Examples 1 to 3, when a single solvent was used, a stable emulsion of PFPE oil was obtained when EtOH, PGM, acetone, or DME, which have a water-octanol partition coefficient between -0.33 and 0, was used. MeOH, which has a water-octanol partition coefficient of -0.77, or IPA, which has a water-octanol partition coefficient of 0.05, did not result in an emulsion with fine particle size, and a stable emulsion was not obtained.

[0082] In Examples 4 and 5 and Comparative Examples 4 and 5, a mixed solvent of MeOH and nPrOH was used for investigation. When the relationship between the mass average water-octanol partition coefficients of MeOH and nPrOH and emulsion stability was examined, stable emulsions were obtained when the mass average partition coefficients were between -0.33 and 0. On the other hand, stable emulsions were not obtained when the mass average partition coefficients were 0.05 or -0.36.

[0083] In Examples 7 to 11, the type of PFPE carboxylate was changed to examine emulsion stability. In Examples 12 to 14, the type of PFPE oil was changed to examine emulsion stability. In all cases, stable emulsions were obtained.

[0084] In Example 15, four types of mixed solvents (EtOH, nPrOH, IPA, DME) were used for the study. In Example 16, a mixed solvent of EtOH and DME was used for the study. In both cases, stable emulsions were obtained.

[0085] In Comparative Example 6, an attempt was made to prepare an emulsion without using a water-soluble organic solvent, but it was confirmed that no emulsification occurred and that layers separated after stirring was stopped.

Claims

1. (A) a perfluoropolyether oil represented by the following formula (I), (B) a perfluoropolyether carboxylate represented by the following formula (II), (C) a water-soluble organic solvent; (D) Water An emulsion comprising: The emulsion has a mass average value of the water / octanol partition coefficient (log P) of the water-soluble organic solvent (C) in the range of −0.33 to 0. 【Chemistry 1】 (In the formula, Rf and Rf′ are the same or different and each represents a perfluoroalkyl group having 1 to 3 carbon atoms. p, q, and r each independently represent an integer of 0 or more, and p+q+r=3 to 120. C ３ F ６ O group, C ２ F ４ O group, and CF ２ The O groups may be attached in any order. 【Chemistry 2】 (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 single bond or a divalent group having 1 to 10 carbon atoms, n is 7 to 20, and M is an ammonium base or an organic amine base.)

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

3. 2. The emulsion according to claim 1, wherein the weight average molecular weight of the perfluoropolyether carboxylate (B) is in the range of 1,800 to 3,000.

4. 2. The emulsion according to claim 1, wherein the content of the perfluoropolyether carboxylate (B) is 1 to 20 parts by mass per 100 parts by mass of the perfluoropolyether oil (A).

5. 2. The emulsion according to claim 1, wherein the content of the water-soluble organic solvent (C) is 5 to 100 parts by mass per 100 parts by mass of the perfluoropolyether oil (A).

6. The total amount of the emulsion is 100% by mass, 0.2 to 40% by mass of the perfluoropolyether oil (A), 0.005 to 8% by mass of the perfluoropolyether carboxylate (B), 0.05 to 40% by mass of the water-soluble organic solvent (C), 50 to 99% by mass of the water (D) 2. The emulsion of claim 1, comprising:

7. A lubricant comprising the emulsion of claim 1.

8. The total amount of the emulsion is 100% by mass, (A) 0.2 to 40 mass% of a perfluoropolyether oil represented by the following formula (I), (B) 0.005 to 8% by mass of a perfluoropolyether carboxylate represented by the following formula (II); (C) 0.05 to 40% by mass of a water-soluble organic solvent having a mass average value of the water / octanol partition coefficient (log P) in the range of −0.33 to 0; (D) Water 50-99% by mass A lubricant consisting of an emulsion consisting solely of 【Transformation 3】 (In the formula, Rf and Rf' are the same or different and are perfluoroalkyl groups having 1 to 3 carbon atoms. p, q, and r each independently represent an integer of 0 or more, and p+q+r=3 to 120. The C 3 F 6 O group, C 2 F 4 O group, and CF 2 O group may be bonded in any order.) 【Chemistry 4】 (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 single bond or a divalent group having 1 to 10 carbon atoms, n is 7 to 20, and M is an ammonium base or an organic amine base.)

9. (A) a perfluoropolyether oil represented by the following formula (I), (B) a perfluoropolyether carboxylate represented by the following formula (II), (C) A water-soluble organic solvent having a mass average value of the water / octanol partition coefficient (log P) in the range of −0.33 to 0. a first step of mixing the above to prepare a dispersion; A second step of adding (D) water to the dispersion while stirring it. A method for producing an emulsion, comprising: 【Transformation 5】 (In the formula, Rf and Rf' are the same or different and are perfluoroalkyl groups having 1 to 3 carbon atoms. p, q, and r each independently represent an integer of 0 or more, and p+q+r=3 to 120. The C 3 F 6 O group, C 2 F 4 O group, and CF 2 O group may be bonded in any order.) 【Transformation 6】 (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 single bond or a divalent group having 1 to 10 carbon atoms, n is 7 to 20, and M is an ammonium base or an organic amine base.)

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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