Perfluoropolyether phosphate ester or salt thereof, surface treatment agent, coating agent, mold release agent, and method for producing perfluoropolyether phosphate ester or salt thereof

Abstract

The present invention relates to a perfluoropolyether phosphate ester represented by general formula (1) or a perfluoropolyether phosphate ester salt represented by general formula (2). (In general formulae (1) and (2), n is an integer of 1-20, M1 is an alkali metal, an ammonium base, or an organic amine base, and M2 is a hydrogen atom, an alkali metal, an ammonium base, or an organic amine base.)

Description

Perfluoropolyether phosphate ester or its salt, surface treatment agent, coating agent, mold release agent, and method for producing perfluoropolyether phosphate ester or its salt

[0001] The present invention relates to a perfluoropolyether phosphate ester or a salt thereof, a surface treatment agent, a coating agent, a mold release agent, and a method for producing a perfluoropolyether phosphate ester or a salt thereof.

[0002] Fluoroalkylphosphonic acids are used as raw materials for surface treatment agents. Compounds with a perfluoroalkyl group containing 8 to 12 carbon atoms are most likely to exhibit surface treatment properties, and CF ３ (CF ２ ) ７ CH ２ CH ２ -P(O)(OH) ２ Telomer compounds having eight carbon atoms and the structural formula shown below are widely used as active ingredients in surface treatment agents (see Patent Documents 1 to 4).

[0003] On the other hand, it has been reported that telomer compounds having a perfluoroalkyl group with 8 to 12 carbon atoms are biodegraded in the environment and converted into compounds with relatively high bioaccumulation and environmental concentration, raising concerns about exposure during the treatment process, release into the environment from waste, treatment substrates, etc. On the other hand, compounds having a perfluoroalkyl group with 14 or more carbon atoms are extremely difficult to handle due to their physical and chemical properties, and are therefore rarely used in practice.

[0004] Furthermore, in the manufacturing process of telomer compounds having a perfluoroalkyl group with 8 or more carbon atoms, the generation or contamination of perfluorooctanoic acids, which are highly bioaccumulative, is unavoidable. For this reason, the use of telomer compounds having 8 carbon atoms has been restricted in recent years, and compounds having a perfluoroalkyl group with 6 or less carbon atoms, such as CF ３ (CF ２ ) ５ CH ２ CH ２ -P(O)(OH) ２ The replacement of telomer compounds with six carbon atoms having the following structural formula is currently underway.

[0005] However, when a compound having a perfluoroalkyl group with 6 or fewer carbon atoms is used as a surface treatment agent, the orientation on the surface of the target substrate is significantly reduced, and the melting point, glass transition point (Tg), etc. are significantly lower than those of a compound having a perfluoroalkyl group with 8 carbon atoms, so that the agent is significantly affected by the environmental conditions of use, such as temperature, humidity, stress, and organic solvents. As a result, the required sufficient performance cannot be obtained from such a surface treatment agent, and durability, etc. are also affected.

[0006] By the way, compounds containing perfluoropolyether groups have extremely low surface energy and therefore have properties such as water and oil repellency, chemical resistance, lubricity, mold release properties, stain resistance, etc. By utilizing these properties, compounds containing perfluoropolyether groups are widely used industrially as oil repellents for equipment, mold release agents, cosmetics, protective films, etc.

[0007] Japanese Patent Publication No. 2-45572 Publication No. 3-78244 Publication No. 4-4923 Publication No. 4-11366

[0008] An object of the present invention is to provide a perfluoropolyether phosphate ester or a salt thereof that can impart excellent oil repellency, durability, and releasability to a substrate, and a method for producing the same.

[0009] The perfluoropolyether phosphate ester according to this embodiment is a perfluoropolyether phosphate ester represented by the following general formula (1). (In the above general formula (1), n ​​is an integer of 1 to 20.)

[0010] The perfluoropolyether phosphate salt according to this embodiment is a perfluoropolyether phosphate salt represented by the following general formula (2). (In the above general formula (2), n is an integer of 1 to 20, and M １ is an alkali metal, ammonium base or organic amine base; M ２ is a hydrogen atom, an alkali metal, an ammonium base, or an organic amine base.

[0011] The method for producing a perfluoropolyether phosphate ester or a salt thereof according to this embodiment comprises the steps of: a) reacting a perfluoropolyether alcohol represented by the general formula (4) with a fluorocarbon; (wherein n is an integer of 1 to 20) in the presence of phosphorus oxychloride; and b) reacting the compound represented by general formula (5) obtained in step a). (wherein n is an integer of 1 to 20), and c) optionally a step of neutralizing the perfluoropolyether phosphate ester obtained in step b), wherein the equivalent ratio of the phosphorus oxychloride to the perfluoropolyether alcohol is 10 or more and 20 or less in terms of molar ratio.

[0012] According to the present invention, it is possible to provide a perfluoropolyether phosphate ester or a salt thereof that can impart excellent oil repellency, durability, and releasability to a substrate, and a method for producing the same.

[0013] <Perfluoropolyether phosphate or its salt> Hereinafter, an embodiment of the present invention will be described in detail. The perfluoropolyether phosphate of the present invention is represented by the following general formula (1), and is a perfluoropolyether phosphate ester having a single perfluoropolyether (PFPE) chain. Such perfluoropolyether phosphate ester has improved hydrophilicity compared to a two-chain perfluoropolyether phosphate ester having two hydrophobic PFPE chains, so it can be dispersed in water without using an organic solvent, reducing the burden on the environment. Furthermore, when this dispersion is applied to various substrate surfaces, such as metal surfaces, the number of hydroxyl groups on the phosphorus atom coordinated on the metal surface increases from one to two, resulting in stronger bonding of the hydroxyl groups on the metal surface. Therefore, the durability of the film formed by coating and curing the perfluoropolyether phosphate ester on a substrate is improved.

[0014]

[0015] In the general formula (1), n ​​is an integer of 1 to 20, preferably 1 to 10, and more preferably 2 to 6.

[0016] The perfluoropolyether phosphate of the present invention may be in the form of a salt from the viewpoint of workability. Such a perfluoropolyether phosphate salt is represented by the following general formula (2).

[0017]

[0018] In the general formula (2), n is an integer of 1 to 20, preferably 1 to 10, and more preferably 2 to 6. １ is an alkali metal, an ammonium base or an organic amine base, M ２ is a hydrogen atom, an alkali metal, an ammonium base, or an organic amine base. １ and M ２ When is an alkali metal, ammonium base, or organic amine base, they may be the same or different.

[0019] M １ and M ２ In the formula, examples of the alkali metal include sodium (Na), potassium (K), and lithium (Li). Examples of the ammonium base include NH ４ ＋ Examples of the organic amine base include ammonium salts substituted with an alkyl group such as monoethyl, monoisopropyl, diethyl, dicyclohexyl, or triethyl, or a cycloalkyl group having 3 to 7 carbon atoms, and ammonium salts substituted with a hydroxyalkyl group such as monoethanol, diethanol, triethanol, or diisopropanol. Examples of the organic amine base include pyridine, DMAP (4-dimethylaminopyridine), DBU (diazabicycloundecene), DBN (diazabicyclononene), imidazole, and polyalkoxyalkylamine.

[0020] In addition to the durability described above, the perfluoropolyether phosphate ester or its salt of the present invention exhibits excellent oil repellency when applied to the surface of various substrates, preferably metal surfaces, and the oil repellency does not significantly decrease even after durability tests.Furthermore, when a resin molded product is released from a mold coated with a solution containing the perfluoropolyether phosphate ester or its salt of the present invention, the release load is small and the release property is excellent.Therefore, the perfluoropolyether phosphate ester or its salt of the present invention can be used as an active ingredient in surface treatment agents and release agents.In addition, the perfluoropolyether phosphate ester has good durability when coated on a substrate and cured, so it is also effective as a coating agent.

[0021] The perfluoropolyether phosphate ester or its salt contained in the surface treatment agent, release agent, or coating agent may be diluted with an organic solvent for economical and workability reasons. Examples of such organic solvents include fluorine-containing organic solvents such as alcohols such as methanol, ethanol, n-propanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; polyhydric alcohol derivatives such as methyl cellosolve, ethyl cellosolve, methyl carbitol, and ethyl carbitol; and halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, trichloroethylene, perchloroethylene, trichloroethane, trichlorofluoromethane, tetrachlorodifluoroethane, and trichlorotrifluoroethane. Among these, fluorine-containing organic solvents are preferred as the organic solvent. Examples of commercially available fluorine-containing organic solvents include "NOVEC 7200" (manufactured by 3M), "NOVEC 7300" (manufactured by 3M), and "AE-3000" (manufactured by AGC).

[0022] On the other hand, since the perfluoropolyether phosphate ester or its salt is dispersible in water, from the viewpoints of economy, workability, environmental friendliness, etc., the surface treatment agent, release agent or coating agent, particularly the release agent, may contain water but preferably does not contain an organic solvent, such as the organic solvents mentioned above.

[0023] The surface treatment agent, release agent or coating agent containing the perfluoropolyether phosphate ester or its salt is prepared by diluting it with an organic solvent, water or a mixture thereof to give a solution having a solids concentration of 0.01% by weight or more and 30% by weight or less, preferably 0.03% by weight or more and 3% by weight or less.

[0024] Furthermore, when water is used as a solvent for a surface treatment agent, a release agent, or a coating agent, the dispersion containing a perfluoropolyether phosphate ester or a salt thereof and water preferably further contains an organic amine represented by the following general formula (3): By using an organic amine represented by general formula (3) for a perfluoropolyether phosphate ester or a salt thereof having a single PFPE chain, it is possible to prepare a surface treatment agent, a release agent, or a coating agent that can be dispersed in water alone without using an organic solvent.

[0025] R １ -N-(R ２ ) ２ (3)

[0026] In general formula (3), R １ is an alkyl group having 1 to 40 carbon atoms, preferably an alkyl group having 5 to 30 carbon atoms, and more preferably an alkyl group having 12 to 24 carbon atoms. The alkyl group may be linear or branched.

[0027] R ２ Ha-(C ａ H ２ａ O) ｂ -R ３ a is an integer of 1 to 22, b is an integer of 1 to 100, and R ３is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. a is preferably an integer of 1 to 10, and more preferably an integer of 2 or 3. b is preferably an integer of 1 to 100, and more preferably an integer of 1 to 30. R ３ When R is a hydrocarbon alkyl group having 1 to 12 carbon atoms, the alkyl group may be linear or branched. ３ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0028] Examples of such organic amines include higher aliphatic amine derivatives such as polyoxyethylene stearylamine, polyoxyethylene oleylamine, and polyoxyethylene laurylamine.

[0029] The surface treatment agent, release agent or coating agent may contain, as necessary, various surfactants such as ionic and nonionic surfactants for improving wettability, silicone oil or silicone varnish for improving lubricity, etc.

[0030] Substrates that can be treated with the above-mentioned surface treatment agents, release agents, or coating agents include substrates made of various materials such as metals and their oxides, porcelain, ceramics, resins, plastics, glass, and rubber. Specific examples of substrates for surface treatment agents and coating agents include molded products of metals, metal oxides, and ceramics, while examples of substrates for release agents include molds and molded products of resins and rubber. The thickness of the cured coating formed on the surface of the above-mentioned various substrates is not particularly limited and can be appropriately selected depending on the type of substrate.

[0031] <Method for producing perfluoropolyether phosphate or its salt> The perfluoropolyether phosphate in the present invention is produced by reacting a perfluoropolyether alcohol having a specific structure in the presence of phosphorus oxychloride, and hydrolyzing the resulting compound.In addition, in the reaction between perfluoropolyether alcohol and phosphorus oxychloride, a large excess of phosphorus oxychloride is used relative to the perfluoropolyether alcohol.Specifically, phosphorus oxychloride is used in an amount of 10 or more and 20 or less equivalents relative to the perfluoropolyether alcohol in terms of molar ratio.Thereby, perfluoropolyether phosphate chloride with a single PFPE chain is selectively synthesized over perfluoropolyether phosphate chloride with a double PFPE chain, and then hydrolysis can produce perfluoropolyether phosphate ester represented by the above general formula (1).In addition, by neutralizing the obtained perfluoropolyether phosphate ester represented by the general formula (1), perfluoropolyether phosphate ester salt represented by the above general formula (2) can be formed.

[0032] The method for producing a perfluoropolyether phosphate or a salt thereof of the present invention comprises the steps of: a) reacting a perfluoropolyether alcohol represented by the following general formula (4) in the presence of phosphorus oxychloride; b) hydrolyzing the compound represented by the general formula (5) obtained in step a); and c) optionally neutralizing the perfluoropolyether phosphate obtained in step b). Each step will be described in detail below.

[0033] (Perfluoropolyether alcohol) In step a), a perfluoropolyether alcohol represented by the following general formula (4) is used as a raw material. Such perfluoropolyether alcohol has a hydroxyl group at the end of the molecule, and this hydroxyl group reacts with phosphorus oxychloride to synthesize perfluoropolyether phosphate chloride.

[0034]

[0035] In the general formula (4), n is an integer of 1 to 20, preferably 1 to 10, and more preferably 2 to 6.

[0036] (Phosphorus oxychloride) In step a), phosphorus oxychloride is used and reacted with the perfluoropolyether alcohol represented by the general formula (4) so ​​that the molar equivalent ratio of phosphorus oxychloride to perfluoropolyether alcohol is 10 to 20. The molar equivalent ratio of phosphorus oxychloride to perfluoropolyether alcohol is preferably 13 to 18, more preferably 15 to 17.

[0037] In step a), perfluoropolyether alcohol is reacted in the presence of phosphorus oxychloride at a temperature of 100°C to 120°C for 10 to 30 hours. Next, low boiling points are removed under reduced pressure at an internal temperature of 90°C to 110°C, followed by vacuum distillation to form a chloride of a predetermined perfluoropolyether phosphate ester. In step a), calcium chloride as a dehydrating agent may not be used.

[0038] In step b), the compound represented by the following general formula (5) obtained in step a) is hydrolyzed to form the perfluoropolyether phosphate ester represented by the above general formula (1). Water is slowly added dropwise to the compound represented by general formula (5) so that the internal temperature does not exceed 60°C, thereby initiating the hydrolysis reaction. Water is then removed from the resulting reaction mixture under reduced pressure to obtain the perfluoropolyether phosphate ester represented by general formula (1).

[0039]

[0040] In the general formula (5), n is an integer of 1 to 20, preferably 1 to 10, and more preferably 2 to 6.

[0041] In step c), the perfluoropolyether phosphate ester represented by general formula (1) obtained in step b) can be optionally neutralized to form a perfluoropolyether phosphate ester salt represented by general formula (2). The salt formation is generally carried out by titrating the perfluoropolyether phosphate ester represented by general formula (1) with a salt-forming reactant such as sodium hydroxide, ammonium hydroxide, triethylamine, morpholine, triethanolamine, or tris(2-hydroxyethyl) while checking the equivalence point with pH. This results in the formation of a monovalent alkali metal salt, ammonium salt, or organic amine salt, such as that shown in the perfluoropolyether phosphate ester salt represented by general formula (2).

[0042] Based on the above embodiments, the present invention relates to the following [1] to [8]: [1] A perfluoropolyether phosphate ester represented by general formula (1). (In the above general formula (1), n ​​is an integer of 1 to 20.) [2] A perfluoropolyether phosphate ester salt represented by general formula (2): (In the above general formula (2), n is an integer of 1 to 20, and M １ is an alkali metal, ammonium base or organic amine base; M ２ is a hydrogen atom, an alkali metal, an ammonium base or an organic amine base.) [3] A surface treatment agent comprising the perfluoropolyether phosphate ester according to [1] above or the perfluoropolyether phosphate ester salt according to [2] above. [4] A coating agent comprising the perfluoropolyether phosphate ester according to [1] above or the perfluoropolyether phosphate ester salt according to [2] above. [5] A release agent comprising the perfluoropolyether phosphate ester according to [1] above or the perfluoropolyether phosphate ester salt according to [2] above. [6] The release agent according to [4] above, further comprising water. [7] The release agent according to [6] above, further comprising an organic amine represented by general formula (3). R １ -N-(R ２ ) ２ (3) (In the above general formula (3), R１ is an alkyl group having 1 to 22 carbon atoms, and R ２ Ha-(C ａ H ２ａ O) ｂ -R ３ wherein a is an integer from 1 to 22, b is an integer from 1 to 100, and R ３ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.) [8] a) Perfluoropolyether alcohol represented by general formula (4) (wherein n is an integer of 1 to 20) in the presence of phosphorus oxychloride; and b) reacting the compound represented by general formula (5) obtained in step a). (wherein n is an integer of 1 to 20), and c) optionally a step of neutralizing the perfluoropolyether phosphate ester obtained in step b), wherein the equivalent ratio of the phosphorus oxychloride to the perfluoropolyether alcohol is 10 or more and 20 or less in terms of molar ratio. [9] The production method according to the above item [8], wherein calcium chloride is not used in step a).

[0043] Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, but includes all aspects encompassed by the concept of the present invention and the scope of the claims, and can be modified in various ways within the scope of the present invention.

[0044] Examples of the present invention will be described below, but the present invention is not limited to these examples as long as they do not deviate from the spirit of the present invention. Furthermore, unless otherwise specified, room temperature is assumed to be within the range of 20°C ± 5°C.

[0045] Example 1 A 2-L flask was charged with 1,226 g (approximately 8.0 mol) of phosphorus oxychloride and stirred, and then 500 g (approximately 0.51 mol) of perfluoropolyether alcohol (PO-6-OH) having the following structural formula was added, and the internal temperature was raised to 110°C, followed by stirring for 24 hours. １The disappearance of PO-6-OH was confirmed by H-NMR, and the reaction was terminated. Subsequently, low boiling points were removed under a reduced pressure of 4.5 kPa at an internal temperature of 90 to 110°C, and then the reduced pressure was reduced to 0.1 KPa and vacuum distillation was carried out at an internal temperature of 160°C to obtain 468.9 g (yield 85%) of perfluoropolyether phosphoric acid chloride (PO-6-PAECl) having the following structural formula and a purity of 99.2 GC%.

[0046]

[0047] Thereafter, 468.9 g of the obtained PO-6-PAEC1 was placed in a 1 L flask, and 3.9 g of water was slowly added dropwise thereto so that the internal temperature did not exceed 60° C., followed by stirring for 24 hours. １ The disappearance of PO-6-PAEC1 was confirmed by H-NMR, and the reaction was terminated. Subsequently, dehydration was carried out under reduced pressure of 0.1 kPa at an internal temperature of 50°C, yielding 404.4 g of a transparent liquid (yield 90%). １ H-NMR and １９ F-NMR measurement and spectrum analysis revealed that the obtained liquid was the target product, perfluoropolyether phosphate ester (PO-6-PAE) having the following structural formula:

[0048]

[0049] 1 H NMR (CDCl3, TMS): ppm 4.4ppm(CFCH2) 10.9ppm(OH) 19 ​F NMR (CDCl3, C6F6): ppm -85.3ppm(CF3) -83.0~-85.3ppm(CF3CF2CF2) -83.0~-85.3ppm CH2CFCF3(OCF2CFCF3) -83.0~-85.3ppm CH2CFCF3(OCF2CFCF3) -83.0~-85.3ppm CH2CFCF3(OCF2CFCF3) -132.8ppm(CF3CF2) -137.6ppm CH2CFCF3(OCF2CFCF3) -147.5ppm CH2CFCF3(OCF2CFCF3)

[0050] Example 2 A 500 mL flask was charged with 215 g (approximately 1.4 mol) of phosphorus oxychloride and stirred, and then 124 g (approximately 0.085 mol) of perfluoropolyether alcohol (PO-L-OH) having the following structural formula was added, and the internal temperature was raised to 110°C and stirred for 24 hours. １ The disappearance of PO-L-OH was confirmed by H-NMR, and the reaction was terminated. Subsequently, low boiling points were removed under a reduced pressure of 4.5 kPa at an internal temperature of 90 to 110°C, and then the reduced pressure was reduced to 0.1 KPa and the reaction mixture was distilled under reduced pressure at an internal temperature of 100°C to obtain 127 g (yield 78%) of perfluoropolyether phosphate chloride (PO-L-PAECl) having the following structural formula:

[0051]

[0052] Thereafter, 127 g of the obtained PO-L-PAEC1 was placed in a 200 mL flask, and 3.9 g of water was slowly added dropwise thereto so that the internal temperature did not exceed 60° C., followed by vigorous stirring at an internal temperature of 50° C. for 24 hours. １ The disappearance of PO-L-PAEC1 was confirmed by H-NMR, and the reaction was terminated. Subsequently, dehydration was carried out under reduced pressure of 0.1 kPa at an internal temperature of 50°C, yielding 94 g of a brown, opaque liquid (yield 77%). １ H-NMR and １９F-NMR measurement and spectrum analysis showed that the spectral assignments were the same as those of PO-6-PAE, and the obtained viscous liquid was the target product, a perfluoropolyether phosphate ester (PO-L-PAE) having the following structural formula:

[0053]

[0054] [Contact Angle Test] Example 3 0.5 g of PO-6-PAE obtained in Example 1 was added to 99.5 g of a fluorine-containing organic solvent (NOVEC 7200, manufactured by 3M) and stirred for about 30 minutes to prepare Preparation Solution A-1.

[0055] A chrome-plated copper plate test piece (25 × 75 × 1.2 mm) was dip-coated in this Preparation Solution A-1 under conditions of an immersion time of 5 seconds and a withdrawal rate of 2 mm / sec, and then baked at 150°C for 1 hour. The contact angle of the resulting coating film was measured to evaluate the oil repellency and durability. The oil repellency was evaluated by the static contact angle of the resulting coating film using hexadecane, and the durability was evaluated by applying 20 g / cm of hexadecane to the coating film using a 100% cotton cloth. ２ After 2000 sliding cycles under a load of 1000 psi, the static contact angle was measured using hexadecane. The results are shown in Table 1.

[0056] Example 4 The same procedures as in Example 3 were carried out, except that Preparation Solution A-2 was prepared using PO-L-PAE obtained in Example 2 instead of PO-6-PAE, and the contact angle of the coating film obtained using this was measured to evaluate the oil repellency and durability. The results are shown in Table 1.

[0057] Comparative Example 1 Instead of PO-6-PAE, a perfluoropolyether phosphate ester (R ｆ C ６ The same procedures as in Example 3 were carried out except that Preparation Solution A-3 was prepared using the same acrylic acid as in Example 1, and the contact angle of the coating film obtained using this was measured to evaluate the oil repellency and durability. The results are shown in Table 1. ｆ C ６ The PAE contains perfluoropolyether phosphate ester with m=2: perfluoropolyether phosphate ester with m=1 in a ratio of 100:0 to 20:80.

[0058]

[0059]

[0060] As shown in Table 1, in Examples 3 and 4, the resulting coating films had a high initial contact angle of 73°, excellent oil repellency, and excellent durability, as the oil repellency did not decrease significantly even after the durability test. On the other hand, in Comparative Example 1, the resulting coating film had an initial contact angle of about 60°, lower oil repellency than in Examples 3 and 4, and the oil repellency decreased significantly after the durability test.

[0061] [Mold Release Test] Example 5 To 0.1 g of PO-6-PAE obtained in Example 1, 65 g of isopropanol and 34.7 g of water were added, and then 0.2 g of triethylamine was added thereto with stirring, and the mixture was stirred for about 30 minutes to prepare a mold release agent B-1.

[0062] The release agent B-1 was sprayed onto a stainless steel mold (45 mm diameter, 50 mm depth) and dried at 120°C for 5 minutes. Furthermore, 100 parts by weight of a polyurethane prepolymer ("Coronate C-4090" manufactured by Nippon Polyurethane Co., Ltd.) heated to 80°C and 12.8 parts by weight of a heat-melted curing agent (methylene bis-o-chloroaniline "Iharacuamine MT" manufactured by Ihara Chemical Co., Ltd.) were stirred and mixed while avoiding the entrapment of air bubbles to prepare a prepolymer mixture. This prepolymer mixture was then poured into a stainless steel mold coated with the release agent B-1 and cured by heating at 120°C for 1 hour to form a polyurethane molded product. A hook previously installed in the center of the mold cavity for removing the polyurethane molded product was then pulled, and the mold release resistance load when removing the polyurethane molded product from the mold was measured.

[0063] After measuring the release resistance load in this manner, the number of times (number of releases) that the polyurethane molded article could be released from the mold under a release load of 50 N or less with one application of the release agent B-1 was measured. The results are shown in Table 2.

[0064] Example 6 To 0.1 g of the PO-L-PAE obtained in Example 2, 99.7 g of water and polyoxyethylene stearylamine ("Nymeen S-220", manufactured by NOF Corporation) were added, and the mixture was stirred for about 30 minutes to prepare a release agent B-2.

[0065] The same procedure as in Example 5 was carried out except that the release agent B-2 was used instead of the release agent B-1, and the number of releases was measured. The results are shown in Table 2.

[0066] Example 7 To 0.1 g of the PO-L-PAE obtained in Example 2, 65 g of isopropanol and 34.7 g of water were added, and then 0.2 g of triethylamine was added with stirring, followed by stirring for about 30 minutes to prepare a release agent B-3.

[0067] The same procedure as in Example 5 was carried out except that the release agent B-3 was used instead of the release agent B-1, and the number of releases was measured. The results are shown in Table 2.

[0068] Comparative Example 2: R obtained in Comparative Example 1 ｆ C ６ To 0.1 g of -PAE, 65 g of isopropanol and 34.7 g of water were added, and then 0.2 g of triethylamine was added with stirring, followed by stirring for about 30 minutes to prepare release agent B-4.

[0069] The same procedure as in Example 5 was carried out except that release agent B-4 was used instead of release agent B-1, and the number of releases was measured. The results are shown in Table 2.

[0070] Comparative Example 3 The above-described mold release test was carried out without using a mold release agent.

[0071]

[0072] As shown in Table 2, in Examples 5 to 7, the polyurethane molded articles could be released from the SUS mold many times, demonstrating excellent releasability. In particular, in Example 2, the number of releases was 30, demonstrating significantly excellent releasability. On the other hand, in Comparative Example 2, the number of releases was only two, demonstrating poor releasability. Furthermore, in Comparative Example 3, the polyurethane molded article adhered to the SUS mold and could not be released.

Claims

1. A perfluoropolyether phosphate ester represented by general formula (1) or a perfluoropolyether phosphate salt represented by general formula (2). (In the above general formulas (1) and (2), n is an integer of 1 to 20, and M １ is an alkali metal, an ammonium base or an organic amine base; M ２ is a hydrogen atom, an alkali metal, an ammonium base, or an organic amine base.

2. A surface treatment agent comprising the perfluoropolyether phosphate ester or perfluoropolyether phosphate ester salt according to claim 1.

3. A coating agent comprising the perfluoropolyether phosphate ester or perfluoropolyether phosphate ester salt according to claim 1.

4. A release agent comprising the perfluoropolyether phosphate ester or perfluoropolyether phosphate salt according to claim 1.

5. The release agent according to claim 4, further comprising water.

6. The release agent according to claim 4, further comprising an organic amine represented by general formula (3). １ -N-(R ２ ) ２ (3) (In the above general formula (3), R １ is an alkyl group having 1 to 22 carbon atoms; R ２ Ha-(C ａ H ２ａ O) ｂ -R ３ wherein a is an integer from 1 to 22, b is an integer from 1 to 100, and R ３ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

7. a) Perfluoropolyether alcohol represented by general formula (4) (wherein n is an integer of 1 to 20) in the presence of phosphorus oxychloride; and b) reacting the compound represented by general formula (5) obtained in step a). (wherein n is an integer of 1 to 20) and c) optionally, a step of neutralizing the perfluoropolyether phosphate obtained in step b), wherein the equivalent ratio of the phosphorus oxychloride to the perfluoropolyether alcohol is 10 or more and 20 or less in terms of molar ratio.

8. The method according to claim 7, wherein calcium chloride is not used in step a).

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