PERFLUOROPOLYETHER PHOSPHATE ESTER, METHOD FOR PRODUCING THE SAME, AND SURFACE TREATMENT AGENT COMPRISING THE SAME AS ACTIVE INGREDIENT

Abstract

A perfluoropolyether phosphate ester represented by the general formula:

[C.sub.3F.sub.7O{CF(CF.sub.3)CF.sub.2O}.sub.nCF(CF.sub.3)CH.sub.2O].sub.2PO(OH)

(wherein n is an integer of 1 to 20). This compound is obtained by reacting a perfluoropolyether alcohol represented by the general formula:

C.sub.3F.sub.7O{CF(CF.sub.3)CF.sub.2O}.sub.nCF(CF.sub.3)CH.sub.2OH

(wherein n is an integer of 1 to 20) with phosphorus oxychloride, and hydrolyzing the obtained compound represented by the general formula:

[C.sub.3F.sub.7O{CF(CF.sub.3)CF.sub.2O}.sub.nCF(CF.sub.3)CH.sub.2O].sub.2POCl

(wherein n is an integer of 1 to 20). Moreover, the perfluoropolyether phosphate ester or a salt thereof forms a surface treatment agent comprising the perfluoropolyether phosphate ester or a salt thereof as an active ingredient.

Claims

1-7. (canceled)

8. A method for producing a perfluoropolyether phosphate ester represented by the general formula:
[C.sub.3F.sub.7O{CF(CF.sub.3)CF.sub.2O}.sub.nCF(CF.sub.3)CH.sub.2O].sub.2PO(OH) wherein n is an integer of 1 to 20), comprising reacting a perfluoropolyether alcohol represented by the general formula: C.sub.3F.sub.7O{CF(CF.sub.3)CF.sub.2O}.sub.nCF(CF.sub.3)CH.sub.2OH wherein n is an integer of 1 to 20, with phosphorus oxychloride in the presence of a calcium chloride dehydrating agent and hydrolyzing the obtained compound represented by the general formula:
[C.sub.3F.sub.7O{CF(CF.sub.3)CF.sub.2O}.sub.nCF(CF.sub.3)CH.sub.2O].sub.2POCl wherein n is an integer of 1 to 20.

9. A mold release agent, comprising the perfluoropolyether phosphate ester represented by the general formula:
[C.sub.3F.sub.7O{CF(CF.sub.3)CF.sub.2O}.sub.nCF(CF.sub.3)CH.sub.2O].sub.2PO(OH) wherein n is an integer of 1 to 20, or a salt thereof as an active ingredient.

10. The mold release agents according to claim 9, which is prepared as an organic solvent solution.

11. The mold release agents according to claim 10, wherein the organic solvent solution is a fluorine-containing organic solvent solution.

Description

EXAMPLES

[0029] The following describes the present invention with reference to Examples.

Example 1

[0030] (1) In a flask with a capacity of 2 L, 1226 g (8.0 mol) of phosphorus oxychloride and 5.5 g (0.05 mol) of calcium chloride were charged, and the mixture was stirred for 10 minutes. Then, 1000 g (1.0 mol) of the following compound:

CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.4CF(CF.sub.3)CH.sub.2OH [PO-6-OH]

was added. The internal temperature was raised to 110° C., and the mixture was stirred for 24 hours. It was confirmed by .sup.1H NMR that PO-6-OH disappeared, and the reaction was completed.

[0031] After removing low boiling substances at an internal temperature of 90 to 110° C. under a reduced pressure of 4.5 KPa, the degree of reduced pressure was set to 0.1 KPa, and vacuum distillation was performed at an internal temperature of 160° C., thereby obtaining 937.9 g (yield: 85%) of the following compound:

[CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.4CF(CF.sub.3)CH.sub.2O].sub.2POCl [PO6PAECl]

having a purity of 99.2GC %.

[0032] (2) 937.9 g of the obtained PO6PAECl was charged into a flask with a capacity of 1 L, 7.8 g of water was slowly added dropwise so that the internal temperature did not exceed 60° C., and the mixture was vigorously stirred at an internal temperature of 50° C. After stirring for 24 hours, it was confirmed by .sup.1H NMR that PO6PAECl disappeared, and the reaction was completed.

[0033] Dehydration was performed at an internal temperature of 50° C. under a reduced pressure of 0.1 KPa, thereby obtaining 808.9 g (yield: 90%) of a transparent liquid. .sup.1H NMR and .sup.19F NMR measurements were performed, and it was confirmed from the spectrum assignments that it was the desired product.

[CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.4CF(CF.sub.3)CH.sub.2O].sub.2PO(OH) [PO6PAE]

[CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.4CF(CF.sub.3)CH.sub.2O]PO(OH).sub.2

([CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.4CF(CF.sub.3)CH.sub.2O]PO(OH).sub.2 was in a small amount and inseparable.) [0034] .sup.1H NMR (CDCl.sub.3, TMS): ppm 4.4 ppm (CFCH.sub.2) [0035] 10.9 ppm (OH) [0036] .sup.19F NMR (CDCl.sub.3, C.sub.6F.sub.6): ppm −85.3 ppm (CF.sub.3) [0037] −83.0 to −85.3 ppm (CF.sub.3CF.sub.2CF.sub.2) [0038] −83.0 to −85.3 ppm CH.sub.2CFCF.sub.3(OCF.sub.2CFCF.sub.3) [0039] −83.0 to −85.3 ppm CH.sub.2CFCF.sub.3(OCF.sub.2CFCF.sub.3) [0040] −83.0 to −85.3 ppm CH.sub.2CFCF.sub.3(OCF.sub.2CFCF.sub.3) [0041] −132.8 ppm (CF.sub.3CF.sub.2) [0042] −137.6 ppm CH.sub.2CFCF.sub.3(OCF.sub.2CFCF.sub.3) [0043] −147.5 ppm CH.sub.2CFCF.sub.3(OCF.sub.2CFCF.sub.3)

Example 2

[0044] (1) In a flask with a capacity of 500 ml, 215 g (1.4 mol) of phosphorus oxychloride and 0.94 g (0.0085 mol) of calcium chloride were charged, and the mixture was stirred for 10 minutes. Then, 300 g (0.17 mol) of the following compound:

CF.sub.3CF.sub.2CF.sub.2O {CF(CF.sub.3)CF.sub.2O}.sub.7CF(CF.sub.3)CH.sub.2OH [PO-L-OH]

was added. The internal temperature was raised to 110° C., and the mixture was stirred for 24 hours. It was confirmed by .sup.1H NMR that PO-L-OH disappeared, and the reaction was completed.

[0045] After removing low boiling substances at an internal temperature of 90 to 110° C. under a reduced pressure of 4.5 KPa, the degree of reduced pressure was set to 0.1 KPa, and vacuum distillation was performed at an internal temperature of 100° C., thereby obtaining 255 g (yield: 78%) of the following compound:

[CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.7CF(CF.sub.3)CH.sub.2O].sub.2POCl [POLPAECl].

[0046] (2) 255 g (0.13 mol) of the obtained POLPAECl was charged into a flask with a capacity of 300 mL, 7.8 g of water was slowly added dropwise so that the internal temperature did not exceed 60° C., and the mixture was vigorously stirred at an internal temperature of 50° C. After stirring for 24 hours, it was confirmed by .sup.1H NMR that POLPAECl disappeared, and the reaction was completed.

[0047] Dehydration was performed at an internal temperature of 50° C. under a reduced pressure of 0.1 KPa, thereby obtaining 189 g (yield: 77%) of a brown cloudy liquid. The spectrum assignments of .sup.1H NMR and .sup.19F NMR measurements were the same as those in Example 1.

[CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.7CF(CF.sub.3)CH.sub.2O].sub.2PO(OH) [POLPAE]

[CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.7CF(CF.sub.3)CH.sub.2O]PO(OH).sub.2

([CF.sub.3CF.sub.2CF.sub.2O{CF(CF.sub.3)CF.sub.2O}.sub.7CF(CF.sub.3)CH.sub.2O]PO(OH).sub.2 was in a small amount and inseparable.)

Example 3

[0048] 0.5 g of PO6PAE obtained in Example 1 was added to 99.5 g of a fluorine-containing organic solvent (NOVEC 7200, produced by 3M Company), and the mixture was stirred for about 30 minutes to prepare a preparation liquid A-1.

[0049] A chrome-plated copper plate test piece (25×75×1.2 mm) was dip-coated in the prepared solution A-1 for a dipping time of 5 seconds, a pulling speed of 2 mm/sec, and baking was performed at 150° C. for 1 hour.

[0050] The initial performance (the static contact angle was measured using hexadecane) was 73°, and the durability performance (sliding was performed 2000 times while applying a load of 20 g/cm.sup.2 to the test piece using 100% cotton cloth, and then the static contact angle was measured using hexadecane) was 65°.

Example 4

[0051] In Example 3, POLPAE obtained in Example 2 was used in place of PO6PAE to prepare a preparation liquid B-2, and the initial performance and durability performance were measured using this liquid. As a result, the obtained values were 73° and 66°, respectively.

Comparative Example 1

[0052] In Example 3, the following compound:

(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2O).sub.2PO(OH) [C6PAE]

(CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2O)PO(OH).sub.2

((CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2O)PO(OH).sub.2 was in a small amount and inseparable.)
was used in place of PO6PAE to prepare a preparation liquid C-3, and the initial performance and durability performance were measured using this liquid. As a result, the obtained values were 60° and 30°, respectively.

Example 5

[0053] 65 g of isopropanol and 34.7 g of water were added to 0.1 g of PO6PAE obtained in Example 1, 0.2 g of triethylamine was added while stirring, and the mixture was stirred for about 30 minutes, thereby preparing a surface treatment agent A-4.

[0054] In an aluminum mold (diameter: 45 mm, depth: 50 mm) spray-coated with the surface treatment agent A-4 and preheated to 80° C., 100 parts by weight of polyurethane prepolymer (Coronate C-4090, produced by Nippon Polyurethane Industry Co., Ltd.) heated to 80° C. and 12.8 parts by weight of heated and melted methylenebis-o-chloroaniline curing agent (Iharacuamine MT, produced by Ihara Chemical Industry Co., Ltd.) were injected by stirring and mixing while avoiding inclusion of bubbles.

[0055] Before heat curing, a hook for removing the cured molded article was installed in the center of the injection part. After heat curing the injected material at 120° C. for 1 hour, the mold release load was measured when the molded article was removed from the mold by pulling the hook. The result was 10 N.

[0056] Further, after determining the mold release properties in this manner, the mold release agent (surface treatment agent A-4) was applied once, and the number of mold releases was measured at a mold release load of 50 N or less. As a results, mold release was possible up to 9 times.

Example 6

[0057] In Example 5, the surface treatment agent A-5 prepared using POLPAE obtained in Example 2 was used in place of the surface treatment agent A-4. As a result, the mold release properties were 10 N, and the mold release life was 11 times.

Comparative Example 2

[0058] In Example 5, the preparation liquid C-5 prepared using C6PAE obtained in Comparative Example 1 was used in place of the surface treatment agent A-4. As a result, the mold release properties were 15 N, and the mold release life was 2 times.

Comparative Example 3

[0059] In Example 5, a mold release test was performed using an aluminum mold to which a surface treatment agent was not spray-coated. As a result, the resulting polyurethane molded article was closely attached to the mold and could not be released from the mold.