JPS59204197A - Production of fluorine-containing phosphoric acid ester composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition useful as an oil repellent for paper, etc., economically in an industrial scale, by treating an aqueous medium containing the reaction product of a specific polyfluoroalkyl phosphate and an alkanolamine compound with a homogenizer and ultrasonic vibrator, etc. CONSTITUTION:The objective composition is obtained in a highly dispersed state, by reacting a polyfluoroalkyl phosphate with an alkanolamine compound, and treating the aqueous medium containing the resultant alkanolamine salt of formula [Rf is 5-14C perfluoroalkyl; R is 1-4C bivalent alkylene; R<1>, R<2> and R<3> and H, CH2CH2OH, CH2CH2CH2OH, CH(CH3)CH2OH, etc.; average of the number m is 1-25] with a homogenizer and/or an ultrasonic vibrator.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves the reaction of a polyfluoroalkyl phosphate with an alkanolamine, and the use of a "homogenizer" and/or an ultrasonic irradiation device to obtain an aqueous solution of the resulting alkanolamine salt for good dispersion. The present invention relates to a method for producing a fluorine-containing phosphoric acid ester composition.

The alkanolamine salt of polyfluoroalkyl phosphate obtained according to the present invention is known to have properties useful as a strong oil agent for textile fibers, paper, leather, ceramics, etc., or as a water-soluble surfactant. . The present applicant has already reported in Japanese Patent Publication No. 1987-29875 that a fluorine-containing phosphoric acid ester obtained by reacting a polyfluoroalkyl phosphate with ethanolamines in a large amount of water greatly improves distillate performance. We have reported that this can be significantly improved. In addition, in order to stabilize the obtained fluorine-containing phosphoric acid ester in water in a proper dispersion state, the temperature must be 80°C.
It was also reported that it is preferable to hold the above condition for about 5 to 8 hours, and that if a stable dispersion state cannot be obtained, it will have a negative effect on oil repellency. The present inventors, based on the recognition that the dispersibility and stability of the fluorine-containing phosphate ester in a water bath liquid have a large effect on oil repellency, attempted to improve the method for producing the fluorine-containing phosphate ester. As a result of extensive research, we aimed to produce an alkanolamine salt o water i solution.
It was found that by treating with a "homogenizer" and/or irradiating with ultrasonic waves, it is possible to easily form an aqueous solution with good dispersibility in a short period of time, and the dispersion stability thereof is also excellent.

That is, the present invention is based on the general formula (wherein Rf is a perfluoroalkyl group having 5 to 14 carbon atoms, R is a divalent alkynone group having 1 to 4 carbon atoms, and Bl, R2, and R3 are hydrogen atoms) Or -C!H20H
20H, -OH, 0H20H, OH, -0H (OH3)
cH20H.

-C(OH3) 31 is 6D, and m represents the number of average values 1 to z5. The present invention relates to a method for producing a fluorine-containing phosphate ester composition, which comprises treating an aqueous medium containing an alkanolamine salt represented by the following with a homogenizer and/or ultrasonic waves.

In the production method of the general formula (1), the reaction of polyfluor, t0fluor and oxyno-10 phosphorus, and the reaction of polyfluoroalkyl phosphate and alkanolamines are all carried out in the presence of water, and the obtained Preferably, the alkanolamine salt is also in the form of an aqueous solution. If an organic solvent is contained, poor oil repellency is observed. The dispersibility of an alkanolamine salt in an aqueous solution, which affects oil resistance, can be determined by the viscosity of the aqueous solution and the transparency after dilution. or,
Regarding dispersion stability, it is characterized by freeze stability, which means that the uniform dispersion state is not impaired even after repeated freezing and thawing, and by the fact that suspended matter such as scum is not observed when diluted with hard water. can be determined. Uniform dispersibility and dispersion stability are important for improving oil repellency. For example, when external additives are applied to oil-resistant paper, the generation of floating substances such as scum can lead to contamination of the paper surface. For,
Dispersion stability is extremely important depending on the object to be treated with oil repellency.

In the production method of the general formula (1), first the polyfluoroalcohol and the phosphorus oxyhalide are reacted with the addition of water, and the molar ratio of the polyfluoroalcohol/phosphorus oxyhalide/water is 1. 0~2.5/1/
[lL 2-2.0, preferably 1.5-1.8/1
10.5 to 1.0, and the following general formula (1■)
A polyfluoroalkylphosphorogenide represented by is obtained.

() The reaction temperature is 70 to 100°C, preferably 80 to 90°C, and the reaction time is about 1 to 4 hours, preferably about 2 to 3 hours. The partially hydrolyzed polyfluoroalkylphosphohalide has a water/partially hydrolyzate molar ratio of 1.3 to 1, preferably 2.0 to 5 o/1.
/1 to obtain a polyfluoroalkyl phosphate represented by the following general formula (II).

1 (RfRO)mP(OH)3-m...-(III) The reaction temperature is 70-100°C, preferably 80-90°C, and the reaction time is 0.5-4 hours, preferably 1-2 It takes about an hour. In the reaction for producing (IT) and (Ill), it is desirable to carry out the reaction under the introduction of an inert gas such as nitrogen gas to sufficiently drive out by-product hydrogen halide from the reaction system.

The obtained polyfluoroalkyl phosphate is reacted with alkanolamines such as monoethanolamine, jetanolamine, and triethanolamine, each singly or in a mixture of two or more, in the presence of a large amount of water.

The molar ratio of ethanolamines/polyfluoroalkyl phosphate is 1°5~! 11. O/1, preferably 2.
0 to 3.0/1, and 200 weight % or more of water to the polyfluoroalkyl phosphate, preferably 4
A large amount of about 00 to 600% by weight is used to cause the reaction. The reaction is carried out at room temperature to 100°C for 1 to 3 hours, preferably 3 hours.
Carry out at 0-60°C for 1-2 hours. In order to stably disperse the alkanolamine salt thus produced in water, it has conventionally been maintained at 80 to 100°C for about 5 to 8 hours. In the present invention, in order to obtain a highly uniform and stable dispersion state, in addition to this holding operation,
Alternatively, a "homogenizer" and/or an ultrasonic treatment is carried out along with the holding operation. By performing such operations,
Depending on the object to be treated with the alkanolamine salt aqueous solution,
The holding operation can be omitted.

When using a homogenizer, for example, MantonGa
When using Ulin type 15 M, the normal temperature is 40
~95℃, preferably 65~90℃, and the pressure is preferably 10OK17cm2 or more and 300Kg/c
-2 is more preferred ij: 450 K, it is appropriate to process in 7 countries 2. The appropriate number of times of treatment is 1 to 2 degrees, preferably 6 to 12 times.

When irradiating ultrasonic waves, for example, the irradiation time is 0.5 to 6 hours per IKg, preferably 1 to 3 hours; if it is less than this, the irradiation effect will be small, and if it is more than this, the dispersion state will deteriorate. Deteriorate. Ultrasonic intensity is usually 100-4
00 mA is suitable, preferably 200-550 mA
About mA is adopted. Outside this range, the irradiation effect is small. When irradiating the alkanolamine salt aqueous solution with ultrasonic waves, the temperature of the aqueous solution is preferably maintained at 40 to 90°C, preferably 60 to 80°C. The processing time can be shortened by using both methods, such as performing ultrasonic irradiation after homogenizer treatment, or performing homogenizer treatment after ultrasonic irradiation.

The alkanolamine salt water solution treated with ultrasonic waves and/or a homogenizer in this way can suppress the viscosity to an extremely low level even at high U degrees, and can significantly improve oil repellency, freezing stability, etc. The fluorine-containing phosphate ester composition comprising an alkanol aban salt obtained by the present invention is particularly useful for oil repellent purposes. For example, textile fabrics, textile threads, leather, paper, plastic sheets, wood,
It is used in the oil-repellent treatment of various solid materials such as ceramics, clays, etc. and articles made therefrom, such as clothing, wallpaper, paper bags, cardboard boxes, porous ceramics, etc. It is particularly effective for oil-repellent treatment of wrapping paper or packaging containers for oil-based foods such as margarine, donuts, chocolate, and dog food.

In the application for oil repellency, in the general formula (1), m
When m is 2, the efficacy is higher than when m is 1, so when using a mixture with different m values, m is 1.5 on average.
It is desirable to adopt the above. In addition, when m is 3, oil repellency is impaired, but this only has a diluting effect, so as a mixture, the average value of m is 2 or more to 2.5.
It is possible to use up to a certain extent. Therefore, in the present invention, it is possible to employ a material having an average value of 1 to 2.5. The reaction product, ethanolamine salt aqueous solution, usually has a concentration of 5 to 6
It is preferably obtained at a concentration of about 0% by weight, particularly about 15 to 20% by weight.

Of course, the oil repellent treatment can be done by diluting it appropriately. Usually, it is preferable to use an aqueous solution diluted to about 0.6 to 1.0% by weight. When used for the purpose of oil repellency on paper, not only the internal addition method, that is, the method of adding during paper making, but also methods such as buzzing, spraying, brush coating, and dip coating can be adopted.

Next, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited to such explanations.

Example 1 In a 500°-round bottom flask, with slow stirring (C
sFtsC! zH40)tyyP(OH)5380t
was added dropwise over 15 minutes to a water bath solution of jetanolamine 221 and water 3952 heated to 801°C, followed by stirring at 50°C for 2 hours to disperse the mixture. Then, this dispersion homogenizer (M
anton Gaulin 15M) total 15M, temperature 8
The treatment was carried out 10 times at 0°C and a pressure of 500 Kg/cm2.

The viscosity of the product was 6 centepoise (25°C). When this product was diluted to 1% by weight, the light transmittance was 88 degrees, and even when diluted with hard water (@! degree 1o), no floating matter was observed. Bleached kraft paper (basis weight 4097 cm) externally treated with this product diluted to 0.3% by weight
The oil repellency of 2) was 12.

Examples 2 to 8 In the same manner as in Example 1, divine products were obtained by changing the concentration of the ethanolamine salt bath solution, treatment pressure, temperature, and number of times.

Examples 9-14 A dispersion was obtained in the same manner as in Example 1.

Next, irradiation was performed using a 150W ultrasonic irradiator (manufactured by Eranson) at various concentrations, irradiation intensities, and times.

Comparative Example 1 The same phosphoric ester as in Example 1 was dropped into an aqueous jetanolamine solution, and the mixture was stirred at 90° C. for 10 hours to obtain a product. Note that no ultrasonic irradiation or homogenizer treatment was performed.

Comparative Examples 2 and 5 Products with different concentrations were obtained in the same manner as in Comparative Example 1.

The evaluation results of various physical properties of the product obtained above are shown in Tables 1 and 2 below.

I4) Table 1 Homogenizer method Table 2 Ultrasonic method Oil repellency is determined by placing one drop of the test oil shown in Table 3 below on treated paper and observing the state of oil penetration after 15 seconds. evaluate. The highest number that does not penetrate is considered the oil repellency of the treated paper. The higher the number, the better.

Table 6 Test oil test amount for oil repellency measurement (%)

Claims (1)

[Claims] 1. General formula (wherein Rf is a perfluoroalkyl group having 5 to 14 carbon atoms, R is a divalent alkylene group having 1 to 4 carbon atoms, R1, B2, R3 is hydrogen or -0H2C!H2
0H, -0H20H20H20B. -0H(OH3)OHzOH, -0(OH3)3.
6C1m indicates the number of OH average values 1 to 2.5. ) A method for producing a fluorine-containing phosphate ester composition, which comprises treating an aqueous medium containing an alkanolamine salt represented by the following formula with a homogenizer and/or ultrasound.