JPS6318596B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous dispersion of a phosphoric acid ester containing a perfluoroalkyl or alkenyl group, and more particularly to an aqueous dispersion containing tris(perfluoroalkyl or alkenyl group-containing alkyl) phosphate. Tris phosphate (perfluoroalkyl or alkenyl group-containing alkyl) is one of three types of perfluoroalkyl or alkenyl group-containing phosphate esters, namely phosphoric acid monoesters, phosphoric diesters and phosphoric triesters, These three types of phosphoric esters are usually produced as a mixture. For example, a perfluoroalkyl group-containing phosphoric acid ester is produced by reacting a perfluoroalkyl group-containing phosphoric acid alkanol with phosphorus oxyhalide, dichlorophosphoric acid, phosphorus oxyhalide and water, or phosphorus oxyhalide and phosphoric acid, and then, It is produced by a method of hydrolyzing the obtained perfluoroalkyl group-containing phosphohalide (Tokuko Sho
No. 40-6857, No. 48-4770, No. 54-7776, Japanese Patent Application Publication No. 53-77015, and Japanese Patent Application No. 100498-1983).
In this case, the following three types of compounds, for example, are obtained as products. [In the formula, R′ _f represents a perfluoroalkyl group having 3 to 21 carbon atoms. ]. Such perfluoroalkyl or alkenyl group-containing phosphoric esters and salts thereof can be used for fabrics,
It is widely used as a surface treatment agent or as an intermediate for imparting water and oil repellency to paper, leather, and metals, particularly for imparting oil resistance to paper. Typically, these esters are used as aqueous dispersions or solutions, so some or all of them are in the form of salts to increase their miscibility with water, and then they can be dispersed or dispersed by adding a water-soluble organic solvent such as isopropyl alcohol. dissolve. Among the three types of esters, phosphoric acid diesters, such as ester [-2], have excellent dispersibility in water, good binding to materials to be treated such as paper, and are the most effective in imparting water and oil repellency. . Therefore,
Although efforts have been made to selectively produce this, some formation of phosphotriesters, e.g. ester [-3], is unavoidable;
It is difficult to keep it below. By the way, phosphoric acid triesters have poor dispersibility and poor binding to objects to be treated such as paper, and therefore contribute little to imparting water and oil repellency. For this purpose, an aqueous dispersion of a perfluoroalkyl or alkenyl group-containing phosphate ester is prepared by removing the phosphate triester by centrifugation or filtration;
It is prepared and used by mechanically forced dispersion. An object of the present invention is to easily disperse trisphosphate (perfluoroalkyl or alkenyl group-containing alkyl) in water and utilize it effectively. The purpose is to (a) tris (perfluoroalkyl or alkenyl group-containing alkyl) phosphates, (b) mono (perfluoroalkyl or alkenyl group-containing alkyl) phosphates and/or bis (perfluoroalkyl or alkenyl group-containing alkyl) phosphates. This can be achieved by adding (d) a fluoro- or chlorofluoro-aliphatic hydrocarbon to an aqueous dispersion containing (alkyl-containing alkyl) and/or a salt thereof, and (c) a water-soluble organic solvent. By forming such a composition, tris phosphate (perfluoroalkyl or alkenyl group-containing alkyl) is dispersed in water to the extent that it is transparent to the naked eye, increasing its contribution to the surface treatment effect of the object to be treated. Tris phosphate (perfluoroalkyl or alkenyl group-containing alkyl) in the present invention is an ester produced by reacting three molecules of perfluoroalkyl or alkenyl group-containing alkanol with one molecule of phosphoric acid. The perfluoroalkyl or alkenyl group-containing alkanol used herein refers to a compound having a perfluoroalkyl or alkenyl group at one end and a hydroxyl group at the other end, which are bonded via a divalent crosslinking group. Examples of the phosphoric acid triester are as follows. [In the formula, R _f is a perfluoroalkyl group or perfluoroalkenyl group having 3 to 21 carbon atoms; B is
A divalent bridging group that connects R _f and the —(CH ₂ ) _n — group; l
is 0 or 1; m represents an integer of 1 to 4. ] R _f represents a perfluoroalkyl group or a perfluoroalkenyl group as described above, and this includes structures that are linear, branched, cyclic (for example, perfluorocyclohexyl), or a combination thereof. In addition, B also represents a crosslinking group as described above, which includes, for example, -CO ₂ -,
-SO ₂ -, -O-, -(CH ₂ ) ₃ -O-, -S-,
―(CH ₂ ) _p ―NR―, ―CO―NR―, ―SO ₂ ―NR
-or

[Formula] (where p is an integer of 1 to 6; R represents hydrogen or an alkyl group having 1 to 5 carbon atoms). More specific examples of phosphoric acid triesters are as follows. Tris phosphate (2-perfluorobutylethyl) Tris phosphate (2-perfluoroisononylethyl) Tris phosphate (2-perfluorooctylethyl) Tris phosphate (2-perfluorodecylethyl) Tris phosphate [2] -(N-Ethyl-perfluorooctanesulfonamido)ethyl] Tris[2-(N-propyl-perfluorooctanesulfonamido)ethyl] Tris[2-N-ethyl-perfluorooctanesulfonamido)ethyl phosphate ] Tris phosphate [2-(N-methyl-perfluorooctanesulfonamido)ethyl] Tris phosphate (1-trifluoromethyl-2,
(2-Bisheptafluoroisopropyl-ethenyloxybenzyl) The fluoro or chlorofluoro aliphatic hydrocarbon (d) added to the aqueous dispersion of the present invention is a linear, branched or cyclic carbon atom having 2 to 9 carbon atoms. Fluoro or chlorofluoro aliphatic hydrocarbons having the same number of fluorocarbons as or more than carbon atoms, and which are liquid, are preferred, especially those having a melting point of 30
℃ or lower, and preferably has a boiling point of 150℃ or lower. Specifically, they include dimers and trimers of trichlorotrifluoroethane, tetrachlorohexafluorobutane, tetrachlorodifluoroethane, and hexafluoropropene. Therefore, the aliphatic hydrocarbon (d) is present in a proportion of at least 2 parts by weight, preferably at least 3 parts by weight, and at most twice the weight of the ester (b), per 1 part by weight of the phosphoric triester (a). It is preferable to add it at When the amount is less than this, the phosphoric acid triester is not sufficiently dispersed, or the resulting dispersion is unstable, causing reprecipitation when left for a long time. Furthermore, if more than twice the amount of ester (b) is added, the aliphatic hydrocarbon (d) itself may separate from the composition, which is not preferable. Mono- or bis(perfluoroalkyl or alkenyl group-containing alkyl) phosphate is an ester produced by the reaction of one or two molecules of perfluoroalkyl or alkenyl group-containing alkanol with one molecule of phosphoric acid. Note that the perfluoroalkyl or alkenyl group-containing alkanol is a compound as described above. Examples of phosphoric acid mono- or diesters include:
It is as follows. or [In the formula, R _f , B, l and m have the same meanings as above. ] R _f and B specifically include the groups and crosslinking groups described above, respectively. More specific examples are as follows. Monophosphate (2-perfluorobutylethyl) Monophosphate (2-perfluoroisononylethyl) Monophosphate (2-perfluorooctylethyl) Monophosphate (2-perfluorodecylethyl) Monophosphate [2] -(N-ethyl-perfluorooctanesulfonamide)ethyl] Mono[2-(N-propyl-perfluorooctanesulfonamide)ethyl] phosphate mono[2-(N-ethyl-perfluorooctanesulfonamide)] Ethyl] Mono[2-(N-methyl-perfluorooctanesulfonamido)ethyl] Mono(1-trifluoromethyl-2,2 phosphate)
-bisheptafluoroisopropyl-ethenylbenzyl) Bis(2-perfluorobutylethyl) phosphate Bis(2-perfluoroisononylethyl) phosphate Bis(2-perfluorooctylethyl) phosphate Bis(2- Perfluorodecylethyl) Bis[2-(N-ethyl-perfluorooctanesulfonamido)ethyl] phosphate Bis[2-(N-propyl-perfluorooctanesulfonamido)ethyl] Bis[2-(N-propyl-perfluorooctanesulfonamido)ethyl phosphate] N-ethyl-perfluorocyclohexane sulfonamido)ethyl] Bis[2-(N-methyl-perfluorooctanesulfonamido)ethyl] Bis(1-trifluoro-2,2-bisheptafluoroisopropyl-ethyl phosphate) Therefore, mono(perfluoroalkyl or alkenyl group-containing alkyl) phosphate and/or bis(perfluoroalkyl or alkenyl group-containing alkyl) phosphate is tris(perfluoroalkyl or alkenyl group-containing alkyl) phosphate. ) It is usually preferable to use 2 parts by weight or more per 1 part by weight. It is preferable that some or all of these phosphoric acid monoesters and phosphoric diesters be in the form of a salt in order to increase their miscibility with water. Formation of the salt can be carried out by conventional methods. For example, some or all of these phosphoric acid monoesters and phosphoric diesters can be substituted with alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonium hydroxide, dimelamine, trimethylamine, ethylamine, diethylamine, n-propyl The number of carbon atoms in the alkyl group of amine, isopropylamine, etc. is 1
A salt is formed by neutralizing a hydroxyalkyl group such as ~3 mono-, di-, or trialkylamine or ethanolamine, diethanolamine, or triethanolamine with a mono-, di-, or trialkanolamine having 1 to 3 carbon atoms. in this case,
The ester is preferably used as a mixture with 10 to 20% by weight of water and has a pH in the range of 3 to 9. The water-soluble organic solvent (c) is blended to increase the miscibility of the ester (b) with water. Examples of such solvents include methanol, ethanol, n-propanol, isopropanol, acetone, tetrahydrofuran, dioxane, glyme, ethylene glycol, glycerin, and the like. Among these, isopropanol is particularly preferred. The water-soluble organic solvent is usually blended in an amount of 2 parts by weight or more, preferably 4 to 36 parts by weight, per 1 part by weight of the phosphoric acid triester. The amount of water in the aqueous dispersion of the present invention is usually at least the same weight as the total weight of esters (a) and (b), preferably at least 1.5 times the total weight. Preferred methods for producing the aqueous dispersion of the present invention are as follows. As the perfluoroalkyl or alkenyl group-containing phosphoric ester, it is preferable to use a mixture of phosphoric acid mono-, di- and triester obtained by the above-mentioned synthesis method in a predetermined ratio. Add water and a water-soluble organic solvent to this mixture,
Disperse the mixture with heating if necessary. Then, if necessary, an alkali metal hydroxide, aqueous ammonia, or an amine is added to neutralize part or all of the phosphoric acid mono- or diester and convert it into a salt. After this, the fluoro or chlorofluoro aliphatic hydrocarbon is added. This addition is preferably carried out at a high temperature below the boiling point of the hydrocarbon, usually between 40
Perform at 80℃. However, it is also possible to carry out the reaction under pressure using a hydrocarbon with a low boiling point. The addition step is preferably carried out with stirring, for example, with strong stirring using a homogenizer.
It is advisable to allow a sufficient amount of time, and in order to obtain a stable dispersion, it is usually preferable to take 2 to 3 hours. The aqueous dispersion of the present invention obtained in this way is
It has excellent properties as a surface treatment agent for imparting water and oil repellency to textiles, paper, leather, and metals. Next, examples and comparative examples will be shown to specifically explain the present invention. Example 1 (CF ₃ ) ₂ CF (CF ₂ CF ₂ ) _q CH ₂ OH ₂ OH (q is 3,
[(CF ₃ ) ₂ CF
(CF ₂ CF ₂ ) _q CH ₂ CH ₂ O〕 _o POCl _3-o (where n is 1
- an integer of 3). (However, q has the same meaning as above.) Add 150 g of isopropanol and 200 g of water to 100 g of the composition consisting of and the remaining solid matter. Neutralize by adding 28% ammonia water (about 5 g) to pH 6 while stirring at about 50°C. 20 g of C ₂ Cl ₂ F ₃ and 30 g of Cl(C ₂ ClF ₃ ) ₂ Cl are added to the obtained neutralized solution while stirring at 40°C. In this way, 500 g of a transparent dispersion having a solid content concentration of 18.0% by weight was obtained. The solid content concentration was measured by evaporating a certain amount of the dispersion to dryness under atmospheric pressure at 80°C for 2 hours, then at 105°C for 3 hours, and measuring the weight of the residue. The same applies to comparative examples.) Comparative Example 1 When a neutralized solution obtained in the same manner as in Example 1 was left to cool to room temperature, [(CF ₃ ) ₂ CF (CF ₂ CF ₂ ) _q
CH ₂ CH ₂ O] ₃ A precipitate containing P=O as a main component is precipitated. This is removed using a centrifuge to reduce the solid concentration.
435 g of a clear solution of 16.8% by weight were obtained. Example 2 Perfluoroisononyl ethanol is reacted with phosphoric acid and phosphorus oxychloride to obtain perfluoroisononylethylphosphone chloride, which is then hydrolyzed. 150 g of isopropanol and 200 g of water are added to 100 g of the composition consisting of the remaining solids. Add 28% aqueous ammonia while stirring at approximately 50°C to neutralize to pH 6. In the resulting neutralized solution
Add 40 g of Cl (C ₂ ClF ₃ ) ₂ Cl while stirring at 70°C to obtain a transparent dispersion with a solid content concentration of 18.1% by weight.
Obtained 480g. Example 3 The same procedure as in Example 2 was repeated except that 30 g of C ₂ Cl ₃ F ₃ was added instead of Cl (C ₂ ClF ₃ ) ₂ Cl with stirring at 30°C to obtain a transparent solution with a solid content concentration of 18.1% by weight. dispersion
Obtained 475g. _Example 4 480 _g of a clear dispersion with a solids concentration of ₁₈ wt. Obtained. Example 5 The same procedure as in Example 2 was repeated except that neutralization with aqueous ammonia was carried out to pH 4 until the solid content concentration was 18.
478 g of a clear dispersion of % by weight were obtained. Example 6 The same procedure as in Example 2 was repeated except that neutralization with aqueous ammonia was carried out to pH 8. Example 7 150 g of isopropanol and 200 g of water are added to 100 g of the composition consisting of the remaining solids. Add 28% ammonia water while stirring at approximately 50°C to neutralize to pH 7. In the resulting neutralized solution
Add 40 g of Cl (C ₂ ClF ₃ ) ₂ Cl while stirring at 70°C to obtain a transparent dispersion with a solid content concentration of 17.5% by weight.
Obtained 485g. Example 8 Using 100 g of the composition consisting of Cl(C ₂ ClF _{3 ) 2 Cl and the remaining solids, the same procedure as in Example 2 was repeated except that the amount of Cl(C 2 ClF 3} ) ₂ Cl used was changed to 50 g to determine the solid content concentration.
500 g of a 17.8% by weight clear dispersion were obtained. Example 9 In order to examine the performance of the aqueous dispersion of the present invention, paper was treated for oil resistance using the dispersions obtained in each of the Examples and Comparative Examples, and the ability to impart oil resistance was measured. First, each dispersion liquid is diluted with water to a predetermined solid content concentration. 80% of the obtained diluted solution was applied to a sizeless base paper made from pulp (NBKP) by the tub size method, and then heat treated at 110°C for 3 minutes. The base paper treated in this way was heated at 20°C.
The test sample is kept in a constant temperature and humidity room with a relative humidity of 65% for 24 hours. Oil resistance is determined by 3M kit test (TAPPI-RC-
338). The 3M kit test method is a test to determine whether a test sample, which has been conditioned as described above, is penetrated by a test oil formulated as shown below.

[Table] Lay the test sample flat with the measurement surface facing up, drop drops in the order of the kit number from a height of approximately 2.5 cm above the measurement surface, and observe the traces of oil droplets 15 seconds after dropping. The oil resistance is determined by the highest kit number that does not cause black spots due to penetration of the test liquid. The results are shown in Table 1.

【table】

[Table]
From this result, the liquid of Comparative Example 1, which does not contain phosphoric triester, and the dispersion liquid of each example, which has the same solid content concentration and contains phosphoric triester as solid content, show equivalent oil resistance. That is understood.

Claims (1)

[Claims] 1 (a) Formula: [Wherein, R _f is a perfluoroalkyl group or a perfluoroalkenyl group having 3 to 21 carbon atoms;
B is a divalent bridging group that connects R _f and the --(CH2)m- group; l is 0 or 1; m is an integer of 1 to 4; ] Tris phosphate (perfluoroalkyl or alkenyl group-containing alkyl), (b) formula: [In the formula, R _f , B, l and m have the same meanings as above. ] Phosphate mono(perfluoroalkyl or alkenyl group-containing alkyl) and/or formula: [In the formula, R _f , B, l and m have the same meanings as above. ] Bis(perfluoroalkyl or alkenyl group-containing alkyl) phosphate represented by
or a salt thereof; (c) a water-soluble organic solvent; and (d) a fluoro or chlorofluoroaliphatic hydrocarbon having 2 to 9 carbon atoms; at least 2 parts by weight of (b) per 1 part by weight of (a); , (c) and at least 2 parts by weight of (d), but not more than twice the amount of (b). 2 4 to 30 parts by weight of (b), 4 to 60 parts by weight of (c), and
The aqueous dispersion according to claim 1, containing at least 3 parts by weight of (d) and at most twice the amount of (b). 3. The aliphatic hydrocarbon (d) is a linear, branched, or cyclic fluoro or chlorofluoro aliphatic hydrocarbon in which the number of fluorine atoms is the same as or greater than the number of carbon atoms, and is a liquid compound. An aqueous dispersion according to claim 1 or 2. 4 Aliphatic hydrocarbon (d) has a melting point of 30℃ or less and a boiling point of
The aqueous dispersion according to claim 3, which has a temperature of 150°C or less.