JPS6119670B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent agent containing a suitable metal salt of a fluorine-containing surfactant containing perfluoroalkenyl aryl ether as a hydrophobic group and having a carboxyl group as a hydrophilic group as an active ingredient. Conventionally, perfluorocarboxylic acid-based water and oil repellents have been known as fluorine-containing surfactant-based water and oil repellents, but because the raw materials are expensive, they are only used for special purposes. The present inventors invented a manufacturing method for supplying perfluoroalkenyl aryl ethers at low cost (see Japanese Patent Application No. 49-26959; Japanese Patent Publication No. 57-56454). As a result of studying the water- and oil-repellent effects of the derived compounds, the present invention was completed. The fluorine-based water and oil repellent according to the present invention has the general formula: [In the formula, Rf is a perfluorohexenyl group or a perfluorononenyl group, Y is hydrogen, a methyl group or a hydroxyl group, m is 1 or 2, and X is (Rf
-O) attached to the meta- or para-position to m;
General formula: -COOM [] -CON(R)・(CH ₂ )nCOOM [] −SO ₂ N(R)・(CH ₂ )nCOOM [] −CH ₂ N(R)・(CH ₂ )nCOOM [] (In the formula, R is hydrogen, methyl or ethyl group, M is a metal element other than an alkali metal or its oxide,
(n is an integer from 1 to 3); ], where R is particularly preferably hydrogen, a methyl group, or an ethyl group, and n is an integer from 1 to 3.
It is sufficient that M is a metal that makes the compound [ ] insoluble or a double salt with its oxide, and any metal other than an alkali metal can achieve this purpose. Generally, it is preferable that the resulting water and oil repellent is not colored, and from the viewpoint of toxicity and cost, zirconium, titanium, aluminum, zinc, calcium, magnesium, barium, etc. are preferable. However, there are some objects to be treated that do not abhor coloration, and the present invention is not limited thereto. Furthermore, as described later, these metal salts can be obtained not only as simple metal salts but also as double salts with their oxides. The compound represented by the general formula [] has a good yield of raw material perfluoroalkenyl aryl ethers, can be produced at an extremely low cost for a fluorine-based compound, and has excellent water and oil repellency, so it has a wide range of applications. It is something. Especially textiles, textile products, paper, leather, wood, cardboard, cement, mortar, slate, bricks,
In addition to imparting water repellency, oil repellency, and stain resistance to porous materials such as ceramics, it is also effective on glass and metal plastics. The water and oil repellent according to the present invention is a perfluoroalkenyl aryl obtained by reacting a dimer or trimer obtained by oligomerization of hexafluoropropene with an aromatic compound having at least one hydroxyl group. It can be easily obtained from ethers by the following method. (1) Perfluoroalkenyloxyarylcarboxylate is obtained by hydrolyzing phenyl perfluoroalkenyloxyarylcarboxylate obtained by reacting a hexafluoropropene dimer or trimer with phenyl hydroxyarylcarboxylate. (2) N-perfluoroalkenyloxyarylcarbamoyl-(N-alkyl)aminoalkylcarboxylate is obtained by converting perfluoroalkenyloxyarylcarboxylic acid into a carboxylic acid chloride with thionyl chloride, and then reacting it with an alkali metal salt of an amino acid. (3) N-perfluoroalkenyloxyarylsulfonyl-(N-alkyl)aminoalkylcarboxylate can be obtained by chlorosulfonating perfluoroalkenyl aryl ether with chlorosulfonic acid and reacting this with an alkali metal salt of an amino acid. (4) N-perfluoroalkenyloxyarylmethylene-(N-alkyl)aminoalkylcarboxylate is obtained by reacting perfluoroalkenyl aryl ether with chlorodimethyl ether, and reacting this with an alkali metal salt of an amino acid. Here, M′ represents an alkali metal, but since it does not exhibit water repellency as it is, it is necessary to add an appropriate neutral salt aqueous solution of the metal to this aqueous solution and precipitate insoluble carboxylic acid salts by double decomposition. The acid obtained by neutralizing the alkali metal salts of the acid and an appropriate metal oxide, hydroxide, or carbonate are directly melt-reacted at high temperature, or carboxylic acids and metal alkoxides are reacted. Obtainable. The easiest method to use is double decomposition. Further, if necessary, the object can be achieved by treating an object to be treated, such as a fiber, with the alkali metal salt of the carboxylic acid, and then re-treating it with a solution of an appropriate metal salt. Examples of metal salts used in this metathesis include the following. For example, zirconium oxychloride (ZrOCl _{2.8H 2} O), zirconium tetrachloride,
(ZrCl ₄ ), zirconyl sulfate (ZrOSO ₄・nH ₂ O), zirconyl nitrate (ZrO(NO ₃ ) ₂・4H ₂ O), zirconyl acetate (ZrO(C ₂ H ₃ O ₂ ) ₂・H ₂ O), Zirconium sulfate (Zr(SO ₄ ) ₂・4H ₂ O), zirconium nitrate (Zr(NO ₃ ) ₄・5H ₂ O), titanium oxysulfate (TiOSO ₄ ), titanium oxychloride (TiOCl ₂ ), titanium sulfate (Ti (SO ₄ ) ₂ ), aluminum acetate (Al
(C ₂ H ₃ O ₂ ) ₃ ), aluminum chloride (AlCl ₃ ), aluminum nitrate (Al(NO ₃ ) ₃・9H ₂ O), aluminum sulfate (Al ₂ (SO ₄ ) ₃・18H ₂ O), acetic acid Calcium (Ca(C ₂ H ₃ O ₂ ) ₂・H ₂ O), Calcium chloride (CaCl ₂・2H ₂ O), Calcium nitrate (Ca(NO ₃ ) ₂・
4H ₂ O), zinc sulfate (ZnSO ₄・7H ₂ O), zinc acetate (Zn(C ₂ H ₃ O ₂ ) ₂・2H ₂ O), zinc nitrate (Zn
(NO ₃ ) ₂ ·6H ₂ O), zinc chloride (ZnCl ₂ ), etc., but are not limited thereto. The metal salts obtained from the above metal compounds are oxyzirconium (zirconyl) salts in the case of zirconium, and oxytitanium (titanyl) salts in the case of titanium. These metal salts can be used as solutions or dispersions in porous materials such as fibers, textile products, paper, leather, wood, cardboard, cement, mortar, slate, bricks, and porcelain, as well as glass,
Water and oil repellency can be easily obtained by coating, dipping, or spraying on the surface of metals, plastics, etc. It is particularly effective for porous materials, and exhibits even better effects through curing. Examples will be described below. Example 1 p-perfluorononenyloxybenzoic acid (p
Preparation of the zirconyl salt of -C ₉ F ₁₇ OC ₆ H ₄ COOH): Dissolve 29.5 g (0.05 mol) of sodium p-perfluorononenyloxybenzoate in 500 ml of isopropyl alcohol-water (1:3 (by volume)) solution. death,
A solution of 7.9 g (0.025 mol) of zirconium oxychloride (ZrOCl ₂ .8H ₂ O) dissolved in 50 ml of water is added dropwise with stirring at room temperature. Immediately, a milky white insoluble substance precipitates out. After adjusting the pH of the liquid to 6.5,
Insoluble substances are fractionated, washed with methanol, and dried. This is 1,1,2-trifluoro-1,
Extraction with 2,2-trichloroethane and removal of the solvent yielded 27.9 g of the zirconyl salt of p-perfluorononenyloxybenzoic acid as a white powder. The obtained zirconyl salt was well dissolved in 1,1,2-trifluoro-1,2,2-trichloroethane, and paper and tanned leather were added to 5 g/solution.
After soaking for 30 seconds, suspend for 1 minute, drain the liquid,
Dry at 110±5°C for 5 minutes. Treated paper and leather completely repel water droplets and also repel Nujiyor's oil droplets.
It lasts for more than an hour and shows good water and oil repellency. The results of the fiber test are (1) in Table 1 and (1) in Table 2.
Shown below. Example 2 Preparation of titanyl salt of p- _{perfluorononenyloxybenzoic} acid ( _C9F17O - _C6H4COOH ): 29.5 g ( _0.05 mol) of sodium p-perfluorononenyloxybenzoate was dissolved in isopropyl alcohol. - dissolved in 500 ml of water (1:3 (by volume)) solution,
Titanium oxysulfate (TiO・
Add dropwise a solution of 4.0 g of SO ₄ ) dissolved in 100 ml of warm water. An insoluble precipitate immediately separates out. The pH of the liquid
7.0, fractionated the precipitate, washed with methanol, and dried to obtain 22.4 g of titanyl salt as a white powder. Dissolve 0.5 g of the obtained titanium salt in 100 ml of a mixed solvent of 1,1,2-trifluoro-1,2,2-trichloroethane-isopropyl alcohol (1:1 (volume)), and dissolve paper, tanned leather, and gauze. Soak for 30 seconds each. When dried in the same manner as in Example 1, water droplets are completely repelled, and the treated paper and tanned leather retain the oil droplets of Nujiyol for more than 24 hours, exhibiting good water and oil repellency. Example 3 Preparation of aluminum p-perfluorononenyloxybenzoate: 29.5 g (0.05 mol) of sodium p-perfluorononenyloxybenzoate are dissolved in 500 ml of isopropyl alcohol-water (1:3 (by volume)) solution. . Aluminum nitrate (Al
A solution of 6.25 g (0.017 mol) of ( _{NO 3} ) 3.9H ₂ O) dissolved in 50 ml of water is added dropwise. An insoluble precipitate immediately separates out. Thereafter, p-
26.0 g of aluminum salt of perfluorononenyloxybenzoic acid (white powder) is obtained. Paper, tanned leather, and gauze treated with the obtained aluminum salt in the same manner as in Example 1 completely repelled water droplets, and the treated paper and tanned leather retained oil droplets of Nujiyor for more than 24 hours, showing good results. Shows excellent water and oil repellency. Example 4 Production of calcium p-perfluorononenyloxybenzoate: 29.5 g of sodium p-perfluorononenyloxybenzoate and calcium acetate (Ca
( _CH3COO ) _2.H2O ) 4.4g are reacted in the same manner as _in Example 1. The product was extracted with a 1,1,2-trifluoro-1,2,2-trichloroethane-isopropyl alcohol (1:1 (by volume)) solution and the solvent was distilled off, yielding 26.4 g of calcium salt as a white powder. can get. The obtained calcium salt exhibits excellent water and oil repellency similar to the zirconyl salt. Example 5 Production of p-perfluorononenyloxybenzoic acid: 29.5 g of zinc sodium p-perfluorononenyloxybenzoate and zinc sulfate (ZnSO ₄ 7H ₂ O)
7.2g was reacted and treated in exactly the same manner as in Example 1 to obtain 27.3g of white powder zinc salt (yield 91%).
is obtained. The obtained zinc salt exhibits excellent water and oil repellency similar to that of zirconyl salt. Example 6 N-(p-perfluorononenyloxybenzenesulfonyl)glycine (p-
Preparation of zirconyl salt of C ₉ F ₁₇ OC ₆ H ₄ SO ₂ NHCH ₂ COOH): 34.1 g (0.05
mol) and 7.9 g (0.025 mol) of zirconium oxychloride are reacted in the same manner as in Example 1 to obtain 30 g of the zirconyl salt as a white powder. The obtained zirconyl salt was subjected to a water and oil repellency test in the same manner as in Example 1. The results are shown in Tables 1 and 2 (2). Similarly (N-(p-perfluorononenyloxybenzenesulfonyl)glycine aluminum salt, titanium salt, zinc salt,
Calcium salts were produced and all exhibited excellent water and oil repellency. Example 7 N-(p-perfluorononenyloxybenzoyl)glycine (p-
Production of zirconyl salt of C ₉ F ₁₇ OC ₆ H ₄ CONHCH ₂ COOH): 32.3 g (0.05 mol) of sodium N-(p-perfluorononenyloxybenzoyl) glycine and 7.9 g (0.025 mol) of zirconium oxychloride. When the reaction is carried out in the same manner as in Example 1, 30.5 g of the zirconyl salt as a white powder is obtained. The water and oil repellency of the obtained zirconyl salt is shown in Tables 1 and 2 (3). Similarly, titanium salts, aluminum salts, zinc salts, calcium salts, and iron salts were produced and examined for their water and oil repellency, and the same excellent results as in Example 1 were obtained for all of them. Example 8 N-(p-perfluorononenyloxybenzyl)glycine (p-
Preparation of zirconyl salt of C ₉ F ₁₇ OC ₆ H ₄ CH ₂ NHCH ₂ COOH): 31.6 g (0.05 mol) of N-(p-perfluorononenyloxybenzyl)glycine sodium salt
and 7.9 g (0.025 mol) of zirconium oxychloride
and were reacted in the same manner as in Example 1 to obtain 30 g of zirconyl salt as a white powder. The water and oil repellency of the obtained zirconyl salt is shown in Tables 1 and 2 (4). Similarly, the same excellent water and oil repellency as in Example 1 was confirmed for titanium salts, aluminum salts, zinc salts, and calcium salts. Example 9 Zirconyl salts of various carboxylic acid derivatives having a perfluoroalkenyloxyaryl group were produced according to the method of Example 1, and their water and oil repellency tests were conducted. The test results are shown in Table-1 and Table-2.
However, (1) to (4) are the results obtained in Examples 1, 6, 7, and 8, respectively. Test method: The treatment methods and water/oil repellency tests in Examples 1 to 9 were conducted as follows. (1) Treatment: The test piece was immersed in 5 g of each carboxylic acid salt/solution for 30 seconds, suspended for 1 minute, and then 100 ± 5
Dry for 5 minutes at °C. (2) Water repellency test: According to JIS.L1006 (7.25.2) (spray method). (3) Oil repellency test: White Mineral Oil (commonly known as
Mix Nujol) and n-Heptane (first grade reagent) in the ratio shown in the table below, and apply this on the sample.
Place several drops (approximately 4 mm in diameter) in two places and judge by the penetration state (whether or not it has penetrated into the fabric) after 3 minutes.

【table】

[Table] Nujol's standards are as follows. White Mineral Oil 100% Liquid Petrolatum Color: Colorless Odor: Odorless Viscosity: SAYHOLT 360-390 (SUS), 38℃ Specific gravity: 0.880-0.900, 15.5℃ Comparative example 1 Regarding the free forms of various carboxylic acid derivatives used in Example 9 The water repellency and oil repellency were evaluated, and the water repellency was 0 to 50 in all cases, indicating no oil repellency.

【table】

【table】

[Table] In Tables 1 and 2, A, A', A'', and A represent the structures of the following general formulas. Compounds (17) and (18) in Tables 1 and 2 are represented by the following formulas:

Claims (1)

[Claims] 1. General formula: [In the formula, Rf is a perfluorohexenyl group or a perfluorononenyl group, Y is hydrogen, a methyl group or a hydroxyl group, m is 1 or 2, and X is (Rf
-O) attached to the meta- or para-position to m;
General formula: -COOM [] -CON(R)・(CH ₂ )nCOOM [] −SO ₂ N(R)・(CH ₂ )nCOOM [] −CH ₂ N(R)・(CH ₂ )nCOOM [] (In the formula, R is hydrogen, methyl or ethyl group, M is a metal element other than an alkali metal or its oxide,
(n is an integer from 1 to 3); ] A fluorine-based water and oil repellent containing a compound represented by as an active ingredient.