JP2005232425A - Water and oil repellent composition with low-temperature workability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water and oil repellent composition composed of a water dispersed type fluorine water and oil repellent processed at low temperatures and exhibiting excellent water and oil repellent workability. <P>SOLUTION: The excellent water and oil repellent property is obtained by low temperature processing of a water dispersed type fluorine water and oil repellent agent by addition of an organic polyvalent metal compound as a cross-linking agent or a cross-linking accelerator. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a water / oil repellent composition that exhibits excellent water / oil repellency by using a water-dispersed fluorine-based water / oil repellent at a low processing temperature.

  Conventionally, when imparting water / oil repellency to textiles, etc., an emulsion copolymer of a fatty acid ester having a perfluoroalkyl group and a monomer copolymerized therewith has been used as a water-dispersible fluorine-based water / oil repellent. Has been. Various attempts have been made to improve the performance. For example, with respect to the polymer itself and the copolymer's partner monomer, developments have been made to improve performance and improve physical properties by examining the type and production conditions, and adding various additives.

  However, some processing conditions for imparting water and oil repellency are difficult to solve by improvement. For example, in general, the processing temperature of a water-soluble repellent is generally required to be heat-treated at a temperature of 120 ° C. to 160 ° C. or higher after drying at 100 ° C. or higher for 1 to several minutes. If the heat treatment temperature is lower than 120 ° C. and the treatment can be performed in the same time as before, there is a great expectation in terms of efficiency, cost, handling and safety. Now, even if it is dried or heat-treated at a low temperature of, for example, 110 ° C. or less over time, it may become undried or performance may not be achieved. Various attempts have been made, but the current situation is that adequate products that satisfy this purpose have not been fully developed.

Problems to be solved by the invention

The problem to be solved is that, in order to impart water and oil repellency to a textile or the like, it is an essential condition that the heat treatment is generally performed at a processing temperature of 120 ° C. to 160 ° C. or higher. On the other hand, it is to provide a water / oil repellent composition that can be processed efficiently at a very low temperature, for example, at a temperature of 120 ° C. or lower.

Means for solving the problem

  In the present invention, a water-dispersible fluorine-based water / oil repellent is added to a fiber product or the like by adding an organic polyvalent metal compound as a crosslinking agent or crosslinking accelerator in a specific ratio and making it into an aqueous solution or emulsion. A water-dispersed fluorine-based water / oil repellent composition exhibiting excellent water / oil repellency and low-temperature processability is provided by treatment by conventional methods such as immersion, spraying and the like.

The invention's effect

An aqueous solution mixture obtained by adding an organic polyvalent metal compound as a crosslinking agent or crosslinking accelerator to the water-dispersible fluorine-based water / oil repellent of the present invention is processed into a fiber product or the like at a very low temperature, for example, 120 ° C. or less. it can. Moreover, excellent water and oil repellency can be imparted to carpets and the like that have been considered relatively difficult.

  In the present invention, the water-dispersible fluorine-based water / oil repellent is an emulsion copolymer of a fatty acid ester having a polyfluoroalkyl group and a monomer copolymerizable therewith, and the polymerization system is a cationic system. , Nonionic or zwitterionic, but preferably cationic or nonionic.

The organic polyvalent metal compound as a crosslinking agent or crosslinking accelerator to be added to the water-dispersible fluorine-based water / oil repellent includes a metal complex or a metal chelate. In particular, titanium, aluminum or zirconium is suitable as the polyvalent metal, or an organic acid salt such as an oxide, hydroxide, basic salt, or acid salt can be used as the metal compound. Moreover, the compound of 2 or more types of combinations from these groups may be sufficient. Of these, organic fatty acid salts are preferred.

  Examples of the organic fatty acid include those having 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, stearic acid, and palmitic acid. An aqueous solution or emulsion of these organic fatty acid polyvalent metal salts or mixtures thereof can be used, and these may be metal complexes or metal chelates. Of the above organic fatty acids, metal salts of organic fatty acids having a small number of carbon atoms are preferred because of solubility.

  In the present invention, the organic polyvalent metal compound as a crosslinking agent or crosslinking accelerator can be added in an amount of 0.1 to 20% by weight with respect to the water-dispersed fluorine-based water and oil repellent. When the addition rate is 0.1% by weight or less, the effect as a crosslinking agent or a crosslinking accelerator is small, and when the addition rate is 20% by weight or more, the effect is not changed or remains in the liquid and may have an adverse effect during the treatment. .

  The total of the water-dispersed fluorine-based water / oil repellent and the organic polyvalent metal compound is preferably in the range of 0.01 to 15.0% by weight based on the total weight. Particularly preferred is 0.1 to 5.0% by weight. In the range of 0.01% by weight or less or 15% by weight or more with respect to the total weight, the level is lowered or the effect is low with the water and oil repellency performance and the low temperature workability expected of the present invention. Not.

  As a single use of an organic polyvalent metal compound, for example, an organoaluminum compound is used as a catalyst or the like, but it is an organic solvent type, and an organic titanium compound or an organic zirconium compound is known alone as a waterproofing agent or the like. As in the case of a commercially available fluorine-based water / oil repellent composition alone, it is still poor in low-temperature processability. However, when an organic polyvalent metal fatty acid salt is added as a crosslinking agent or crosslinking accelerator to a fluorine-based water / oil repellent agent such as a textile product as in the present invention, there is no example that shows the effect for the first time. Moreover, when an organic acid salt of a specific polyvalent metal is added in a specific ratio, as shown in the Examples, it exhibits extremely excellent water and oil repellency and exhibits low-temperature processability. It is epoch-making that the target textile product is suitable not only for fabric but also for carpets. This is one of the major features of the present invention.

  In addition, the time-dependent change of the water / oil repellent composition of the present invention was examined, but no physical property change was observed even when it was left at room temperature for about 1 month or more.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.

  In a 300 cc glass container, 2.50 wt% (active ingredient 0.75 wt%) of a commercially available cationic water-dispersed fluorine-based water / oil repellent (hereinafter referred to as F-1) is used as a crosslinking accelerator. A metal organic acid was added, and water was added to this mixture to make it 100% by weight. The mixture was sufficiently stirred to obtain a water-repellent / repellent composition. Then, after confirming that it was in a uniform state, it was placed at room temperature (15 ° C.) for about 30 minutes.

  Next, as a sample 1, four carpets (150 mm square made of nylon) were prepared, and each surface was uniformly sprayed with an aqueous solution of the water / oil repellent composition prepared above. After the treatment, it was air-dried at room temperature (15 ° C.) for about 30 minutes. The treated carpet was then heat treated at room temperature (15 ° C.) for 24 hours, 55 ° C. for 3 minutes, 90 ° C. for 2 minutes and 110 ° C. for 2 minutes at the respective processing temperatures and treatment times. Except for room temperature, all were independently heat-treated with a constant temperature dryer.

  Each of the above heat-treated carpets is subjected to a water repellency test (Method B) by the method shown below, the results are shown in Table 2, and the oil repellency test is conducted by the method shown below, and the results are shown in Table 3. Indicated.

  Next, as a sample 2, three cotton cloths (twill, 100 mm square) were prepared, and each surface was uniformly sprayed with an aqueous solution of the water / oil repellent composition described above. After the treatment, it was air-dried at room temperature (15 ° C.) for about 30 minutes. The treated cotton fabric was heat-treated at room temperature (15 ° C.) for 24 hours, 55 ° C. for 15 minutes, and iron (about 165 ° C.) for 5 seconds at each processing temperature and treatment time. After the treatment, a water repellency test was performed by the following method A, and the results are shown in Table 1.

  Regarding the performance evaluation method, the water repellency was evaluated by the following two test methods (1) A method and (2) B method.

  Water repellency (1) Expressed by the water repellency number according to the A method and the spray method of JIS-L-1092. Water repellent number: 100 surface with no adhesion wetness, 90 surface with slight adhesion wetness, 80 surface with partial wetness, 70 surface with wetness, 50 surface wetness One, both front and back surfaces are completely wet.

  Water repellent (2) Method B, a small drop of isopropyl alcohol / water mixture having the composition shown below is gently placed on the surface of the above treated carpet fabric, and the liquid shape is maintained after 3 minutes. It was expressed as the maximum content of isopropyl alcohol. Mixed composition (volume%) Isopropyl alcohol: water 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, respectively 10, It was represented by 20, 30, 40, 50, 60, 70, 80, 90.

  In addition, in the oil repellency test, a test solution was dropped on the surface of a carpet cloth having the same treatment as described above to a diameter of about 4 mm, and the penetration state into the carpet after 30 seconds was visually observed. AATCC-TM118-1966 The oil repellency was evaluated accordingly. The surface tension of the test solutions used in these test methods was as follows, and the performance was evaluated. Oil repellency 8: N heptane 20.0 (dyn / cm, hereinafter abbreviated units), 7: N-octane 21.8, 6: N-decane 23.5, 5: N-dodecane 25.0, 4: N- Tetradecane 26.7, 3: N ^ hexadecane 27.3, 2: N-hexadecane / Nujol = 35/65 (Wt% / Wt%) 29.6, 1: Nujol 31.2, 0: 1 .

An organic polyvalent metal compound similar to that of Example 1 is used as a commercially available nonionic water-dispersible fluorine-based water / oil repellent (hereinafter referred to as F-2) different from that of Example 1 to prepare a water / oil repellent composition. Tables 2 and 3 show the results of the preparation, the same treatment as in Example 1, and the same performance evaluation.
In addition, the water repellent performance evaluated by the A method was subjected to water repellent treatment on the cotton cloth in the same manner as in Example 1, and the performance evaluation results are shown in Table 1.

Comparative Example 1

  For comparison, the organic polyvalent metal compound as a crosslinking accelerator in Example 1 is not included, that is, only F-1 is used as a water-dispersible fluorine-based water / oil repellent, and the same treatment as in Example 1 is performed. A similar performance evaluation was performed. This can be said to be the same as a treatment example of a water / oil repellent composition generally performed. The results are shown in Tables 2 and 3 as examples without a crosslinking accelerator. The water repellent performance evaluated by Method A is shown in Table 1 with the same treatment using cotton cloth as in Example 1.

Comparative Example 2

  For comparison, in Example 2, F-2 was used, and the organic polyvalent metal compound as a crosslinking accelerator was not included as in Comparative Example 1, and only F-2 was a water-dispersed fluorine-based water / oil repellent. Then, the same processing as in Example 1 was performed, and the same performance evaluation was performed. This can be said to be the same as a treatment example of a generally used water / oil repellent composition. The results are shown in Tables 2 and 3 with no crosslinking accelerator. In addition, what evaluated water-repellent performance by A method performed the same process using cotton cloth similarly to Example 1, and showed it in Table 1.

Claims (3)

  A mixture obtained by adding an aqueous solution or emulsion of an organic polyvalent metal compound as a crosslinking agent or crosslinking accelerator to a water-dispersible fluorine-based water- and oil-repellent agent, the mixing ratio of On the other hand, the total of the active ingredients of the water-dispersed fluorine-based water / oil repellent and the organic polyvalent metal compound is in the range of 0.1 to 20.0% by weight of the organic polyvalent metal compound and the total weight, A water and oil repellent composition characterized by being 0.01 to 15.0% by weight.   The water-dispersed fluorine-based water / oil repellent according to claim 1 is an emulsion copolymer of a fatty acid ester having a polyfluoroalkyl group, and the organic polyvalent metal compound according to claim 1 is any of titanium, aluminum, or zirconium. A water / oil repellent composition, which is one or a mixture of two or more selected from the group consisting of such polyvalent metals, or organic fatty acid salts of the compounds thereof. (3) When imparting water / oil repellency to a textile or the like using the water / oil repellent composition according to any one of the above (1) and (2), the processing temperature is 120 ° C. or less, and excellent water repellency is obtained. A water / oil repellent composition characterized by being able to obtain water / oil repellency.