JPH0219233B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for antifouling treatment of textile products, and more particularly to a method for imparting durable antifouling properties using a simple and economical treatment method. BACKGROUND ART Conventionally, methods for stain-proofing, water- and oil-repelling textile products using fluorine-containing polymers, particularly fluorine-containing polymers having perfluoroalkyl groups, have been known and have been applied to various textile products. However, the only conventionally known treatment methods include immersing a textile product in an aqueous dispersion of a fluorine-containing polymer, squeezing it, and drying it with heat. In this kind of processing method,
The fabric that has gone through the previous process is once dried, then impregnated with a treatment liquid, dried, and heat treated, which not only consumes a large amount of thermal energy, but also causes uneven adhesion of the treatment agent due to movement of the treatment agent during drying. It has the disadvantage of being easy to use and less effective. Furthermore, because the dipping and squeezing process is carried out in an extremely short period of time, it is easy for the treatment agent to adhere to spots, which, combined with the mileage of the treatment agent due to drying, results in uneven treatment, which ultimately results in a lack of durability of the effect. produce defects. For this reason, it becomes necessary to increase the amount of treatment agent applied, which is not only uneconomical but also has drawbacks such as impairing the texture of the treated product. In addition, in order to overcome these drawbacks, methods such as polymerizing fluorine-containing ethylenically unsaturated monomers on the fiber surface and methods of mixing and spinning fluorine-containing compounds have been considered, but neither method has been effective enough to be put into practical use. It has not yet become a reality. The present inventors conducted intensive research to develop an antifouling method that is highly durable and economical, and as a result, they arrived at the method of the present invention. That is, the present invention involves immersing textile products in an aqueous treatment solution prepared by adding a polyester polyoxyalkylene ether block copolymer to an aqueous dispersion containing a fluorine-containing polymer having a perfluoroalkyl group and an inorganic salt. It is characterized by being heat treated in an immersed state. When using the method of the present invention, the treatment agent is applied uniformly, and excellent water and oil repellency and stain resistance can be imparted with a small amount of treatment agent. Further, it has the advantage that the treatment process is simple and economical, and that when applied to dyed products, the effect of improving color development can be obtained. The fluorine-containing polymer having a perfluoroalkyl group used in the present invention has 3 carbon atoms.
As mentioned above, preferred are fluorine-containing polymers having 6 to 21 perfluoroalkyl groups, specifically polymers of ethylenically unsaturated monomers having perfluoroalkyl groups as shown in the following formula and monomer and other ethylenically unsaturated monomers, such as ethylenically unsaturated acid esters of polyoxyalkylene glycols, hydroxyalkyl acrylates, glycidyl methacrylate, methacrylic acid,
Examples include copolymers with at least one selected from acrylamide, acrylic esters, acrylonitrile, vinyl acetate, methyl vinyl ether, and the like. In particular, a copolymer with an ethylenically unsaturated monomer having a polyoxyalkylene chain is a preferable fluorine-containing polymer because it provides uniform adhesion and stain removability. (However, R ₁ , R ₂ : hydrogen or lower alkyl group) In addition, the inorganic salt used in the present invention includes a salt having an anion having a larger salting-out power (hydration power) than a bromine anion, and a monovalent salt. In the case of a divalent salt, a potassium cation is preferable, and in a divalent case, a salt with a cation having a larger salting power than a barium cation is preferable, and among them, the cations include NH ₄ ⁺ , Na ⁺ , Li ⁺ , K ⁺ , Mg ⁺⁺
and SO ₄ ^-- as the anionic group,
Salts with CH ₃ COO ⁻ , Cl ⁻ , Br ⁻ are particularly preferred. Specific examples include sodium sulfate, sodium chloride, potassium sulfate, ammonium sulfate, and ammonium chloride. In the present invention, an aqueous dispersion containing the above-mentioned fluorine-containing polymer and an inorganic salt is used as a treatment liquid, and by using a polyether-based hydrophilic finishing agent in combination, the uniform adhesion of the fluorine-containing polymer and the stain resistance of the treated product can be improved. can be further improved, and an antistatic effect can be imparted. Examples of polyether hydrophilic finishing agents include polyester polyether block copolymers, polyether polyamide block copolymers, polyether acrylate/acrylonitrile copolymers, and polyester polyether block copolymers are particularly preferred. Polyester polyether block copolymers contain aromatic polyesters such as polyethylene terephthalate, polyoxyethoxybenzoate, polyethylene terephthalate/isophthalate, polybutylene terephthalate, polyethylene naphthalate, and polycyclohexane dimethylene terephthalate as hydrophobic components, and polyethylene glycol Examples include block copolymers containing polyalkylene glycol as a hydrophilic component, such as polypropylene glycol, ethylene oxide, and propylene oxide copolymers. Typical examples of the copolymer are disclosed in Japanese Patent Publication No. 10794/1983 and Japanese Patent Publication No. 13197/1983.
It is disclosed in the publication number etc. The copolymer may further include a sulfonic acid metal base-containing ester-forming component, or may have a part of the aromatic carboxylic acid component replaced with an aliphatic carboxylic acid component. Textile products to which the method of the present invention is applied include synthetic fibers such as polyester, polyamide, acrylic, and polyurethane; natural fibers such as cotton, linen, and wool; recycled or semi-synthetic fibers such as rayon, Bemberg, and acetate; Mixed products of these can be mentioned, but it is particularly effective when applied to products containing synthetic fibers. In addition, its forms include cotton, filament, sliver, yarn, fabric,
It may be any of non-woven fabrics, rugs, sewn products, etc. As a treatment method, fluorine-containing polymers are usually used at 0.05
~3% owf, preferably 0.1-1% owf, inorganic salts
0.5-10g/, if desired, polyether hydrophilic finishing agent used in combination with 1% owf or less, preferably
The fibers are immersed in an aqueous dispersion containing 0.02 to 0.5% OWF at normal temperature, and after stirring for usually 5 to 10 minutes, the temperature is gradually raised, and the mixture is heated at any temperature of 80°C or higher for 5 minutes or more, preferably 10 to 30 minutes. After fractional processing, lower the temperature, wash with hot water, wash with water, deliquify,
dry. After this, heat treatment is further performed at 130°C or higher depending on the case. The desired water and oil repellency and antifouling properties can be obtained by the simple treatment described above. Further, the treatment of the present invention can be carried out in the same bath as the dyeing, or the temperature of the residual liquid can be lowered after dyeing, the treatment agent of the present invention is added, and the temperature is raised again for treatment. In addition, the treatment solution of the present invention may optionally contain a dispersion stabilizer, especially an anionic surfactant, a PH regulator, a carrier or a swelling agent, and other treatments to adjust the affinity or exhaustion property of the treatment agent for the fibers. Treatment agents having fiber affinity, such as ultraviolet absorbers and antifungal agents, can also be used in combination. The treatment method of the present invention differs from the conventional treatment solution impregnation-drying-heat treatment method in that the fibers to be treated are sufficiently uniform even in a wet state, and it is possible to modify each fiber one by one. Excellent antifouling effects, durability, and abrasion resistance can be obtained with this modifier. The present invention will be explained below with reference to Examples. In addition,
Performance evaluation in the examples was performed by the following method. 1. Water repellency evaluation method A liquid was prepared by mixing isopropyl alcohol and water at a certain ratio, and a small drop of this liquid was placed on the fabric surface to observe wetting.

[Table] 2 Oil repellency evaluation method AATCC 118-1975 Example 1 After scouring a polyester processed yarn knitted fabric, it was treated in a bath having the treatment bath composition shown in Table 1 at 90°C for 20 minutes. After treatment, the cloth was washed with hot water, washed with water, dried, and heat treated at 150° C. for 2 minutes. Table 1 shows the water repellency and oil repellency of the treated cloth.

[Table] Example 2 The same knitted fabric as in Example 1 was treated in the treatment bath shown in Table 2.
It was treated at 100°C for 30 minutes. Thereafter, it was washed with hot water, washed with water, dried, and set at 150°C for 2 minutes. The oil repellency and re-staining prevention properties of the obtained treated fabrics are shown in Table 2.

[Table] The combined use of polyester polyether block copolymer improved not only the oil repellency but also the re-staining prevention property. Example 3 The same knitted fabric as in Example 1 was treated with the treatment bath shown in Table 3. The results are shown in Table 3. As a comparative example, an example of the usual dipping-squeezing-drying method is also shown in Table 3. Invention Asahi Guard LS-317 Sodium sulfate 0.5% owf 5g/100℃ x 20 minutes treatment, then washed with water, dried, bath ratio 1:20 set (160℃ x 2 minutes) Comparative example Asahi Guard LS-317 1% solution Pad (Squeezing ratio 60%) -Drying (110℃ x 3 minutes)-
Heat treatment (160℃ x 2 minutes)

[Table] Evaluation was carried out after digitization.
Compared to the conventional pad method, the performance per amount of fluorine-containing polymer used was significantly improved. Example 4 A polyester table 6 ^d -152 mm was packed into an Overmyer type dyeing machine and scoured by a conventional method. After scouring, dyeing was carried out using the following recipe and conditions. After dyeing, it was washed with hot water, water, and dried. A needle-punched sheet was made using this dyed cotton, and after applying a backing material, it was heat-treated at 160°C for 3 minutes. The water repellency of the needle punch carpet obtained in this way is grade 5.
The oil repellency was level 4. Treatment bath formulation Sumikalon Orange SE-B (Sumitomo Chemical Co., Ltd. disperse dye) 0.05% owf Disper TL (Meisei Chemical Co., Ltd. dispersant) 1 g / Sodium sulfate 3 g / Asahi Guard LS-317 1% owf Acetic acid 0.5 cc / Treatment conditions 30 After stirring at ℃ for 5 minutes, the temperature was raised to 130℃ in about 50 minutes, treated at the same temperature for 30 minutes, cooled down, drained, washed with hot water, washed with water, dehydrated, and dried. Example 5 Polyester dioset was dyed using the following recipe. The obtained black dyed fabric exhibited water repellency, had a smaller L value, and appeared darker than the dyed fabric of the comparative example.

【table】 Processing conditions After staining at 130°C for 30 minutes, reduction washing was performed using a conventional method.

Claims (1)

[Scope of Claims] 1. Antifouling treatment for textile products, characterized by immersing the textile products in an aqueous dispersion containing a fluorine-containing polymer having a perfluoroalkyl group and an inorganic salt, and heat-treating the textile products in the immersed state. Law. 2. A textile product characterized in that the textile product is immersed in an aqueous dispersion containing a fluorine-containing polymer having a perfluoroalkyl group, a polyester polyoxyalkylene ether block copolymer, and an inorganic salt, and then heat-treated in the immersed state. antifouling treatment method.