JPS6246672B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a processing method for improving the depth of color of dyed textile products. Synthetic fibers, especially fiber products whose main component is polyester fibers, are widely used in all kinds of textile structures due to their excellent functional properties, but one major drawback is that compared to natural fibers such as wool and silk, It is said that the depth of color of dyed products is inferior. Particularly in the field of formal wear, etc., there is a problem in that it is not possible to obtain a deep black color, which is commonly referred to as "crow's feather color" or "telephone black." For this reason, various methods have been attempted, including improvements in terms of dyes and improvements in fibers, but at present none of them has achieved sufficient effects. By the way, we have experienced that when an organism gets wet, its color becomes more bathochromic, as seen in the example of "the color of a crow's wet feathers." The reason why the bathochromic degree increases with wetting is explained as follows. Except for objects that emit light from themselves, such as radiators, the color of an object is generally determined by the reflection and absorption of light, but in order to make the color appear deeper, it is necessary to reduce the reflection of light and increase the absorption of light. It is. Regarding light reflection, it is particularly important to reduce surface reflected light. This is because the surface-reflected light is reflected as white light, so it hardly contributes to the deepening of the color of the colored body. Theoretically, as a method to reduce the amount of surface reflected light, there is a technique to apply a material with a lower refractive index to the surface of the object substrate than the object that makes up the substrate.
It is also known from experience. An example of this is lens coating technology. This is a technology that reduces the amount of surface reflected light by coating the lens surface with a transparent thin film that has a lower refractive index than glass. The above-mentioned phenomenon of improving the bathochromic degree due to wetting is also a result of the amount of surface reflected light being reduced by covering the surface with a thin film of water having a lower refractive index than the substrate. Several attempts have been proposed to apply this principle to improve the deep color and sharpness of textile products. For example, a method of attaching silicone to the surface of textile products (Japanese Unexamined Patent Publication No. 13695/1989), and a method of forming a thin film of a polymer having a refractive index lower than that of the constituent fibers on the surface of textile products by plasma polymerization or discharge grafting. (Unexamined Japanese Patent Publication No. 53-111192). However, even if silicone is simply applied to the surface of textile products as an aqueous dispersion or an organic solvent solution as in the former method, sufficient adhesion is not achieved and a satisfactory deep color effect cannot be obtained. Furthermore, in order to form a thin polymer film on the surface of a textile product by plasma polymerization or electrical discharge grafting, as in the latter method, very expensive special equipment is required, and it cannot be called a general processing method. The inventors of the present invention have made extensive studies to solve the drawbacks of the conventional methods, and have found that if an electrolytic substance is added to the polymer emulsion or dispersion, an excellent method can be achieved without using any special equipment. It was discovered that a deep color effect can be produced, and the present invention was achieved. That is, the present invention involves attaching to the surface of a dyed textile product a treatment agent in which a hydrophobic polymer containing an electrolytic substance and having a refractive index lower than that of the fiber is emulsified or dispersed, and then drying. This is a deep color processing method for textile products. The present invention includes natural fibers, regenerated fibers, semi-synthetic fibers,
It can be applied to dyed fiber products made of synthetic fibers or mixtures of these fibers (mixed fibers, twisted twists, blended fibers, etc.), and is particularly suitable for synthetic fibers, especially polyester fiber products with poor dyed color depth. When applied, the effect is noticeable. Further, the present invention can be applied to all types of textile products such as tows, filaments, yarns, woven and knitted fabrics, and nonwoven fabrics. Examples of polymers with a low refractive index as used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, and tetrafluoroethylene-tetrafluoroethylene copolymer. Fluoropropylene copolymer, polyfluorovinylidene, polypentadecafluorooctyl acrylate, polyfluoroethyl acrylate, polytrifluoroisopropyl methacrylate,
Fluorine-containing polymers such as polytrifluoroethyl methacrylate, silicon-containing compounds such as polydimethylsilane, polymethylhydrodiene siloxane, and polydimethylsiloxane, ethylene-vinyl acetate copolymers, polyethyl acrylate, polyethyl methacrylate, etc. Examples include acrylic esters, and among these, one having a refractive index smaller than that of the fiber matrix constituting the textile product may be appropriately selected and used. In this case, it is desirable to select a material that has as large a difference in refractive index as possible with the substrate fiber. As the emulsifying or dispersing agent for emulsifying or dispersing these hydrophobic polymers, acids and/or anionic activators are suitable. Examples of acids include hydrochloric acid, sulfuric acid, formic acid, phosphoric acid, aliphatic carboxylic acid, aliphatic sulfonic acid, alkylbenzenesulfonic acid,
Organic and inorganic acids such as alkylnaphthalene sulfonic acids, halogen-substituted aliphatic carboxylic acids, and polyoxyethylene alkyl ether sulfates can be mentioned. Examples of anion activators include higher fatty acid salts, higher alcohol sulfate ester salts, and alkyl sulfones. Examples include acid salts, alkylaryl sulfonates, formalin condensed naphthalene sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphates, and the like. These emulsifying or dispersing agents may be added during the polymerization process of the hydrophobic polymer, or may be added when the hydrophobic polymer is emulsified or dispersed in water. Examples of electrolytic substances in the present invention include common salt, sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium sulfate, ammonium chloride, sodium nitrate, potassium nitrate,
Examples include ammonium acetate, sodium acetate, and organic and inorganic acids, among which inorganic salts are preferred, particularly when potassium hydrogen sulfate is used,
A favorable result with a large bathochromic effect can be obtained. As a method for attaching the treatment agent to the surface of the textile product, methods such as a spray method, a padding method, a kiss roll method, a knife coating method, and a gravure coating method can be employed. After the treatment agent has been applied to the surface of the textile product in this way, it is dried, and then heat set is applied if necessary. In addition, the method of the present invention can be carried out by improving the dye to give it bathochromic properties, or by improving the dye to give it bathochromic properties, or by
As disclosed in Japanese Patent Publication No. 54-120728, Japanese Patent Publication No. 54-44300, etc., the deep color property can be further improved even when applied to textile products in which the fiber surface is given unevenness to deepen the color. The effect is recognized. Although the reason why the addition of an electrolytic substance, which is a feature of the present invention, exhibits an extremely outstanding effect is still not clear, the dispersion stability of hydrophobic particles is generally determined by the electrostatic repulsion formed around the particles, Balance and stability are maintained due to mutual potential energy such as Del Waals attraction, but the addition of electrolytic substances disrupts this balance and greatly reduces the dispersion stability of hydrophobic particles, resulting in the dispersion of hydrophobic objects such as synthetic fibers. This is interpreted to be due to the fact that it becomes selectively and easily adsorbed on the surface of. Furthermore, since the processing agent used in the present invention is a hydrophobic polymer, it also has the advantage of being highly resistant to aqueous washing. The present invention will be explained in more detail with reference to Examples below, and all proportions in the Examples mean percent by weight unless otherwise specified. In addition, the viscosity of siloxane indicates the viscosity of the siloxane itself, and all values are 25°C.
It was measured with Furthermore, the bathochromic degree (K/S) is used as a measure to indicate the bathochromic effect, and this value is determined by measuring the spectral reflectance (R) of the sample using a Shimadzu RC-330 self-recording spectrophotometer. Kubelka Munch (Kubelka) shown below
−Munk). The larger this value is, the greater the deep color effect is. K/S=(1-R) ² /2R In addition, K shows an absorption coefficient and S shows a scattering coefficient. Example 1 200 g of deionized water, 1.1 g of ammonium persulfate, and 0.15 g of ammonium perfluoro-n-octoate as an emulsifier were added to a 400 c.c. stainless steel autoclave under a protective atmosphere of nitrogen, and the container was closed with dry ice/ The mixture was cooled in an acetone bath and evacuated to 1 mmHg, and then 40 g of tetrafluoroethylene and 20 g of propylene were introduced, and while shaking, the temperature of the container was raised to 80° C., and polymerization was carried out for 8 hours. The reaction was then stopped and cooled to room temperature to obtain an extremely stable emulsion of tetrafluoroethylene-propylene copolymer with a dry solids content of 20%. Dianix Black is a 100% polyester dioset fabric with a basis weight of 150g/ ^m2 that has been subjected to alkali weight loss.
HG-FS (Mitsubishi Chemical Industries, Ltd. product) 130 at 15% owf
After staining at ℃ for 60 minutes, stain with an aqueous solution containing 1 g of caustic soda and 2 g of hydrosulfite.
℃ for 20 minutes, K/S value 16.5 (measurement wavelength
A black dyed cloth of 500 mμ) was obtained. On this black dyed cloth, 3 g of the tetrafluoroethylene-propylene copolymer obtained in the above reaction in terms of individual particles and potassium hydrogen sulfate were added.
After drying, apply an emulsion treatment agent consisting of 0.15g and 300g of water (80% pick-up).
Heat set at 160°C for 1 minute. The K/S value (measured wavelength: 500 mμ) of the obtained treated cloth was 23.5, showing a remarkable bathochromic effect compared to the untreated cloth. On the other hand, for comparison, the treatment was carried out under the same conditions as the above method except that potassium hydrogen sulfate was not included in the treatment agent, and the K/S value (measured wavelength 500 mμ) of the obtained treated cloth was 17.3. Compared to untreated cloth,
Almost no bathochromic effect was observed. Example 2 150 g of cyclic dimethylsiloxane, 2 g of dodecylbenzenesulfonic acid, 5 g of sodium dodecylbenzenesulfonate, and 333 g of water were placed in a reactor and polymerized at 80° C. for 24 hours with vigorous stirring to obtain a good white emulsion. An emulsion treatment agent consisting of 5 g of the obtained polymer solids, 2 g of glacial acetic acid, and 300 g of water was prepared, and this treatment agent was puttered onto the same 100% polyester black dyed cloth used in Example 1 (Pickup 80g). %) and after drying
Heat set at 160°C for 1 minute. The K/S value (measured wavelength: 500 mμ) of the obtained treated cloth was 22.5, and a remarkable deep color effect was observed compared to the untreated cloth. Example 3 30g of dimethylpolysiloxane with a viscosity of 1000CS,
2g tall oil fatty acids containing basic oleic acid, 28
An emulsion was obtained by mixing 0.5 g of wt% ammonia water, 0.75 g of triethanolamine, and 66.75 g of water using a homogenizer. After dyeing 100% polyester processed yarn fabric with a basis weight of 120 g/m ² with Miketon Polyester Red 2BSF (product of Mitsui Toatsu Chemical Industries, Ltd.) at 130°C for 60 minutes with 7% owf, 1 g of caustic soda and 1 hydrosulfite were dyed.
A red dyed cloth with a K/S value of 2.41 (measured at a wavelength of 600 mμ) was obtained by reduction washing at 70° C. for 20 minutes with an aqueous solution containing g/. This red dyed cloth was padded with an anionic emulsion treatment agent (pickup 75%) consisting of 5 g of the polymer obtained under the above conditions, 2 g of glacial acetic acid, and 300 g of water, and after drying, it was heat set at 160° C. for 1 minute. The K/S value (measured at a wavelength of 600 mμ) of the obtained treated cloth was 3.22, showing a remarkable bathochromic effect compared to the untreated cloth. Example 4 A fabric with a basis weight of 180 g/m ² made of a mixed filament system with a weight ratio of polyester filament and diacetate filament of 1:1 was fabricated with Terasil Navy.
After dyeing with 8% owf of Blue RL (product of Ciba Geigy) and 10% owf of Dianix Black RB-UP (product of Mitsubishi Chemical Industries, Ltd.) at 120°C for 60 minutes, dyeing was carried out in an aqueous solution containing 1 g of soda ash. 20 at 40℃
Soaping was carried out for a minute to obtain navy blue and black dyed fabrics. An anionic emulsion treatment agent consisting of 5 g of epoxy-modified dimethylpolysiloxane, 0.15 g of potassium hydrogen sulfate, and 300 g of water was prepared and applied to the navy-dyed fabric and black-dyed fabric obtained under the above conditions (pickup 80%). After drying, it was heat set at 150°C for 1 minute. The bathochromic degree (K/S) (measured wavelength: 500 mμ) of the obtained treated fabric is compared with that of the untreated fabric as shown in the following table.

[Table] The treated fabric showed a significant deep color effect compared to the untreated fabric.

Claims (1)

[Claims] 1. A treatment agent made by emulsifying or dispersing a hydrophobic polymer containing an electrolytic substance and having a refractive index lower than that of the fiber is attached to the surface of a dyed fiber product,
A deep color processing method for textile products, which is characterized by subsequent drying. 2. The processing method according to claim 1, wherein a hydrophobic polymer is emulsified or dispersed with an acid and/or anionic activator. 3. The processing method according to claim 1 or 2, wherein the fiber is a polyester fiber. 4. The processing method according to claim 1, 2 or 3, wherein the hydrophobic polymer is a fluorine-containing polymer or a silicon-containing polymer. 5. The processing method according to claim 1, 2, 3, or 4, wherein the electrolytic substance is an inorganic salt. 6. The processing method according to claim 5, wherein the inorganic salt is potassium hydrogen sulfate.