Method for dyeing polyvinyl chloride fibers

Abstract

Shaped articles of polyvinyl chloride having a syndiotactic index higher than 2 (fully defined) are dyed with an aqueous dyebath containing a dissolved or dispersed dye either at a temperature above 100 DEG C. and at superatmospheric pressure or at the boil in the presence of a carrier. The polyvinyl chloride may be a copolymer containing at least 85% vinyl chloride units. Suitable carriers are listed. Examples of dyeing fibres are given.

Description

Method for dyeing polyvinyl chloride fibers. The invention relates to a method for dyeing polyvinyl chloride with a high syndiogram index (SI), in particular to a Methods for dyeing lasers, films or similarly shaped bodies made of polyvinyl chloride with a high syndi-o-tactic index (SI). The term polyvinyl chloride with a high syndiotactic index, used in this description and the patent claims, refers to based on polyvinyl chloride homopolymers that, at a temperature in the range of approximately -10 to -600°C, have a limiting viscosity (j\) above 0.7 dl / g and with a syndi-tactical index of approximately 2 (where the syndi-tactical index is determined by the absorption ratio of the IR band D 635 and D 692 cm""1 is defined, as Burleigh, JAÖ.S. 82, page 749, I960 describe), as well as their copolymers or their Mixtures containing at least 85% wt. vinyl chloride. 8 0 98 08 / 0.6 6 9 In general, these vinyl chloride polymers with a high syndic tactile index have a low affinity for dyes and they absorb aqueous liquids not easily; consequently, it is very difficult to achieve a satisfactory coloration when they are in the form of strongly oriented products are available. It has now been found that vinyl chloride polymers with a high syndi-tactic index can be satisfactorily combined with one or more Dyes that have been dissolved or dispersed in aqueous solutions can be used to color the dyes if the coloring process is carried out at a temperature of either above 1000°C and a pressure above atmospheric pressure or at boiling temperature in the presence of a "carrier" swelling agent. The object of the invention is therefore a method for dyeing polyvinyl chloride with a high SI, in which these polyvinyl chlorides with high SI with a solution or aqueous dispersion of one or more dyes at a temperature above 100°C and at a pressure above can be colored at atmospheric pressure or at boiling temperature in the presence of a "carrier" swelling agent. The term "dye" is used here in its broadest sense, as it is commonly used in the dyeing industry and is intended to not only include intrinsically colored dyes that also have an affinity for one or more textile materials, such as e.g. Vat dyes, which can be used either as a dispersion in reduced form or as a dispersion in unreduced form, furthermore the dispersed insoluble dyes or dyes of sulfuric acid esters, such as those used for cellulose acetate, but also Substances that need to be converted into dyes on textiles, such as those used in azo dyeing. High SI polyvinyl chloride can be in the form of threads, fibers, yarns, films, fabrics, cloths or 809808 / 0669 similarly shaped products can be colored. Suitable dyes include, for example, the dispersed dyes sold under the trade name Acetoquinone dyes from Francolor or as Foron dyes. or artisil dyes distributed by Sandoz. As already mentioned, polyvinyl chloride staining can also be carried out in the presence of a "carrier" swelling agent. Suitable swelling agents include: those used for aromatic polyesters, such as phenols like phenol, m-gresol, m-methoxyphenol, β-naphthol and cathecol, amines such as e.g. α-Naphthylamine, guanidine, aniline and water-soluble aniline salts, carboxylic acids, e.g. β-naphtholic acid, silicylic acid and methacrylic acid, amides such as e.g. Dimethylformamide, diethylformamide, dimethylaoetamide, p-toluenesulfonamide and melamine; alcohols, such as benzyl alcohol; ketones, such as acetophenone and Cyclohexanone; nitriles, such as glutaronitrile and adiponitrile, ethylene cyanohydrin and lactonitrile; and other substances, such as nitrobenzene, tetrachloroethane- Tricresyl phosphate and tetramethylsulfonylmethane. Some of these compounds are marketed under the trade name "Levegal PiD" by Bayer, "Dilatina TC" distributed by Sandoz or "Solvant FT" by Franeolor. The swelling agent is most conveniently dissolved or dispersed in water or an aqueous medium, and this solution or dispersion is used as Liquid used for pretreatment, preferably at a high temperature, e.g. at 90-110 C. If desired, the swelling agent can be added to the dye solution. Water-insoluble swelling agents are most advantageously dissolved, for example, using a salt of a long-chain fatty alcohol sulfonate. The methods used according to the invention lead to excellent results in the coloring of shaped objects made of high SI polyvinyl chloride and er-809808 / 0663 allow for the achievement of very dark colors, high lightfastness, "crook" resistance, resistance to dry cleaning, etc. own. The invention is explained in the following examples: Example 1* In a dyeing plant with a total capacity of approximately 20 l, 1000 g of polyvinyl chloride staple fibers are dyed under pressure with a Syndi-Agric Index introduced. The fibers are washed at 127-128°C for 20-30 minutes with a solution containing 1 g of a non-ionic Cleaning agent, e.g. Ultrawon 1099 from Ciba, and contains 0.5 ^ sodium pyrophosphate. The system is then filled with an aqueous solution containing 2 g / l of a dispersing agent (Ultravon WM from Oiba) and 30 g of a blue Foron. The BGrL dye is from Sandoz. When applying a pressure of approximately 2.8 kg / cm² in the dyeing system, the bath temperature is maintained within a 3A range. Standard temperature increased to 120°0. Inside the system, the temperature is kept at 1200°C for 90 minutes, then the system is cooled down and the fibers are rinsed with cold water. washed and treated with an antistatic agent (Avitex NA from DuPont 2.5 1% based on the fibers) for 20 minutes at 30°C, then The system will be emptied. The dyed fiber obtained in this way is centrifuged and dried in the air at about 800°C. The staple fibers have a deep blue color and the following durability values: 809 8 0 8 / 0669 "orock" resistance 5 Sun resistance 5-6 Resistance to 4 dry cleaning cycles Resistance to washing with water at 40°C 5 The "Orock" durability was measured according to the "UNI" standards using the "Orock" knife. Sun resistance was determined according to the "UITI" standards using the blue color scale.* The resistance to dry cleaning and their in determined. Washing in water at 400°C was performed according to the "UNI" standards. Example 2: A dye bath 2 g / l of an Ultrawon WM dispersing agent from Oiba, 4 g of PT Levegal from Bayer as a carrier, 30 g of Foron GFL scarlet dye in a finely divided form 100 g of polyvinyl chloride fibers with a high syndiotactic index, which were previously purified as in Example 1, are added. The bath temperature is raised to 98-1000 within approximately 3 hours and this temperature is maintained for 90 minutes. Finally, the bath is cooled, the fibers are washed in water and an antistatic agent is added (Avitex NA from DuPont); then The fibers are then "pulled off, centrifuged and dried". The fiber has a deep scarlet color and the following properties: 809806 / 0669 11 crpck-Be ständigkeit 5. Sun resistance 5-6 Resistance to dry cleaning 4 Resistance to 5 Washing with water 809808 / 0669

Claims

Patent claims > A method for dyeing vinyl chloride polymers with a high syndiotactic index, characterized in that the polymers are treated with a dye dissolved or dispersed in water at a temperature above 1000°C and at a pressure above atmospheric pressure or at Boiling temperature in the presence of a "carrier" swelling agent causes coloration.

2. Method according to claim 1, characterized in that the vinyl chloride polymers with a high syndiotacticity index are in the form of fibers, threads or yarns, fabrics, finished garments or similarly shaped products.

3. Method according to claims 1 and 2, characterized in that a "carrier" swelling agent of the type used for aromatic polyesters is used. used. For AOSA-Applicazioni Ohimische SpA