RU2158793C1 - Composition for dyeing materials based on aromatic heterocyclic polymers - Google Patents

Abstract

FIELD: textile industry. SUBSTANCE: when performing dyeing with cationic dyes from aqueous solutions, sodium alkyl sulfates with gross formulas C₁₂H₂₅OSO₃Na, C₁₅H₃₁OSO₃Na, and C₁₆H₃₃OSO₃Na are used as intensifiers. Aqueous dyeing bath contains 0.1-0.5 g/l cationic dye, 0.5-2 g/l sodium alkyl sulfate, and 2-5 g/l acetic acid. Invention can be used in manufacture of heat- and fire-resistant high-strength fibrous materials based on aromatic heterocyclic polymers with high hygienic characteristics. EFFECT: enabled uniform and intensive dyeing with better hygienic characteristics. 1 tbl, 17 ex

Description

 The invention relates to the textile industry and can be implemented in the production of heat-resistant high-strength fibrous materials based on aromatic heterocyclic polymers (PHA) with high hygienic characteristics.

 Known compositions for dyeing difficult-to-color structurally heterogeneous PHA fibers and materials based on them using cationic dyes in a pyridine solution [US Patent 3595606, 1971; Moore R.A., Weigman H / D / - AATCC, Nat. Tech. Conf., 1982. - vol. 6, p. 94-99.]. The composition provides high-quality coatings of high intensity, but its practical use is limited by environmental requirements, since it is proposed to use a potent toxic substance as a medium for pre-treatment and subsequent dyeing.

 Compositions based on cationic dyes and dimethylformamide (DMF) or dimethylacetamide (DMAA) are proposed [US Patent 4227885. - 1980; Sysoev V.A., Silantyeva T.Yu. Research in the field of dyeing of polyimide fibers.- in Sat. scientific, tr. : Chemistry and chemical technology in the textile and light industries. - L, 1977, p. 101-106] for dyeing PHA of textile materials in the color scheme of medium and dark tones. The technology is based on the use of pressurized equipment and requires equipping with a DMF recovery system (DMAA), which can be implemented only for small experimental batches of fiber due to the high toxicity of the polar organic solvent.

 In order to increase the uniformity of color in an aqueous solution of a cationic dye, it is recommended [G. Krichevsky Chemical technology of textile materials. - M .: Legprombytizdat, 1985, p. 405. Kharkharov A.A. Preparation and dyeing of textile materials. - L .: Leningrad State University, 1988, p. 133] to introduce a surfactant (surfactant), for example, equalizer A in an amount of 2% by weight of fiber and acetic acid (30%) in an amount of 2% by weight of fiber with a bath module of 20 or a surfactant composition (in% by weight of fiber): sulfanol - 2; "OS-20" -1. The proposed equalizers are effective if they are used for dyeing PAN materials, but are not suitable for dyeing PHA, because even at high dye concentrations (20% by weight of the fiber) they do not provide intensive or uniform coloring of PHA.

The closest analogue to the proposed technical solution is a composition for dyeing materials based on PHA fibers [Dyankova T.Yu., Vogman S. D. Dyed decorative fabric based on fiber Tulen. - Inform. Leaflet, N 823-84, LenCSTI, 1984, p. 3], including (in g / l): cationic dye 2.4: salicylic acid 7.5; DMF 30, water. Dyeing is carried out at temperatures of 120 ^o C for 45 minutes, then the material is washed and dried. The resulting midtones are resistant to wet treatments and dry friction. The disadvantage is the high concentration of the dye and intensifier of salicylic acid, which increases the cost of decoration and reduces the competitiveness of products. In addition, aromatic carboxylic acid, for example, salicylic acid, being retained on the fiber during washing, is sublimated during the drying process, which leads to a deterioration in the sanitary and hygienic conditions for servicing the process. Dyeing using the above recipe cannot be realized for fabrics or yarn produced from various batches of polymer, because the different shades of individual batches of fiber (from lemon to dark brown) are enhanced and emphasized by different intensities.

 The technical result of the proposed solution is to eliminate these drawbacks, namely the achievement of uniform and intense colors, improving hygienic characteristics, the use of compositions of dye solutions that meet environmental requirements while maintaining the physico-mechanical and fire-retardant characteristics of the PHA material at the prototype level.

This object is achieved in that sodium alkyl sulfates are used as intensifiers for dyeing with cationic dyes from aqueous solutions: C ₁₂ H ₂₅ OSO ₃ Na, or C ₁₅ H ₃₁ OSO ₃ Na, or C ₁₆ H ₃₃ OSO ₃ Na. The composition of the dye bath includes in g / l:
Cationic dye - 0.1-0.5
Sodium Alkyl Sulfate - 0.5-2
Acetic acid - 2 -5
Water - x.

The bath module is 200. The fibrous material is dyed at a temperature of 95 - 100 ^o C for 30 minutes, washed for 10 minutes with hot and cold water and dried. The composition provides uniform coatings on PHA of medium and dark tones that are resistant to wet treatments and dry friction while maintaining the valuable physicomechanical and fire retardant properties of the material at relatively low dye and intensifier concentrations compared to the prototype while improving sanitary and hygienic processing conditions. Heat-resistant fabrics based on PHA designed for protective clothing are dyed in Khaki using a brilliant green dye. The required shade is achieved by applying the coloristic characteristics of the dye and PHA fiber, which has a natural yellow-brown color. Used dye is used in medicine ("green") to disinfect injured skin areas, it is an environmentally friendly product, which is especially important for products that protect against bullet wounds and injuries.

For example, to obtain equally intense colors according to the prototype, it is required to use a cationic pink 2C dye in an amount of 2.4 g / l, which corresponds to the value of the Gurevich-Kubelka-Munk function, characterizing the color intensity of 2.91; according to our recipe, the amount of dye can be reduced to 0.5 g / l, and the concentration of the intensifier can be reduced from 7.5 to 2 g / l. In addition, unlike the prototype, when using sodium alkyl sulfates of the specified composition as intensifiers of the PHA dyeing process, materials do not require the use of textile auxiliary toxic substances DMF, salicylic acid and a high dyeing temperature of 120 ^o C created by compressed air pressure, which makes it possible to realize technical solution on any installed dyeing equipment of periodic operation with economical energy consumption. The proposed composition due to the use of alkyl sulfates of the specified structure, taken in optimal concentrations, ensures the achievement of colors of higher intensity and evenness compared to the prototype. The use of known compositions does not allow to level the natural heterogeneity of the fiber structure, which is a distinctive feature of PHA filaments in comparison with traditional natural and chemical fibers and manifests itself during dyeing in the form of "zebra" and "striped" fabric or melange yarn. A distinctive feature of the proposed composition is to give the material hygienic properties, since the substances used are harmless to human health, and the individual components are disinfecting drugs, for example, brilliant green dye. Alkyl sulfates of a similar composition are widely used as detergents and wetting agents (TU 6-09-64-70; Frotscher G. Chemistry and physical chemistry of textile auxiliary materials. T. 1, p. 136). The advantage of the composition is environmental safety, as the products used are easily decomposable compounds and are included in the processing bath in extremely low concentrations: according to the prototype, the concentration of salicylic acid intensifier required by the formulation is 7 g / l; in accordance with the proposed technical solution, the concentration of the intensifier does not exceed 2 g / l. A feature of the composition, which is of great practical importance, is that all the substances used are cheap and readily available products. In addition, the cost of the composition can be reduced due to the implementation of the synthesis of an intensifier (surfactant) in the conditions of a chemical station for finishing production, or a chemical laboratory, since the reaction proceeds without the release of harmful substances, it does not require complicated hardware design and the use of labor of special qualifications (Frotscher G. Chemistry and Physical Chemistry of Textile Auxiliary Materials (T.1, p. 136).

 To compare the technical level of the indicators of the quality of the paint and the main operational characteristics (tensile strength and elongation at break), the table shows the test data and processing conditions corresponding to the proposed technical solution (examples 3-5, 9, 10) and the prototype (examples 1 and 2).

 The essence of the technical solution is disclosed in the examples.

Example 1 (prototype). Prepare 100 ml of a dyeing solution, including, g / l:
Cationic dye blue O - 2,4
Salicylic acid - 7.5
DMF - 30.0
Water (MB 200) - 960.9
The solution is heated until the components are completely dissolved. A sample of the CBM multifilament yarn is immersed in the form of a skein weighing 0.5 g. Dyeing is carried out at a temperature of 120 ^o C for 45 min, then the dye bath is cooled to 80 ^o C, the skein of yarn is washed successively for 10 min with hot water (70 ^o C), a solution (0.05%) of WOF-100 precocel, hot water, cold water and dried at a temperature of 110 ^o C for 10 minutes

 Example 2 (prototype). Stain a sample (0.5 g) of Tulen fiber fabric (article: "Hope") with a cationic pink dye 2C. The remaining processing conditions correspond to example 1.

 Below are examples 4, 9, 10 of the implementation of the proposed technical solution and analysis of its effectiveness.

Examples 4 (optimal conditions). Prepare 100 ml of a dyeing solution of the composition (in g / l):
Cationic dye blue O - 0.5
Sodium lauryl sulfate C ₁₂ H ₂₅ OSO ₃ Na - 2.0
Acetic acid - 5.0
Water (MB 200) - 992.0
A bundle of CBM multifilament yarn in an amount of 0.5 g is dyed at a temperature of 95-100 ^° C for 30 minutes, washed for 10 minutes with hot (80-85 ^° C) and cold water and dried.

Example 9. A sample (0.5 g) of Tulen fiber fabric (article: “Hope”) is stained with a cationic pink 2C dye in the presence of a C ₁₅ H ₃₁ OSO ₃ Na alkyl sulfate intensifier (2 g / l). The remaining processing conditions correspond to example 4.

Example 10. A sample (0.5 g) of Terlon fiber yarn is dyed with a brilliant green dye; C ₁₆ H ₃₃ OSO ₃ Na (2 g / L) alkyl sulfate is used as an intensifier. The remaining processing conditions correspond to example 4.

 Examples 3 and 6 show the effect of the dye concentration in the solution on the color intensity. The values of the GCM function (0.02%) are below the color discrimination threshold for stained samples at a dye concentration in solution below the lower limit of the recommended interval.

 Examples 4 and 7 show data on the intensity of the dye, showing the inappropriateness of exceeding the recommended dye concentration in the solution, since this does not lead to more intense dyes, but reduces the elongation at break of complex CBM filaments.

 Examples 4, 11-14 contain data illustrating the effect of acid concentration on the intensity of coloring of PHA samples and indicators of physical and mechanical properties, which show that the presence of more than 5 g / l of acid in the dye solution leads to a loss of physical and mechanical properties and a decrease in acid concentration, for example, to 1 g / l, determines the irrational use of the dye: the color intensity decreases to GKM values of 0.36%.

 In examples 14, 16, the results of determining the physicomechanical properties are shown, and in examples 3.15, indicators of the color intensity confirming the optimal values of the concentration of sodium alkyl sulfate in solution.

 In examples 5, 13, 18 it is shown that the use of components of the dyeing solution in amounts corresponding to the median values of the recommended concentration ranges, helps to achieve high intensity and color fastness while maintaining the physico-mechanical properties of the PHA material.

 In the sample processed according to the prototype (example 1), there are areas of non-color in the places of dressing (without tightening) of the skeins of thread. Threads taken from different batches are colored with different shades of 2 to 3 thresholds for color discrimination [Kirillov S.A. Floristics, M. - 1987.]. The value of the Gurevich-Kubelka-Munk (GCM) function, which characterizes the color intensity, is 0.04%. The breaking load is reduced compared with the index for the original untreated fiber from 9.5 N to 6.25 N, the elongation at break after dyeing is reduced from 6% (for the initial filament) to 4%.

 The thread dyed in accordance with example 4 is characterized by a uniform and intense color. GKM dyed yarn 2.91%. The evenness of the color is also manifested in the fact that during the dyeing process a uniform distribution of the dye is achieved on the threads belonging to different lots and differing in their natural color, i.e. the composition used provides a leveling of the natural heterogeneity of the PHA, which provides a significant advantage of the proposed composition.

The data of differential thermal analysis of samples of complex CBM filaments dyed under optimal conditions show that the resistance to thermal oxidative degradation characterizing the fire-retardant properties of the material does not decrease compared to unpainted fiber. The temperature of the beginning of decomposition of the initial and colored samples (example 4), respectively, 490 and 495 ^o C (when heated in air at a speed of 5 ^o C / min).

 Tests of color fastness to physical and chemical influences were determined according to the standards: GOST 9733.0-83 - GOST 9733.27-83.

 Breaking load was determined according to GOST 6309-80.

 To characterize the unevenness of dyeing, a generalized indicator was used that takes into account the simultaneous difference in color and lightness in the G.Vyshetsky system [Kirillov S.A. Floristics, M. - 1987.].

 The color intensity was estimated by the value of the GCM function (Gurevich-Kubelka-Munk) and calculated by the values of the reflection coefficients, which were determined on the FMSh-56 device in accordance with GOST 18054-72.

Claims (1)

Composition for dyeing materials based on aromatic heterocyclic fibers, consisting of an aqueous solution of a cationic dye, an intensifier and a textile auxiliary substance TBB, characterized in that it contains sodium alkyl sulfates as an intensifier: C ₁₂ H ₂₅ OSO ₃ Na, or C ₁₅ H ₃₁ OSO ₃ Na, or C ₁₆ H ₃₃ OSO ₃ Na in a concentration of 0.5 - 2.0 g / l, as a textile auxiliary substance includes acetic acid in an amount of 2 - 5 g / l, the concentration of cationic dye is 0.1 - 0.5 g / l

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