JPH0633522B2 - Method for producing colored wet spun fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a colored wet-spun fiber that exhibits an unprecedentedly vivid color tone.

Colored wet-spun fibers spun from a mixture of an inorganic or organic conventional coloring material added to and mixed with a wet-spinning stock solution,
It is well known that there are high demands in many fields because of their excellent various fastnesses and uniform hues. However, on the other hand, while showing high fastness, the sharpness of the color tone is far worse than that obtained by dyeing a pre-spun uncolored fiber with a dye.
Until now, the development of coloring materials aimed at improving this defect
Many studies have been conducted. In the process, some improvements were made by modifying the molecular structure of the coloring material and changing the crystal form, but these were uniformly sacrificed for some fastness and compared with those dyed with a dye. In addition, the sharpness of the color tone was much worse.

The present inventor, as a result of earnest researches on the development of a coloring material, finally found a coloring agent capable of having a vivid color tone and fastness never before, and succeeded in producing a wet spun fiber colored with the coloring material. It is a thing.

The colorant referred to in the present invention is hydrophobic and has a mechanical strength capable of withstanding dispersion treatment by a ball mill or the like, and heat, a solvent encountered during the fiber manufacturing process or product yarn and secondary products,
Resins having resistance to various treatments such as acids and alkalis and compatible with dyes such as reactive dyes, fluorescent dyes, acid dyes, basic dyes and direct dyes, for example, melamine resin, urea resin, benzoguanamine resin, etc. It is a fine particle having a uniform particle size in which any dye is adsorbed or included.

The particle size of the fine particles depends on the dispersion stability in the spinning dope, spinnability,
Also, it has a great influence on the sharpness of the color tone of the obtained colored yarn, and when it is less than 0.1 μm, the particles are rather coarsened due to secondary aggregation in the spinning dope, dispersion stability, spinnability, and sharpness of the colored yarn. I couldn't get anything satisfying in terms of. On the other hand, if the particle size exceeds 20 μm, the spinnability is mainly impaired and the mechanical properties of the fiber are largely deteriorated, although there is a relationship with the spinning nozzle diameter and filament diameter. Therefore, the diameter of the fine particles is preferably in the range of 0.1 to 20 μm, and more preferably adjusted to 0.3 to 5 μm, which can provide suitable results in all respects.

Further, in order to disperse the colorant in the spinning dope, either a powder is directly added and mixed, or a solvent or a part of the spinning dope is dispersed and mixed, and either method is adopted. In the case of powder addition, some undispersed agglomerates are unavoidably generated, and a decrease in spinnability due to this is not a little recognized, so it is preferable to use a solvent of the spinning dope, or one dispersed in a part thereof. It was preferable to add and mix it to the spinning dope. However, even in that case, it is necessary to adjust the concentration of the dispersion liquid of the coloring material to within 50%, and if it exceeds this, the dispersion becomes significantly unstable and the separation and sedimentation of the dispersion liquid occur. Occurs easily.

The addition rate of the coloring material to the fiber is limited to 20%, and if it exceeds this, the spinnability is remarkably impaired, and normal spinning cannot be continued or even if spinning is possible. However, the mechanical properties of the resulting fiber were extremely low. It is considered that, even in the case of the colorant, if a large amount of the colorant is added and mixed as in the conventional colorant, the structuring of polymer molecules constituting the fiber is hindered in the process of coagulation or regeneration of the wet spun fiber.

In addition, when adding and mixing the conventional coloring material to the wet spinning dope,
As a result of attempting to use the colorant together as an auxiliary agent for imparting sharpness to the color tone of the conventional colorant, the colorant was added and mixed at a ratio of at least 5% or more to the conventional colorant. It was found that the color tone of the colored yarn spun from the spinning dope had a remarkable improvement in the sharpness. But,
If it is less than 5%, it is not so different from the color tone of the colored yarn made only by the conventional coloring material.

The examples described below are for convenience of description and do not limit the present invention. Although the following examples describe very general representatives, they can also be modified for atypical filaments, denier, temperature, spinning speed and other conditions. Similarly, naturally, from the excellent properties of the coloring material and the easy mixing and mixing property with the wet spinning dope, it is possible to widely substitute other wet spinning fibers without departing from the spirit of the present invention. .

Example 1 Viscose of 8% cellulose and 6% alkali was mixed with three kinds of colorants (reactive dye content 8% / benzoguanamine resin) having an average particle size of 0.1μ, 5.0μ, and 25μ, using a commercially available activator. Water containing 20% was added and mixed, and the mixture was passed through a nozzle with a nozzle hole diameter of 0.07 mm and 30 holes to obtain H ₂ SO ₄ 1
25 g /, ZnSO ₄ 15 g /, Na ₂ SO ₄ 300 g /, spun into a spinning bath at a temperature of 55 ° C., passed through a draft of 15%, and wound as a pot type as 120 denier (dr) / 30 filament (f) fibers. The cake was rolled into a cake and then subjected to conventional refining and drying. The amount of colorant added is 4, 10, 25 in the fiber
% So that the average particle diameter of the coloring material is 25μ.
However, even if the amount added was 4%, the spinnability was remarkably deteriorated, and as a result, the mechanical properties of the fiber were also 0.51.
The g / dr wet elongation was 15%, which was extremely low. This is considered to be because the calculated filament diameter was about 20 μm and the average particle diameter of the coloring material exceeded it.

Further, when the average particle diameter of the coloring material was 5.0 μm, if a high addition ratio of 25% was aimed at for the purpose of dark color, the spinning tone was deteriorated and a good coloring material-containing rayon yarn could not be obtained. However, when the addition rate is 4% and 10%, the spinnability and mechanical properties are of course
The sharpness of the color tone was also extremely excellent. Table 1 above
Shown in.

On the other hand, as a comparative control of fastness, a 20% aqueous dispersion of a coloring material having an average particle size of 5.0 μm and a direct dye content of 10% / benzoguanamine resin was prepared and spun in the same manner. acid,
The fastness to alkali and washing is different from the value specific to the dye, and is fast as a coloring material stable to these treatments, and is improved to the fifth to sixth grade regardless of the reactive dye or the direct dye. However, the light fastness was almost the same as the intrinsic value of the dye, that is, the reactive dye was 6th grade and the direct dye was 4th grade. This is shown in Table 2.

Example 2 In viscose of 8% cellulose and 6% alkali, the alkali concentration was 6.1%, the coloring agent concentration was 25%, and the coloring agent was An aqueous dispersion of the colorant having a mixing ratio of 100 was added and mixed so that the total content of the colorant in the fiber was 3%, and H ₂ SO ₄ 135 g / was passed through a nozzle having a nozzle hole diameter of 0.07 mm and a hole number of 40.
, ZnSO ₄ 18 g /, Na ₂ SO ₄ 290 g /, spinning was carried out at a temperature of 47 ° C. under the condition of a fineness of 120 dr, and post-treatment was carried out according to Example 1, and as a result, the conventional coloring material and the coloring material were obtained. When used in combination, the auxiliary effect on the sharpness of the colorant was extremely remarkable, and it was difficult to use the colorant alone, and it was possible to spin a colorant-containing rayon yarn having a deep and clear color tone. . Of course, its spinnability is good, wet strength 0.85-0.95g / dr,
A wet elongation of 30 to 35% was also shown, and the fastness was 5 to 6 except for the light fastness 2 which was determined by the dye contained in the coloring material.

Example 3 PVA polymerization degree 1500, residual acetic acid group 0.2 mol% PVA concentration 1
5%, for spinning dope at 85 ℃ To Add and mix an aqueous dispersion with a concentration of 20% and adjusted to 85 ° C,
Through a nozzle with a nozzle hole diameter of 0.08 mm and a number of holes of 1000, it was spun into Na ₂ SO ₄ 400 g /, ZnSO ₄ 30 g /, a weak acid 50 ° C. spinning bath, and this was hot-stretched in air at 200 ° C. Total draw ratio is 500%, acetalization degree is 35 mol%
The color tone of the coloring agent-containing vinylon staple fiber having a coloring agent concentration of 2% in the fiber is clear and vivid as never before, and the coloring agent is almost free from high heat during hot drawing. I didn't know. Further, the fiber strength was 5.5 g / dr and the elongation was 15%, which was the same as the colorant-free yarn.

Claims (4)

[Claims] 1. A method for producing a colored wet spun fiber, comprising:
In the wet spinning dope, a coloring material made of a granular synthetic resin having an average particle diameter of 0.1 to 20 μm, which has hydrophobicity, chemical resistance, and heat resistance in which 5 to 10% of a dye is adsorbed, is used in the fiber. % Of a wet-spun fiber having a vivid color tone, which is added and mixed so as to be present in an amount of not more than%. 2. A colorant is directly or previously dispersed uniformly in a solvent of the wet spinning dope or a part thereof, and the dispersion is adjusted so that the concentration of the colorant is 50% or less, and then added and mixed to the wet spinning dope. The method for producing a colored wet-spun fiber having a vivid color tone according to claim 1. 3. A method for producing a colored wet-spun fiber, comprising:
In the wet spinning dope, a general colorant and 5 to the colorant
% Or more of a coloring material made of a granular synthetic resin having an average particle diameter of 0.1 to 20 μm, which is hydrophobic and has chemical resistance and heat resistance in which 5 to 10% of a dye is adsorbed.
% Of a wet-spun fiber having a vivid color tone, which is added and mixed so as to be present in an amount of not more than%. 4. A colorant is directly or previously dispersed uniformly in a solvent of a wet spinning dope, or a part thereof, and further dispersed and adjusted so that the concentration of the colorant is 50% or less, and then added to the wet spinning dope. The method for producing a colored wet-spun fiber having a vivid color tone according to claim 3, wherein the wet-spun fiber is mixed.