JPH07126917A - Polyamide fiber and preparation thereof - Google Patents

Abstract

PURPOSE: To manufacture a polyamide fiber having improved washfastness and heat stability and reduced in yellowing. CONSTITUTION: The polyamide contains (a) a fiber forming polyamide; (b) an additive selected from a group consisting of water, an alcohol, an amine and their mixtures; and (c) a heat satabilizer selected from a group consisting of a phenolic compound, a phosphite containing aryl groups and their mixture.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is directed to nylon fibers having improved washfastness and heat stability of dyes, and in particular additives and phenols such as water, alcohols or amines. Phosphites containing compounds or aryl groups
e) or nylon fibers which contain mixtures thereof as heat stabilizers, and further to a process for their production.

[0002]

BACKGROUND OF THE INVENTION Anionic acid dyeing of polyamide yarns involves the reaction of the amino end groups of nylon yarns with the sulfonic acid end groups of dye molecules.

Depending on the chemical structure of these yarns, the anionic dyes could have mono-, di-, or tri-sulphonic acid end groups. The reactivity of dye and fiber is
It is directly proportional to the number of functional groups present on the dye and / or fiber. Therefore, the greater the number of dye molecules attached to the amino end groups of the fiber, the better the washfastness of the fiber.

Some applications involve heat treating the fabric prior to dyeing. A typical example is the case of an elastic fabric knitted with an elastomeric yarn, such as Lycra (registered trademark, DuPont, Wilmington), which imparts elasticity to the fabric. Heat setting of the fabric before dyeing is essential to avoid curling of the fabric. Typical heat setting temperatures range from as low as 90 ° C to 20
It is in a very severe temperature range of 0 ° C. When heat setting is carried out in air at elevated temperatures, such as 140 ° C. and above, destruction of the functional groups present on the fiber occurs due to oxidative collapse of the amino end groups. This loss of amino end groups reduces the dye molecule's affinity for the fiber. It retains less dye than fabrics that have not been heat set. The fabric has poorer washfastness and dull appearance. In more severe cases, the pre-heat-set and dyed fabrics have a non-uniform appearance. Therefore, there is a need to improve the resistance of polyamide yarns to thermal degradation in order to retain the brightness of the fabric, improve the washfastness of the fabric and further improve the uniformity of the dyed fabric.

Dyeing methods are modified to increase dye uptake in heatset fabrics. In some cases it involves increasing the temperature of the dyebath and / or in many cases decreasing the pH of the dyebath. The modified dyeing method increases the dye's affinity for the fiber, which is a temporary phenomenon. This is because, after dyeing, the fabric is thoroughly washed to remove the acidity in the fabric. Due to the lack of chemical reaction sites in the fiber, the dye molecules captured in the fiber are loosely bound. Such molecules tend to diffuse out of the fabric during subsequent washing. The physical size of these entrapped dye molecules has a significant effect on the diffusion of the dye from the fiber and, therefore, the washfastness of the fabric. Fabrics dyed with smaller dye molecules will exhibit poorer washfastness than larger ones. In many cases,
The smaller dye molecules are those with one sulfonic acid group, ie the least functional group, and therefore have a more inferior affinity for the fiber. Preheated polyamide yarns dyed with such dyes show the worst washfastness.

Several methods have been invented to alleviate this problem. Many of these methods involve chemical treatment after the dyeing step. DE-A-4,131,926 describes a dyed substrate such as nylon treated with a dispersion of sterically hindered cycloaliphatic amines, which results in gloss and washfastness. A method of improving sex is described.

Published German patent application No. 3,33
No. 0,120, a polyamide woven fabric dyed with an anionic dye is post-treated with a polybasic compound, which is a reaction product of a polyamine and a cyanamide derivative, to obtain moisture fastness and wash fastness. It is disclosed to improve the sex.

Further, another method is disclosed in JP-A-56-5329.
No. 3, which discloses that acid-dyed polyamide fibers are treated with a dye-fixing agent. This dye fixative is based on polysulfones, compounds containing amino and sulfonic acid groups, and condensation products of aldehydes. The polyamide fibers treated with this agent have improved wash fastness.

Similarly, JP-A-55-71884 discloses polymeric quaternary ammonium compounds which improve the dye fastness of textiles when applied to the surface of printed polyamide textiles. There is.

Although chemical post-treatment steps have claimed improvements in washfastness, there are still significant deficiencies in some applications. These relate to the basic problem of the reduced affinity of the dye for the fiber due to the depletion of amino end groups during the pretreatment of polyamide fabrics. More important is the increased cost of textile processing. Chemical work-up not only involves the costs of additional treatment steps, but also the costs of chemical treatment of waste liquors and wastewater. The economics of post-treatment will become limiting as environmental regulations on the types of waste products that can be treated become stricter.

[0011] Therefore, there is a need for polyamide fibers having good washfastness to polyamides and methods for their production, without increasing or changing the chemicals currently used in dye baths. . Furthermore, there is a need to achieve better consumption of the dyebath, as it reduces the dyes and chemicals emitted as waste products in the wastewater.

US Pat. No. 4,863,664 describes
A rapid method of making polyamide filaments is disclosed which comprises melt mixing the polyamide with additives such as water, alcohols or organic acids prior to spinning. Although this method claims improved yarn quality, fabric treatment performance and dye fastness to washing, it does not discuss the thermal stability of fibers produced from such methods. The poor thermal stability and the resulting uneven dyeing are significant drawbacks of this method.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to reduce or eliminate the deficiencies present in current polyamide fibers and processes in relation to the wash fastness and heat stability of textiles and to provide improved dyes. The present invention was to provide polyamide fibers having wash fastness and heat stability, and methods for producing the same.

Yet another object was to provide polyamide fibers for the production of yarns having reduced yellowing and capable of retaining the whiteness of textiles after heat treatment and a process for producing such yarns.

Yet another object was to provide polyamide fibers for producing dyed fabrics having improved uniformity even after heat setting and a process for producing such polyamide fibers.

Another object is to provide polyamide fibers and a process for their production which are able to achieve a greater consumption of dye baths at an increased rate, thereby reducing the emission of waste dyes and chemicals into the wastewater. Was to provide.

In addition, another object was to provide polyamide fibers for producing dyed fabrics having a deep dyeing shade and a process for producing such polyamide fibers.

Swimming suits are one of the useful uses of the yarn according to the invention.
Since resistance to fading in chlorinated swimming pools is one of the major requirements, another object of the present invention is improved resistance to fading in chlorinated swimming pools. It is to provide a polyamide fiber having: and a method for producing such a polyamide fiber.

[0019]

The above objects of the invention are: (a) polyamide forming fibers; (b) additives selected from the group consisting of water, alcohols, amines and mixtures thereof; and (c) phenol. Achieved with a polyamide fiber containing a heat stabilizer selected from the group consisting of compounds, phosphites having aryl groups and mixtures thereof.

Fiber-forming polyamide (a) is "nylon"
It is widely known by the generic name of, which is a long chain synthetic polymer with amide (-CO-NH-) bonds along the polymeric backbone. Suitable fiber-forming or melted spinnable polyamides of interest for the present invention include those obtained by polymerization of lactams or amino acids, or those polymers formed by condensation of diamines and dicarboxylic acids. . Typical polyamides include nylon 6, nylon 6/6, nylon 6/9, nylon 6/1
0, nylon 6/12, nylon 6T, nylon 11,
Nylon 12 and copolymers thereof or mixtures thereof are included. In addition, polyamide is a copolymer of nylon 6 or nylon 6/6 and a dicarboxylic acid component such as terephthalic acid, isophthalic acid, adipic acid or sebacic acid, and hexamethylenediamine, meta-xylenediamine, or 1,4-bisamino. It can be a nylon salt obtained by reacting a diamine such as methylcyclohexane. Preferred are poly-epsilon-caprolactam (nylon 6) and adipic acid or sebacic acid and hexamethylene diamine, meta-xylene diamine,
Or with 1,4-bisaminomethylcyclohexane. Preferred are poly-epsilon-caprolactam (nylon 6) and polyhexamethylene adipamide (nylon 6/6). Optimal is nylon 6.

Suitable additives (b) are water, monoalcohols and polyalcohols, monoamines and diamines and mixtures thereof. Suitable monoalcohols are C2-C18 alcohols such as ethanol, propanol, butanol, hexanol, decanol, undecanol, octadecanol; aryl substituted alcohols such as benzyl alcohol and benzoin.

Suitable polyalcohols are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol,
Glycols such as neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane and pentaerythritol.

Suitable amines as additive (b) are monoamines and diamines, preferably diamines such as hexamethylenediamine, meta-xylenediamine and 1,4-bisaminomethylcyclohexane.

Suitable additives (b) are triethylene glycol and hexamethylene diamine.

The additive (b) is usually 0.05 to 5% by weight, preferably 1 to 4% by weight, and most preferably 1.5 to 3% by weight, based on the total amount of polyamide fibers. .

Suitable heat stabilizers (c) are phenolic compounds, aryl group-containing phosphites and mixtures thereof.

Suitable phenolic compounds have at least one phenolic group with two lower alkyl substituents on the aromatic ring, at least one of which is in the ortho position to the hydroxyl group. It is a compound. A lower alkyl group is a suitably branched group such as t-butyl.
Examples of alkyl-substituted phenolic groups are 3-t-butyl-6-methyl-4-hydroxyphenyl and 3,5-dimethyl-4-hydroxyphenyl.

Examples of phenolic compounds are described in US Pat.
No. 187 212, the disclosure of which is hereby incorporated by reference. Preferred is 2,2'-methylene-bis (6-t-butyl-4-
Methylphenol), 2,2'-methylene-bis (6-
t-butyl-4-ethylphenol), 2,2-bis (3,5-di-t-butyl-4hydroxyphenyl)-
Propane, 1,3,5-tris- (3,5-di-t-butyl-4-fudroxyphenyl-propionyl) -hexahydro-s-triazine, N, N'-di (3,5-di-t -Butyl-4-hydroxyphenyl-propionyl) -hexamethylenediamine, 1,3,5-tri (3,5-di-t-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, pentaerythritol-tetra- [3- (3,5-di-t-butyl-4-
Hydroxy-phenyl) -propionate], β (3,
5-t-butyl-4-hydroxyphenyl) -propionic acid-n-octadecyl ester, thiodiethylene glycol-β- [4-hydroxy-3,5-di-t-butyl-phenyl] propionate, 2,6-di- t-Butyl-4-methyl-phenol and 3,9-bis [1,1
Phenolic compounds such as dimethyl-2- (3,5-di-t-butyl-4-hydroxy-phenyl) -ethyl] -2,4,8,10-tetraoxaspiro- [5,5] -undecane Is.

US Pat. Nos. 3,358,4047 and 3
677965 discloses polyamides having these alkyl-substituted phenolic groups, more particularly polyamides derived from alkylhydroxyphenylalkanoic acids and polyamides. These compounds are particularly suitable for the present invention, the disclosures of these patents are incorporated herein by reference.

Suitable phosphites having aryl groups are disclosed, for example, in US Pat. No. 4,187,212, the disclosure of which is incorporated herein by reference.

Suitable phosphites are the following: tris- (2,5-di-t-butylphenyl) -phosphite, tris- (2-t-butylphenyl) -phosphite, tris- (2 -Phenylphenyl) -phosphite, tris- (2- (1,1-dimethylpropyl)-
Phenyl] -phosphite, tris- [2,4-di-
(1,1-Dimethylpropyl) -phenyl] -phosphite, tris- (2-dichlorohexylphenyl) -phosphite and tris- (2,4-di-t-butylphenyl) -phosphite and tris- (2-t- Butyl-4
-Phenylphenyl) -phosphite.

Particularly useful are mixtures of phenolic compounds with phosphites.

The heat stabilizer (c) is usually 0.01 to 3% by weight, preferably 0.1 to 1.5% by weight, optimally 0.15 to 5% by weight, based on the total weight of the polyamide fibers. Used in an amount of 1.25% by weight.

There are many ways to make the polyamide fibers of the present invention. In a preferred embodiment, the method for producing polyamide fibers comprises: (I) a fiber-forming polyamide (i) an additive (b) selected from the group consisting of water, alcohols, amines and mixtures thereof; And (ii) a thermal stabilizer (c) selected from the group consisting of phenolic compounds, aryl group-containing phosphites and mixtures thereof;
(II) melt spinning the polyamide fibers from the homogeneous mixture through a spinneret; (III) cooling the polyamide fibers; (IV) spinning the polyamide fibers. And (V) winding the polyamide fiber, in which case, if necessary, a drawing process may be performed before and after the step (V), and a process of weaving may be appropriately added after the drawing process. Good.

In another preferred embodiment, the stretch ratio is usually 1.0 to 4.0, optimally 1.0 to 3.0. In one step, the heat stabilizer (c) can be added before or during the polymerization of the polyamide and the additive (b) can be added to the fiber before or during the treatment of the polyamide.

In another preferred embodiment, both the heat stabilizer (c) and the additive (b) can be added simultaneously or separately before or during the polymerization of the polyamide and the mixture can be added to the fiber in the next step. Can be processed. Further, the heat stabilizer (c) and the additive (b) may be uniformly mixed and added to the polyamide during the processing into the fiber shape. Thermal stabilizer (c) during processing of the fibers
And adding the additive (b) to the polyamide can be done in several ways. In one case, a suitable supply system, such as Colotron
onics: registered trademark) (Corotronics) or K-
A TRON gravimetric feeder (registered trademark, K-tron, Switzerland) can be used to feed components (b) and (c) separately or as a mixture to the extruder while being volumetrically or gravimetrically measured. In other cases, component (b)
And (c) can be mixed homogeneously in a suitable non-reactive inert liquid and this mixture can be injected into an extruder to obtain a molten mixture with polyamide. Also, if one or both of the components is in liquid form, the mixture may be injected directly into the extruder without dispersing it in an inert liquid.
In another method, a mixture of the two components (b) and (c) can be melted and this melt can be injected into the extruder using a liquid injection system.

In addition, another method of treating the polyamide fibers of the present invention is to produce a concentrated masterbatch of polyamide chips containing high levels of one or both of components (b) and (c), This masterbatch comprises mixing with a polyamide polymer to achieve the desired level of ingredients in the fiber. The mixing of the two polymers, namely the master bag tip and the polyamide tip, can be done using a volumetric or gravimetric feed device at the opening of the extruder, or by mixing a molten stream of the two polymers. Possible side pushers (side-
arm) can be used. The homogenization of the two streams can be done using an in-line electrostatic mixer.

The methods described herein may be used as described, or may be used in combination with two or more methods. Other treatments of this mixture are carried out as follows: Melt mixing is 200 ° C above the melting point of the polyamide used.
It can be carried out in extruders at temperatures up to -40 ° C.
Additives (b) and heat stabilizers (c) may be added together or separately to the polymer chips or granules before they are placed in the extruder, or may be added to the openings of the extruder together with the polyamide. Alternatively, it may be added directly to the melt through a sub-extruder, where it is mixed into a homogenous mixture.

Fiber-forming polyamide (a), additive (b)
And a homogeneous mixture of heat stabilizer (c) is spun through a conventional spinneret to form fibers which are air cooled and solidified. The fibers may be treated with lubricating oils or mixed oils and finishes such as antistatic agents. The application of finish provides efficient handling of the fibers in the spinning machine and in subsequent processing steps. The fibers can be spun in any of the following ways: 1) 400 m / min to 1500 m / min, preferably 600.
a two-step process of stretching in the second step at a speed of m / min to 1200 m / min, or 2) a one-step spinning-drawing and one winding process, or 3) at least 3000 m / min, preferably at least 35.
One-step high-speed spinning process at a speed of 00 m / min without stretching the yarn.

Suitable steps are, for example, weaving the fibers with an air jet, gear crimping, Atuffer box or edge crimping treatment. In some cases, stretching and weaving is a one-step bulked continuous filament for carpet end use.
It can also be carried out in one step, such as the uons filament (BCF) thread step. The woven thread produced in this process is wound into a package.

The fibers of the present invention typically have a denier in the range of 0.5 to 20.0 denier / filament (dpf) (denier = gram weight of a single filament having a length of 9000 meters). The preferred range is 0.7-
It is 3.0 dpf.

The fiber of the present invention is usually 15 to 70 mez /
Amino end group (AEG) content of kg, preferably 35-50 meg / kg and 2.0-3.2, preferably 2.2.
Relative viscosity (RV) of 3.0 (measured in formic acid at 25 ° C., the values given correspond to measurements in sulfuric acid at a temperature of 25 ° C. and a concentration of 1 g of fiber per 100 ml of 96% strength by weight sulfuric acid. Calculated value).

In one preferred embodiment, the polyamide fibers according to the present invention have a 2 to 380 ° F (193 ° C).
It has improved thermal stability, measured by spectrophotometric yellowing value Δb of less than about 8 after a minute of exposure.

In another preferred embodiment, the polyamide fibers according to the invention contain at least 3 parts by weight of fibers.
It has an uptake at a dye saturation value of%.

In another preferred embodiment, the polyamide fibers according to the invention have an improved dye wash fastness as measured by a cigar bleed test discoloration rate of at least 3.5 for color-matched samples. Have.

In another preferred embodiment, the polyamide fibers according to the invention have a toughness of 2 to 5.5 g / den and an elongation of 25 to 75%.

The increased AEG combined effect of the polymers obtained from the heat stabilizer (c) and the additive (b) is:
It results in increased dyeability, improved washfastness, improved heat stability. An additional advantage results from the reduction of the starting concentration of the dyebath to achieve a shade similar to that of the yarn. Also, deep shades not possible with the control yarn are possible with the present invention.

Other advantages are apparent from the examples below.

[0049]

【Example】

Example: 272 through a spinneret with a circular cross section of 12 holes with a pore size of 200 microns and a capillary length of 400 microns.
Nylon 6 (Ultramid (Ultrami
d) (registered trademark) BS 700F, BASF, Freeport, TX) was extruded. Triethylene glycol (TEG) was injected into the throat of the extruder while yarn protection was provided by the Zenith metering pump at different levels. The filament is 100 ft / min (30.5 m) of air at 55 ° F (12.8 ° C) and 65% relative humidity in a cooling cabinet.
/ Min) for cooling. The filaments were passed through a mixed jet and picked up by a set of godets operating at 5000 m / min. The thread was then passed through the steam chamber, here 13
Steam at a temperature of 0 ° C. was maintained at a pressure of 65 psi (448 kPa). This thread is Barmag
It was wound with a SW-6 winder at a speed of 5390 m / min.

Table I shows relative viscosity, amine end group content (A
EG) and various levels of triethylene glycol (T
EG) shows the mechanical properties of the resulting yarn.

[0051]

[Table 1]

[0052]

[Table 2]

The morphological properties of the fibers are listed in Table II. The density of the fiber is Quantachrome
-Measured using a registered trademark) Helium Pycnometer. No correction was made for the added volume. Two typical high speed spun polyamide fibers have two crystal structures,
That is, it indicates alpha and gamma. The percent composition of each of the presented crystal forms is determined by wide-angle x-ray diffraction (WAX).
D) can be obtained using the method. Nylon 6 in 1
Theta 2 Theta Equatorial
l) In the WAXD scan, 5 peaks can be analyzed, 4 of which are assigned as crystalline peaks, namely α ₂₀₀₀ , γ ₀₀₁ , γ ₂₀₀ , and α ₀₀₂ . The relative fractions of alpha and gamma crystals can be obtained as the ratio of the integrated intensities of the analyzed peaks. The Ectorial θ-2θ Diffraction scan is a Cu-generated at 40 KV and 25 mA in a Siemens D500 X-ray generator.
Obtained by Kα irradiation. A 5-line moldel developed by Heuvel and Huismann was used to analyze the peaks and obtain the α / γ ratio (HM Heuvel and R. Hui.
Smann, J .; Appl. Polym. Sci. , P
olym. Phys. Ed. , 19, 121 (198
1)).

The crystallinity is expressed by the following formula:

[0055]

[Equation 1]

[Wherein Xc is volume fraction crystallinity (volu
me fraction crylinity)
Where ρ is the density of the fiber, ρa is the density of the amorphous phase (1.10 gm / cc), and ρc is the density of the pure crystalline phase,

[0057]

[Equation 2]

Show what is obtained from
Calculated based on the fiber density obtained from the e-pycnometer and α-γ crystal fraction.

Pure alpha phase has a density of 1.23 gm /
be understood as cm ^3, and that of a pure gamma phase 1.2
It is estimated to be 1 gm / cm ³ [“Polymer
Handbook, "J. Brandup and E.
H. Immergut, J. Am. Wiley and S
ons, New York (1989)].

The mechanical properties of the fiber are
Atm) tensile tester was used with a pull rate of 24 cm / min and a casing length of 20 cm.

The toughness (Ten) is the breaking load (gms).
/ Defined as denier. Elongation (E
lo) is

[0062]

[Equation 3]

It is defined as

To measure the shrinkage (BWS) of boiling water,
0.0m of 90m skeins, l _o ) thread
Measured with a pre-tension of 56 gm / den, 1 in a boiling water bath
Shrink free for minutes. The skein (l) length was again measured with the same pretension and the percent shrinkage was dl / l _o [where
dl is the change in length of the sample (l _o -1)].

The relative viscosity of the yarn was measured by the one-point method. The flow time (ts) of a 1 wt% thread solution in formic acid was measured using a Ubelhode viscometer and compared to that of pure solvent (to). Relative viscosity (RV) was calculated as ts / to. The RV thus obtained was converted to that which would be obtained using sulfuric acid as solvent by using a calibration curve.

Amino end group (AEG) concentrations were obtained by standard potentiometric titration. 3.33 of dry polymer or yarn
A wt% (bw) solution is prepared in wt% phenol / 32 wt% methanol and brought to a predetermined pH of 0.0
Titrated against 2N hydrochloric acid. AEG, known AEG
It was calculated from the calibration curve obtained using s polymer chips.

The yarn was woven into a woven fabric and dyed by the following method.
The unbleached, undyed fabric was preheat set at 193 ° C for 60 seconds. A dyebath having a liquor ratio of 15 = 1 was prepared, this dyebath being 1% owf Irgalev PBF,
2% owf ammonium sulphate and 2% owf 5
It had a 6% concentration of acetic acid. To test this sample, the unstable shade of a commercial swimsuit was used.

Tint Dye Formulation Red 1.0% by weight of Intrazone Red G 190% (Crompton & Knowles 2.5% by weight Erio Acid Red XB (Ciba Geigy) Blue 2.5% by weight Of Erionyl Brilliant Blue RL 200% (Ciba Geigy) of 1.0% by weight of Solo phenyl Turquoise BLue GRL 250% (Ciba Geigy) was carried out at 96 ° C. for 1 hour. After staining, wash the sample,
Acetic acid 1.0% by weight (28%), tannic acid 3% by weight and fixative XP-10 4.0% by weight (Piedmont)
Treated in a bath containing Chemical Industries, Inc. at 60 ° C. for 30 minutes. This post-treated sample was treated with Peregal ST with a bath ratio of 40: 1.
Washed in a 0.5 wt% bath. The washed sample was then dried and tested for washfastness.

The dye washfastness of the samples was measured using the "cigar bleed" test described below. 2 ″ × 4 ″ of dyed fabric
A (5.08 cm x 10.16 cm) sample was wrapped in a 2 "x 4" (5.08 cm x 10.16 cm) white nylon fabric in the shape of a cigar. The cigar rolls were supported in a moist bath for 24 hours at room temperature. The fabric is dried and the dyeing level obtained on the white fabric is divided into stages of 1 to 5, 5 being the least dyed. Table III shows the results of the cigar bleed tests performed on Examples 1-6. No attempt was made to match the shade to the control.

[0070]

[Table 3]

The reflectance (% R) in%, which is an indicator of the amount of light reflected from a sample dyed with a blue tint, is a CS-5 Chroma Sensor manufactured by Applied Color Systems. It was measured using a (registered trademark) spectrophotometer. 0.223 for spectrophotometer
Mirror-based measurement mode with 6 (0.6 cm) field of view and 10 ° field of view angle (specular-inclu
The ratio of the absorption coefficient to the scattering coefficient (K / S), which is an index of the degree of color depth, is measured by the Kublekar Munk (K
calculated using the ubleka-Munk) approximation:

[0072]

[Equation 4]

[0073]

[Outer 1]

[0074]

[Table 4]

In a separate experiment, an attempt was made to compare the shade obtained using Example 6 with the shade obtained with the control. In order to achieve the same shade as the control sample, the amount of dye in the dyebath of Example 6 had to be significantly reduced. Table V shows the starting dyebath densities of the respective dyes after matching the shades.

[0076]

[Table 5]

Jigger bleed tests were performed on samples that were matched to these colors. The jigger bleed test results set forth in Table VI clearly show the excellent dye fastness of the tests containing TEG.

[0078]

[Table 6]

Examples VII and VIII of Table VII are the results of separate tests carried out under processing conditions similar to those of Examples 1-6, except that the amount of additive and the viscosity of the polymer were different. is there. To process Example 8, using a wear ring mixer, TEG, Irganox B-1171® and TiO ₂ were added at 76 wt% TEG, 14 wt% T.
A uniform slurry was prepared using iO ₂ and 10 wt% Lrganox B1171 and this mixture was injected in the stro section of the extruder. The injection method is described in Examples 2-6.
The injection rate was similar to that used in Example 1 such that the pour rate was 1.6% by weight of TEG, 0.25% by weight of Irga nox® B1171 and 0.3% by weight of TiO _{2 in} the yarn. I adjusted.

[0080]

[Table 7]

Knitting of Examples 1-8 into a woven fabric, 380 ° F.
Heat set for 1 minute and 2 minutes. The degree of yellowing was measured with a spectrophotometer. The Δb value indicates the degree of yellowing compared to the yellowing of the knitted fabric that has not been heat set. Higher Δb values indicate more pronounced yellowing. Table VI presents the Δb values for Examples 1-8.

[0082]

[Table 8]

During dyeing, a small aliquot of dye bath solution was taken to measure the density at regular intervals with a precalibrated spectrophotometer. The dye uptake rate was tectilon blue dye in the dye bath. 1.5% by weight
Was obtained using. Table IX shows the amount of dye on the fabric expressed as a percentage.

[0084]

[Table 9]

Clearly Example 8 shows a higher dyeing rate as well as a higher dye uptake.

In another embodiment, Examples 7 and 8 were dyed to saturation and the residual equilibrium dyebath densities were determined in each. The amount of dye on the fabric was calculated after being normalized to the weight of the sample in the bath.

According to the data in Table X, TEG and Ir
Greater amounts of dye uptake and confirmation are found in samples containing ganox® B1171.

[0088]

[Table 10]

A test for color fastness to water in chlorinated pools was performed according to the standard AATCC test method 162-1986.
(AATTCC Technical Manual / 1988, 295) and carried out in Examples 7 and 8. Results are compared to controls and graded on a gray scale of 1-5,
In this case, 5 indicates that fading in the pool is minimal. The results in Table XI show that the resistance to fading to water in the chlorinated pool was clearly increased.

[0090]

[Table 11]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location D01F 1/10 7199-3B 6/60 311 J 7199-3B

Claims (2)

[Claims] 1. A fiber-forming polyamide; (b) an additive selected from the group consisting of water, alcohols, amines, and mixtures thereof; and (c) a phenolic compound, an aryl group-containing phosphite, and these. A heat stabilizer selected from the group of mixtures of. 2. (a) a fiber-forming polyamide, (i) an additive selected from the group consisting of water, alcohols, amines and mixtures thereof; and (ii) phenolic compounds, phosphites containing aryl groups and these. Melt-mixing with a heat stabilizer selected from the group consisting of
Forming a homogeneous mixture; (b) melt spinning polyamide fibers from the homogeneous mixture through a spinneret; (c) cooling the polyamide fibers; (d) applying a spin finish to the polyamide fibers; and (e) A method for producing a polyamide fiber, which comprises winding the polyamide fiber.