JP2003193380A - Method for dyeing polyamide-based fiber structure and fiber structure obtained therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for dyeing a polyamide-based fiber structure excellent in moisture-absorbing and desorbing properties and having high color development and good color fastness and to provide a fiber structure obtained therefrom. <P>SOLUTION: This method for dyeing the polyamide-based fiber structure comprises dyeing a fiber structure containing a polyamide-based fiber having ≥2.5% difference (ΔMR) between a moisture-absorbing and desorbing rate MR2 at 30°C and 90% RH and a moisture-absorbing and desorbing rate MR1 at 20°C and 65% RH in a dyeing bath having pH 3-7 by using a reactive dye. This polyamide-based fiber structure is composed of a colored polyamide fiber having ≥2.5 difference (ΔMR) between a moisture-absorbing and desorbing rate MR2 at 30°C and 90% RH and a moisture-absorbing and desorbing rate MR1 at 20°C and 65% RH and having a covalently bonded dye. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for dyeing a fiber structure containing a polyamide fiber and a fiber structure comprising the same.

[0002]

2. Description of the Related Art Polyamide fibers have excellent properties such as mechanical strength, chemical resistance, heat resistance, color development, washing durability, and soft touch feeling, and are therefore suitable for clothing, socks and industrial applications. Widely used in the subject. However, on the other hand, although the moisture absorption and desorption of polyamide fibers is higher than that of polyester fibers, it is extremely lower than that of natural fibers such as cotton, so that it can come into direct contact with the skin like sportswear, swimwear, underwear, and socks. Or, it is not used for these applications because it has a drawback that it causes a stuffy feeling or sticky feeling due to sweating from the skin, and that it is not used for these applications.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Polyamide fibers are inferior to natural fibers typified by cotton and cellulosic semi-synthetic fibers typified by rayon in terms of comfort, and have become a major issue to be solved when used in applications where they come into contact with the skin. It was

In order to solve the above-mentioned drawbacks of the polyamide fiber, the moisture absorption / release property has been improved by polymer blending or polymer modification. When dyeing these polyamide fibers having moisture absorption and desorption properties, acid dyes and metal complex salt dyes are used as in general polyamide fibers. However, since the acid dye binds to the fiber by an ionic bond, there is a drawback in that the dye fastness is significantly lowered when the moisture absorption / release property is high. Further, the metal complex salt dye has a relatively small decrease in dyeing fastness, but has a problem that it is poor in vividness and vivid color cannot be dyed.

As described above, the polyamide fiber has a problem that the moisture absorption and desorption property is not compatible with the good dyeing fastness.

In view of such background of the prior art, the present invention has been made.
The present invention provides a method for dyeing a polyamide-based fiber structure, which has excellent color development and excellent dyeing fastness while having excellent moisture absorption and desorption properties, and a fiber structure comprising the same.

[0007]

The present invention employs the following means in order to solve the above problems. That is, the method for dyeing a polyamide-based fiber structure according to the present invention provides a moisture absorption / release rate MR2 at 30 ° C. × 90% RH.
And a fiber structure containing a polyamide-based fiber having a difference (ΔMR) of 2.5% or more in moisture absorption / release rate MR1 at 20 ° C. × 65% RH, dyed at a pH of 3 to 7 using a reactive dye. It is characterized by dyeing in a bath.

The polyamide-based fiber structure of the present invention has a moisture absorption / release rate MR2 at 30 ° C. × 90% RH and 2
Difference with moisture absorption / release rate MR1 at 0 ° C x 65% RH (ΔM
R) is 2.5% or more and is composed of a colored polyamide fiber formed by covalently bonding a dye.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been earnestly studied on the above-mentioned problems, that is, a method for dyeing a polyamide fiber having excellent color development and good dyeing fastness while being excellent in moisture absorption and desorption.
By dyeing a specific polyamide fiber having high moisture absorption and desorption with a reactive dye on the acidic side, it was clarified that these problems can be solved at once.

The polyamide fiber of the present invention has a moisture absorption / desorption parameter, that is, a moisture absorption / desorption rate MR2 at 30 ° C. × 90% RH and a moisture absorption / desorption rate MR1 at 20 ° C. × 65% RH.
It is important that the polyamide fiber has a moisture absorption / desorption property with a difference (ΔMR) of 2.5% or more. That is, the fiber structure composed of such a polyamide-based fiber does not necessarily have to be composed of the moisture-absorbing and desorbing polyamide-based fiber alone, and depending on the purpose, other fibers may be mixed or woven or knitted. May be

In the present invention, "moisture absorption / release parameter ΔM
“R” means moisture absorption / release rate MR2 at 30 ° C. × 90% RH
And the moisture absorption / release rate MR1 at 20 ° C. × 65% RH, which is expressed by the following equation.

Moisture absorption / release parameter ΔMR (%) = MR2-MR1 That is, the moisture absorption / release parameter ΔMR is a drying force for obtaining comfort by releasing moisture in clothes to the outside air when wearing the clothes. Is a light exercise ~
Moisture absorption and desorption rate at humidity of clothes represented by 30 ° C. × 90% RH, and moisture absorption and desorption rate at ambient temperature humidity represented by 20 ° C. × 65% RH during middle exercise Represents the difference between.

In the present invention, this moisture absorption / release parameter ΔM
R is used as a scale for moisture absorption / desorption evaluation, and the larger the value is, the higher the moisture absorption / desorption power is, and the better the wearing comfort is.

The moisture absorptive and desorptive polyamide fiber used in the present invention is required to have the moisture absorptive and desorptive parameter ΔMR of 2.5% or more, more preferably the moisture absorptive and desorptive polyamide fiber. Dehumidification parameter △ MR is 3-8
%, And more preferably 4 to 8%, which can further improve the comfort when worn as clothes.

The moisture absorption / release parameter ΔMR is 2.
If it is less than 5%, it is difficult to prevent stuffiness and stickiness due to sweating from the skin because the moisture absorption and desorption rate is low.
The object of the present invention cannot be achieved. Further, if the moisture absorption / release parameter ΔMR is larger than 8%, the sticky feeling due to the absorbed sweat becomes large.

The polyamide fibers used in the present invention are nylon 6, nylon 66, nylon 610 and nylon 46.
Alternatively, it is not particularly limited as long as it is a polyamide fiber composed of a copolymer of these polyamides. The cross-sectional shape of these polyamide fibers may be any of a round cross section, a trilobal cross section, a four lobe cross section, a hollow cross section, etc., and is not particularly limited.

Further, to the polyamide fiber, pigments such as titanium oxide and carbon black, various antioxidants, anti-coloring agents, light-proofing agents, antistatic agents, etc. are added to the polyamide fiber within the range not impairing the object of the present invention. May be.

The polyamide fiber used in the present invention is not particularly limited as long as it contains a polyamide component and has a moisture absorbing / releasing performance with a moisture absorbing / releasing parameter ΔMR of 2.5% or more. In view of synthetic properties such as spinnability, knitting and weaving properties, dyeability, and durability of yarn performance, it is preferable to use fibers having the following constitution.

That is, the polyamide fiber used in the present invention preferably contains 3 to 15% by weight of polyvinylpyrrolidone (hereinafter referred to as PVP) having a pyrrolidone content of 0.10% by weight or less. This particular PVP
Contains 0.10% by weight of pyrrolidone.
It is characterized by being extremely small as follows. This PVP
Is a moisture absorbing / releasing component and is preferably 3 to 15% by weight, more preferably 4 to 8% by weight, based on the polyamide, in order to suppress stuffiness and stickiness when worn as clothes. It is preferably contained. When the content of PVP is less than 3% by weight, the moisture absorption and desorption property is insufficient, and it becomes impossible to obtain the clothes intended by the present invention. Also, 1
If the amount is too much, such as more than 5% by weight, the sticky feeling becomes strong and the wearing comfort becomes poor. In addition, it becomes difficult to stably produce yarn.

The content of pyrrolidone in PVP is
Preferably 0.10 wt% or less, more preferably 0.0
It is 5% by weight or less, and particularly preferably 0.03% by weight or less. If the content of this pyrrolidone is too high,
The color tone in the greige state after weaving and knitting has a yellowish tint, so that the color tone after dyeing gives a dull feeling, and the desired color tone and high-grade feeling cannot be obtained.

When a polyamide fiber having a moisture absorption / desorption parameter ΔMR of 2.5% or more is dyed with a dye ionically bonded to a fiber such as an acid dye used in ordinary polyamide fibers, the moisture absorption / desorption parameter is The dyeing fastness is lower than that of a normal polyamide fiber having a ΔMR of less than 2.5%. Particularly, the fastnesses such as washing fastness and sweat fastness, which are evaluated in a wet state, are significantly deteriorated. It is considered that this is an adverse effect caused by imparting moisture absorbing / releasing properties to the polyamide fiber.

To solve this problem, the present invention has found that by using a reactive dye in place of the acid dye, the dye fastness is not deteriorated even if the moisture absorption / release property is high. The reactive dye refers to a dye that can be covalently bonded to the polyamide fiber in the dye molecule. For example, the Color Index (Color), which is classified and published by The Society of Dyes and Colorists (SDC) in the United Kingdom.
Index reactive dye (Reactive Dye)
It is a dye classified as s). Specific reactive groups include dyes having at least one reactive group such as a halogenated triazine group, a carboxypyridiniotriazine group, a vinyl sulfone group, a sulfatoethyl sulfone group, a halogenated pyrimidine group, and a halogenated acrylamide group. But
Not limited to these, any dye having a reactive group capable of reacting with a polyamide fiber can be used without particular limitation.

There is no particular limitation as long as it is a dye having one or more of these reactive groups. For example, a homofunctional polyfunctional reactive dye having two or more monochlorotriazine groups in the molecule, or monochlorotriazine. It may be a heteropolyfunctional reactive dye containing a group or a monofluorotriazine group and a sulfatoethylsulfone group in the same molecule.

In the dyeing method of the present invention, pH 3 to 7 is used.
It is characterized in that it is dyed in the dye bath. Adjusting the pH within this range is preferable from the viewpoint of improving the dye utilization rate or the dye exhaustion rate. When the pH of the dyebath is less than 3, the dye exhaustion rate is improved, but the fastness of the dyed material is significantly reduced, and the object of the present invention cannot be achieved. On the other hand, when the dyeing bath has a pH of more than 7, the exhaustion rate and the utilization rate of the dye are lowered, and the dye cannot be dyed in a dark color, the utilization rate of the dye is small, and it is not preferable in terms of drainage load and economical efficiency. The more preferable pH of the dye bath is 4-6.
In this range, the balance between fastness and dye exhaustion rate is optimum. Further, in order to prevent uneven dyeing, a method in which the pH of the dyeing bath at the dyeing start stage is made near neutral and the pH of the dyeing solution is shifted to an acidic side with an increase in time and / or temperature is also an effective and preferable form. As a method of shifting,
Although not particularly limited, for example, a method of adding acetic acid, formic acid or the like during dyeing, a method of previously adding a pH slide agent that shifts to an acidic side, and the like can be used. p
The H slide agent is not particularly limited as long as it is a compound capable of generating an acid depending on temperature and / or time. For example, ammonium sulfate and other commercially available products can be used.

In the present invention, it is preferable to add a leveling agent to the dye bath. As such a leveling agent, a normal fiber-affinity leveling agent or a dye-affinity leveling agent can be used, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric interface can be used. Various substances such as surfactants such as activators and inorganic salts such as mirabilite can be used.

Further, in the dye bath, an antifoaming agent, a light fastness improver,
It is also possible to add a wet fastness improver or the like, or post-process various fastness improvers or functional agents after dyeing.

In the present invention, it is preferable to carry out soaping treatment for removing unfixed dye after dyeing. The soaping treatment is not particularly limited, but it is preferable to use various surfactants. Further, after dyeing with a reactive dye, it is also possible to carry out a fixing treatment using tannic acid or the like as in the case of dyeing with an acid dye, or a fixing agent for a reactive dye.

As the form of the polyamide fiber at the time of dyeing,
Dyeing with a reactive dye is possible in any state of yarn such as a case and cheese, and in a state of cloth such as a woven or knitted fabric, and is not particularly limited.

The colored polyamide fiber structure of the present invention thus obtained has a moisture absorption / release rate MR2 at 30 ° C. × 90% RH and a moisture absorption / release rate MR1 at 20 ° C. × 65% RH.
(ΔMR) is 2.5 or more, and is composed of a colored polyamide fiber formed by covalently bonding a dye, and the colored polyamide fiber structure may be used for clothes. Or, it may be partially used for a part of clothes, and its use is not limited in any way.

[0030]

EXAMPLES In the examples of the present invention described below, the evaluation of characteristics and the like was obtained by the following method. [Moisture absorption and desorption parameter ΔMR] Raw yarn or knitted fabric 1 to 3
g, dry weight and 20 ° C x 65% R
The moisture absorption and desorption rate of the following equation was calculated from the weight change from the weight after standing for 24 hours in a commercially available constant temperature and humidity chamber under an atmosphere of H and 30 ° C. × 90% RH.

Moisture absorption / desorption rate (%) = [(weight after moisture absorption / desorption-weight when dried) / weight when absolutely dry] × 100 Moisture absorption / desorption rate under the condition of 20 ° C. × 65% RH. From the moisture absorption / release rate MR2 under the conditions of MR1 and 30 ° C. × 90% RH, the moisture absorption / release rate difference ΔMR (%) = MR2-MR
Let 1 be the moisture absorption and desorption parameter. [Pyrrolidone content] 1 to 3 g of raw yarn is dissolved in chloroform, and a gas chromatogram analysis is performed by a conventional method using a GC14A type apparatus manufactured by Shimadzu Corporation. The pyrrolidone content is calculated by the following formula.

Pyrrolidone content = [(GC peak area /
Calibration curve coefficient) (mg / ml) × solution amount (ml) / sample amount (mg)] × 100 [Washing fastness measurement] JIS L0844 “Dyeing fastness test method for washing” was measured. [Friction fastness measurement] Measured according to JIS L0849 "Test method for fastness to dyeing with respect to friction".

Example 1 PVP was synthesized by a conventional method using isopropyl alcohol as a solvent, and the content of pyrrolidone was 0.02% by weight.
Was obtained. This PVP was kneaded into nylon 6 using an extruder to obtain a master polymer chip having a PVP concentration of 30% by weight.

A normal nylon 6 chip and the master polymer chip were blended at a predetermined ratio, and the content of PVP with respect to nylon 6 in the blended chip was 3% by weight.

This blended chip was subjected to an ordinary nylon melt spinning method to obtain a nylon 6 filament of 33 dtx10 filament (single yarn fineness 3.3 dtex) containing 3% by weight of PVP and 0.02% by weight of pyrrolidone.

The moisture absorption / release parameter ΔMR of this raw yarn was 3.9%. Aiming at a knit for running shirts / pants, using 100% of this filament to knit a raw fabric with a half structure of a tricot knitting machine 36G, and then finishing density 51 wells / inch, 73 according to a normal nylon tricot dyeing method. Course / inch, basis weight 86
A knitted fabric of g / m ² was produced.

This was dyed with a reactive dye using a jet dyeing machine under the following conditions.

Dye: Kayacion Blue P-3R 2% owf Auxiliary: (acetic acid: sodium acetate = 8: 15) 1.0 g / l Bath ratio: 1:30 pH: 5.5 Dyeing cam: 40 ° C. → (2 Table 1 shows the results of drainage. Good results were obtained for both washing fastness and rubbing fastness.

Comparative Example 1 Nylon 6 knitted fabric used in Example 1 (Basis weight 86 g / m ² ).
Was dyed with an acid dye using a jet dyeing machine under the following conditions.

Dye: Nylosan Blue FL 150% SGR 2% owf Auxiliary agent: Acetic acid (100%) 0.24 g / l Leveling agent: Migregal N-85 (manufactured by Senka Co., Ltd.) 1.2 g / l Bath ratio: 1: 20 pH: 5.5 Dyeing cam: 40 ° C. → (2 ° C./min)→100° C. × 60 min → 80 ° C. → Wastewater absorption / desorption parameter ΔMR was 3.9%. The results are shown in Table 1. As compared with Example 1, both the wash fastness and the rub fastness were poor.

Comparative Example 2 Nylon 6 knitted fabric used in Example 1 (Basis weight 86 g / m ² ).
Was dyed with a reactive dye using a jet dyeing machine under the following conditions.

Dye: Kayacion Blue P-3R 2% owf Auxiliary agent: Acetic acid 1.0 g / l Formic acid 1.0 g / l Bath ratio: 1:30 pH: 2.0 Dyeing cam: 40 ° C. → (2 ° C./min ) → 100 ° C. × 60 min → 80 ° C. → Drainage results are shown in Table 1. Both the wash fastness and the rub fastness were worse than those of Example 1.

Comparative Example 3 Nylon 6 knitted fabric used in Example 1 (Basis weight: 86 g / m ² ).
Was dyed with a reactive dye using a jet dyeing machine under the following conditions.

Dye: Kayacion Blue P-3R 2% owf Auxiliary agent: Soda ash 1.0 g / l Bath ratio: 1:30 pH: 8.0 Dyeing cam: 40 ° C. → (2 ° C./min)→100° C. × Table 1 shows the results of 60 minutes → 80 ° C. → drainage. The washing fastness and rubbing fastness were not bad, but the dye exhaustion was poor.

COMPARATIVE EXAMPLE 4 The same 33 dte as in the example was used using regular nylon.
A nylon 6 filament of x10 filament (single yarn fineness: 3.3 dtex) was obtained. The moisture absorption / release parameter ΔMR of this yarn was 0.4%. Aiming at knitting for running shirts and pants, using 100% of this filament to knit a raw machine with a half structure of the tricot knitting machine 36G, then according to the usual nylon tricot fabric dyeing processing method,
A knitted fabric having a finish density of 51 wells / inch and a course weight of 73 courses / inch and a basis weight of 86 g / m ² was produced.

This was dyed with a jet dyeing machine under the following conditions.

Dye: Nylosan Blue FL 150% SGR 2% owf Auxiliary agent: (acetic acid: sodium acetate = 8: 15) 1.0 g / l Bath ratio: 1:30 pH: 5.0 Dyeing cam: 40 ° C. → ( 2 ° C./min)→100° C. × 60 min → 80 ° C. → Drainage results are shown in Table 1. Good results were obtained in both washing fastness and rubbing fastness, but there was a feeling of stuffiness when worn, and it was not comfortable.

[0048]

[Table 1]

[0049]

EFFECTS OF THE INVENTION According to the present invention, it is possible to reduce the stuffiness and stickiness caused by the low moisture absorption and desorption, which is a defect of the polyamide fiber, and to improve the mechanical strength characteristic of the polyamide fiber.
It is possible to provide a polyamide-based fiber structure having high moisture absorption and desorption, a soft texture, and excellent dyeing fastness while maintaining chemical resistance and dyeability.

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Claims (2)

[Claims] 1. A moisture absorption / desorption rate M at 30 ° C. × 90% RH
Using a reactive dye, a fiber structure containing a polyamide-based fiber having a difference (ΔMR) between R2 and moisture absorption / release rate MR1 at 20 ° C. × 65% RH of 2.5% or more was adjusted to pH 3 to 7. A method for dyeing a fiber structure, which comprises dyeing in a dye bath. 2. A moisture absorption / desorption rate M at 30 ° C. × 90% RH
The difference (ΔMR) between R2 and the moisture absorption / release rate MR1 at 20 ° C. × 65% RH is 2.5 or more, and the dye is covalently bonded to the colored polyamide fiber. Characteristic polyamide fiber structure.