JPH0474474B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for improving the color fastness of dyed products of polyamide fibers spun at high speed. (Prior Art) In recent years, in order to improve productivity, there has been an increasing demand for speeding up the spinning process of polyamide fibers. Broadly speaking, there are two methods that can satisfy this demand for higher speeds:
One method is to wind polyamide fibers that have been melt-spun at extremely high speeds, such as 3000 m/min or higher, without being stretched, to create fibers with physical properties and structure that can be used in practical applications. Another method is to continuously stretch polyamide fibers that have been prevented from melting without first winding them up, and then wind them up at a high spinning speed of, for example, 1000 m/min or more and a drawing ratio of 1.1 times or more. It's a method. (Problems to be Solved by the Invention) The thus obtained high-speed spinning polyamide fibers are processed by conventional methods such as spinning, winding once, conditioning under constant temperature and humidity, and then conditioning at a predetermined magnification. Compared to polyamide fibers obtained by a method of drawing, the fibers have almost similar physical properties, but the crystal structure is unstable. For example, polyamide fibers obtained by conventional methods often have an α-type crystal structure, whereas polyamide fibers produced by high-speed spinning have a low birefringence and a γ-type crystal structure.
As a result, when polyamide fibers spun at high speed are dyed with acid dyes or metal-containing dyes that are generally used for dyeing polyamide fibers, it is easy to dye vivid colors. It has poor color fastness, which poses a problem when used for sports equipment or clothing, especially sportswear. On the other hand, in order to improve the color fastness of dyed polyamide fibers, tannic acid/
Various methods have been investigated for treating polyamide fibers using tartarite two-bath treatment agents or single-bath type synthetic tannin compounds such as phenol derivatives and tannic acid derivatives. Even when applied to dyed products, sufficiently satisfactory color fastness cannot be obtained. An object of the present invention is to improve the color fastness of dyed products of such high-speed spinning polyamide fibers. (Means for Solving the Problems) As a result of extensive research to achieve the above object, the present inventors discovered that it is sufficient to treat with a water and oil repellent, and have arrived at the present invention. That is, the present invention provides a high-speed spun polyamide fiber characterized in that a dyed product of polyamide fiber spun at high speed and having a birefringence index of 0.035 to 0.550 is treated for color fastness and then treated with a water and oil repellent. This is a method for improving color fastness. The polyamide fibers in the present invention include aliphatic polyamide fibers such as nylon 6 and nylon 66;
Examples include xylylene diamine polyamide fibers and other aromatic polyamide fibers, with nylon 6 and nylon 66 fibers being particularly preferred. The high-speed spun polyamide fibers used in the present invention generally refer to fibers obtained by spinning at a speed of 3000 m/min or more and winding without drawing, or fibers obtained by continuous spinning and drawing, with a drawing ratio at a spinning speed of 1000 m/min or more.
Refers to fibers obtained by stretching the fibers to 1.1 times or more, heat-treating them, and then winding them up. The refractive index of the obtained fibers is generally 0.0035 to 0.0035 for the former method.
0.042, and 0.042 to 0.055 for the latter method. Acidic dyes and metal-containing dyes are generally used to dye high-speed spinning polyamide fibers.Among them, acidic dyes are available in a wide variety and are advantageous in terms of cost, and can produce vivid colors ranging from light colors to deep colors. In order to be able to
Suitably used. In the present invention, water and oil repellents used for treating dyed products of high-speed spinning polyamide fibers include water and oil repellents made of fluorine-based polymers, silicone-based polymers, etc. ,
Those containing a fluorine-based water and oil repellent, one or more ethyleneimine compounds shown in (A) below, and a melamine compound shown in (B) are the dyeing objects of the present invention. Not only does it improve fastness, but it also eliminates the need for ironing or heat pressing.
This is desirable because a sufficiently durable water- and oil-repellent coating is formed on the fiber surface. Here, the ethyleneimine compound (A) preferably contains two or more of the functional groups, and for example, the following are preferable. Furthermore, as the melamine compound (B), polymers of the following compounds are preferably used. In the formula, R ₁ to R ₆ are each independently -H, -
OH, −OC _o H _2o+1 , −CH ₂ OC _o H _2o+1 , −CH ₂ OH, −
_{CH2CH2OH , -CH2CH2CH2OH} , _{-CONH2 , -}
CONHCH ₂ OH or

[Formula] where n represents a positive integer, particularly an integer from 1 to 16. In this case, the amount of finishing agent used is 0.5% owf to 2% owf of the pure fluorine-based water and oil repellent.
The ethyleneimine compound in (A) is also pure,
0.02%owf~0.2%owf, (B) melamine compound is
A desirable example is 0.05% to 1% owf. If the amount of each used is less than this, the color fastness will not be improved sufficiently, and the durability of the water repellent effect will be poor, and if the amount is more than this, problems such as a hard texture will occur, which is not preferable. As a method for applying these processing agents, any method such as an adsorption method, a pad method, a coating method, or a spray method can be adopted. After application, dry at 100℃
Heat treatment is performed at a temperature higher than 150-190℃, but it is usually 1-3℃.
Perform heat treatment for 1 minute. Furthermore, in the present invention, prior to the water- and oil-repellent treatment, the dyed product of high-speed spinning polyamide fiber is treated with:
If the dye is treated with a dye fixative, the color fastness will be further improved. As a dye fixing agent, it has been used conventionally. Examples include a two-bath treatment agent of tannic acid/tartarite, and a single-bath type synthetic tannin compound that has been frequently used recently. Synthetic tannin compounds are generally classified into several types, but the main ones include oligomer types in which sulfonated products of naphthylamine, phenol, and naphthol are bonded with formalin. Furthermore, those having polar groups such as carbonamide, sulfonamide, and ureido may also be used. Particularly suitable is a formalin condensate of dihydroxyphenyl sulfone, which has excellent properties such as not only the ability to improve color fastness but also little adverse effect on sunlight fastness, etc., and less coloring of fabrics. The concentration of the dye fixing agent used is 2 to 10% by weight based on the weight of the fabric, and the processing temperature is
Preferably, the temperature is 80 to 100°C and the pH of the treatment bath is 2 to 4. Methods for treating dyed polyamide fibers with a dye fixing agent treatment bath include a method in which the dyed article is immersed in a heat treatment bath, and a method in which the dyed article is impregnated with the treatment bath,
There are methods such as steam treatment using a steamer, etc., and the method may be selected as appropriate depending on the processing step. The method of the present invention can be applied to the dyed high-speed spinning polyamide fibers in any form such as yarn, cotton, woven or knitted fabrics, or needle-punched or tufted fabrics such as carpets. Furthermore, the dyed polyamide fiber may be made of 100% polyamide fiber, or may be a mixture of polyamide fiber and other fibers. (Function) According to the method of the present invention, the color fastness of dyed polyamide fibers is improved because the surface of the dyed products is coated with a water- and oil-repellent, and the polyamide fibers themselves are protected against washing water, sweat, etc. It is thought that this reduces the chance of contact and prevents the dye from falling off from the dyed product. In particular, by using a water and oil repellent containing a fluorine-based water and oil repellent, an ethyleneimine compound, and a melamine compound, the fluorine-based water and oil repellent is The cross-linked structure maintains the extremely strong structure of the fluorine-based water and oil repellent polymer, which prevents the arrangement of fluoroalkyl or fluoroalkenyl groups from being disturbed by washing, resulting in dye fastness that is durable against washing. It is believed that performance can be obtained. Furthermore, if a dyed polyamide fiber is treated with a dye fixing agent and then treated with a water and oil repellent, the dye fixing effect and the water and oil repellent effect are combined, and the color fastness is further improved. (Example) The present invention will be explained below with reference to Examples. In addition, in each example, the water repellency evaluation was
The test was conducted in accordance with JISL1092 5.2 Repellency (spray test). The laundry was carried out using a household washing machine, using Super Zabu (registered trademark: manufactured by Kao Soap) as a detergent, and repeating the following steps a predetermined number of times. Detergent 2g/→ Dehydration → Water washing → Dehydration bath ratio 1:3 1:30 40℃×5 minutes 2 minutes → Water washing → Dehydration → Air drying 1:30 2 minutes In addition, the color fastness to washing is JISL0844-70, and the color fastness is JISL0846−67, dye sweat fastness is JISL0848
-65, was tested by the alkaline method, and visually compared and evaluated based on gray scale, and was graded into grades 1 to 5. The higher the grade, the better the fastness. Example 1 Poly-ε-caproamide chips were spun (drawn) under the following three conditions to obtain nylon 6-filament fibers of 70 de/34 fils. Fiber (A): Melt-spun at a spinning speed of 3750 m/min and wound without stretching. Obtained fiber (A)
had a strength of 4 g/de, an elongation of 60%, and a birefringence of 37×10 ^-3 . Fiber (B): Melt-spun at a spinning speed of 3500 m/min, continuously stretched to 1.10 times without winding, heat treated at 180°C, and then wound. The obtained fiber (B) has a strength of 5 g/de and an elongation of 50
%, and the birefringence was 42×10 ^-3 . Fiber (C): Melt-spun at a spinning speed of 1000 m/min, wound once, and then stretched at a drawing speed of 800 m/min to 3.0 m/min.
It was stretched to double its original size, heat treated at 150°C, and then rolled up. The obtained fiber (C) has a strength of 5 g/de,
It had an elongation of 40% and a birefringence of 58×30 ^-3 . These fibers (A), (B), and (C) were used for the warp and weft, respectively, to weave a taffeta fabric, and after scouring relax and presetting, it was dyed under the following conditions. Dye: Kayanol Mill Red RS [Registered trademark: Nippon Kayaku Co., Ltd.] 3% owf Leveling agent: Migre Girl 2N [Registered trademark: Nippon Someka Co., Ltd.] 1% owf PH adjuster: 90% acetic acid 0.2cc/ The dyeing is done using a 12-color rotary dyeing machine.
It was carried out for 60 minutes at ℃. Furthermore, the dyed fabrics prepared in Test Nos. 1 and 4 in Table 1 were treated with a dye fixing agent according to the following recipe. <Dye fixative treatment method> (1 bath treatment) Tannic acid (pharmacopoeia) (owf%)...5 <80℃ x 30 minutes> (2 bath treatment) Tartarite (reagent) (owf%)...3 <80°C x 30 minutes> Next, after washing and drying, the fabric was subjected to the water repellent treatment shown in Table 1. After drying, it was heat set at 160°C for 1 minute to finish the fabric. The water repellency and color fastness of the obtained fabric were as shown in Table 1. As is clear from Table 1, high-speed spinning polyamide fibers treated with water and oil repellents (Test No.
2 and 5) have improved color fastness compared to the untreated ones (Test Nos. 3 and 6), but it is not sufficient. , when using something containing an ethyleneimine compound and a melamine compound (Test Nos. 1 and 4)
A remarkable effect of improving color fastness was observed. Note that ordinary polyamide fibers that are not subjected to high-speed spinning originally have high color fastness, and even when treated with water and oil repellents, no significant effect of improving color fastness was observed. (Test No. 7, 8, 9).

【table】

[Table] Yes.
(*) Sumitekus Resin M-3 is trimethylolmelamine.
Example 2 Tannic acid/tartar dye fixing agent 2 conducted on the dyed fabrics of Test Nos. 1 and 4 in Example 1
Instead of bath treatment, one bath treatment of formalin condensate of dihydroxydiphenyl sulfone (fixed concentration 5%) was used.
owf, treatment temperature 90°C, treatment time 30 minutes), and other conditions were the same as in Example 1. When water repellent treatment was applied, fibers (A: corresponding to test No. 1),
(B: Corresponds to test No. 4) Each color fastness is 5.
It showed extremely excellent color fastness. (Effects of the Invention) According to the present invention, the color fastness of dyed products of high-speed spinning polyamide fibers can be significantly improved.

Claims (1)

[Claims] 1. When treating a dyed product of polyamide fiber spun at high speed with a birefringence index of 0.035 to 0.550 with a water and oil repellent, after treating the dyed product with a dye fixing agent,
As the water and oil repellent, a fluorine-based water and oil repellent and the following are used.
Color fastness of high-speed spun polyamide fibers characterized by being treated with one or more of the ethyleneimine compounds shown in (A) and the melamine compounds shown in (B) How to improve. However, ethyleneimine compound (A): Melamine compound (B): In the formula, R ₁ to R ₆ are each independently -H, -
OH, −OC _o H _2o+1 , −CH ₂ OC _o H _2o+1 , −CH ₂ OH, −
_{CH2CH2OH , -CH2CH2CH2OH} , _{-CONH2 , -}
CONHCH ₂ OH or ##STR1## where n is a positive integer, especially an integer from 1 to 16. 2. The method according to claim 1, wherein the dye fixing agent is treated by a two-bath treatment of tannic acid/tartarite. 3. The method according to claim 1, wherein the dye fixing agent is treated using a synthetic tannin compound.