JP2003227006A - Hosiery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To speedily supply fashionable hosiery having soft touch feeling which polyamide multifilaments have to markets by changing the colors of a ground yarn and a pattern yarn together with patterns by knitting. <P>SOLUTION: The hosiery is obtained by knitting at least two or more kinds of polyamide multifilaments or a polyamide multifilament and a cation-dyeable polyester multifilament into a knitted pattern structure and dyeing the knitted product. In the hosiery, at least one kind of multifilament among these multifilaments is dyed in a color different from any one of other multifilaments. <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 socks having excellent fashionability, and more particularly to socks having a pattern and free color development.

[0002]

2. Description of the Related Art Up to now, when trying to express socks with a pattern knitting structure in multiple colors, it is necessary to prepare a yarn dyed yarn of cotton / acrylic blend or nylon in advance. It often happened that people would lose the opportunity to sell because they had a problem or lack of products.

For example, taking pantyhose as an example, it was often dyed with a complexion color for spring and summer and a dark color such as black or navy blue for autumn and winter. More often. In addition to the plain surface, various patterns are available on the market, and novelty is always required to attract the attention of consumers.

However, pantyhose are often dyed in a single color, and in order to make them different colors, for example, polyethylene terephthalate (hereinafter referred to as PET) is used.
The dyed false twisted yarn is used, but the cost is high,
It is necessary to prepare yarns of various colors, which makes it difficult to put products on the market quickly. Furthermore, PET yarn-dyed yarns have a weak crimp, a tight texture, and poor knitting properties. was there. Further, as described in Patent Document 1, for example, a polyamide multifilament and a PET yarn that is not dyed with an acid dye are used, and only the polyamide multifilament is dyed to give a different color.
In this case as well, variations in color are similarly limited, and problems remain in texture and knitting property.

On the other hand, as described in Patent Document 2, a double-coated elastic yarn in which two cover yarns which are dyed differently by post-dyeing are covered with elastic yarns aiming at a visual effect in which the color tone changes depending on the viewing direction. Is proposed. However, when viewed from a distance, it looks like only a single color, and it is not intended to enhance fashionability by combining colors with patterns.

[0006]

[Patent Document 1] JP-A-48-16735 (page 2, lines 4 to 21)

[Patent Document 2] Japanese Patent Laid-Open No. 5-163626 ([00
17]-[0025] paragraph)

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention provides a sock that can be dyed differently by post-dyeing so that the color combination of the pattern structure can be freely and quickly adapted to the needs of the market. is there.

[0008]

In order to solve this problem, the sock of the present invention has one of the following configurations. That is, (1) a sock obtained by knitting at least two or more kinds of polyamide multifilaments into a pattern knitting structure and then dyeing, wherein at least one kind of the polyamide multifilaments is another polyamide multifilament. A sock characterized by being dyed with a different color from any one of filaments.

(2) A sock using at least one polyamide multifilament as a ground yarn and another polyamide multifilament as a pattern yarn among the above-mentioned at least two or more polyamide multifilaments, which is anionic dyeable. A sock according to (1), characterized in that a part of the pattern yarn is dyed in a different color to the ground yarn after knitting by using the volatile polyamide multifilament and the metachromatic polyamide multifilament.

(3) The sock according to (2), characterized in that the anion-dyeable polyamide multifilament or / and the heterochromatic polyamide multifilament is used as a covering thread covering each.

(4) A sock according to (2) or (3), which is dyed in three or more different colors using at least anion-dyeable polyamide multifilament and heterochromatic polyamide multifilament. .

(5) The socks according to any one of (2) to (4), characterized in that the metachromatic polyamide multifilament is a cationic dyeable polyamide multifilament, (6) at least the polyamide multifilament and cationic A sock obtained by knitting into a pattern knitting structure using a dyed polyester multifilament, wherein the polyamide multifilament and the cationic dyeable polyester multifilament are dyed in different colors. socks. Is.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The sock of the present invention is a sock obtained by knitting at least two or more types of polyamide multifilaments into a pattern knitting structure and then dyeing, wherein at least one kind of the multifilaments is a multifilament. It is formed by dyeing a different color from any one of the other multifilaments. That is, the polyamide multifilament is dyed differently after being knitted with knitted socks. Therefore, the socks can be made more fashionable than ever by the arrangement of threads, the pattern, and the combination of colors. In addition, after the knitting, the products can be dyed differently, so that it is possible to stock the knitted products after the knitting, dye the color combination according to the needs of the market, and then quickly arrange the products in the store.

Alternatively, a sock obtained by knitting into a pattern knitting structure using at least a polyamide multifilament and a cationic dyeable polyester multifilament, wherein the polyamide multifilament and the cationic dyeable polyester multifilament are formed. , By dyeing different colors. That is, it is a sock with a handle, and after knitting, polyamide multifilaments and polyester multifilaments are dyed differently.

As a method for dyeing, at least one type of multifilament is an anion-dyeable polyamide multifilament, and the other multifilament is a dye-dyed polyamide multifilament or a cationic dyeable polyester, and one or all of the polyamide multifilaments are formed after knitting. By dyeing a filament or a cationic dyeable polyester, it is possible to perform dyeing separately.

Above all, at least the anion-dyeable polyamide multifilament and the metachromatic polyamide multifilament, or the metachromatic dyed polyamide multifilament and the anion-dyeable polyamide multifilament are used for the pattern yarn and the ground yarn in the pattern knitting structure, respectively. After the knitting is performed, by dyeing with a different color, a part of the pattern has a color different from that of the ground yarn, so that the pattern is further raised and the pattern can be effectively produced, which is preferable. In addition, the anion-dyeable polyamide multifilament and the heterochromatic polyamide multifilament are used as the surface yarn and the pattern yarn, respectively.
It is also possible to dye different colors by using them as back yarns, which is within the scope of the present invention. Furthermore, it is also preferable to use an anion-dyeable polyamide multifilament and a metachromatic dyed polyamide multifilament as the ground yarn and the handle yarn, respectively, and to switch between them. The same combination can be obtained when an anion-dyeable polyamide multifilament and a cation-dyeable polyester are used.

Here, the pattern knitting organization is "sock engineering" (edited by the Japan Socks Industry Association, published by the Japan Socks Association in 1979) P47 II-1 Flat knit socks-pattern-color shown in the pattern classification of socks. It refers to the structure belonging to the pattern and the structure belonging to the rib knit sock-pattern-color pattern, and includes the mixed pattern described in the above publications. In the present invention, the thread that appears on the surface material of the portion that constitutes the handle is called the handle thread, and the thread that is used in the portion other than the handle is called the ground thread. For example, the thread forming the polka dot pattern is called the pattern thread, and the other portions are called the ground thread. Even if it is composed of only a pattern like a net pattern, for example, using anion-dyeable polyamide multifilament and metachromatic polyamide multifilament, if a pattern such as a stripe is expressed, it is within the scope of the present invention. Yes, or the pattern may be expressed by front and back threads like plating.

Here, at least yarns of different colors are used for durability, fastness, heat retention, softness to the touch,
A polyamide multifilament is preferable in terms of color developability. Further, the polyamide referred to in the present invention is a high molecular weight body in which a so-called hydrocarbon group is linked to the main chain via an amide bond, and the type thereof is not particularly limited,
A polyamide mainly composed of polycapramide or polyhexamethylene adipamide is preferable from the viewpoint of excellent dyeability, washing fastness and mechanical properties.
The term "mainly" as used herein means 80 mol% or more as a capramide unit or hexamethylene adipamide unit, and more preferably 90 mol% or more. Other components are not particularly limited, but include, for example, polydodecanamide, polyhexamethyleneadipamide, polyhexamethyleneazeramide, polyhexamethylenesebacamide, polyhexamethylenedodecanoamide, polymetaxylyleneazide. Examples include units such as aminocarboxylic acid, dicarboxylic acid, and diamine, which are monomers constituting pamide, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, and the like. Further, if necessary, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a terminal group adjusting agent, a dyeability improving agent and the like may be added. Further, it is preferable to add a matting agent such as titanium oxide to the extent that mechanical properties are not impaired.

The anion-dyeable polyamide multifilament is a so-called general polyamide having an amino terminal group. Anion dyeable polyamide multifilaments can be dyed with acid dyes, reactive dyes, metal-containing dyes and the like. On the other hand, a heterochromatic polyamide multifilament refers to a polyamide multifilament that is dyed with a dye other than an anionic dye (excluding disperse dyes and slene dyes). For example, a polyamide multifilament that is dyed with a cationic dye by introducing a sulfone group, a so-called cation A dyeable polyamide multifilament is preferably used. Here, as a method of introducing a sulfone group, when polymerizing polyamide, 5-
Sodium sulfoisophthalic acid, its diester, 3-
It can be realized by adding sodium carboxybenzene sulfonate, sodium 3,5-dicarboxybenzene sulfonate, or a lithium salt thereof and copolymerizing. Further, the cationic dyeable polyamide multifilament can be dyed with a cationic dye.

As the cationic dyeable polyester, an isophthalic acid component containing a metal sulfonate group is copolymerized in an amount of 2.4 to 5 mol% with respect to the total acid component in the polyester, and a glycol component is added in an amount of 2 to 7% by weight. % Copolymerized polyester multifilament is preferable. This is because the cation dyeable polyester that is usually used has an insufficient dye exhaust amount unless dyed at a temperature higher than 100 ° C. (105 to 130 ° C.). On the other hand, elastic fibers are often mixed in order to improve the fit of socks, and such a dyeing temperature is not preferable because the strength is deteriorated. Further, since it is dyed under normal pressure, it is not necessary to prepare an expensive pressure type dyeing machine.

The isophthalic acid component containing a metal sulfonate group is particularly preferably copolymerized in an amount of 2.5 to 4.0 mol%. If the copolymerization amount of the isophthalic acid component containing a metal sulfonate group is less than 2.4 mol%, satisfactory cationic dyeability cannot be obtained even if the copolymerization amount of the glycol component is increased. When the copolymerization amount of the isophthalic acid component containing a metal sulfonate group exceeds 4 mol%, the melt viscosity of the polymer is remarkably increased due to the thickening action of the isophthalic acid component containing a metal sulfonate group, and the yarn is spun under normal spinning conditions. Is impossible.

The isophthalic acid component containing a metal sulfonate group as used in the present invention is specifically a metal such as 5-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid dimethyl ester, 5-sodium sulfoisophthalic acid diethyl ester. Examples thereof include benzenedicarboxylic acid having a sulfonate group and 4-sodium sulfo-2,6-naphthalenedicarboxylic acid.

Further, in the present invention, the glycol component must be copolymerized in an amount of 2 to 7% by weight based on the total polyester. From the viewpoint of easy dyeability and light fastness, the average molecular weight of the glycol component to be copolymerized is preferably 90 to 6000. Examples of the glycol component in the present invention include neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 4,4-dihydroxybisphenol, and the like. Examples of the glycol include polyethylene glycol to which ethylene oxide is added, and polyethylene glycol, and the like, and polyethylene glycol having a large viscosity reducing effect is more preferable. It is important that the copolymerization amount of the glycol component in the present invention is 2 to 7% by weight based on the total polyester obtained. When the copolymerization amount of the glycol component is less than 2% by weight, the melt viscosity of the polyester becomes too large, making it difficult to form a yarn and significantly reducing the dyeability of the obtained polyester fiber. If the amount of copolymerization exceeds 7% by weight, the heat resistance of the polyester will decrease. A copolymerization amount of 3 to 6% by weight is more preferable.

In the present invention, a cationic dyeable polyester having a dye exhaustion rate of 60% or more was evaluated as a normal pressure cationic dyeable polyester by the dyeability evaluation of the cationic dyeable polyester described in Examples.

These anion dyeable polyamide multifilaments, metachromatic polyamide multifilaments, and cation dyeable polyesters are subjected to false twisting for imparting elasticity, and elastic yarns for imparting higher elasticity. It is also preferable to use as a covering yarn in which the core yarn is used as a side yarn. This makes it possible to impart not only fashionability but also comfort such as touch and elasticity.

As the elastic fiber forming the core thread of the covering elastic fiber, polyurethane elastic fiber, polyamide elastomer elastic fiber, polyester elastomer elastic fiber, natural rubber fiber, synthetic rubber fiber, butadiene fiber are used. Among them, polyurethane-based elastic fibers and polyamide-based elastomer elastic fibers are preferable for socks because of their elastic properties, thermal properties, durability and the like.

The thickness of the elastic fiber varies depending on the application of the sock and the setting of the tightening pressure, but it is generally about 9 to 80 decitex. Preferred is 11 to 44 decitex. If it is less than 9 decitex denier, the yarn strength will be insufficient, and troubles such as core yarn breakage during covering and knitting will easily occur, and the elasticity and durability of socks will be insufficient, such being undesirable. On the other hand, if it exceeds 80 decitex, the tightening force becomes too strong and the feeling of pressure becomes strong, and the feeling of coarseness and hardness tends to increase, which is not preferable.

From the standpoint of durability and texture, these anion-dyeable polyamide multifilaments, metachromatic polyamide multifilaments, and cation-dyeable polyesters are
It is preferable to select in the range of a multifilament having a yarn fineness of 6 to 150 decitex and a filament number of 1 to 144.

The reason why the anionic dyeable polyamide multifilament is combined with the metachromatic polyamide multifilament is that it is a material satisfying a high level of durability, touch and washing fastness, which are important for stockings. When using polyester, as described in the prior art, when dyeing polyester with a disperse dye, only the dyeing or the dyed yarn is colored due to the problem of washing fastness, and the color variation is limited. This is because it is inferior to polyamide multifilament in terms of durability and touch. However, in order to pursue fashionability, it is also preferable to use at least an anion-dyeable polyamide multifilament and a heterochromatic polyamide multifilament and further dye them with three or more different colors. For that purpose, in addition to the above-mentioned anion-dyeable polyamide multifilaments and metachromatic polyamide multifilaments, other dyed yarns which are not dyed by post-dyeing are combined, for example, PET.
It is possible to use the multifilament without dyeing it, or to dye it like wool, but it is also possible to use that it has a different color from nylon. In addition, anionic dyeable polyamide multifilaments have different amino end groups.
By combining more than one kind, it becomes possible to impart a difference in shade and a slight difference in color tone.

Further, an anion-dyeable polyester is a multifilament having a metachromatic property to anion-dyeable polyamide. Anion dyeable polyester is superior in wash fastness to anion dyeable polyamide.
In addition, since the dyed polyester is false-twisted, the cheese is soft-wound again and dyed with cheese, which results in higher costs, and the crimp becomes sweeter and the texture becomes harder. When used as a twisted yarn, the crimpability is improved and the texture is excellent. Therefore, by combining the anion-dyeable polyamide and the cation-dyeable polyester, it is possible to provide socks with excellent texture, which is an object of the present invention, and has excellent fashionability.

Further, the cross-sectional shape of the polyamide multifilament to be used is not limited to a circle, and there is no problem even if it has a flat cross section, a convex lens shape, a square shape, and various cross sections or hollow cross sections. There is no problem even if the cross section is deformed by processing.

Here, the socks to which the present invention is applied are three types of foot covers consisting of only the foot, the mouth rubber, the body, and the foot.
Socks that consist of parts, stockings whose body is significantly longer than stockings, tights with panties on top, and pantyhose.

The knitting machine is not limited as long as it can express a pattern, and may be warp knitting or weft knitting.

As the dyeing method, by using a suspending agent, whether dyeing at once in one bath or dyeing in two baths, further dyeing with, for example, a cationic dye and then soaping, and then using an anionic dye. You may dye. As the soaping, in addition to washing with a surfactant, an alkali such as an aqueous solution of sodium carbonate may be used. Of course, there is no limitation on the combination of colors, and the point that the color development is free is also a feature of this patent. Further, after dyeing, post-processing with an antistatic agent or a softening agent is also preferably performed. Furthermore, when combining an anion-dyeable polyamide and a cation-dyeable polyester, taking advantage of the difference in dyeing temperature, after dyeing the polyamide with an anionic dye at around 60 ° C, raise the temperature and dye the polyester side with a cationic dye. Good.

[0035]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Each measured value in Examples and Comparative Examples is obtained by the following method.

A. A 98% sulfuric acid relative viscosity (a) sample is weighed and dissolved in 98% by weight concentrated sulfuric acid so that the sample concentration (C) is 1 g / 100 ml. (B) The solution of item (a) is 25 ° C. with an Ostwald viscometer.
The number of seconds (T1) of the fall is measured. (C) 25 ° C. of 98% by weight concentrated sulfuric acid in which the sample is not dissolved
The number of seconds (T2) of the fall is measured in the same manner as in the item (2). (D) The 98% sulfuric acid relative viscosity (ηr) of the sample is calculated by the following formula. The measurement temperature is 25 ° C. (Ηr) = (T1 / T2) + {1.891 × (1.00
0-C)}.

B. Amino end group quantification method After pulverizing the polyamide-based polymer and removing low molecular weight components and water as necessary, 1 g of the polyamide-based polymer is mixed with phenol / ethanol mixed solvent (ethanol 20 ml / phenol 80 g mixing ratio) 40 to 50 ml.
Shake at room temperature to dissolve it into a solution.
Neutralization titration with 2N hydrochloric acid is carried out to determine the required amount of 0.02N hydrochloric acid. Further, only the above phenol / ethanol mixed solvent (the same amount as above) was neutralized and titrated with 0.02N hydrochloric acid to a required value of 0.
Determine the amount of 02N hydrochloric acid. Then, the amount of amino terminal groups per 1 kg of the polyamide polymer is determined from the difference.

C. Sulfonic acid group quantification method Add 0.3 g of absolutely dry sample to 25 ml of 10N sulfuric acid solution and add 1
Hydrolyze for 18 hours at 05 ° C. After cooling this to room temperature, the absorbance at a wavelength of 283 nm is measured by a self-recording spectrophotometer using a 10 mm quartz cell. 283 nm is CB
It is the absorption wavelength of the benzene ring contained in the S molecule. Using this absorbance, the amount of sulfonic acid groups is calculated from the calibration curve prepared in advance.

D. Cation-dyeable polyester dyeability evaluation After polyester fiber was knitted, the knitted fabric was made of malachite green (trade name, manufactured by Kanto Kagaku) 5% owf, acetic acid 0.5.
It was dyed under the conditions of g / l, sodium acetate 0.2 g / l, bath ratio 1: 100, and temperature 98 ° C., and evaluated by the exhaustion rate of the dye. The dye exhaustion rate is measured by a spectrophotometer (Hitachi, 6
(Type 07) was used, and the difference in absorbance due to dyeing of the dye solution was measured and determined by the following formula. Dye exhaustion rate (%) = {(B−A) × 100} / BA A: Absorbance at maximum absorption wavelength of dye solution after dyeing B: Absorbance at maximum absorption wavelength of dye solution before dyeing Those having a rate of 60% or more were determined to be dyeable under normal pressure.

E. Washing fastness evaluation Sample yarn is tubular knitted by a single knitting machine, and cationic dye (Cathilon Red GTLH (manufactured by Hodogaya Chemical Co., Ltd.): 1 against the weight of cationic dyeable polyamide
% Owf, pH of dye liquor adjusted to 5.5, and bath ratio 1:20
The temperature was raised at 1 ° C./min to dye at 98 ° C. × 60 min. After that, after washing with hot water and washing with water, JIS0844
Discoloration was evaluated according to the 1986 A-2 method.

Example 1 Nylon 6 chips (amino terminal groups 5.9 × 10 ⁻⁵ mol / g, no sulfonic acid group) with 98% sulfuric acid relative viscosity 2.8 and no titanium oxide were melted at 270 ° C. Then, the mixture is discharged from a spinneret having a round discharge hole, cooled, lubricated, and taken out, and subsequently stretched to have an elongation of 45%, and then heat treated at 150 ° C. and then at 4000 m / min. It was wound up to obtain an anion-dyeable polyamide multifilament having 13 decitex 7 filaments. This multifilament is used as a covering thread, and "LYCRA" ((registered trademark), T-178C) manufactured by Toray Dupont Co., Ltd., a yarn fineness of 20 decitex is used as a core thread, and a covering draft is set to 2.9 times. A single covering elastic yarn (SCY) was manufactured by single-covering the yarn in the S-twisted and Z-twisted directions with a twist number of 1800 t / m.

Further, the same chip was used to discharge from a spinneret having a round discharge hole, and cooling, lubrication and take-up were carried out,
Then, after stretching so that the elongation becomes 45%, 15
Heat treated at 0 ° C and then wound at 4000m / min, 17
Anionic dyeable polyamide multifilament having 3 decitex filaments was obtained.

Further, it contained 0.3% by weight of titanium oxide having a relative viscosity of 98% sulfuric acid of 2.7 and an average particle size of 0.6 μm, and 5-sodium sulfoisophthalic acid was added at the time of polymerization of nylon 6 to remove a sulfonic acid group. Copolymerized nylon having 4.6 × 10 ⁻⁵ mol / g (amino terminal group 1.0 × 10 ⁻⁵ mol
/ G) Chips are melted at 270 ° C., discharged from a spinneret having round-shaped discharge holes, cooled, oiled, collected, and subsequently stretched to have an elongation of 62%, and then 4,000 m
It was wound up at a speed of 1 / min to obtain a cationic dyeable polyamide multifilament having 41 decitex 10 filaments.
Using IVF805 (manufactured by Ishikawa Seisakusho Co., Ltd.) as a drawing false-twisting machine, setting a processing speed of 600 m / min, a draw ratio of 1.24 times, a heater temperature of 180 ° C. and a D / Y ratio of 1.8, false-twisting is performed. Was performed to obtain a false-twisted yarn having 10 filaments of 33 decitex.

When the wash fastness of the false twisted yarn was evaluated, it was as good as grade 4.

Model P-48 manufactured by Nagata Seiki Co., Ltd.
2 (400 needles), from the toe part to the leg part, the anion dyeable polyamide SCY (S twist, Z twist) and two anion dyeable polyamide raw yarns are set as the ground yarn so that a knitting pattern is formed. Cationic dyeable polyamide false twisted yarn 4
I set a book. The pantyhose was knitted so that an Argyle pattern could be expressed by cutting and bossing.

This pantyhose was preset with steam at 80 ° C. for 10 minutes in a conventional manner, and after the scouring step with a surfactant, it was dyed with the following dyes and dyeing aids. Acid dye (Kayanol Yellow N
5G (manufactured by Nippon Kayaku Co., Ltd.): 1% owf based on the weight of anion-dyeable polyamide, a precipitation inhibitor (Neotex CA-5 (manufactured by Nichika Chemical Co., Ltd.)), acetic acid 1 g / l,
Cationic dye GTLH
(Hodogaya Chemical Co., Ltd.): 1% owf based on the weight of the cationic dyeable polyamide, softening agent (Nikka Silicon A)
M-202 (Nika Kagaku Co., Ltd.): 4% owf based on the weight of panty hose was prepared, and the bath temperature was set to 40 ° C. using a drum dyeing machine (bath ratio 1:20), and then →→
In order, heating up to 90 ° C. at 1.5 ° C./minute, maintaining a constant temperature for 60 minutes, then cooling,
After washing with water, the bath temperature was set to 30 ° C. with a bath ratio of 1:20.
Then, after softening using a bath temperature of 40 ° C., a final set at 110 ° C. for 30 seconds was performed using a sock setter.

In the obtained pantyhose, the ground thread is dyed yellow and the argyle pattern is dyed red. By making the pattern thread different from the ground thread together with the pattern, the pattern can be effectively embossed and fashionable. Became. Also, since the surface is knitted with polyamide, a handle thread,
Both the ground thread had a soft feel and a good wearing feeling. Also,
The pattern yarn and the ground yarn were also excellent in color development. The results are shown in Table 1.

Example 2 Nylon 6 containing 0.3% by weight of titanium oxide having a relative viscosity of 98% sulfuric acid of 2.7 and an average particle size of 0.6 μm (amino terminal group: 5.9 × 10 ⁻⁵ mol / g, sulfonic acid) (No base is included) Chips are melted at 270 ° C, discharged from a spinneret having round discharge holes, cooled, lubricated, and taken over, and then 1.05 times to have an elongation of 62%. Stretched at 4000 m / min and rolled up at 64 decitex 17
Anion dyeable polyamide multifilament of filament was obtained. This is false-twisted under the same conditions as in Example 1, and an anion of 110 decitex 34 filaments in which S-twisted false-twisted yarn and Z-twisted false-twisted yarn processed with adjacent weights are combined and entangled at the upstream of the winder and wound up A dyeable SZ twin yarn false twisted yarn was obtained.

Further, 98% sulfuric acid has a relative viscosity of 2.5 and contains 0.3% of titanium oxide. When nylon 6 is polymerized, ε-caprolactam is added so that amino end groups are 9.4 × 10 ^-5 m.
270 chips with ol / g (without sulfonic acid groups)
Melted at ℃, discharged from a spinneret having circular discharge holes, cooled, lubricated, and taken over.
% At a draw ratio of 1.05 and then 4000 m /
It was wound in minutes to obtain an anion-dyeable polyamide multifilament having 41 decitex 10 filaments. This is also false twisted under the same conditions as the SZ twin yarn false twisted yarn, and 6
6 decitex 20 filament anion dyeable SZ
A twin yarn false twisted yarn was obtained. Further, the cationic dyeable polyamide multifilament having 41 decitex 10 filaments used in Example 1 was also false twisted to obtain a cationic dyeable SZ double twist false twisted yarn having 66 decitex 20 filaments.

When the washing fastness of the above SZ twin-twisted false twisted yarn was evaluated, it was found to be 4th grade.

K-17 SINGL manufactured by Nagata Seiki Co., Ltd.
EK type (240 needles), two ground yarns (front yarn, back yarn), 110 decitex 34 filaments of anion dyeable SZ twin-twisted false twist yarns are prepared, and 6 yarns are used as handle yarns.
6 decitex 20 filament anion dyeable SZ
Two pairs of each of the twin yarn false twisted yarn and the cation dyeable SZ twin yarn false twisted yarn of 66 decitex 20 filaments were prepared, and a stocking was knitted by setting a computer so as to have a polka dot Mole pattern by cut and boss.

This stocking was dyed and finished in the same manner as in Example 1. However, the dyeing process is carried out by a so-called two-bath method in which dyeing is performed separately, and after using a drum dyeing machine (bath ratio 1:20) to bring the bath temperature to 40 ° C., put in at 1.5 ° C./min. After raising the temperature to 90 ° C. and maintaining it at a constant temperature for 60 minutes, after cooling and washing with water, Granup US20 (manufactured by Sanyo Kasei Co., Ltd.) was soaped at 0.2 g / l and further washed with water. . Then, with the same bath ratio of 1:20 and a bath temperature of 40 ° C, put and 1.5 ° C.
The temperature is raised to 90 ° C./min and kept at a constant temperature for 60 minutes.
After that, cooling and washing were performed. After the subsequent FIX treatment, the same procedure as in Example 1 was performed.

The stockings thus obtained had yellow as the ground thread and dark yellow and red polka dots as the Mole pattern, and could have three different colors including the difference in shade of yellow. In addition, since all of them were knitted with polyamide multifilament, both the handle yarn and the ground yarn were soft to the touch and had excellent wearing feeling. Further, the pattern yarn and the ground yarn were also excellent in color development.

Example 3 Dimethyl terephthalate (hereinafter abbreviated as DMT) 94k
g, 60 kg of ethylene glycol, lithium acetate (0.2% by weight of DMT) and antimony oxide (0.04% by weight of DMT) as a reaction catalyst, 3.7 kg of 5-sodium sulfoisophthalic acid methyl ester and 1000 of average molecular weight were added. Polyethylene glycol 4.0
kg was added and gradually heated from 150 ° C. to 250 ° C. in a nitrogen atmosphere, transesterification reaction was performed while continuously distilling generated methanol out of the system, and the reaction was completed 3 hours after the reaction was started. . Next, 41 g of trimethyl phosphate,
Titanium dioxide 16% by weight ethylene glycol slurry 5
00 g was added.

Then, the polymerization reaction system was gradually depressurized to 13.3 Pa over 1 hour and 30 minutes and heated to 280 ° C. 1
Polymerization was carried out at a polymerization temperature of 280 ° C. for a further 2 hours under a reduced pressure of 3.3 Pa to obtain a polyester chip having an intrinsic viscosity of 0.74 at 84 k.
g was obtained. The obtained copolyester is spun at a spinning temperature of 29.
Spinning was performed at 0 ° C. and a spinning speed of 3000 m / min, the fineness was 48 decitex, 10 filaments, and the birefringence was 25 × 10 ⁻³ .
A highly oriented undrawn yarn having an elongation of 155% was obtained.

The highly oriented undrawn yarn was drawn using the drawing false twisting machine described in Example 1 at a processing speed of 400 m / min and a draw ratio of 1.
The false twisting process was performed under the conditions of 45 times, heater temperature 160 ° C. and D / Y ratio of 1.8 to obtain false twisted yarn of 33 decitex 10 filaments.

The drawn yarn is knitted by a FAX knitting machine, and the temperature is 98 ° C.
After scouring with the above hot water, the dyeability of the cation dyeable polyester was evaluated, and the dye exhaustion rate was 97.3%, showing extremely excellent atmospheric dyeability. In addition, when the wash fastness was evaluated, it was as good as 4-5 grade.

Model P-48 manufactured by Nagata Seiki Co., Ltd.
2 (400 needles), the toe part to the leg part used as the ground yarn, and the anion dyeable polyamide SCY (S used in Example 1
Twist, Z twist) and two anion dyeable polyamide raw yarns were laid so as to be interwoven, and four atmospheric pressure cation dyeable polyester false twist yarns were laid as pattern yarns. The pantyhose was knitted so that an Argyle pattern could be expressed by cutting and bossing.

This pantyhose was preset with steam at 80 ° C. for 10 minutes in a conventional manner, and after the scouring step with a surfactant, it was dyed with the following dyes and dyeing aids. Acid dye (Kayanol Yellow N
5G (manufactured by Nippon Kayaku Co., Ltd.): 1% owf based on the weight of anion-dyeable polyamide, a precipitation inhibitor (Neotex CA-5 (manufactured by Nichika Chemical Co., Ltd.)), acetic acid 1 g / l,
Cationic dye GTLH
(Hodogaya Chemical Co., Ltd.): 1% owf based on the weight of the cationic dyeable polyamide, softening agent (Nikka Silicon A)
M-202 (Nika Kagaku Co., Ltd.): 4% owf based on the weight of panty hose was prepared, and the bath temperature was set to 40 ° C. using a drum dyeing machine (bath ratio 1:20), and then →→
In order, heating up to 98 ° C. at 1.5 ° C./min, maintaining a constant temperature for 60 minutes, then cooling,
After washing with water, a surfactant (Laccor PSK, 2 g / l,
It was soaped (60 ° C. × 30 min) with 1 g / l of soda ash and Meisei Chemical Co., Ltd.). Then, after softening using a bath temperature of 40 ° C, 110 with a sock setter
A final set was performed at 30 ° C. for 30 seconds.

In the obtained pantyhose, the ground thread is dyed yellow and the argyle pattern is dyed red. By making the pattern thread different from the ground thread together with the pattern, the pattern can be effectively embossed and fashionable. Became. Further, the atmospheric pressure cationic dyeable polyester used for the pattern yarn was bulky as a false twisted yarn, and thus had a soft texture. The results are shown in Table 1.

Comparative Example 1 PET having 33 decitex 10 filaments as a pattern yarn instead of the cationic dyeable polyamide false twisted yarn of Example 1
PE which is dyed in red after softly winding false-twisted yarn
Only using T-dyed yarn, knitting pantyhose without changing the knitting machine and knitting conditions. While knitting, there was no problem with the cationic dyeable polyamide false twist yarn,
When the PET yarn-dyed yarn was used, the yarn was stiff and the binding property was poor, so it was necessary to add oil before knitting.

The above pantyhose was dyed and finished under the same dyeing conditions except that the cationic dye and the suspending agent of Example 1 were not used. In the obtained pantyhose, the pattern thread can be effectively highlighted by dyeing the pattern thread differently in the same manner as in the example, but when the texture of the pattern thread is tightly worn, the pattern thread will be on the skin. I felt uncomfortable in the part and was not comfortable. In addition, since the pattern yarn is a PET yarn-dyed yarn and has a higher refractive index than the nylon multifilament and is dyed with a disperse dye,
It was inferior in sharpness compared to.

[0064]

[Table 1]

[0065]

EFFECTS OF THE INVENTION In the stocking of the present invention, the pattern knitting structure is dyed in multiple colors to enhance fashionability, and different colors can be developed by dyeing the product so that the product can be quickly supplied in accordance with market needs. Is possible.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Akira Suzuki             1-1-1 Horikoshi, Nishi-ku, Nagoya City, Aichi Prefecture             Toray Industries, Inc. Aichi factory F term (reference) 3B018 AA00 AC01 AC04 AC05 AC10                       AD02 AD06 AD07                 4L002 AA06 AB02 AB04 AC01 AC06                       BA01 BB02 DA01 DA03 DA04                       EA00 FA05                 4L036 MA06 MA33 MA39 PA47 RA25                       UA12 UA16

Claims (6)

[Claims] 1. A sock obtained by knitting at least two or more kinds of polyamide multifilaments into a knitted structure and then dyeing, wherein at least one kind of the polyamide multifilaments is another polyamide. Socks characterized by being dyed with a different color from any one of multifilaments. 2. A sock using at least one polyamide multifilament as a ground yarn and another polyamide multifilament as a handle yarn among the at least two or more polyamide multifilaments, and having anion dyeability. The sock according to claim 1, wherein a part of the pattern yarn is dyed with a different color after knitting by using the polyamide multifilament and the metachromatic polyamide multifilament after knitting. 3. The sock according to claim 2, wherein the anion-dyeable polyamide multifilament and / or the metachromatic dyed polyamide multifilament is used as a covering thread covering each of them. 4. The sock according to claim 2 or 3, which is dyed in at least three different colors using at least an anion-dyeable polyamide multifilament and a metachromatic polyamide multifilament. 5. The sock according to claim 2, wherein the metachromatic polyamide multifilament is a cationic dyeable polyamide multifilament. 6. A sock obtained by knitting a patterned knitting structure using at least a polyamide multifilament and a normal pressure cationic dyeable polyester multifilament, which is dyed, wherein the polyamide multifilament and the cationic dyeable polyester multifilament are used. A sock characterized in that the filament is dyed in a different color.