JP2003183903A - Socks having grain pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide different colored socks of which can be timely dyed in various combinations of colors to bring it to the market, having soft texture of polyamide multifilaments. <P>SOLUTION: The socks comprise that at least one kind of polyamide multifilaments among at least two kinds of polyamide multifilaments is anion dyeable, and at least the other polyamide multifilaments are a metachromatic polyamide multifilament. The socks can be obtained by the following process; combining at least two kinds of these polyamide multifilaments knitting the gathered polyamide multifilaments, and thereafter, dying the anion dyeable polyamide multifilaments and the metachromatic polyamide multifilaments into different colors. <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 sock having a heddle tone and excellent in fashionability, and more particularly to a sock in which a color combination of a hemp can be freely selected after knitting.

[0002]

2. Description of the Related Art Up to now, various socks having a heddle tone have been proposed, but casual socks using spun yarn have been mainly used. This is because spun yarns composed of different materials were suitable for dyeing in heather. In recent years, however, socks made of long fibers having a plain and elegant surface feel have been demanded, and socks having a heavier tone also need to be made of long fibers having a similar surface feel. It has become possible to be.

Therefore, in order to obtain a sock having multi-filament heather, two yarns of yarn-dyed nylon are prepared and aligned or knitted, or dyed or undyed polyethylene terephthalate (hereinafter PE).
The socks were constructed by aligning the multifilament and nylon, knitting them, and then dyeing the nylon side with an acid dye. However, preparing the yarn-dyed yarn is poor in quick response, and there are many cases in which a large amount of stock cannot be sold and the sales opportunity is missed due to lack of products.

On the other hand, as described in Japanese Patent Application Laid-Open No. 5-163626, two cover yarns, which are dyed differently by post-dying, are respectively twisted and twisted in order to achieve a visual effect in which the color tone changes depending on the viewing direction. As a double-coated elastic yarn coated with an elastic yarn, a different color is seen when the viewing direction is changed, but it is a single color when seen from one direction, and the heaviness targeted by the present invention cannot be obtained.

[0005]

In order to solve this problem, the sock of the present invention has one of the following configurations.

(1) Among at least two or more polyamide multifilaments, at least one polyamide multifilament is an anion-dyeable polyamide multifilament, and at least one of the other polyamide multifilaments is a metachromatic polyamide multifilament. Heel-like socks used as filaments, wherein two or more kinds of polyamide multifilaments are aligned and knitted, and then anionic dyeable polyamide multifilaments and metachromatic polyamide multifilaments are dyed in different colors. Heeled socks characterized by.

(2) A sock having a heddle as set forth in (1), characterized in that the yarn in which the two or more kinds of polyamide multifilaments are aligned is used as a covering yarn which is covered as a side yarn of an elastic yarn. .

(3) Anion-dyeable polyamide multifilament, metachromatic polyamide multifilament, and other yarns are aligned and knitted, and dyed in three or more different colors (1) or (2) Socks described in).

(4) The sock according to any one of (1) to (3), wherein the metachromatic polyamide multifilament is a cationic dyeable polyamide multifilament.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the sock of the present invention, at least one kind of polyamide multifilament among at least two kinds of polyamide multifilaments is used as anion-dyeable polyamide multifilament, and at least one of other polyamide multifilaments is used. Heel-like socks whose species are metachromatic polyamide multifilaments, wherein after anionic dyeable polyamide multifilaments and metachromatic polyamide multifilaments are respectively formed by aligning and knitting the two or more kinds of polyamide multifilaments. It is dyed in a different color and has a so-called heather tone. Further, since it can be dyed in a different color after knitting, it is possible to stock the knitted fabric after the knitting, dye the combination of colors according to the needs of the market, and then quickly arrange the products in the store.

The socks to which the present invention pertains are foot covers consisting only of feet, socks consisting of three parts of a mouth rubber, a body and a foot, stockings whose body is significantly longer than stockings, and an upper part. Examples include tights with panties and pantyhose. In both cases, it is possible to express a casual texture while using a multifilament by using a heat treatment.

The knitting machine is not limited, and it may be either warp knitting or weft knitting. Further, knitting may be performed using an existing sock knitting machine.

The term "aligned" means that both the anionic dyeable polyamide multifilament and the metachromatic dyed polyamide multifilament are present, and in order to improve the length and smoothness of each heather, There is no restriction on intertwining or twisting the filaments. Further, there is no problem even if the fibers are spun at the same time as the spinning or drawn after the spinning.

Here, as the yarn for expressing the heather tone, it is preferable to use polyamide multifilament in terms of durability, fastness, heat retention, softness to the touch, color developability and the like. 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 through an amide bond, and the type thereof is not particularly limited, but the dyeability, washing fastness, and mechanical properties are not limited. From the viewpoint of superiority, a polyamide mainly composed of polycapramide or polyhexamethylene adipamide is preferable. 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, for example, polydodecanamide,
Consists of polyhexamethylene adipamide, polyhexamethylene azeramide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide, polymetaxylylene adipamide, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, etc. Examples of the monomer include aminocarboxylic acid, dicarboxylic acid, and diamine units. If necessary, light stabilizer, heat stabilizer,
Antioxidants, antistatic agents, terminal group regulators, dyeability improvers and the like may be added. It is also preferable to add a matting agent such as titanium oxide.

The anion-dyeable polyamide multifilament is a multifilament made of 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.

These anionic dyeable polyamide multifilaments and metachromatic dyeing multifilaments are
As a covering yarn obtained by performing false twisting for imparting stretchability, or covering a yarn obtained by aligning two or more types of polyamide multifilaments in order to impart higher stretchability as a side yarn of an elastic yarn. It is also preferably used. This makes it possible to impart not only fashionability but also comfort such as touch and elasticity.

Here, as the elastic thread forming the core thread of the covering elastic thread, polyurethane elastic thread, polyamide elastomer elastic thread, polyester elastomer elastic thread, natural rubber fiber, synthetic rubber fiber, butadiene fiber are used. However, polyurethane elastic yarns and polyamide elastomer elastic yarns are preferable for socks because of their elastic properties, thermal properties and durability.

The thickness of the elastic thread varies depending on the use of the sock and the setting of the tightening pressure, but it is generally 9 to 80 decitex. Preferred is 11 to 44 decitex. If it is less than 9 decitex, 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.
Coarse and hard feeling tends to increase, which is not preferable.

From the viewpoint of durability and texture, these anion-dyeable polyamide multifilaments and metachromatic polyamide multifilaments can be selected in the range of the filament fineness of 6 to 150 decitex and the number of filaments of 1 to 144. preferable. Further, the fineness ratio of each of the constituent multifilaments may be appropriately adjusted according to the desired tone of the heather, but it is preferably 5: 1 to 1: 5.

Further, as a means for controlling the pitch of the heather, it is possible to draw polyamide multifilaments having different dyeing properties and then to entangle them, or to add a real twist. Also, the pitch of the heather can be controlled by covering the elastic yarn as a side yarn.

As means for aligning polyamide multifilaments having different dyeability, simultaneous spinning, aligning at the time of stretching, aligning before false twisting, after false twisting,
It can be obtained by aligning before winding or by aligning with an H bobbin, and may be appropriately selected according to the purpose.

The reason why the anionic dyeable polyamide multifilament and the heterochromatic polyamide multifilament are combined is that it is a material satisfying the highest level of durability, touch and washing fastness important for stockings. This is because when polyester is used, it is colored only by the dyeing or the dyed yarn due to the problem of fastness to washing, the color variation is limited, and the durability and the touch are inferior to the polyamide multifilament. However, in order to pursue fashionability, it is also preferable to dye at least three different colors by aligning at least the anion-dyeable polyamide multifilament and the metachromatic polyamide multifilament with other materials. For that purpose, in addition to the above-mentioned anion-dyeable polyamide multifilaments and metachromatic polyamide multifilaments, other dyed yarns of other materials that are not dyed by post-dyeing may be combined, for example, PET multifilaments may be used without dyeing. ,
It is possible to take advantage of the fact that it is dyed like wool but has a different color than nylon. In addition, even in an anion-dyeable polyamide multifilament, by combining two or more kinds having different amino terminal groups, the difference in shade
Further, it becomes possible to give a slight color difference.

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.

As a dyeing method, dyeing may be carried out in one bath at a time, in two baths, and further, for example, after dyeing with a cationic dye, soaping, and then dyeing with an anionic 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. In addition, FIX treatment is preferably performed to improve wash fastness. Further, after dyeing, post-processing with an antistatic agent or a softening agent is also preferably performed.

[0025]

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.

Example 1 Nylon 6 chips containing 98% sulfuric acid relative viscosity of 2.8 and containing no titanium oxide (amino end groups of 5.9 × 10 ⁻⁵ mol / g, not containing sulfonic acid groups) were melted at 270 ° C. Then, it is discharged from a spinneret having a round discharge hole, cooled, lubricated, and taken out, and then stretched to have an elongation of 64% and then wound at 4000 m / min, 60 decitex 40 filaments. An anion-dyeable polyamide multifilament was obtained. This is used as a drawing false twister IVF80
5 (manufactured by Ishikawa Seisakusho) using a processing speed of 600 m / m
in, draw ratio 1.1 times, heater temperature 180 ° C., D /
The Y ratio was set to 1.8 and false twisting was performed to obtain an S twist false twisted yarn of 40 filaments of 55 decitex.

Further, 98% sulfuric acid has a relative viscosity of 2.7 and contains 0.3% of titanium oxide, and 5-sodium sulfoisophthalic acid is added at the time of polymerization of nylon 6 to give sulfonic acid groups of 4.
Copolymerized nylon (amino terminal group 1.0 × 10 ⁻⁵ mol / g) chip having 6 × 10 ⁻⁵ mol / g was melted at 270 ° C., discharged from a spinneret having round discharge holes, and cooled, After feeding oil, taking it out, stretching it so that the elongation would be 62%, and winding it at 4000 m / min, a cationic dyeable polyamide multifilament having 41 decitex 10 filaments was obtained. This is used as a drawing false twisting machine I
Processing speed of 60 using VF805 (manufactured by Ishikawa Seisakusho)
0 m / min, draw ratio 1.24 times, heater temperature 18
Perform false twisting at 0 ° C and D / Y ratio of 1.8,
A Z twist false twisted yarn of 10 filaments of decitex was obtained.

After the false twisted yarns were aligned and entangled, additional twisting of 100 T / m was performed to wind up the entangled yarn. This entangled yarn is used as a covering yarn, and "LYCRA" ((registered trademark), T-178C, yarn fineness 20 manufactured by Toray Dupont Co., Ltd.
Using decitex as the core yarn, set the covering draft to 2.9 times, and perform single covering at 800 t / m in the S twist and Z twist directions to obtain a single covering elastic yarn (SC
Y) was produced.

The obtained SCY was used for plain knitting the leg portion of the tights with a sock knitting machine having four needles and 360 needles. The obtained dough is steamed at 80 ° C as usual.
After 10 minutes of presetting and scouring with a surfactant, dyeing was performed using the following dyes and dyeing aids. Acid dye (Kayanol Yellow N5G (manufactured by Nippon Kayaku Co., Ltd.)): 1% owf based on the weight of the anion-dyeable polyamide, precipitation inhibitor (Die Disper CD (manufactured by Nihonsha Co., Ltd.)), pH adjuster : Adjust to pH 4 with acetic acid + sodium acetate buffer, cationic dye (Kay
acryl RedGL (manufactured by Nippon Kayaku Co., Ltd.): 1% owf, FI based on the weight of the cationic dyeable polyamide.
X agent (Nylon Fix 501 (Senka Corporation)
)): 2% o based on the weight of the anion-dyeable polyamide
wf, softening agent (Nikka Silicon AM-202 (Nika Kagaku Co., Ltd.): 4% by weight of pantyhose
owf was prepared and using a drum dyeing machine (bath ratio 1: 2
0) After adjusting the bath temperature to 40 ° C, put → → in order, increasing the temperature to 90 ° C at 1.5 ° C / min, maintaining a constant temperature for 60 minutes, cooling, and washing with water. Similarly, with a bath ratio of 1:20, the bath temperature was set to 30 ° C., the temperature was raised to 60 ° C. by adding, the temperature was kept constant for 30 minutes, and then cooling and washing were performed. 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.

The leg part of the obtained tights is in yellow,
It was a heather pattern in which red was scattered. Further, since the surface was knitted with polyamide, it was soft to the touch and had an excellent feeling of wearing. It was also excellent in color development.

Example 2 98% sulfuric acid having a relative viscosity of 2.5 and containing 0.3% of titanium oxide, ε-caprolactam was added during the polymerization of nylon 6, and 9.4 × 10 ⁻⁵ mol / g of amino end groups was added. The chips (having no sulfonic acid group) that they have are melted at 270 ° C., and the chips are discharged from a spinneret having a round discharge hole, cooled, lubricated,
It was taken up, and subsequently stretched at 1.05 times to have an elongation of 62%, and then wound at 4000 m / min.
Anion-dyeable polyamide multifilament having 41 decitex 10 filaments was obtained. This was false twisted under the same conditions as for the cationic dyeable polyamide multifilament of Example 1 to obtain a Z twist false twisted yarn of 33 decitex 10 filaments.

The anionic dyeable false-twisted yarn and the cationic dyeable false-twisted yarn used in Example 1 were aligned with the anionic dyeable false-twisted yarn to give entanglement, and then 100 T /
m additional twisting was performed and the entangled yarn was wound up. This entangled yarn is used as a covering yarn, and "LYCRA" ((registered trademark), T-178C, yarn fineness 20 decitex manufactured by Toray Dupont Co., Ltd. is used as a core yarn, and a covering draft is set to 2.9 times, and S twist and Single-covering elastic yarn (SCY) was manufactured by single-covering in the Z-twisting direction at a twist number of 600 t / m.

The obtained SCY was used for plain knitting the leg portion of the tights using a sock knitting machine with a four-needle feed having 360 needles. The obtained fabric 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 the dyeing is performed separately, and after using a drum dyeing machine (bath ratio 1:20) to bring the bath temperature to 40 ° C.
The temperature is raised to 90 ° C at a heating speed of / min, the temperature is kept constant for 60 minutes, then cooled and washed with water, and then Granup US2.
0 (manufactured by Sanyo Kasei Co., Ltd.) was soaped at 0.2 g / l and further washed with water. After that, the same bath ratio 1:20
The bath temperature was set to 40 ° C., the temperature was raised to 90 ° C. at 1.5 ° C./min by adding and, and the temperature was kept constant for 60 minutes, followed by cooling and washing with water. After the subsequent FIX treatment, the same procedure as in Example 1 was performed.

The leg portion of the obtained tights had a heather pattern in which a dark yellow and a red were scattered in a relatively pale yellow color. Further, since the surface was knitted with polyamide, it was soft to the touch and had an excellent feeling of wearing. It was also excellent in color development.

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 T-dyed yarn was used to knit the pantyhose without changing the knitting conditions.

The above pantyhose was dyed and finished under the same dyeing conditions except that the cationic dye of Example 1 and the suspending agent were not used. The obtained pantyhose had a heat effect similar to the example, but P
When the texture of the ET false twisted yarn was firmly worn, the skin felt a feeling of coarseness and was not comfortable. Further, PET has a higher refractive index than nylon multifilament and is dyed with a disperse dye, so that the sharpness of the red yarn is inferior to that of the example.

[0041]

[Table 1]

[0042]

The socks of the present invention can be dyed after being knitted in a heather pattern by combining various colors.
It is possible to quickly supply socks that have a casual texture with a heather pattern to meet market needs.

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Claims (4)

[Claims] 1. At least one polyamide multifilament among at least two or more polyamide multifilaments is an anion-dyeable polyamide multifilament, and at least one of the other polyamide multifilaments is a metachromatic polyamide multifilament. Heel-like socks, wherein the two or more types of polyamide multifilaments are aligned and knitted, and then the anion-dyeable polyamide multifilament and the metachromatic polyamide multifilament are dyed in different colors. Socks with a characteristic heather. 2. The sock having a hedonic tone according to claim 1, wherein the yarn in which the two or more kinds of polyamide multifilaments are aligned is used as a covering yarn covering a side yarn of an elastic yarn. 3. An anion-dyeable polyamide multifilament, a metachromatic polyamide multifilament, and other yarns are aligned and knitted to dye three or more different colors. Socks with a heather tone. 4. The sock having a hedonic tone according to claim 1, wherein the metachromatic polyamide multifilament is a cationic dyeable polyamide multifilament.