JPH02229201A - Stockings excellent in fitness - Google Patents

Abstract

PURPOSE:To obtain the subject stockings excellent in color fastness, especially color fastness to washing of deep color dyed materials without impairing excellent physical properties of elastic yarns by knitting the elastic yarns of a specific polyester polyether block copolymer. CONSTITUTION:The objective stockings obtained by using (A) 50-90wt.% polyester units containing >=60mol% polytetramethylene terephthalate units or polyethylene terephthalate units in hard segments and (B) 10-50wt.% polyalkylene ether glycol units containing >=60mol% polytetramethylene ether glycol units having 500-4000 molecular weight in soft segments in at least leg parts and mainly knitting (C) false twist textured yarn of 5-60 denier total size consisting of a polyester polyether block copolymer, containing a sulfonated metal salt compound in an amount of 0.5-2.0mol% based on the total acid component of the polymer and having >=160 deg.C melting point.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to stockings with excellent fit that are knitted from processed yarn of a specific polyester elastomer. More specifically, the present invention relates to improving the color fastness of the stockings. (Prior Art) False-twisted yarns of so-called inelastic yarns such as nylon-6, nylon-66, and polytetramethylene terephthalate, or elastic yarns such as polyurethane have been widely used as polymers constituting stockings. ．． However, stockings knitted from false-twisted inelastic yarns do not have satisfactory finning properties, and stockings made from a combination of inelastic yarns and elastic yarns are expensive and thick. Each has its own drawbacks, such as the possibility of As a result of extensive research in order to eliminate these drawbacks and obtain stockings with excellent fining properties at low cost, the present inventors have developed a stocking fabric knitted with processed yarn made of a specific polyester/polyether block copolymer. However, as a result of further investigation, stockings made of a specific copolymer were found to have poor color fastness,
In particular, it was found that the washing fastness of dark dyed products was sufficiently satisfactory for practical use. (Problems to be Solved by the Invention) The purpose of the present invention is to improve the color fastness of stockings using elastic yarns made of a specific polyester/polyether block copolymer, and in particular to improve the washing fastness due to the excellent physical properties of the elastic system. The goal is to improve without impairing. As a result of intensive research for this purpose, we found that polyester/polyether block copolymers are generally dyed with disperse dyes because they do not have dyeing groups for dyes, and therefore the bonding strength between the substrate and dye is weak. It was also found that because the elastic yarn has a loose molecular structure, dyes tend to migrate, resulting in poor color fastness. For this improvement,
It is effective to introduce dyeing groups into polyester/polyether block copolymers and dye them with ionic dyes.
Furthermore, it has been found that basic dyeability modification is superior to acidic dyeability modification in terms of the physical properties and manufacturing conditions of the polymer.

(Means for Solving the Problems) The present invention provides that at least the resog portion of the stocking contains 60 mol% of polytetramethylene terephthalate units or polyethylene terephthalate units as hard segments.
Borite 1 containing 50 to 90% by weight of polyester units and a molecular weight of 500 to 4000 as a soft segment
・10 to polyalkylene ether glycol units containing 60 mol% or more of ramethylene ether glycol units
50% by weight, and further contains 0.5 to 2.0 mol% of a sulfonic acid metal base compound based on the total polymer components, and has a melting point of 160'C or higher. These stockings are knitted using false twisted yarn with a fineness of 5-60 deniers as the main knitting yarn and have excellent phyto properties.

The present invention will be explained in detail below.

One of the important features of the present invention is the use of a specific polyester-polyether block copolymer for the knitting yarn constituting the stockings. The block copolymer contains 60 mol% or more of polytetramethylene terephthalate units or polyethylene terephthalate units,
Preferably, polyester units containing 80 mol% or more are used as hard segments, and polytetramethylene ether glycol units are 60 mol% or more, preferably 80 mol%.
This is a block copolymer having the polyether containing the above as a soft segment. As polyester units, in addition to polytetramethylene terephthalate units or polyethylene terephthalate units, one or more types of polymethylene terephthalate units, polypropylene terephthalate units, polyethylene isophthalate units, etc. are copolymerized in a proportion of up to 40 mol%. You can. In addition to the polytetramethylene ether glycol unit, the polyether units include one or two types of polyethylene ether glycol units, polybropylene ether glycol units, polyhexamethylene ether glycol units, etc. in a proportion of up to 40 mol%. The above may be copolymerized. Copolymerization ratio (weight ratio) of the aromatic polyester as a hard segment and the polyalkylene ether glycol as a soft segment: 50
~9 0 it I. It is necessary to set the content to 0 to 50% by weight. The reason is that the hard segment is 5D weight%
If it is less than that, the melting point will decrease and problems will occur in false twisting processability.
This poses problems in terms of process and quality, such as reducing the strength of the stockings. If the soft segment is less than 10% by weight, the resulting stockings will have poor elongation recovery properties and will not be able to provide a sufficient fit. In addition, the number average molecular weight of the polyalkylene ether glycol is preferably 500 to 4000, more preferably 500 to 4000, in order to increase the melting point of the fibers and especially to obtain the elasticity of the final stockings. iooo~2000 is good. A further requirement for the characteristics of the polyester/polyether block copolymer used in the present invention is that the copolymer has a melting point of 160'C or higher. The reason for this is that polymers with melting points below 160°C generally have small molecular weights and insufficient strength, resulting in poor durability as stockings. Preferably it is 190"C or higher. Here, the melting point is defined as Perkin Elmer 9;
J Differential Scanni
This is a value expressed as an endothermic peak temperature measured using an ngCalorimeter (DSC-IB type) at a heating rate of 10°C/min.

Another important feature of the present invention is that a sulfonic acid metal salt compound is added to the polyester/polyether block copolymer in an amount of 0.5 to 2.0% based on the total acid component of the polymer.
The content is 0 mol%.

In the present invention, the content of the sulfonic acid metal salt compound is
The reason why it is set at 0.5 to 2.0 mol% with respect to the gold acid component in the polyester/polyether block copolymer is 0.5
If it is less than 2.0 mol%, there will be a shortage of dyeing groups and a deep-colored dyed product will not be obtained, and if it is less than 2.0 mol%? This is because the physical properties of the elastic body will otherwise deteriorate. Here, specific examples of metals in the sulfonic acid metal salt compound include sodium, potassium, lithium, calcium, barium, lead-lanthanum, etc., and these may be used alone or in a mixture of two or more. good. The method for adding the above sulfonic acid metal salt compound to the polyester/polyether block copolymer is as follows:
The most preferred method is to add -5 monometallic sulfoisophthalic acid or its ester-forming derivative at any stage before the synthesis of the polyester is completed, and to copolymerize it into the block copolymer. In addition, the polyester used in the stockings of the present invention
A heat-resistant agent, an antioxidant, a light-resistant agent, a matting agent (TiO2), etc. may be added to the polyether block copolymer as necessary.

The polyester/polyether block copolymer which is the knitting yarn for the stockings of the present invention has been described above in detail.
In order to obtain stockings with excellent fit, which is the object of the present invention, after melt-spinning the polymer, it is necessary to simultaneously or sequentially subject it to stretching and false twisting. Here, the stretching and false twisting conditions can be selected from various ranges as in the case of ordinary nylon, but from the characteristics of the stocking product, it is desirable to use the following conditions.

(1) For stockings that emphasize transparency and stitch beauty in addition to fit, use torque-type processed yarn. In other words, by false-twisting the yarn with a total fiber width of 5 to 60 deniers and a filament count of 1 to 3 filaments/Yarn, the processed yarn becomes a torque-type processed yarn that has only torque without crimp. It becomes possible to manufacture stockings with excellent transparency and beautiful stitches. Here, the torque level of the torque type processed yarn is 300 to 1, the same as normal nylon 6.
000 T/M is preferable from the viewpoint of stitch beauty. (2) For stockings that emphasize one-size-fits-all in addition to fit, use woolly type processed yarn. That is, the total fineness is 5 to 60 deniers, the number of filaments is 4 to 15, and the yarn processed by false twisting with /Yarn becomes a woolly processed yarn with crimp and torque, and therefore has excellent fit and other properties. It becomes possible to manufacture stockings with excellent stretch recovery and one-size-fits-all properties. Here, it is desirable that the expansion/contraction recovery rate, which indicates the degree of crimp, be 20% or more, preferably 40% or more.

The expansion/contraction recovery rate was determined by applying a weight of (2/1000 g) to the skeined sample.
/d+2/10g/d) and put it in water.
Measure the length after 21 minutes, then remove the load of 2/Log/d, measure the length under the load of 2/IOOOg/d, and make it 1L (j2i-j2t)/fiXJ0
0 (%).

The stockings are knitted using the false twisted yarn of the specific polyester/poI1 ether block copolymer as described above, and the knitting method may be nine stitches or full fascine stitches. Further, in the stockings of the present invention, at least the leg portions are knitted with the above-mentioned false twisted yarn, but the other portions, that is, the ankle portion, heel portion, sole portion, and toe portion are knitted only with the above-mentioned false twisted yarn. Alternatively, some parts may be knitted with other yarns. Since the length part is the part that causes sagging, it is necessary to increase the elongation rate of this part. Normal stocking manufacturing processes (I-standing, presetting, sewing, dyeing final setting) are carried out using the false twisted yarn of the specific polyester/polyether block copolymer as described above as the main knitting yarn. At this time, it is preferable to dye with a cationic dye. The obtained stockings have an elongation rate (elongation rate under a load of 200 g per 5 CI of grip width in the warp and weft directions) of at least 80% or more in the upper part of the leg in both the length and width directions, and have elasticity in both the weft and weft directions. have

As described above, the feature of the present invention is to supply elastic yarn, which is obtained by melt-spinning a specific polymer and subjecting it to normal drawing and false twisting, as stocking Akebono yarn. These stockings have an excellent fit that cannot be obtained with conventional stockings, and can be manufactured at low cost. In addition, the color fastness, especially the washing fastness of deeply dyed products, is improved.

The stockings of the present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited by the Examples below.

In Examples 1 to 4 and Comparative Examples 1 to 4 shown below,
The DSN molar ratio, unraveled yarn strength (g/d), dyeing amount and washing fastness were determined as follows.

However, DSN': 3,5 di(carbomethoxy)benζ
Sodium sulfonate DMT: Dimethyl terephthalate Disassembled yarn strength: The yarn strength was measured using a Tensilon type tensile tester using a constituent yarn from a stocking product, tensile speed 20 cm/min, sample length 20 CI, initial load 1/20 g /d Dyeing amount: dyeing rate x dye concentration (%owf) Here, the dyeing rate was determined by the residual bath colorimetric method using a Hitachi 150-20 spectrophotometer. Washing fastness: According to JIS L-08441-2 method.
Elongation rate: 50 per grip width of 51 in longitudinal and latitudinal directions
This means under a load of 0g. Elongation recovery rate: Conditions for the knee part of stocking products using an Instron tensile tester: grip width in the warp and weft directions of 6 CI, sample length of 5 cm, tensile speed of 20 cm/o+tn, and cheat speed of 20 cm'/sin. A constant load of 500 g is applied, stress relaxation is performed for 1 minute, strain recovery is performed for 3 minutes, and then elongation, recovery, and re-elongation are performed, and the calculation is performed using the following formula. (ab) / a (hereinafter referred to as DAT)
and sodium 3,5-di(carbomethoxy)benzenesulfonate (hereinafter referred to as DSN) as the acid component, DSN
The molar ratio of DSN expressed as the number of moles/([]SN + DMT) was prepared to be 0.84%, and 1.4 butanediol and polytetramethylene were added in a molar amount 165 times the total acid component. Ether glycol (hereinafter referred to as PTG) and (D+nsN) number of moles/
Mixed so that the molar ratio expressed by the number of moles of PTG was 15.0, antioxidant (Ionox 330, manufactured by Shell Chemical Co., Ltd.) 0.15%, catalyst (tetrabutoxy titanate) 0.05%. The transesterification reaction was carried out by heating with stirring to 140-230"C, and the generated methanol was distilled out of the system. Thereafter, while reducing the pressure, the temperature was raised to 250"C. Polymerization was carried out at elevated temperature to obtain a polyester/polyether block copolymer with a melting point of 214.5"C. The polyester/polyether blank copolymer was spun using a screw extruder at a temperature of 250°C and a nozzle diameter of 0.4 m.
A + 8 holes, melt spinning at a spinning speed of 1000 m/min,
An undrawn yarn of 90 denier/1 filament was wound up.

The undrawn yarn is stretched and false-twisted at a speed of 800 m/min,
Torque number 500 times/m in both S and Z directions
A torque type processed yarn of 20 denier/1 filament was obtained. The torque-type processed yarn was passed through a 40-gauge sock knitting machine so that the S-direction twist and Z-direction twist were alternately knitted, and then sewn. I applied the set and got the stockings.

Dyeing condition dye: Aizen Calhilon
Black CD-BLH5% owf Auxiliary agent: Acetic acid (10%) 2cc/1 Sodium acetate (10%) 2cc/j! mirabilite
3 g/j! Temperature x time; 98”cX
60 minute bath Ratio: t:SO Example 2 Stockings were obtained in the same manner as in Example 1 except that the DSN molar ratio was prepared to be 1.27%.

Example 3 Stockings were obtained in the same manner as in Example 1, except that the DSN molar ratio was blended to be 1.45%.

Comparative Example 1 Stockings were obtained in the same manner as in Example 1, except that the DSN molar ratio was prepared to be 0% and dyed under the dyeing conditions shown below.

Dyeing condition dye: Foron Black S
-CTL 5% owf dispersant:
Sandozol KB 2%
owf temperature x time: 98°C x 60 minutes bath ratio: 1:50 Comparative Example 2 Stockings were obtained in the same manner as in Example 1, except that the DSN molar ratio was prepared to be 0.30%.

Comparative Example 3 Stockings were obtained in the same manner as in Example 1 except that the DSN molar ratio was 2.30%. Comparative Example 4 A commercially available torque type stocking knitted from 20 denier/1 filament nylon 6 torque yarn. Table 1 shows the strength, dyeing amount, and washing fastness of the disassembled yarns of Examples 1 to 3 and Comparative Examples 1 to 3 described above, as well as the elongation rate and elongation recovery rate of Example I and Comparative Example 4.

As shown in Table 1 below, the stockings manufactured by Comparative Example were dyed with disperse dyes as they did not have a dyeing group for dyeing, but the washing fastness of the stockings was 3-4 in terms of discoloration and fading. The contamination was grade 1 to grade 2, which was a practical problem. In addition, the stockings of Comparative Example 2 had good washing fastness, but the amount of dyeing was low and deep black dyeing could not be achieved. Similarly to Comparative Example 2, Comparative Example 3 had good washing fastness, but low unraveling strength and poor stalking/king durability, making it unsuitable for practical use.

In comparison, the stockings of Examples 1 to 3 had good washing fastness and dyeability.
Although the level was slightly lower than that of Example 2, there was no practical problem even at the level of Examples 1 to 3, and excellent durability was maintained. In addition, the elongation rate is also compared to that of the commercial product of Comparative Example 4.
The stockings of Example 1 have an elongation rate of about 1.5 or more, a high elongation recovery rate, excellent elasticity in both warp and weft directions, excellent transparency, a beautiful pus surface, excellent fit, and no wrinkles. It did not sag, had a soft feel and texture, and had excellent transparency. Example 4 Using the polyester/polyether block copolymer polymerized in Example 2, melt spinning was performed using a screw extruder at a spinning temperature of 250°C, a nozzle hole diameter of 0.35a++, a nozzle hole number of 5 holes, and a spinning speed of 1000 m/min. Then, an undrawn system of 60 denier/5 filaments was wound up. The undrawn yarn was drawn and false-twisted at a speed of 800 m/min to obtain a woolly textured yarn with a stretch recovery rate of 45%, a torque of 800 times/m, and 20 deniers/5 filaments. The woolly processed yarn was knitted alternately in the S direction and Z direction (torque direction @) on a 40 gauge wi machine to form stockings, which were then sewn, and then dyed under the dyeing conditions shown in Example 1. I applied the set and got the stockings.

Comparative Example 5 Using the polyester/polyether block copolymer obtained in Comparative Example 1, melt spinning was carried out under the conditions shown in Example 4.
A woolly processing system was obtained by stretching and false twisting. Stockings were knitted and sewn in the same manner as in Example 4, and then dyed under the dyeing conditions shown in Comparative Example 1 and heat set to obtain stockings.

Comparative Example 6 Commercially available stockings knitted with 20 denier/5 filament nylon 6 woolly processed yarn, unknitted yarn strength, dyeing amount and washing fastness of Example 4 and Comparative Example 5 described above, Examples The elongation rates and elongation recovery rates of Comparative Example 4 and Comparative Example 6 are shown in Table 2. As shown in Table 2 in the margin below, the stockings of Comparative Example 5 had practical problems, with washing fastness of color change and fading of 3rd to 4th grade and staining of 1st to 2nd grade. On the other hand, the stockings of Example 4 are
Compared to Comparative Example 5, the washing fastness was significantly improved, and the color change and fading was grade 5, and the staining was grade 4 to 5, which was good. Furthermore, although the strength of the unknitted yarn was at a slightly lower level than that of Comparative Example 5, it had no practical problems even at the level of Example 4, and maintained excellent durability. Furthermore, compared to the commercially available product of Comparative Example 6, the elongation rate and elongation recovery rate of Example 4 are superior.Especially, the elongation recovery rate is thick《《, and it is highly elastic in both the weft and weft directions, and is transparent. The stockings had excellent texture and a beautiful knitted surface, excellent finning properties, no wrinkles or sagging, and were soft to the touch and had excellent transparency.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] (1) At least the leg portion of the stocking contains 50 to 90% by weight of polyester units containing 60 mol% or more of polytetramethylene terephthalate units or polyethylene terephthalate units as hard segments, and polytetramethylene ether glycol units with a molecular weight of 500 to 4,000 as soft segments. 10 to 50 polyalkylene ether glycol units containing 60 mol% or more of
% by weight, and further contains 0.5 to 2.0 mol% of a sulfonic acid metal salt compound based on the total acid component of the polymer, and has a melting point of 1.
Stockings with excellent fit, characterized in that they are knitted mainly with false-twisted yarn made of polyester/polyether block copolymer with a temperature of 60° C. or higher and a total fineness of 5 to 60 deniers.