TWI613337B - Polyamide black spun-dyed yarn, false-twist yarn, elastic covered yarn and leg knit - Google Patents

Abstract

The present invention is a polyamide dyed yarn before spinning, which is characterized in that it contains furnace carbon black with an average particle size of 1 to 20 μm in an amount of 1 to 5 mass%, and the single fiber fineness is 0.8 to 2 dtex. A false-twisted yarn is prepared by false-twisting the above-mentioned polyamide black pre-spun yarn. A covered elastic yarn uses the aforementioned polyamide black pre-spun dyed yarn or the aforementioned false twisted yarn as a roll yarn. A hosiery product which uses at least one of the polyamide black pre-spun dyed yarn, the false twisted yarn, and the covered elastic yarn on at least a part of a leg.

The present invention provides stockings or tights that have a soft touch and can develop a dark black color.

Description

Polyamide black pre-spun yarn, false twisted yarn, covered elastic yarn and socks

The present invention relates to a polyamide black pre-spun dyed yarn, a false twisted yarn, a covered elastic yarn and socks that have a soft touch and can develop a dark black color.

Socks such as stockings and tights are mainly made of polyamide yarns represented by nylon 6 or nylon 66. Previously, in order to obtain the softness of hosiery products, the single fiber fineness of polyamide yarns was generally reduced. However, although the fineness of the single fiber is reduced, the softness can be obtained, but the appearance of hosiery products becomes white due to the diffusion of light, which makes it difficult to obtain a dark color, and the single fiber breaks and fuzzes during wearing. Problems such as appearance and deterioration of appearance. In particular, as consumer demand for pantyhose, in addition to soft touch, durability, and reasonable market price, color (color development) is an important factor, and it is expected that one that can develop color as pantyhose color Mainstream dark black polyurethane yarn.

Prior art literature Patent literature

In order to solve this problem, Patent Document 1 exemplifies that ultrafine fibers having good black color properties can be obtained by including carbon black in a polyamide yarn.

Patent Document 1 Japanese Patent Laid-Open No. 2002-146624

The method described in Patent Document 1 is obtained by removing the sea component of the sea-island composite yarn to obtain a very fine polyamide yarn with a single fiber fineness of 0.0001 to 0.06 dtex. Although it can be used in hosiery products such as stockings and tights, a soft On the other hand, there are problems in that deep black hair color cannot be obtained, fluffing (durability, appearance) occurs, and the cost of removing sea ingredients increases. In addition, since it is necessary to dissolve the PE of the sea component with toluene or the like, the elastic yarns such as the elastic fibers that become the core yarn of the covering yarn are deteriorated, and the strength is weakened and the stretchability is impaired.

In the present invention, the problem is to solve the previous problems as described above and provide a polyamide black pre-spun dyed yarn having a soft touch and capable of developing a dark black color. Furthermore, the subject is to provide a polyamide black pre-spun dyed yarn, false twisted yarn, covered elastic yarn, and socks that can develop a dark black color.

In order to solve the above-mentioned problems, the polyamide black pre-spun yarn of the present invention has the following configuration. That is, a polyamide black pre-spun dyed yarn is a polyamide black pre-spun dyed yarn containing 1 to 5 mass% of carbon black, wherein the average particle diameter of the carbon black in the polyamide is 1 to 20 μm and The single fiber fineness of the polyamide black pre-spun yarn is 0.8 ~ 2dtex.

The false twisted yarn of the present invention has the following configuration. That is, a false-twisted yarn is obtained by false-twisting the above-mentioned polyamide black pre-spun dyed yarn.

The covered elastic yarn of the present invention has the following configuration. That is, a covered elastic yarn using the polyamide black pre-spun dyed yarn or the false-twisted yarn as a roll yarn.

The socks of the present invention have the following structure. That is, a sock product using at least one of the polyamide black pre-spun yarn, the false-twisted yarn, and the covered elastic yarn on at least a part of the leg.

Furthermore, the polyamide black pre-spun dyed yarn of the present invention, wherein polyamide 6 is preferred.

In the polyamide black pre-spun dyed yarn of the present invention, the CV value of the dry heat shrinkage stress is preferably 4.0% or less.

According to the present invention, a polyamide black pre-spun dyed yarn, false twisted yarn, and covered elastic yarn suitable for socks that have a soft touch and can develop a dark black color, such as stockings or tights, can be obtained.

Hereinafter, the present invention will be described in more detail.

The polyamide constituting the polyamide black pre-spun yarn of the present invention is a so-called resin composed of a high-molecular weight body in which a hydrocarbon group is bonded to the main chain via a polyamide bond, and the polyamide is a yarn produced. Excellent properties and mechanical properties, mainly polyhexamide (Nylon 6) and polyhexamethylene adipamide (Nylon 66) are preferred. When it contains carbon black, it is not easy to gel, and yarn is produced. Good performance, polyhexamide (Nylon 6) is better. "Mainly" as used herein means The epsilon-caprolactam unit constituting the polyhexamide is preferably 80 mol% or more, and more preferably 90 mol% or more of the all-monomer unit. The other components are not particularly limited, but examples thereof include polydodecylamine, polyhexamethylenehexamidine, polyhexamethylenenonamide, polyhexamethylenedecanamine, Polyhexamethylene dodecanediamine, polym-xylylenehexamidine, polyhexamethylene-p-xylylenediamine, polyhexamethylene-m-xylylenediamine and other monomers Units of acids, dicarboxylic acids, diamines, etc.

In addition, the degree of polymerization of polyamides used in polyamide black pre-spun yarns can be suitably based on the characteristics required for false twist processing, knitted fabrics, and fiber products, or in order to obtain these appropriate ranges stably. Select, but the relative viscosity of 98% sulfuric acid at 25 ° C is preferably in the range of 2.0 to 3.6, and more preferably in the range of 2.4 to 3.3.

Examples of the type of carbon black used in the polyamide black pre-spun yarn of the present invention include furnace black, groove black, thermal carbon black, acetylene black, and lamp black, and the like is not particularly limited, but furnace black is preferred . The carbon black production method is divided into acetylene black which is thermal decomposition method and thermal black, which adopts the soot of incomplete combustion (so-called lamp black) or furnace black. Depending on the production method, different characteristics are given to carbon black. The thermal decomposition method, which must maintain a reaction environment near 2,000 ° C, requires a lot of energy at the time of manufacturing, and has low practicality in terms of cost and environmental aspects during manufacturing. On the other hand, the incomplete combustion method has high practicality in terms of cost and environmental aspects at the time of manufacture. In addition, the typical furnace method of the incomplete combustion method is easy to control the particle size or the size of the structure. From the viewpoint of the hue or yarn making property of the polyamide black spinning dyed yarn, it is preferable to use the furnace black obtained by the furnace method. In particular, the production of small-diameter furnace black is more preferably obtained by an oil furnace method.

In addition, the structure of carbon black is formed during its manufacturing stage. The structural unit is the smallest unit of carbon black, and its index can be expressed by DBP oil absorption. Here, the oil absorption amount is a value measured in accordance with JIS K6217-4 (2008). The DBP oil absorption of carbon black used in the polyamide black pre-spun yarn of the present invention is preferably 10 to 300 ml / 100 g. If the amount of DBP oil absorption is in the above-mentioned preferred range, when it is made into a polyamide black pre-spun dyed yarn, it can easily develop a dark black color. On the other hand, it has good dispersibility to the polyamide polymer, and is used in the manufacture of polyamines. Coarse black pre-spun dyed yarn will not increase coarse particles, good yarn-making properties, and high mechanical strength of polyamide black pre-spun dyed yarn.

The carbon black contained in the polyamide black pre-spun yarn of the present invention must have an average particle diameter of 1 to 20 μm. Here, the average particle diameter is a structure having a large particle diameter generally referred to as coarse particles. The measurement method is to use an optical microscope to load 0.1 g of a sample of a polyamide black pre-spun yarn on a heated polyurea. A sample of a microscope with a melting point of amine black before spinning and a temperature of + 20 ° C is clamped on a glass slide and stretched into a thin film. The photograph is taken at a magnification of 500 times. The longest length of the carbon black structure is arbitrarily determined from 20 samples. The average value of 20 pieces was calculated. At this time, the photograph taken can also be enlarged to a size where the particle diameter can be easily measured. If the average particle diameter is more than 20 μm, yarn breakage and yarn-making properties deteriorate during the manufacture of polyamide black pre-spun dyed yarns. Not only will the product grade be deteriorated due to the inclusion of fluff or the like when making hosiery products, but also polyurea The strength of the mechanical properties of amine black pre-spun dyed yarn will decrease. When the thickness is less than 1 μm, the kinematic friction coefficient of the yarn becomes higher than that when worn, and a lot of fluffing occurs in a part with high friction such as fingertips, heels, or knees. It is preferably 1 to 10 μm. In order to make the polyamide black pre-spun yarn of the present invention The average particle diameter of carbon black is 1 ~ 20μm, which can be used to filter the molten polymer containing carbon black during the manufacture of polyamide black pre-spun dyed pieces and the manufacture of polyamide black pre-spun dyed yarn. . The filtering method is not particularly limited, and it is preferable to provide a filter in the path of the molten polymer or a spinning bag. It is better to set the filter in the spinning bag, and the filter used in the spinning bag is better to have a mesh of 10 ~ 20μm.

In addition, when carbon black is contained in the polyamide melt polymer, the carbon black particles become secondary particles or tertiary particles and easily become coarse particles. Therefore, if a filter is provided only in the spinning bag, the carbon black is easily clogged, the filtration pressure is increased, the life of the bag is shortened, and the productivity is easily reduced. As a preferred melt spinning method for making carbon black contained in polyamide, in addition to setting a filter in a spinning bag, a small piece of masterbatch containing carbon black at a high concentration in polyamide is mixed with Carbon black is a small piece of polyamide and melt-spun. Further, when manufacturing the masterbatch tablet, a filter is provided to eliminate coarse particles, which can suppress the increase in filtration pressure in the manufacture of polyamide black pre-spun dyed yarn, which can increase the life of the bag and improve productivity. . In addition, the filter used in the manufacture of small pieces of master batch is preferably a mesh of 20 to 50 μm.

The content of carbon black contained in the polyamide black pre-spun yarn of the present invention must be 1 to 5 mass%. Here, the content is measured by using TG-DTA under the conditions of temperature range: room temperature to 900 ° C, heating rate: 100 ° C / min, and air flow rate: 20ml / min. The change was calculated from the ratio of the weight loss in the region of 650 to 900 ° C as the disappearance of carbon black and the carbon black content in the polyamide black pre-spun yarn. When the content is less than 1% by mass, then When making hosiery products such as stockings and tights, it is not possible to obtain dark hair. If the content exceeds 5% by mass, not only the yarn breakage during the production of the polyamide black pre-spun yarn will be increased, but the yarn making properties will be deteriorated, but also the strength of the mechanical properties of the polyamide black pre-spun yarn will be reduced. The content is preferably 2 to 4% by mass.

In addition, if the amount and type are within the range that does not impair the object of the present invention, additives for improving productivity such as heat resistance may also be blended, and they may be blended to have matting, moisture absorption, antibacterial, ultraviolet shielding, Functional additives such as insulation. However, since the yarn-making property, the durability of hosiery products such as stockings or pantyhose, and the black hair color are reduced, it is not good to add inorganic particles exceeding 1 μm. It is added, but it is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, compared to the polyamide black pre-spun yarn.

The polyamide black pre-spun dyed yarn of the present invention is preferably a CV value of dry heat shrinkage stress of 4.0% or less. The CV value of the dry heat shrinkage stress is the shrinkage dispersion of the polyamide black pre-spun dyed yarn in the length direction. The CV value of some heat shrinkage stresses lies in the above-mentioned preferred range. Uneven twisting and the like may occur, and the material surface of products such as socks is good. On the other hand, uneven shrinkage does not occur during heat treatment such as scouring or foot setting. Good grade. In order to reduce the CV value to 4.0% or less, it is better to reduce the dispersion of the carbon black content in the polyamide black pre-spun yarn. To reduce the dispersion of carbon black content in polyamide black pre-spun dyed yarns, for example, in masterbatch pellets that will contain high concentration of carbon black in polyamine and polyamine without carbon black In the case of small pieces blended and melt-spun, kneading is performed by using a 2-axis extruder, or Mixing devices such as static mixers and high-speed mixers installed in polymer pipes can fully knead high-concentration carbon black and reduce the dispersion of carbon black content. The dispersion of the carbon black content is determined by using the above-mentioned TG-DTA to measure the carbon black content of a single fiber. A preferred range is a CV value of 10% or less.

The single fiber fineness of the polyamide black pre-spun yarn of the present invention must be 0.8 to 2 dtex. Previously, in order to obtain the soft touch of hosiery products, the single-fiber fineness was generally reduced. However, when the single-fiber fineness was less than 0.8 dtex, a soft touch could be obtained, but the single fiber would break during wearing. In addition, durability and appearance deterioration such as fluff occur. In addition, when producing a polyamide black pre-spun dyed yarn, yarn breakage is large and yarn spinning properties are deteriorated. If the single-fiber fineness exceeds 2 dtex, the touch will become hard. It is preferably 0.8 ~ 1.5dtex. In addition, the total fineness is not particularly limited. When used as a hosiery product, 8 to 155 dtex is preferred.

The strength of the polyamide black pre-spun yarn of the present invention is preferably 2 cN / dtex or more, and more preferably 2 to 6 cN / dtex. By setting the strength to be 2 cN / dtex or more, yarn breakage during processing in the subsequent steps such as false twisted yarn and covered elastic yarn, and durability (fluffiness) when made into a hosiery product can be made practical. In addition, the upper limit of the strength of the polyamide black pre-spun dyed yarn is not limited. If the strength becomes higher, the elongation becomes lower. When manufacturing the polyamide black pre-spun dyed yarn, the yarn-breaking property is changed. Inferior, from the viewpoint of yarn-making property, it is preferably 6 cN / dtex or less.

The manufacturing method of the polyamide black pre-spun dyed yarn of the present invention will be described.

The polyamide black pre-spun dyed yarn of the present invention is most excellent from the viewpoint of productivity and cost by the manufacturing system of melt spinning. In addition, a method of continuously spinning the spinning-drawing step (direct spinning drawing method) by a method for producing melt-spun yarn (a direct spinning drawing method), a method of drawing an undrawn yarn after winding it (a two-step method), or The spinning speed is as high as 3,000m / min or higher, and any method such as a method (high-speed spinning method) in which the elongation step is substantially omitted can be manufactured. The high-speed spinning method, which is excellent in terms of cost, is preferable. In the following, production by the high-speed spinning method is exemplified.

First, the melting portion will be described. Examples of the molten polyamine include a pressure melting method and an extrusion method, and neither is particularly limited. The melting temperature is preferably the melting point of the polyamine polymer + 20 ° C to the melting point + 60 ° C. For example, when nylon 6 polymer is used, the melting point is 225 ° C, and the melting temperature is preferably 245 to 285 ° C.

Examples of the method for containing carbon black include a method of mixing and spinning a masterbatch containing carbon black at a high concentration in polyamide, and mixing with a tablet containing no carbon black, or by using a feeder. Method for directly containing carbon black. The content of carbon black in the masterbatch tablets is preferably 10 to 30% by mass. By setting the content of carbon black in the masterbatch tablets to 10% by mass or more, it is better from the point of view of the manufacturing cost of the polyamide black pre-spun dyed yarn. From the point of agglutination, it is better.

The carbon black-containing polyamide flowing into the spinning bag can be ejected through a conventional spinning nozzle. In addition, the spinning temperature (the so-called thermal insulation temperature around the polymer piping or the spinning nozzle) is preferably the melting point of the polyamide polymer + 20 ° C to the melting point + 60 ° C.

As described above, since carbon black also easily aggregates in the molten polymer, it is preferable to provide a filter in the spinning bag.

The polyamide black pre-spun dyed yarn ejected from the spinning nozzle is cooled, solidified, and oiled, and then pulled. The stretching ratio is appropriately set in a range of 50 to 70% of the elongation of the dyed yarn before the polyamide spinning, and is wound at a winding speed of 3,000 to 5,000 m / min without thermal shaping during the spinning step. good. In addition, in the steps up to the winding, a conventional associating device can also be used to entangle. If necessary, the number of contacts can be increased by giving a plurality of times. Further, an oiling agent may be additionally applied before winding.

The false twisted yarn of the present invention and a method for manufacturing the same will be described.

The false-twisted yarn of the present invention can be obtained by false-twisting the above-mentioned polyamide black pre-spun dyed yarn, but the method of using the false-twisting of the polyamide black pre-spun dyed yarn as the false-twisted yarn is not particularly limited. The execution method is not limited to the rotating method, the 3-axis twisting method, or the belt clamp method. If you want to strengthen the crimping, it is better to use the rotation method. If you want to increase the processing speed and reduce the production cost, it is better to use the three-axis twister and belt clamp using the friction false twist method. There is no limitation on the heating method. A heating plate or a high-temperature short-circuit heater can be used. As the setting temperature, it can be set freely according to the target's touch. As an indicator, when using a heating plate, it is recommended to use polyhexamide (Nylon 6). At 170 ~ 190 ℃, p-hexamethylene adipamide (Nylon 66) is at 180 ~ 200 ℃. As a cooling method, a cooling plate can be used, and air cooling, water cooling, etc. can also be mentioned, but it is not limited, but it is preferable to use a cooling plate in consideration of efficiency and yarn damage. The shrinkage characteristics of the better false twisted yarn are 3-50%. If the crimping property of the processed yarn lies in the above-mentioned preferred range, then When making socks, it has excellent softness on the one hand, and does not need to be subjected to multiple false twists during false twist processing, and is not easy to fluff. The crimping characteristics described herein are values calculated by measurement by a measurement method described later, and are an index of the volume property of the false twisted yarn.

The covered elastic yarn of this invention and its manufacturing method are demonstrated.

The coiled yarn covered with the elastic yarn of the present invention can be selected and used from polyamide black pre-spun dyed yarn and false twist processing of the polyamide black pre-spun dyed yarn.

As the elastic yarn used as the core yarn covering the elastic yarn, polyurethane-based elastic yarn, polyamide-based elastomeric yarn, polyester-based elastomeric yarn, natural rubber-based yarn, synthetic rubber-based yarn, butadiene can be used. For yarns, etc., for sock products, polyurethane elastic yarns and polyamide elastomer elastic yarns are more preferable in terms of elastic characteristics, thermal characteristics, and durability. In addition, when the elastic yarn contains carbon black or the like, when a black elastic yarn is used to make socks, it is preferable to obtain deeper black.

Although the thickness of the covered elastic yarn varies depending on the application of the socks and the setting of the tightening pressure, it is generally preferably about 8 to 80 dtex. 11 ~ 44dtex is better. If the thickness of the covered elastic yarn is in the above-mentioned preferred range, the yarn strength is sufficiently excellent, and troubles such as core yarn breakage during the manufacture of the covered elastic yarn and the knitting of socks are not easy to occur. On the one hand, it is used as the expansion and contraction of socks. It has sufficient properties and durability, the tightening force will not be too strong, and it will not have a sense of pressure and roughness.

As the number of coatings, as long as the yarn fineness, shrinkage rate, or product feel of the false-twisted yarn made of polyamide black spun-dyed yarn and false-twisted polyamide black-spun dyed yarn are considered, The wear resistance can be designed. When covering false twisted yarns made of black pre-spun dyed yarns, it is (56 / processed yarn fineness) ^1/2 × 500 ~ (56 / processed yarn fineness) ) ^1/2 × 1000T / m is an indicator and it is better to design. For example, when 56dtex false twist yarn is covered by single, 500 ~ 1,000T / m is better. In addition, the extension ratio can also be matched with the target wearing pressure design, for example, it is preferably set to 2.5 to 3.5 times. From the viewpoint of soft touch and elasticity, a single coating is preferred.

Therefore, the polyamide black pre-spun dyed yarn of the present invention, the false twisted yarn and the covered elastic yarn obtained by false twist processing of the polyamide black pre-spun yarn, can be used well in socks.

The socks according to the present invention will be described.

The knitting structure constituting the socks of the present invention is not limited to those produced by plain knitting, rubber knitting, pearl knitting, and the like. It is more preferable to have a part composed of a basic structure, and it is more preferable to have a part composed of a plain weave.

In the socks of the present invention, at least one of polyamide black pre-spun dyed yarn, false twisted yarn, and covered elastic yarn is preferably used for at least one part of the leg. In addition, the above-mentioned leg part refers to the part from the groin (garter belt part) to the toe (bottom stocking).

As the used yarn, a so-called single yarn type in which a false-twisted yarn obtained by using only a polyamide black pre-spun dyed yarn or a false-twist-processed polyamide black pre-spun dyed yarn is used as a covering elastic yarn, or Polyurethane black pre-spun dyed yarn or false twist-processed polyamide black pre-spun dyed yarn is used as the covering elastic yarn of the roll yarn, and it is combined with polyamide black pre-spun dyed yarn or false-twisted process. Twisted Twisted Yarn Made from Black Dyed Yarn It's okay to make a turn. In addition, as the yarn used for constituting the hosiery, for example, a yarn according to necessity is used, for example, a seam or the like is not limited.

In addition, there are no restrictions on the knitting machine to be used, but a hosiery machine is preferred.

Here, the socks of the object of the present invention include stockings, pantyhose, leggings, foot pants, safety pants, foot covers and socks, etc., which are composed of three parts of open rubber, body and feet Socks, stockings that are significantly longer than stockings, tights with trousers on the top, and tights.

In addition, in the case that the socks are composed of pants and legs, and the pants and legs are all made of the polyamide black pre-spun dyed yarn, false twist yarn, and elastic yarn-covered socks ; In the case that the socks are composed of only legs, all of the legs are made of the polyamide black pre-spun dyed yarn, false twisted yarn, and covered elastic yarn of the present invention, and the dyeing step can be omitted. If the dyeing step is further subdivided, there are a scouring step, a dyeing step, and a trimming step, which can be omitted. The manufacturing cost of this dyeing step is not only the cost of the dye, but also the cost of the long-term dyeing at high temperature and the processing cost. It is not only shortening the time, but by reducing the manufacturing cost including the cost of the dye and the cost of the fuel, Provide socks to consumers at reasonable market prices. In addition, in the case where the polyamide yarn was previously dyed in black, in order to obtain a dark black hair color, it is necessary to increase the dye concentration. However, in order to obtain softness, the fineness of the single fiber is thinned and increased. The dye concentration has a problem of deterioration in washing firmness. However, in the present invention, not only the dyeing step can be omitted, but also the problem of deterioration of the washing firmness accompanied by the use of high-concentration dyes can be eliminated, and socks with a persistent dark color can be obtained.

In addition, a trimming agent (softening agent) may be applied as a product. In this case, a functional agent such as antibacterial or anti-UV may be added.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to the following examples as long as the present invention does not exceed the gist. In addition, the physical property measurement method of the polyamide black pre-spun yarn of the present invention is as follows.

A. Average particle size of carbon black (μm)

Using an optical microscope, 0.1 g of a sample of polyamide black pre-spun dyed yarn was placed on a microscope specimen heated to 245 ° C at nylon 6 and 275 ° C at nylon 66, sandwiched by a glass slide and extended. The film was photographed at a magnification of 500 times and the longest diameter of the structure of carbon black was the longest. 20 samples were arbitrarily measured from one sample, and the average value of 20 was calculated.

B. Content of carbon black (% by mass)

Using TG-DTA (made by SII. Nanotechmnology, Inc., thermogravimetric measuring device SII TG / DTA 6200), using a sample of 1.4 mg of polyamide black spun dyed yarn, temperature range: room temperature to 900 ° C, heating rate: 100 ° C / min, atmospheric flow rate: The change in weight of the polyamide black pre-spun yarn was measured under the condition of 20ml / min, and the value was calculated from the reduction ratio in the region of 650 ~ 900 ° C. The measurement was performed 4 times, and the average value was taken as the content of carbon black.

C. Relative viscosity of sulfuric acid (ηr)

0.25 g of a small polyamine tablet (sample) was dissolved in 100 ml of 98% by mass sulfuric acid, and the flow-down time (T ₁ ) at 25 ° C. was measured using an Oshwa type viscometer. Next, the flowing time (T ₂ ) of sulfuric acid having a concentration of only 98% by mass was measured. Let the ratio of T ₁ to T ₂ , namely T ₁ / T ₂ be the relative viscosity of sulfuric acid.

D. Yarn-making property

The yarn breakage per ton at the time of making a yarn of a polyamide black pre-spun dyed yarn is expressed as follows.

a: Yarn breaks less than 2 times, b: Yarn breaks 2 or more and 4 times, c: Yarn breaks 4 or more and 6 times, d: Yarn breaks 6 or more and 8 times, e: Yarn breaks 8 or more times.

E. Fineness, single fiber fineness

Polyamide black pre-spun dyed yarn is applied with 0.35mN × for dtex. False twist yarn processed with polyamine black pre-spun dyed yarn is applied with 8.82mN × for dtex tension. The skein was made 200 times with a 1.125m ruler and dried with a hot air dryer (105 ± 2 ° C × 60 minutes). The skein weight was measured with a Libra, and the fineness was calculated by multiplying the value by a fixed moisture content. The measurement system was performed 4 times, and the average value was made into the fineness. In addition, the value obtained by dividing the obtained fineness by the number of filaments was taken as the single-fiber fineness.

F. Strength and elongation

A sample of false-twisted yarn made of polyamide black spun-dyed yarn and false-twisted polyamide black spun-dyed yarn was prepared by TENSILON (universal testing machine) UCT-100 manufactured by ORIENTEC and JIS L1013 (chemical Fiber silk yarn test method, 2010). Elongation is obtained from the elongation at the point where the maximum strength is shown in the tensile strength-elongation curve. The strength is a value obtained by dividing the maximum strength by the fineness. The measurement was performed 10 times, and the average value was made into strength and elongation. The gripping interval was 50 cm and the stretching speed was 50 cm / min.

G. Rolling characteristics

False twisted yarns made from false-twisted polyamide black spun dyed yarns were subjected to a tension of 0.098cN / dtex on one side, and a perimeter of 1.125m was taken and 5 skeins were wound 10 times. It was left in an environment of 20 ° C and 60% RH for 24 hours. In a state where a treatment load (a load in water) of 1.76 × 0 ^-3 cN / dtex was applied, it was treated in hot water at 98 ° C. ± 1 ° C. for 20 minutes. The heat-treated skein is placed in an environment of 20 ° C and 60% RH for 24 hours to be dried. Water was put in a cylinder in advance, and it was left for 24 hours in an environment of 20 ° C and 60% RH. The hank yarn was put into water in a state where an initial load (a load in water) of 1.76 × 10 ^-3 cN / dtex was applied to the skein sample. Thereafter, a load (load in water) of 0.088 cN / dtex was further applied to a constant load (load in water) of 0.08976 cN / dtex, and the skein length a (mm) after 2 minutes was measured. The fixed load was quickly removed, and the hank length b (mm) after only 2 minutes of the initial load was measured. The crimping characteristics were calculated by the following formula and evaluated as an average of five.

Rolling characteristics (%) = [(a-b) / a] × 100

H. Boiling water shrinkage

False twisted yarns made of polyamide black pre-spun dyed yarns were subjected to a tension of 0.098 cN / dtex on one side, and a perimeter of 1.125 m was taken and five skeins were wound 10 times. It was left in an environment of 20 ° C and 60% RH for 24 hours. Find the initial length L0 under 0.09cN / dtex load. Next, after being treated in boiling water under no load for 30 minutes, it was air-dried. Next, the processed length L _{1 was} calculated under a load of 0.09 cN / dtex, and was calculated by the following formula, and evaluated by an average value of 5 pieces.

Boiling water shrinkage (%) = [(L ₀ -L ₁ ) / L ₀ ] × 100

I. softness

The softness (soft touch) is based on the single yarn pantyhose sample. The touch of the examiner (30 persons) at the 10 cm lower part of the garter belt portion is determined in three stages.

a: Softness equivalent to Comparative Example 7

b: slightly inferior to Comparative Example 7

c: Significantly inferior in flexibility compared to Comparative Example 7

J. Hue

Regarding the hue (dark black color), it was determined in 5 stages based on the vision of the examiner (30 persons) based on the sample of the single yarn pantyhose and the 10 cm portion of the lower part of the garter belt.

a: Darker black than Comparative Example 7 with very good hue

b: Compared with Comparative Example 7, the color of black is better.

c: The same hue as Comparative Example 7

d: slightly whiter than Comparative Example 7

e: Whiter than Comparative Example 7

K. Fluffiness

The single yarn pantyhose sample was subjected to fluffing evaluation in accordance with JIS L 1076 (2012) Appearance Retention C method to the 10 cm lower portion of the garter belt portion to determine the grade.

N: The number of hair balls is the degree of N of the standard photo

L: The number of hair balls is the same as the L number of the standard photo

M: The number of hair balls is the degree of M of the standard photo

H: The number of hair balls is at or above the H level of the standard photograph

L. CV of dry heat shrinkage stress (%)

Using a FTA-500 manufactured by TORAY Engineering, the measurement was performed for 10 minutes using a dry heat treatment device heated to 100 ° C at a length of 15.5 cm under conditions of a supply speed of 10 m / min and a relaxation of 1% for a polyamide yarn. The standard deviation of the dry heat shrinkage stress obtained is divided by the average value and expressed as the obtained value.

[Example 1]

(Manufacture of Polyamide Black Pre-spun Yarn)

As the polyamide, 6 pieces of nylon having a sulfuric acid relative viscosity (ηr) of 2.6 and a titanium oxide content of 0.02% by mass were dried by a conventional method to reduce the moisture content to 0.03% by mass or less.

The obtained 6 small pieces of nylon were kneaded with a 2-axis kneader so that the furnace carbon black content became 15% by mass. After passing through a 30 μm mesh filter, injection was performed to produce small pieces of masterbatch, which were dried in a conventional manner to obtain a moisture content. It is, for example, 300 ppm or less. The obtained masterbatch of nylon 6 containing carbon black and nylon 6 without carbon black were blended in a ratio of 1: 4 (the content of carbon black in the black pre-dyed yarn was 3% by mass), and The melting temperature of 265 ° C is melted, and the polymer piping through 25 stages of the static mixer is filtered through a spinning bag provided with a 10 μm mesh metal filter, and the spinning nozzle is ejected at a spinning temperature of 260 ° C. The spinning nozzle uses a circular number of 68 holes and a sliver / nozzle. After being ejected from the spinning nozzle, it was cooled by cold air at 18 ° C, after oiling, after entanglement, it was extended to 1.2 times by the first godet roller and the second godet roller, and wound at a winding speed of 4,000 m / min. Nylon 6 black spinning dyed yarn of 96 dtex and 68 silk was obtained. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in Table 1.

(Manufacturing false twist yarn)

The nylon 6 black pre-spun dyed yarn was set using a false twister IVF805 made by Ishikawa Manufacturing Co., Ltd. at a processing speed of 500 m / min, an elongation ratio of 1.23 times, a heater temperature of 180 ° C, and a D / Y ratio of 1.7. Twist tension / Twist tension = 1.04), and false twist processing was performed to obtain 78.1 dtex, 68 false twist yarns. The fineness, strength, elongation, boiling water shrinkage, and curling characteristics of the obtained false-twisted yarn were evaluated. The results are shown in Table 1.

(Manufacture of covered elastic yarn)

Using the above false-twisted yarn as the winding yarn, "Mobilon" (registered trademark) 22dtex, G-type (manufactured by Nisshinbo Textile) were used as the core yarn, covering the number of 600T / m and stretching 3.0 times to prepare S twist, Z Twisted single covering yarn.

(Manufacture of single yarn tights)

In Nagata Seiki Co., Ltd., MODEL KT-S4 (380 needles), the above-mentioned single covering yarn was installed to make single yarn pantyhose. The knitted single yarn pantyhose was pre-shaped for 10 minutes at 80 ° C in vacuum, refined for 30 minutes at 98 ° C, and after being softened, the aluminum plate was used to perform heat setting at 110 ° C for 30 seconds to obtain single yarn pantyhose. The obtained single yarn pantyhose was evaluated for softness, hue, and fluff. The results are shown in Table 1.

[Example 2]

Except that the nylon 6 masterbatch containing carbon black and the nylon 6 tablet were blended in a ratio of 1:14 (the carbon black content in the black pre-dyed yarn was 1% by mass), it was the same as in Example 1. Method to manufacture nylon 6 black pre-spun dyed yarn. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Example 3]

Except that the nylon 6 masterbatch containing carbon black and the nylon 6 tablet were blended in a ratio of 33:67 (the carbon black content in the black pre-dyed yarn was 5 mass%), it was the same as in Example 1. Method to manufacture nylon 6 black pre-spun dyed yarn. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Example 4]

A nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that filtration was performed using a spinning bag provided with a 15 μm mesh metal filter. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. Comment The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose are estimated. The results are shown in Table 1.

[Example 5]

A nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that filtration was performed with a spinning bag provided with a metal filter having a mesh of 20 μm. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Example 6]

A nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes using the spinning nozzle was 96 and round. A nylon 6 black pre-spun dyed yarn of 96 dtex and 96 silk was obtained. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Example 7]

A nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes using the spinning nozzle was 52 and round. A nylon 6 black pre-spun dyed yarn of 96 dtex and 52 silk was obtained. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Example 8]

Nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes in the spinning nozzle was 68, round, and 2 slivers / nozzles. 48 dtex, 34 silk nylon 6 black spun dyed yarn. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Example 9]

Nylon 6 black spinning was produced in the same manner as in Example 1 except that the number of holes in the spinning nozzle was 78, round, and 3 slivers / nozzles. Pre-dyed yarn to obtain 43 dtex, 26 silk nylon 6 black pre-dyed yarn. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Example 10]

As polyamide, a piece of nylon 66 having a sulfuric acid relative viscosity (ηr) of 2.8 and a titanium oxide content of 0.02% by mass was dried by a conventional method so as to center the moisture content at 0.11% by mass.

Except for the obtained nylon 66 flakes, kneading was performed so that the furnace carbon black content became 15% by mass, and a 30 μm mesh filter was set to manufacture masterbatch flakes, which were dried by a conventional method so that the moisture content would be centered at 0.11% by mass. The obtained carbon black containing nylon 66 masterbatch pieces and nylon 66 pieces were blended at a ratio of 1: 4 (the content of carbon black in the black pre-dyed yarn was 3% by mass), and melted at 290 ° C. The temperature was melted, and filtration was performed in a spinning bag provided with a 10 μm mesh metal filter. A nylon 66 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that the spinning temperature was 290 ° C. and ejected from a spinning nozzle. To obtain 96 dtex, 68 silk nylon 66 black pre-dyed yarns. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in Table 1.

Using the obtained nylon 66 black pre-spun dyed yarn, a false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1 except that the heater temperature of the false-twisting process was 190 ° C. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 1.

[Comparative Example 1]

A nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that filtration was performed in a spinning bag provided with a metal filter having a mesh of 1 μm. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 2.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 2.

[Comparative Example 2]

A nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that filtration was performed in a spinning bag provided with a metal filter having a mesh of 30 μm. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 2.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 2.

[Comparative Example 3]

A nylon 6 black pre-spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes using the spinning nozzle was 320 and round. Nylon 6 black spinning dyed yarn of 96 dtex, 320 silk was obtained. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 2.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 2.

[Comparative Example 4]

A nylon 6 black pre-dyed yarn was produced in the same manner as in Example 1 except that the number of holes of the spinneret was 20 and round, and a nylon 6 black pre-dyed yarn of 96 dtex and 20 silk was obtained. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 2.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 2.

[Comparative Example 5]

Except that carbon black-containing nylon 6 masterbatch pellets and nylon 6 pellets were blended at a ratio of 3:97 (the carbon black content in the black pre-dyed yarn was 0.5% by mass), it was the same as in Example 1. The same method was used to produce nylon 6 black pre-dyed yarn. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 2.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 2.

[Comparative Example 6]

Except that carbon black-containing nylon 6 masterbatch pellets and nylon 6 pellets were blended at a ratio of 47:53 (the carbon black content in the black pre-dyed yarn was 7% by mass), it was the same as in Example 1. The same method was used to produce nylon 6 black pre-dyed yarn. The yarn-making property, carbon black content, average carbon black particle size, fineness, strength, and elongation of the obtained black pre-spun dyed yarn were evaluated. The results are shown in Table 2.

Using the obtained nylon 6 black pre-spun yarn, false-twisted yarn, covered elastic yarn, and pantyhose were produced in the same manner as in Example 1. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 2.

[Comparative Example 7]

Except for the use of polyamide, only 6 small pieces of nylon (relative viscosity ηr) of 2.6 and titanium oxide content of 0.02% by mass (carbon black content of 0% by mass) were used. Polyamide 6 yarn. The yarn-making property, fineness, strength, and elongation of the obtained nylon 6 yarn were evaluated. The results are shown in Table 2.

Using the obtained nylon 6 yarn, false-twisted yarn and covered elastic yarn were produced in the same manner as in Example 1. In addition, it is the same as in Example 1. Knitted into single yarn tights. The knitted single yarn pantyhose was preformed for 10 minutes at 80 ° C in vacuum, refined for 30 minutes at 98 ° C, and dyed with 4% by mass of Mitsui Nylon Black GL (Mitsui Toka Chemical Co., Ltd.) at 98 ° C for 60 minutes After the softening treatment, the foot mold of the aluminum plate was subjected to heat setting at 110 ° C. for 30 seconds to obtain single yarn tights. The fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluff of the single yarn pantyhose were evaluated. The results are shown in Table 2.

From the results of Table 1 (Examples 1 to 10), it can be seen that the polyamide black pre-spun dyed yarn of the present invention can be obtained by optimizing the carbon black content, average particle size, and single fiber fineness. Single yarn tights with good soft touch (softness), dark hair color (hue), and durability (fuzziness). It can be seen that in Example 10, nylon 66 was used, and the yarn breakage during yarn production was slightly lower than that of nylon 6. Therefore, when the socks are made, the fluff of the raw yarn is mixed in, and the product grade is slightly lowered.

In Comparative Example 1, the presence of carbon black with a small average particle diameter caused the kinetic friction coefficient of the surface of the pantyhose to be high, and the fluffing property was poor.

In Comparative Example 2, the presence of carbon black with a large average particle size increased the filtration pressure in the spinning bag. As a result, not only the life of the bag was shortened, but yarn breakage occurred frequently, resulting in poor yarn making properties. In addition, the strength of the obtained nylon black pre-spun dyed yarn is a low value of 1.5 cN / dtex, and the fluff is slightly inferior.

In Comparative Example 3, the single fiber fineness was fine. As a result, yarn breakage occurred frequently and the fluff was poor.

In Comparative Example 4, the single fiber fineness was too thick, and it became a hard touch, and the soft touch (softness) was inferior.

In Comparative Example 5, the content of carbon black was small, and light was easily transmitted to become white, and the hue (dark black color) was poor.

In Comparative Example 6, because the carbon black content was large, the increase in the filtration pressure in the spinning bag was large. As a result, not only the life of the bag was shortened, but yarn breakage occurred frequently, resulting in poor yarn making properties. In addition, the strength of the obtained nylon black pre-spun dyed yarn was a low value of 0.9 cN / dtex, and the fluff was poor.

Comparative Example 7 was a conventional single-sock pantyhose, and was dyed black. Although a soft touch can be obtained, it becomes white due to the diffusion of light, and the color tone (dark hair color) is poor.

The single yarn pantyhose using the polyamide black pre-spun yarn of the present invention does not have black dyeing, so the processing cost of the dyeing step can be omitted, which can not only reduce the cost, but also has a small environmental load.

[Industrial profitability]

The polyamide black pre-spun dyed yarn of the present invention has a soft touch and can develop a dark black color. This false twisted processed yarn or a covered elastic yarn covered with an elastic yarn is well applicable. For stockings or tights.

Claims (6)

A polyamide black pre-spun dyed yarn, which is a polyamide black pre-spun dyed yarn containing 1 to 5 mass% of carbon black, wherein the average particle diameter of the carbon black in the polyamine is 1 to 20 μm and the poly The single fiber fineness of the amine black pre-spun dyed yarn is 0.8 ~ 2dtex, and the polyamide is mainly composed of nylon 6 or nylon 66. For example, the polyamide black pre-spun dyed yarn of claim 1, wherein polyamide is nylon 6. For example, the polyamide black pre-spun dyed yarn of claim 1 or 2 is a polyamide black pre-spun dyed yarn with a CV value of dry heat shrinkage stress of 4.0% or less. A false-twisted yarn produced by false-twisting a polyamide black pre-spun dyed yarn according to any one of claims 1 to 3. A covered elastic yarn using a polyamide black pre-spun dyed yarn as claimed in any one of claims 1 to 3 or a false twisted yarn as claimed in claim 4 as a roll yarn. A hosiery product using at least a part of a leg a polyamide black pre-spun dyed yarn as in any of claims 1 to 3, a false twisted yarn as in claim 4, or a covering elasticity as in claim 5 At least one kind of yarn.