TW201343995A - Polyamide black spun-dyed yarn, false-twist yarn, elastic covered yarn and leg knit - Google Patents

Abstract

A polyamide black spun-dyed yarn of the invention is characterized in containing 1-5 mass% furnace black which is having an average particle diameter of 1 to 20 μ m, and having single fiber fineness of 0.8 to 2dtex. A false-twist yarn is false twisting the above polyamide black spun-dyed yarn. An elastic covered yarn is using the above polyamide black spun-dyed yarn and the above false-twist yarn as a wound yarn. A leg knit is using at least one of the above polyamide black spun-dyed yarn, the above false-twist yarn and the above elastic covered yarn for at least a part of the leg part. The invention provides tights or stockings with a soft texture, which can develop deep black color.

Description

Polyamide black dyed yarn, false twisted yarn, covered elastic yarn and socks

The present invention relates to a polyamide-black spun dyed yarn, a false twisted yarn, a covered elastic yarn, and a sock having a soft touch and capable of developing a dark black color.

For socks such as stockings or pantyhose, polyacetamide yarns represented by nylon 6 or nylon 66 are mainly used. In the past, in order to obtain the softness of a sock product, the single fiber fineness of the polyamide yarn was generally made fine. However, the fineness of the single fiber is reduced, and although the flexibility is obtained, the appearance of the product of the hosiery is whitened due to the diffusion of light, and it is difficult to obtain a dark color, and the single fiber is broken during wearing, and the durability is generated. Problems such as appearance and appearance deterioration. In particular, as a consumer demand for pantyhose, in addition to a soft touch, durability, and reasonable market price, color (color development) is an important factor, and it is desirable to have the ability to color the color of the pantyhose. The mainstream dark black polyamide yarn.

Prior technical literature Patent literature

In order to solve this problem, Patent Document 1 discloses that an ultrafine fiber having good black color properties can be obtained by containing carbon black in the polyamide yarn.

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

In the method described in Patent Document 1, an ultrafine polyamide yarn having a single fiber fineness of 0.0001 to 0.06 dtex is obtained by removing the sea component of the sea-island composite yarn, and it can be obtained in a sock product such as a stocking or a pantyhose. On the other hand, there is a problem that the darkening of the hair color (durability, appearance) and the increase in the cost of removing the sea component occur. In addition, since it is necessary to elute the PE of the sea component with toluene or the like, the elastic yarn such as the elastic fiber which is the core yarn of the covered yarn is deteriorated, and the strength is weakened and the stretchability is impaired.

In the present invention, the subject is to solve the above problems as described above, and to provide a polyamide-black spun dyed yarn having a soft touch and a dark black color. Further, it is a subject to provide a polyacrylamide black spun dyed yarn, a false twisted yarn, a covered elastic yarn, and a sock which can be colored in dark black.

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

Further, the false twisted yarn of the present invention has the following constitution. That is, a false twisted yarn which is formed by processing the above-mentioned polyamine black spun dyed yarn.

The coated elastic yarn of the present invention has the following constitution. That is, a covered elastic yarn which is obtained by using the above-mentioned polyamine black spun dyed yarn or the above false twisted yarn as a bobbin.

The sock of the present invention has the following constitution. In other words, at least one of the polyacrylamide black spun dyed yarn, the false twisted yarn, and the coated elastic yarn is used in at least one of the leg portions.

Furthermore, the polymethylamine black pre-spun dyed yarn of the present invention, wherein the polyamine is preferably nylon 6.

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

According to the present invention, it is possible to obtain a polyacrylamide black spun dyed yarn, a false twisted yarn, and a covered elastic yarn which are suitable for a sock having a soft touch and a dark black stocking or pantyhose.

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

The polyamine which constitutes the polyacrylamide black pre-spun dyed yarn of the present invention is a resin composed of a high molecular weight body in which a hydrocarbon group is bonded to a main chain via a hydrazine bond, and is used as the polyamine. Excellent in properties and mechanical properties, mainly based on polyhexylamine (Nylon 6) and polyhexamethylenediamine (Nylon 66). When it contains carbon black, it is not easy to gel, and the yarn is made. Good sex, better with polyhexylamine (Nylon 6). "main" as used herein means The ε-caprolactam unit constituting the polyhexylamine is preferably 80 mol% or more in the all monomer unit, and more preferably 90 mol% or more. The other component is not particularly limited, and examples thereof include polydodecylamine, polyhexamethylene adipamide, polyhexamethylenediamine, polyhexamethylenediamine, and polyhexamethylenediamine. Aminocarboxylic acid of a monomer such as polyhexamethylene adipamide, poly-m-xylylene hexamethylenediamine, polyhexamethylene terephthalamide or polyhexamethylene metaxylamine A unit of an acid, a dicarboxylic acid, a diamine or the like.

In addition, the degree of polymerization of the polyamidamide used for the polyacrylamide black pre-spun dyed yarn may be suitably selected according to the characteristics required for the false twist processing, the braid, the fiber product, or in order to stably obtain such an appropriate range. The selection is preferably in the range of 2.0 to 3.6 with a viscosity of 98% sulfuric acid at 25 ° C, and preferably in the range of 2.4 to 3.3.

The type of the carbon black used in the polyacrylamide black-spun dyed yarn of the present invention may, for example, be black, black, thermal black, acetylene black or lamp black, and is not particularly limited, but is preferably furnace black. . The method of producing carbon black is divided into the acetylene black and the thermal black of the thermal decomposition method, the adoption of the soot of the incomplete combustion method (so-called black) or the furnace black, and different characteristics of the carbon black are imparted according to the different methods. It is necessary to maintain a thermal decomposition method in a reaction environment around 2,000 ° C. Since a large amount of energy is required for production, it is low in practicality in terms of cost and manufacturing environment. On the other hand, the incomplete combustion method is highly practical in terms of cost and environment at the time of manufacture. Further, the representative furnace method of the incomplete combustion method is easy to control the particle size or the size of the structure, and it is preferable to use the furnace black obtained by the furnace method from the viewpoint of the color tone or the yarn-making property of the polyacrylamide black-spun dyed yarn. In particular, the manufacture of small particle size furnace black is better by furnace black obtained by the oil furnace method.

In addition, the structure of carbon black is formed at the stage of its manufacture. The smallest unit of structure carbon black, the index of which can be expressed in terms of DBP oil absorption. Here, the oil absorption amount means a value measured in accordance with JIS K6217-4 (2008). The DBP oil absorption of the carbon black used in the polymethylamine black pre-spun yarn of the present invention is preferably 10 to 300 ml/100 g. When the DBP oil absorption amount is in the above preferred range, when the polyamine black pre-spun dyed yarn is produced, the color can be easily developed into a dark black color, and on the other hand, the polyacrylamide polymer has good dispersibility and is produced in a polypolymer. In the case of the black amine pre-spun dyed yarn, the coarse particles do not increase, the yarn-making property is good, and the mechanical properties of the polyamide-dyed black-spun dyed yarn are excellent.

The carbon black contained in the polyacrylamide black spun dyed yarn of the present invention must have an average particle diameter of 1 to 20 μm. Here, the average particle diameter is generally referred to as a structure in which the particle diameter of the coarse particles is large, and the measurement method is carried out by using an optical microscope, and 0.1 g of the sample of the polyacrylamide black spun dyed yarn is placed on the heated polythene. A sample of a microscope with a melting point of +20 ° C at the melting point of the amine black-spun yarn, which was clamped by a glass slide and stretched into a film shape at a magnification of 500 times. The longest diameter of the carbon black structure was determined by one sample, and 20 samples were arbitrarily determined. Calculate the value of the average of 20 pieces. At this time, the photograph taken can also be enlarged to a size where the particle size can be easily determined. When the average particle diameter is more than 20 μm, the yarn is spun and the yarn-making property is deteriorated in the production of the dyed yarn before the black polyamide spinning, and the product grade is deteriorated due to the incorporation of fluff or the like in the formation of the socks. The strength of the mechanical properties of the amine black spun dyed yarn is reduced. When the thickness is less than 1 μm, the dynamic friction coefficient of the yarn becomes higher than that at the time of wearing, and a lot of fluffing occurs in a portion where the fingertip, the heel, or the knee is rubbed more. It is preferably 1 to 10 μm. In order to be included in the polyacrylamide black spun dyed yarn of the present invention The carbon black has an average particle diameter of 1 to 20 μm, and can be used to filter the molten polymer containing carbon black during the production of the polyacrylamide black pre-spun dyed yarn by the production of the polyacrylamide black-spun dyed small piece. . The filtration method is not particularly limited, and it is preferred to provide a filter in a passage of a molten polymer or a spinning bag. It is preferable to set the filter in the spinning bag, and the filter used in the spinning bag is preferably a mesh of 10 to 20 μm.

Further, when carbon black is contained in the polyamide melt polymer, the carbon black particles become secondary particles or tertiary particles and are likely to become coarse particles. Therefore, only the filter is provided in the spinning bag, the carbon black is easily plugged, the filtration pressure is increased, the life of the bag is shortened, and the productivity is easily lowered. A preferred melt spinning method for containing carbon black in polyamine is to contain a masterbatch containing a high concentration of carbon black in polyamine in addition to a filter provided in a spinning bag, and does not contain Melt spinning of carbon black is preferred for melt spinning. Further, when the masterbatch is manufactured, the filter is removed to eliminate the coarse particles, and the filtration pressure in the production of the polyacrylamide black-spun dyed yarn is suppressed, so that the life of the bag is prolonged and the productivity can be improved. . Further, the filter used in the production of the masterbatch small piece is preferably a mesh of 20 to 50 μm.

The content of carbon black contained in the polyacrylamide black spun dyed yarn of the present invention must be 1 to 5% by mass. Here, the content is measured by using TG-DTA, and measuring the weight of the polyaniline black-spun dyed yarn under the conditions of temperature range: room temperature to 900 ° C, temperature increase rate: 100 ° C/min, and atmospheric flow rate: 20 ml/min. The change is a value calculated from the ratio of the amount of reduction in the region of 650 to 900 ° C, which is regarded as the amount of disappearance of carbon black, and is the carbon black content in the pre-spun dyed yarn of polyamine. When the content is less than 1% by mass, then When it is made into a sock product such as a stocking or a pantyhose, it is impossible to obtain a dark black hair color. When the content is more than 5% by mass, not only the yarn breakage in the production of the polyaniline black pre-spun yarn is large, but the yarn-forming property is deteriorated, and the mechanical properties of the polyamide-spun yarn before dyeing are lowered. The content is preferably 2 to 4% by mass.

In addition, if it is an amount or a kind which does not impair the object of the object of the present invention, it may blend an additive for improving productivity such as heat resistance, or blend it to have matting, moisture absorption, antibacterial, ultraviolet shielding, Additives for functions such as heat preservation. However, since the durability and the black color of the products such as the yarn-making property, the stockings, and the pantyhose are reduced, it is not preferable to add the inorganic particles of more than 1 μm, and the inorganic particles including the white pigment are not limited. The addition is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, based on the polyacrylamide black pre-spun dyed yarn.

The polyacetamide black pre-spun dyed yarn of the present invention has a CV value of 4.0% or less of the dry heat shrinkage stress of the polyacrylamide black spun dyed yarn. The CV value of the dry heat shrinkage stress is the shrinkage of the polyacrylamide black spun dyed yarn in the longitudinal direction. The CV value of some heat shrinkage stress is in the above preferred range, and the processing tension during the false twisting process is not easily changed, There is an unevenness in the unwrapped, etc., and the product surface of the product such as the sock is good, and on the other hand, the shrinkage unevenness does not occur in the heat treatment such as refining or foot setting, and the material surface is not Good grade. In order to make the CV value 4.0% or less, it is preferable to reduce the dispersion of the content of the carbon black contained in the black dyed yarn before the polyamine. It is necessary to reduce the dispersion of the content of carbon black contained in the black-spun dyed yarn of polyamine, for example, a masterbatch containing a high concentration of carbon black in polyamine and a polyamine containing no carbon black. Small piece blending and melt spinning, by kneading using a 2-axis extruder, or A kneading device or the like provided in a polymer pipe such as a static mixer or a high-speed mixer can sufficiently knead a high concentration of carbon black to reduce the dispersion of the carbon black content. The content of the carbon black is determined by measuring the content of the carbon black of the single fiber by using the above-described TG-DTA, and the preferred range is 10% or less of the CV value.

The polymethylamine black pre-spun dyed yarn of the present invention has a single fiber fineness of 0.8 to 2 dtex. In the past, in order to obtain a soft touch of a sock product, the single fiber fineness was generally made fine, but when the single fiber fineness was less than 0.8 dtex, although a soft touch was obtained, the single fiber was broken during wearing. The durability and appearance of hair growth are deteriorated. Further, in the case of producing a polyamide yarn before the black spinning, the yarn is broken and the yarn-making property is deteriorated. If the single fiber fineness exceeds 2 dtex, the touch will become hard. It is preferably 0.8 to 1.5 dtex. Further, the total fineness is not particularly limited, and when used as a sock product, it is preferably 8 to 155 dtex.

The strength of the polyacrylamide black spun dyed yarn of the present invention is preferably 2 cN/dtex or more, more preferably 2 to 6 cN/dtex. When the strength is 2 cN/dtex or more, the yarn breakage during processing in the subsequent steps such as the false twisted yarn or the covered elastic yarn, and the durability (hairing property) when the finished product is made into a sock can be made practical. In addition, the upper limit of the strength of the polyacrylamide black-spun dyed yarn is not limited, and if the strength is high, the elongation is lowered, and when the polyamide yarn is dyed before the black spinning, the yarn breakage is changed. In the case of the difference in the yarn making property, it is preferably 6 cN/dtex or less.

A method of producing the polyacrylamide black spun dyed yarn of the present invention will be described.

The polymethylamine black pre-spun dyed yarn of the present invention is the most excellent in terms of productivity and cost, and is manufactured by melt spinning. Further, regarding the method for producing a melt-spinning method, a method in which the spinning-extension step is continuously performed (direct spinning extension method), a method in which the undrawn yarn is taken up and then stretched (two-step method), or a method Any method such as a method in which the spinning speed is 3,000 m/min or more, and the method of substantially omitting the stretching step (high-speed spinning method) can be manufactured, but it can be used as a false twist yarn. The crimping property is preferably a high-speed spinning method excellent in cost. Hereinafter, the production by the high speed spinning method will be exemplified.

First, the molten portion will be described. In the case of melting the polyamine, a pressure melting method or an extrusion method is exemplified, and both are not particularly limited. The melting temperature is preferably from the melting point of the polyamide polymer + 20 ° C to the melting point + 60 ° C. For example, in the case of using a nylon 6 polymer, since the melting point is 225 ° C, the melting temperature is preferably 245 to 285 ° C.

The method of containing carbon black may be a method of mixing a masterbatch containing carbon black at a high concentration in polyamine, a method of melt-spinning with a small piece of polyamine containing no carbon black, or by a feeder or the like. A method that directly contains carbon black. The carbon black content of the masterbatch small piece is preferably 10 to 30% by mass. When the content of the carbon black of the masterbatch pellet is 10% by mass or more, it is preferable from the viewpoint of the production cost of the polyacrylamide black spun dyed yarn, and it is made of carbon black by 30 mass% or less. The point of agglutination is better.

The carbon black-containing polyamine which flows into the spinning bag can be ejected by a conventional spinning nozzle. Further, the spinning temperature (so-called polymer piping or the holding temperature around the spinning nozzle) is preferably a melting point of the polyamide polymer + 20 ° C to a melting point + 60 ° C.

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

The polyacrylamide black spun dyed yarn which is ejected from the spinning nozzle is cooled, solidified, and then drawn after the oil is applied. The stretching ratio is appropriately set to a range in which the polyamide dyed yarn is stretched to a range of 50 to 70%, and is not heated in the spinning step, and is wound at a take-up speed of 3,000 to 5,000 m/min. good. Further, in the step up to the winding, a conventional entanglement device can be used to apply the entanglement. If necessary, the number of contacts can also be increased by giving multiple times. Further, an oil agent may be additionally added before the winding.

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

The false twisted yarn of the present invention can be obtained by subjecting the above-mentioned polyamidamine black-spun dyed yarn to false twist processing, but the method of treating the polyacetamide black-spun dyed yarn by false twisting is not particularly limited. The method of implementation is not limited to the rotation mode, or the 3-axis twisting method, the belt clamp method, and the like. When it is desired to strengthen the crimping, it is preferable to use the rotation method. When it is desired to increase the processing speed and reduce the production cost, it is preferable to use a three-axis twister and a belt clamp using a friction false twist method. There is no limit to the heating method. Use a hot plate or a high-temperature short-circuit heater. As the set temperature, it can be set freely with the target's touch. As an indicator, when using a heating plate, it is recommended to use polyhexylamine (Nylon 6). At 170~190 °C, the polyhexamethylene hexamethyleneamine (Nylon 66) is 180~200 °C. As the cooling method, a cooling plate may be used, and air cooling, water cooling, and the like may be used. However, it is preferable to use a cooling plate in consideration of efficiency and damage of the yarn. The preferred false twist yarn has a crimping characteristic of 3 to 50%. If the crimping characteristics of the processed yarn are in the above preferred range, then When it is made into a sock, it is excellent in softness on the one hand, and it is not necessary to apply a plurality of false twists at the time of false twisting processing, and it is not easy to fluff. In addition, the crimping property described here is a value calculated by measurement by a measuring method described later, and is an index of the bulkiness of the false twisted yarn.

The coated elastic yarn of the present invention and a method for producing the same will be described.

The wrapped elastic yarn of the present invention can be selected from the false crepe yarn obtained by polyacrylamide black spun dyed yarn and false twisted polyamine black spun dyed yarn.

As the elastic yarn to be the core yarn of the elastic yarn, a polyurethane elastic yarn, a polyamide elastic elastomer yarn, a polyester elastomer elastic yarn, a natural rubber yarn, a synthetic rubber yarn, butadiene can be used. As a hosiery, it is preferable that it is a polyurethane-type elastic yarn and a polyamide type elastomer elastic yarn from the viewpoint of the elastic property, the thermal property, durability, etc.. Further, the elastic yarn contains carbon black or the like, and in the case where a black elastic yarn is used as a sock, a deeper black color can be obtained.

The thickness of the covered elastic yarn varies depending on the use of the sock and the setting of the tightening pressure, and is generally preferably about 8 to 80 dtex. Better with 11~44dtex. When the thickness of the covered elastic yarn is in the above preferred range, the yarn strength is sufficiently excellent, and troubles such as breakage of the core yarn when the elastic yarn is wrapped and when the knitted product is knitted are not easily caused. Sexuality and durability are sufficient, the tightening force is not too strong, and there is no sense of pressure or roughness.

As the number of coatings, it is only necessary to consider the fineness, shrinkage or feel of the yarn of the false twisted yarn which is obtained by using the polyacrylamide black-spun dyed yarn or the false twisted polyamide-spun yarn before dyeing, and the fluff resistance, It can be designed for durability. When the false crepe yarn obtained by processing the false-spun black-spun yarn is coated, it is (56/processed yarn) ^1/2 × 500~ (56/machined yarn fineness). ^1/2 × 1000T/m is designed as an index. For example, when a 56 dtex false crepe is coated, it is preferably 500 to 1,000 T/m. In addition, the stretching ratio can also be designed in accordance with the target wearing pressure, for example, it is preferably set to 2.5 to 3.5 times. The coating is soft in touch and stretchable, and it is preferably a single coating.

Therefore, the polydecylamine black-spun dyed yarn of the present invention, the false twisted yarn obtained by processing the polyacetamide black-spun dyed yarn, and the covered elastic yarn can be suitably used for the socks.

The socks related to the present invention are described.

The woven structure constituting the hosiery of the present invention is not limited to those produced by weaving the tissue by plain weave, rubber woven, pearl woven fabric, and the like. It is preferred to have a portion having a basic structure, and it is more preferable to have a portion made of plain weave.

In the hosiery of the present invention, at least one of the polyaniline black spun dyed yarn, the false twisted yarn, and the covered elastic yarn is preferably used for at least one part of the leg portion. Furthermore, the above-mentioned leg means a part of the squid (sock garter portion) to the toe (sock bottom).

As a so-called single-yarn type in which a false twisted yarn obtained by using only a polyamide-black spun dyed yarn or a false twisted polyamide-black spun dyed yarn is used as a coated elastic yarn of a bobbin, or The false crepe yarn obtained by using the polyaniline black pre-spun dyed yarn or the false enamel processing polyylidene black pre-spun dyed yarn as the coated elastic yarn of the coiled yarn, and the polyylidene black-spun dyed yarn or the false twisted yarn False crepe interaction made of black amine dyed yarn It’s fine to make a match. In addition, as a yarn to be used for hosiery, for example, a suture or the like is used, and the yarn is not limited.

Further, as the knitting machine to be used, there is no limitation, but a knitting machine is preferably used.

Here, the socks of the present invention include stockings, pantyhose, inner pants, foot pants, safety pants, foot covers, and socks, and the three parts of the open rubber, the body, and the foot. Socks, stockings that are significantly longer than stockings, pantyhose with pants, and pantyhose.

Further, in the case where the sock is composed of the pants portion and the leg portion, and the pants portion and the leg portion are all used in the case of the polyacrylamide black spun dyed yarn, the false twisted yarn, and the elastic yarn covered with the present invention. In the case where the socks are composed only of the legs, and all of the legs are used in the case of using the polyamine black spun dyed yarn, the false twisted yarn, and the covered elastic yarn of the present invention, the dyeing step can be omitted. If the dyeing step is further subdivided, there are a scouring step, a dyeing step, and a finishing step, and the dyeing step can be omitted. The manufacturing cost of this dyeing step is not only the cost of the dye, but also the cost of the dyeing at a high temperature for a long time and the processing cost, not only shortening the time, but also reducing the manufacturing cost of the dye-containing cost and the fuel cost. Provide socks to consumers at a reasonable market price. In addition, in the case where the polyamide yarn is previously dyed in black, if dark black color is desired, the dye concentration must be increased, but if the flexibility is made, the single fiber fineness is made fine and improved. The dye concentration has a problem that the washing firmness is deteriorated. However, in the present invention, not only the dyeing step can be omitted, but also the problem of deterioration of the washing firmness accompanying the use of a high-concentration dye can be avoided, and a sock having a deep dark color can be obtained.

Further, as a product, a conventional conditioner (softener) may be applied as a trimming. In this case, a functional agent such as antibacterial or anti-UV may be added.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as it does not exceed this point. Further, the method for measuring the physical properties of the polyacrylamide black spun dyed yarn of the present invention is as follows.

A. Average particle size of carbon black (μm)

Using an optical microscope, 0.1 g of the sample of the polyacrylamide black-spun dyed yarn was placed on a nylon microscope at 245 ° C when the nylon 6 was heated, and the specimen was clamped and extended by the slide. The film shape was taken at a magnification of 500 times, and the longest diameter of the carbon black structure was measured by arbitrarily measuring 20 samples from one sample, and the average value of 20 samples was calculated.

B. Content of carbon black (% by mass)

TG-DTA (manufactured by SII. Nanotechnology, thermogravimetric measuring device SII TG/DTA 6200), 1.4 mg of a sample of pre-stained yarn of polyamine black spinning, temperature range: room temperature to 900 ° C, temperature increase rate: 100 ° C / min, atmospheric flow rate: The weight change of the polyacrylamide black spun dyed yarn was measured at a condition of 20 ml/min, and the value was calculated from the reduction ratio in the region of 650 to 900 °C. The measurement system was carried out 4 times, and the average value was used as the content of carbon black.

C. Relative viscosity of sulfuric acid (ηr)

0.25 g of a polyimide film (sample) was dissolved in 98 ml of 98% by mass sulfuric acid, and the flow time (T ₁ ) at 25 ° C was measured using an Oswald type viscometer. Next, the flow time (T ₂ ) of sulfuric acid having a concentration of only 98% by mass was measured. The ratio of T ₁ to T ₂ , that is, T ₁ /T _{2 is taken} as the relative viscosity of sulfuric acid.

D. Yarn making

The yarn breakage per 1 ton at the time of yarn production of the polyacrylamide black spun dyed yarn was expressed by the following criteria.

a: The yarn breakage is less than 2 times, b: yarn breakage 2 or less is less than 4 times, c: yarn breakage 4 or less is less than 6 times, d: yarn breakage 6 or less is less than 8 times, and e: yarn breakage is 8 times or more.

E. Fineness, single fiber fineness

Polyamide black pre-spun dyed yarn system is applied with 0.35mN× for dtex, and false twisted yarn obtained by processing false polyamine black pre-spun yarn is applied with 8.82mN× to indicate the tension of dtex, while one side is framed. The 1.125m ruler machine produces 200 times of skein, and after drying by a hot air dryer (105±2°C×60 minutes), the weight of the skein is measured by the scale, and the fineness is calculated by multiplying the value of the specified moisture rate. The measurement system was carried out 4 times, and the average value was taken as the fineness. Further, the value obtained by dividing the obtained fineness by the number of filaments was taken as the single fiber fineness.

F. Strength, elongation

A crepe yarn obtained by pre-staining a polyaniline black dyed yarn and a false twisted polyaniline black spun dyed yarn, and a TENSILON (universal testing machine) UCT-100 manufactured by ORIENTEC, with JIS L1013 (Chemistry) Determination of the constant elongation conditions shown in the fiber yarn test method, 2010). The elongation is obtained from the elongation at the point where the maximum strength is exhibited in the tensile strength-elongation curve. In addition, the strength is the value obtained by dividing the maximum strength by the fineness. The measurement was carried out 10 times, and the average value was taken as the strength and the elongation. Furthermore, the gripping interval was 50 cm and the drawing speed was 50 cm/min.

G. curling characteristics

The false twisted yarn obtained by processing the polyamine black pre-spun dyed yarn was subjected to a tension of 0.098 cN/dtex on one side, and a skein having a circumference of 1.125 m and a winding of 10 times was taken. It was allowed to stand in an environment of 20 ° C and 60% RH for 24 hours. The treatment load (load in water) of 1.76 × 0 ^-3 cN / dtex was applied and treated in hot water at 98 ° C ± 1 ° C for 20 minutes. The heat-treated skein was allowed to stand in an environment of 20 ° C and 60% RH for 24 hours to be dried. In advance, water was placed in the cylinder and left in an environment of 20 ° C and 60% RH for 24 hours. The skein was placed in water in a state where an initial load of 1.76 × 10 ^-3 cN/dtex (load in water) was applied to the hank yarn sample. Thereafter, a load of 0.088 cN/dtex (load in water) was further applied to a constant load of 0.08976 cN/dtex (load in water), and the skein length a (mm) after 2 minutes was measured. The constant load was quickly removed, and the skein length b (mm) after only 2 minutes of the initial load was measured. The crimping property was calculated by the following formula and evaluated by the average value of five bars.

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

H. boiling water shrinkage

For the false twisted yarn obtained by processing the polyamine black pre-spun yarn, the tension of 0.098 cN/dtex was applied to one side, and the circumference was 1.125 m, and five skeins were wound 10 times. It was allowed to stand in an environment of 20 ° C and 60% RH for 24 hours. Find the initial length L0 under the load of 0.09cN/dtex. Next, after treating for 30 minutes in boiling water without load, it was air-dried. Next, the length L ₁ after the treatment was calculated under a load of 0.09 cN/dtex, which was calculated by the following formula and evaluated by the average of five bars.

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

I. Softness

The softness (soft touch) is determined for the single-yarn pantyhose, and the touch of the examiner (30 people) is determined in three stages at a position of 10 cm in the lower portion of the garter belt portion.

a: the same flexibility as Comparative Example 7

b: slightly less soft than Comparative Example 7

c: significantly less softness than Comparative Example 7

J. Hue

The color tone (dark black color) is determined for the single-yarn pantyhose sample, and the 10 cm portion of the lower part of the garter belt is judged by the examiner (30 persons) in five stages.

a: darker than Comparative Example 7, the color is very good

b: blacker than Comparative Example 7, good color tone

c: the same color tone as in Comparative Example 7

d: slightly whiter than Comparative Example 7, poor color tone

e: whiter than comparative example 7, poor color tone

K. Hairiness

The single yarn gauze sample was subjected to hair raising evaluation according to JIS L 1076 (2012) Appearance Retention C method for the 10 cm portion of the lower part of the garter belt portion, and the grade was determined.

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

L: The number of hair balls is the degree of the L number of the standard photo.

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

H: The number of hair balls is the degree of the H number of the standard photo or exceeds the level

L. CV of dry heat shrinkage stress (%)

Using FTA-500 manufactured by TORAY Engineering Co., Ltd., the measurement was carried out for 10 minutes by a dry heat treatment apparatus heated to 100 ° C by a length of 15.5 cm at a feed rate of 10 m/min and a relaxation of 1%. The standard deviation of the dry heat shrinkage stress obtained is divided by the average value and expressed as the value obtained.

[Example 1]

(Manufacture of polyamide black dyed yarn before spinning)

As the polyamine, a small piece of nylon 6 having a relative viscosity (ηr) of sulfuric acid of 2.6 and a content of 0.02% by mass of titanium oxide was dried by a usual method to have a water content of 0.03% by mass or less.

The obtained nylon 6 pieces were kneaded by a 2-axis kneading machine to have a carbon black content of 15% by mass, passed through a filter of 30 μm mesh, and then ejected to produce a masterbatch piece, which was dried by a usual method to obtain a moisture content. It becomes as below 300ppm. The obtained carbon black-containing nylon 6 masterbatch piece and the carbon black-free nylon 6 were blended at a ratio of 1:4 (the carbon black content in the black spun dyed yarn was 3% by mass), The melting temperature of 265 ° C was melted, and the mixture was placed in a spinning bag provided with a metal filter of 10 μm mesh by a polymer pipe provided in a 25-stage static mixer, and was spun from a spinning nozzle at a spinning temperature of 260 ° C. The spinning nozzle uses a number of holes of 68, a circle, and a sliver/nozzle. After being ejected from the spinning nozzle, it was cooled by cold air at 18° C., and after the oil was injected, it was stretched to 1.2 times by the first godet roller and the second godet roller, and was taken up at a take-up speed of 4,000 m/min. A 96 dtex, 68 filament nylon 6 black spun dyed yarn was obtained. The yarn-forming property, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

(making false crepe)

The above-mentioned nylon 6 black spun dyed yarn was subjected to a false twisting machine IVF805 manufactured by Ishikawa, and a processing speed of 500 m/min, a stretching ratio of 1.23 times, a heater temperature of 180 ° C, and a D/Y ratio of 1.7 (solution) were set.捻 Tension/twisting tension = 1.04), and false twisting was performed to obtain a false twisted yarn of 78.1 dtex and 68 filaments. The denier, strength, elongation, boiling water shrinkage, and crimping characteristics of the obtained false crepe yarn were evaluated. The results are shown in the first table.

(manufacturing of covered elastic yarn)

In the case of the above-mentioned false twisted yarn, the "Mobilon" (registered trademark) 22dtex and the G type (made by Nisshinbo Textile Co., Ltd.) are used as the core yarn, and the number of coatings is 600 T/m and the extension is 3.0 times, and S捻 and Z are prepared. Single covered yarn.

(Manufacture of single yarn tights)

Yu Yongtian Seiki Co., Ltd. (model) has KT-S4 (380 needles), and the single-coated yarn is used to make single-threaded tights. The single-wax pantyhose was placed in a vacuum at 80 ° C for 10 minutes, and scoured at 98 ° C for 30 minutes. After softening, the shoe was molded with an aluminum plate and heat-set at 110 ° C for 30 seconds to obtain a single-ply pantyhose. The softness, hue, and fluffiness of the obtained single-pants tights were evaluated. The results are shown in the first table.

[Example 2]

The same procedure as in Example 1 was carried out except that the nylon 6 masterbatch containing carbon black and the nylon 6 pellet were blended at a ratio of 1:14 (the carbon black content in the black spun dyed yarn was 1% by mass). The method of making nylon 6 black spun dyed yarn. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the first table.

[Example 3]

The same procedure as in Example 1 was carried out except that the nylon 6 masterbatch containing carbon black and the nylon 6 pellet were blended at a ratio of 33:67 (the carbon black content in the black spun dyed yarn was 5% by mass). The method of making nylon 6 black spun dyed yarn. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the first table.

[Example 4]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the filtration was carried out in a spinning bag provided with a metal filter of 15 μm mesh. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. Comment Estimate the fineness, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose. The results are shown in the first table.

[Example 5]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the filtration was carried out in a spinning bag provided with a metal filter of 20 μm mesh. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the first table.

[Example 6]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes of the spinning nozzle was 96, and round, and a 96 dtex, 96 filament nylon 6 black spun dyed yarn was obtained. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the first table.

[Example 7]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes of the spinning nozzle was 52, and round, and a 96 dtex, 52 filament nylon 6 black spun dyed yarn was obtained. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the first table.

[Example 8]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes of the spinning nozzle was 68, a circle, and 2 yarns/nozzles, and 48 dtex, 34 filament nylon was obtained. 6 black spun dyed yarn. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the first table.

[Example 9]

Nylon 6 black spinning was produced in the same manner as in Example 1 except that the number of holes of the spinning nozzle was 78, a circle, and 3 yarns/nozzles. The pre-dyed yarn was obtained into a 43 dtex, 26-filament nylon 6 black spun dyed yarn. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the first table.

[Example 10]

As the polyamine, a small 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 usual method so that the water content was centered at 0.11% by mass.

In addition to the obtained nylon 66 pellets, the carbon black content of the furnace method was set to 15% by mass, and a 30 μm mesh filter was set to produce a masterbatch pellet, which was dried in a usual manner so that the moisture content was centered at 0.11% by mass. The obtained nylon 66 masterbatch containing carbon black and Nylon 66 flakes were blended at a ratio of 1:4 (carbon black content in the black spun dyed yarn was 3% by mass), and melted at 290 ° C. The temperature was melted, and a spinning bag having a metal filter of 10 μm mesh was used for filtration, and a nylon 66 pre-spun dyed yarn was produced in the same manner as in Example 1 except that the spinning temperature was 290 ° C from the spinning nozzle. , obtained 96dtex, 68 filament nylon 66 black spun dyed yarn. The yarn-forming property, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the first table.

Using the obtained nylon 66 black spun yarn, a false twist yarn, a covered elastic yarn, and a pantyhose were produced in the same manner as in Example 1 except that the heater temperature of the false twist processing was 190 °C. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the obtained crepe were evaluated. The results are shown in the first table.

[Comparative Example 1]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the filtration was carried out in a spinning bag provided with a metal filter having a mesh of 1 μm. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the second table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the obtained crepe were evaluated. The results are shown in the second table.

[Comparative Example 2]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the filtration was carried out in a spinning bag provided with a metal filter of 30 μm mesh. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the second table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the obtained crepe were evaluated. The results are shown in the second table.

[Comparative Example 3]

A nylon 6 black spun dyed yarn was produced in the same manner as in Example 1 except that the number of holes of the spinning nozzle was 320, and the circle was used. A 96 dtex, 320 filament nylon 6 black spun dyed yarn was obtained. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the second table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the obtained crepe were evaluated. The results are shown in the second table.

[Comparative Example 4]

A nylon 6 black spun 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 96 dtex, 20 filament nylon 6 black spun dyed yarn was obtained. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the second table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the obtained crepe were evaluated. The results are shown in the second table.

[Comparative Example 5]

Except that the nylon 6 masterbatch containing carbon black and the nylon 6 small piece were blended at a ratio of 3:97 (the carbon black content in the black spun dyed yarn was 0.5% by mass), The same method was used to produce nylon 6 black spun dyed yarn. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the second table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the obtained crepe were evaluated. The results are shown in the second table.

[Comparative Example 6]

Except that the nylon 6 masterbatch containing carbon black and the nylon 6 small piece were blended at a ratio of 47:53 (the carbon black content in the black spun dyed yarn was 7 mass%), The same method was used to produce nylon 6 black spun dyed yarn. The yarn-staining properties, carbon black content, carbon black average particle diameter, fineness, strength, and elongation of the obtained black spun dyed yarn were evaluated. The results are shown in the second table.

A false twisted yarn, a covered elastic yarn, and a tights were produced in the same manner as in Example 1 using the obtained nylon 6 black spun dyed yarn. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the obtained crepe were evaluated. The results are shown in the second table.

[Comparative Example 7]

In the same manner as in Example 1, except that a polyacetamide having a relative viscosity (ηr) of 2.6 and a titanium oxide content of 0.02% by mass of a nylon 6 piece (carbon black content of 0% by mass) was used. 6 yarn. The yarn-making property, fineness, strength, and elongation of the obtained nylon 6 yarn were evaluated. The results are shown in the second table.

A false twisted yarn and a covered elastic yarn were produced in the same manner as in Example 1 using the obtained nylon 6 yarn. Further, the same as in the first embodiment The ground is made into single yarn tights. The single-wax pantyhose was prepared by vacuuming at 80 ° C for 10 minutes, scouring at 98 ° C for 30 minutes, and dyed with 4 mass% of Mitsui Nylon Black GL (manufactured by Mitsui Chemicals Co., Ltd.) at 98 ° C for 60 minutes. After the soft treatment, the foot of the aluminum plate was subjected to heat setting at 110 ° C for 30 seconds to obtain a single yarn pantyhose. The denier, strength, elongation, boiling water shrinkage, shrinkage characteristics, softness, hue, and fluffiness of the single yarn pantyhose were evaluated. The results are shown in the second table.

From the results of the first table (Examples 1 to 10), it is understood that the polymethylamine black spun dyed yarn of the present invention can be obtained by optimizing the carbon black content, the average particle diameter, and the single fiber fineness. Single-threaded tights with a soft touch (softness), dark black color (hue), and durability (hairiness). It can be seen that in Example 10, by using nylon 66, the yarn breakage during yarn making was slightly lower than that of nylon 6. Therefore, when the socks are made, the fluff of the original yarn is mixed, and the product grade is slightly lowered.

In Comparative Example 1, since the carbon black having a small average particle diameter was present, the dynamic friction coefficient of the surface of the pantyhose was increased, and the fuzzing property was poor.

In Comparative Example 2, since the carbon black having a large average particle diameter was present, the increase in the filtration pressure in the spinning bag was large, and as a result, not only the life of the bag was shortened, but also yarn breakage occurred frequently, and the yarn-making property was inferior. Further, the strength of the obtained nylon black spun dyed yarn was a low value of 1.5 cN/dtex, and the fluffing property was slightly inferior.

In Comparative Example 3, the single fiber fineness was fine, and as a result, not only yarn breakage occurred frequently, but also the fluffing property 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 poor.

In Comparative Example 5, since the carbon black content was small, light was easily transmitted and whitened, and the color tone (dark black color) was poor.

In Comparative Example 6, since the carbon black content was large and the filtration pressure in the spinning bag was increased, not only the life of the bag was shortened, but also yarn breakage occurred frequently, and the yarn-making property was inferior. Further, the strength of the obtained nylon black spun dyed yarn was a low value of 0.9 cN/dtex, and was poor in fluffing property.

In Comparative Example 7, a conventional single-ply pantyhose was used, and black dyeing was performed. Although it has a soft touch, it is white due to the diffusion of light, and the color tone (dark black color) is poor.

Since the single-ply pantyhose using the polyamine black-spun dyed yarn of the present invention does not carry out black dyeing, the processing cost of the dyeing step can be omitted, and the cost can be reduced, and the environmental load is small.

[Industry profitability]

The polymethylamine black pre-spun dyed yarn of the invention has a soft touch and can be dark black, and the processed yarn processed by the false twist or the covered elastic yarn coated with the elastic yarn can be suitably applied. In stockings or tights.

Claims (6)

A polymethylamine black pre-spun dyed yarn, which is a polyacrylamide black pre-spun dyed yarn containing 1 to 5% by mass of carbon black, wherein the carbon black in the polydecylamine has an average particle diameter of 1 to 20 μm and a polyfluorene The single fiber fineness of the amine black spun dyed yarn is 0.8 to 2 dtex. The polyamine black pre-spun dyed yarn of claim 1, wherein the polyamine is nylon 6. The polyamine black pre-spun dyed yarn according to claim 1 or 2, which is a polyamine black pre-spun dyed yarn having a CV value of 4.0% or less of dry heat shrinkage stress. A false twisted yarn which is obtained by processing the polyacrylamide black spun dyed yarn of any one of claims 1 to 3. A coated elastic yarn using the polyamine black spun dyed yarn of any one of claims 1 to 3 or the false twisted yarn of claim 4 as a web. A hosiery, which is used at least in part of the leg, using the polyamine black spun dyed yarn of any one of claims 1 to 3, the false crepe yarn of claim 4, and the covering elasticity of claim 5 At least one of the yarns.