JP2007056413A - Blended article of polyester fiber and polyamide fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a blended article of a polyester fiber and a polyamide fiber, which provides a dyed material having a soft and flexible hand, excellent color development and solid dyeing properties, slight dispersion by each color of dyeing batch and high color reproducibility and has excellent color fastness to dyeing. <P>SOLUTION: The blended article comprises a polyester fiber that is a polyester obtained by copolymerizing a polyethylene terephthalate with 3-6 wt.% of a polyethylene glycol having 300-2,000 molecular weight and comprising the polyethylene terephthalate composed of ≥90 wt.% of ethylene terephthalate repeating unit, has ≤1.4 single yarn dtex and a dynamic loss tangent (tanδ) at 110 Hz measured frequency, having a temperature (Tmax) exhibiting the maximum at ≥85°C and ≤105°C and a polyamide fiber. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a mixed article of polyester fiber and polyamide fiber. More specifically, by mixing easily-dyeable polyester, the polyamide fiber's original texture and physical properties are maximized without damaging the polyamide fiber, and it has an unprecedented soft and supple texture, and is dyed. In particular, the present invention relates to a dyed product of a mixed fabric of polyester fiber and polyamide fiber having good color reproducibility and fastness performance and having polyester functionality.

  Fabrics made of polyamide fibers have excellent physical properties such as normal pressure dyeing, good dyeability and high raw yarn strength, but are prone to yellowing, lack of heat setting and dimensional stability. There are disadvantages such as. For this reason, mixing these polyester fibers excellent in functionality lacking in polyamide fibers to compensate for these drawbacks has been performed.

  Polyester fibers are excellent in heat setting properties and dimensional stability, are not easily yellowed, and can compensate for the shortcomings of polyamide fibers. When dyed at 0 ° C., the color development of the polyester fiber is remarkably low, and the same color as the polyamide fiber cannot be obtained. On the other hand, when dyed at a high temperature of 130 to 135 ° C., which is a normal polyester fiber dyeing temperature, the color developability of the polyester fiber is improved, but the same color with the polyamide fiber is not obtained, and the texture of the polyamide fiber is impaired. In addition, there is a problem that yellowing occurs. In addition, when the dyeing temperature is lowered and dyeing is performed using a carrier agent under normal pressure, the same colorability as that of the polyamide fiber cannot be obtained, and the fastness of dyeing is difficult and the carrier removal treatment in the fiber is difficult. There are problems such as deterioration of working environment due to carrier odor.

Therefore, Patent Documents 1 and 2 disclose a method for producing a cationic dye-dyeable polyester fiber in which sodium sulfoisophthalic acid is copolymerized in an amount of 5 mol% or more as a normal-pressure dyeable polyester fiber that can be dyed in the dyeing temperature region of polyamide fiber. Has been. However, although the dyeability is improved, the raw yarn strength is low, the stretch recovery is poor, the soft and supple texture is not obtained, the chemical resistance is low, the light fastness of the cationic dye is poor, and the cationic dye is dyed. There are problems such as large contamination of the machine.
Patent Document 3 discloses a method for producing easily dyeable polyester fibers by copolymerization of polyethylene glycol. However, although the dyeability is good, the boiling water shrinkage ratio of the raw yarn is high, the soft and supple texture cannot be obtained when using the raw yarn, the raw yarn is prone to yellowing, and the sharpness is not obtained in the light color system. There are problems such as.

  Furthermore, Patent Documents 4 and 5 disclose methods for producing easily dyeable polyester fibers in which the fiber internal structure is changed by high-speed spinning at 5000 to 8000 m / min. Polyester fibers produced by these high-speed spinning are easier to dye than conventional polyester fibers, but are not completely normal pressure dyeable. For dyeing in dark colors, a dyeing temperature of 110 to 120 ° C is required. It is necessary, and there is a problem that the same color property as that of the polyamide fiber is inferior and a soft and supple texture cannot be obtained.

Therefore, at present, dyeing conditions that have found a compromise from the balance between the color development of the polyester fiber, the color development of the polyamide fiber, and the texture of the mixed product are adopted for the mixed product of the polyester fiber and the polyamide fiber. The fibers are dyed with disperse dyes. However, when dyed with disperse dyes, when mixed with polyamide fibers, the disperse dyes are also dyed on the polyamide fibers, making it difficult to control the dye distribution between the polyester fibers and the polyamide fibers. There is a problem that blurring is large and the same color as polyester fiber is bad. In particular, mixed fabrics that are dyed darkly have a problem that the fastness of dyeing is reduced due to the greater disperse of disperse dyes on polyamide fibers, and the color development property of polyester fibers is low, and there is a drawback called irritation. The fact is that dyed products with a satisfactory texture have not been obtained. Furthermore, when multi-type polyester fibers are used, a soft texture is easily obtained as high-poly is obtained, but the color developability is greatly reduced, and the color variation between dyeing batches is larger, and the same color as polyamide fibers. In fact, only a dyed product with a lower quality is obtained.
Japanese Patent Publication No. 61-17939 JP-A-61-34022 JP 04-41738 A Japanese Patent Publication No. 01-15610 JP 59-59911 A

  In the present invention, by mixing the modified polyester fiber and the polyamide fiber, the polyester fiber has high color developability, good color matching, high color reproducibility in dyeing, and high color fastness performance. It is an object of the present invention to provide a mixed dyeing product of polyester fiber and polyamide fiber having a remarkably soft and supple texture.

  As a result of earnest research on the polyester fiber mixed with the polyamide fiber, the present inventor has spun a polyester obtained by copolymerizing polyethylene terephthalate with 3 to 6% by weight of polyethylene glycol having a molecular weight of 300 to 2000 at a winding speed of 5000 m / min or more. As a result of finding that a fabric in which the polyester fiber mixed with the polyamide fiber solves the above-mentioned problems and further studying it, the present invention has been made.

That is, the present invention is as follows.
(1) A mixed product of polyester fiber and polyamide fiber, wherein the polyester fiber is a polyester obtained by copolymerizing polyethylene terephthalate with 3 to 6% by weight of polyethylene glycol having a molecular weight of 300 to 2000, and 90% by weight or more is an ethylene terephthalate repeating unit. It is made of polyethylene terephthalate, and has a single yarn decitex of 1.4 or less and a temperature (Tmax) at which the mechanical loss tangent (tan δ) reaches a maximum at a measurement frequency of 110 Hz is 85 ° C. or more and 105 ° C. or less. A mix of polyester and polyamide fibers.

(2) The polyester fiber has a fineness fluctuation value U% of 1.0% or less, and a maximum value of a coefficient of variation CV in a period of 10 to 80 m by a fineness fluctuation frequency analysis is 0.3% or less (however, the fineness fluctuation The value U% is measured over a yarn length of 500 m). The mixed article of polyester fiber and polyamide fiber according to (1) above,
(3) The above-mentioned (1), wherein the fastness to washing in the JIS-L-0844 A-2 method is 3 or higher and the fastness to sweat alkali in the JIS-L-0848 method is 3 or higher. Or the mixed article of the polyester fiber and polyamide fiber as described in (2).

  Easy-dyeable polyester fibers and polyamide fibers obtained by spinning a polyester having a single yarn decitex of 1.4 or less obtained by copolymerizing polyethylene terephthalate with 3 to 6% by weight of polyethylene glycol having a molecular weight of 300 to 2000 at a winding speed of 5000 m / min or more. When mixed, the color of polyester fibers is high, the same color is good, the color reproducibility in dyeing and the fastness of dyeing are high, and a mixed dyeing product with an unprecedented soft and supple texture can be obtained. There is an effect.

The present invention will be described in detail below.
The present invention relates to a mixed article of polyester fiber and polyamide fiber, wherein the polyester fiber is a polyester obtained by copolymerizing polyethylene terephthalate with 3 to 6% by weight of polyethylene glycol having a molecular weight of 300 to 2000, and 90% by weight or more is an ethylene terephthalate repeating unit. It consists of the polyethylene terephthalate which consists of.
Polyethylene glycol, which is a copolymerization component in the polyester fiber used in the present invention, causes an appropriate disturbance in the amorphous structure of the polyester fiber and contributes to an improvement in dyeability.

  Polyethylene glycol having a molecular weight of less than 300 is not preferable because the easy dyeing effect is insufficient and a copolymerization amount of 6% by weight or more is required to achieve atmospheric pressure dyeability, and the polymer color tone deteriorates. In addition, since polyethylene terephthalate is a polyethylene glycol having a molecular weight of less than 300 due to polymerization under vacuum, a part of the polyethylene terephthalate may be scattered outside the product system, resulting in an unstable polymer composition. On the other hand, when the molecular weight of polyethylene glycol exceeds 2000, the ultra-high molecular component increases with block copolymerization, and the decrease in dyeing fastness and light resistance becomes obvious.

  When the copolymerization amount of polyethylene glycol is less than 3% by weight, the dyeability at normal pressure is insufficient, and normal pressure dyeability cannot be obtained. On the other hand, if it exceeds 6% by weight, the dyeability at normal pressure is sufficient, but the color of the polymer deteriorates, and at the winding speed of 5000 m / min or more, yarn breakage and fluffing increase. Stable spinning production becomes difficult. In particular, this problem is remarkable in the region where the fineness is thin. Furthermore, the filament produced is not preferable because light fastness and dyeing fastness deteriorate.

  Since the polyester fiber in the present invention uses an ultra-high speed spinning method, it has a softer texture than the polyester fiber obtained by the conventional method, and further, the crystallization is suppressed by copolymerizing polyethylene glycol, and the softness is further increased. The texture is soft, and the softness can be further increased by reducing the fineness. In order to obtain a blended product that has an unprecedented softness and a supple texture similar to nylon that is required by the present invention, the single yarn decitex of the polyester fiber needs to be 1.4 or less. If the single yarn decitex exceeds 1.4, the unique texture of other materials is impaired and the hard texture of the polyester fiber is emphasized. Preferably it is 1.2 or less.

  The polyester fiber in the present invention is required to have a loss tangent peak temperature (hereinafter referred to as Tmax) determined from dynamic viscoelasticity measurement of 85 ° C. or higher and 105 ° C. or lower. This is because in this range, it is possible not only to ensure a remarkably soft and supple texture that the present invention requires, but also to increase the dyeability and high color developability even when the single yarn decitex is reduced. The amount of disperse dye contamination is reduced, and the same color, color reproducibility for each dye batch, and dye fastness are improved. Since Tmax corresponds to the mobility of molecules in the amorphous part, it can be said that the smaller the value, the easier the dye enters the amorphous part, that is, the higher the dyeability.

When the Tmax exceeds 105 ° C., the polyester fiber in the present invention is not preferred because the effect of improving the dyeing is small, and dyeing at a higher temperature is required and the problem of impairing the texture of the polyamide fiber is likely to occur. However, if Tmax is too low, problems such as a decrease in mechanical properties and heat resistance appear. A particularly preferable range of Tmax is 90 ° C. or higher and 100 ° C. or lower.
Although not as important as Tmax, the loss tangent value at Tmax (hereinafter referred to as tan δmax) is preferably about 0.13 to 0.22. The value of loss tangent corresponds to the amount of amorphous material, and if it is out of this range, not only the texture, dyeability, and color fastness obtained in the present invention will deteriorate, but also the color reproducibility may deteriorate. is there.

  In general, when a fiber is made with a finer fiber, the dyeability of the fabric tends to become lighter. In the present invention, the polyester fiber has improved dyeability by high-speed spinning and copolymerization of polyethylene glycol. Therefore, sufficient dyeability can be obtained even if the fineness is reduced.

Next, the manufacturing method of the polyester fiber in this invention is described.
In the polyester fiber as used in the present invention, at least 90% of the structural unit is ethylene terephthalate, and in addition to the polyethylene glycol component, other components of 5 mol% or less may be copolymerized. For example, a polymer obtained by polymerizing a small amount of a chain branching agent such as pentaerythritol, trimethylolpropane, trimellitic acid, boric acid or the like may be used.
In addition to the copolymer components, ordinary transesterification catalysts, polymerization catalysts, phosphorus compounds, matting agents such as titanium dioxide, coloring inhibitors, oxidative decomposition inhibitors, antifoaming agents, fluorescent whitening agents, pigments, etc. May be included as necessary.

  A known method can be adopted as a method for polymerizing the polymer constituting the polyester fiber in the present invention. That is, polyethylene glycol may be reacted with terephthalic acid, ethylene glycol or the like, or may be reacted after transesterification of dimethyl terephthalate and ethylene glycol, at any stage where the polyester polymerization reaction is completed. It may be added. In addition, any of the batch polymerization method and the continuous polymerization method that are currently being industrially produced can be applied.

  The polyester fiber in the present invention can be obtained by a high speed spinning method having a winding speed of 5000 m / min or more. On the other hand, even if the copolymerized polyester is made into a fiber by using a normal method or a straight-drawing method, it is difficult to obtain a remarkably soft and suppleness as a texture when mixed with a polyamide fiber. Also, the color reproducibility for each dyeing batch is poor. This is due to the fact that the orientation of the amorphous portion of the fiber obtained by high speed spinning is much smaller than that of the fiber obtained by the ordinary method or the straight-drawing method. In particular, since the polymer used in the present invention has polyethylene glycol having a moderately long molecular chain in the amorphous part, the orientation of the amorphous part is further lowered, and the dyeing property is improved, and the soft and supple texture is further promoted. In addition, it is a revolutionary fiber with excellent mechanical properties.

  In the present invention, in order to give a remarkably soft and supple texture in the present invention, when the single yarn decitex is set to 1.4 or less and the yarn is produced by the high speed spinning method, it becomes clear that the dyed spots due to the fineness spots become apparent. It was. In order to avoid this situation, the present inventors have conducted intensive research. As a result, in the high-speed spinning method with a single yarn decitex of 1.4 or less and 5000 m / min or more, the distance between the cores shown in FIGS. It has been found that by using a spinner having a diameter of 8 mm or more, spinning is stabilized, variation in fineness is reduced, and dyeing spots are avoided.

  When the inter-spinning core distance is less than 8 mm, the fineness variation value U% in the fiber longitudinal direction is 1.0% or more, and the fineness variation becomes large. Furthermore, when the fluctuation is subjected to frequency analysis, the periodic fluctuation coefficient of 10 to 50 m by the fineness fluctuation frequency analysis is increased, and the maximum value of the CV value exceeds 0.3%, and the leveling property evaluation by the bite knitted fabric is performed. As a result, streaky dyed spots appear and high-quality easily-dyeable polyester cannot be obtained. Furthermore, when the distance between the cores is less than 8 mm, the influence of the accompanying air flow accompanying necking stretching that is peculiar to ultra-high speed spinning is large, and fineness unevenness occurs due to yarn swinging.

FIG. 4 shows U% of the polyester fiber and its frequency analysis chart in the present invention. As a result, there is very little fluctuation in the longitudinal direction of the fiber fineness, there is no specific frequency fluctuation associated with the longitudinal direction of the fiber, the CV value is as small as 0.3% or less, and the fineness is very stable in the longitudinal direction. It can be said that it is uniform.
In order to make the fineness spots smaller and more stable, the distance between the spinneret cores is preferably 10 mm or more. In addition, when using a spinning facility with a cooling cylinder made of circumferential cooling with high-speed spinning of 5000 m or more, a single-hole arrangement is preferable, but if the center distance is 8 mm or less, a multi-circular circle is used. In this case, the inter-spindle core distance located in the inner layer portion is 10 mm or more, preferably 12 mm or more, because the accompanying airflow of the outer layer spinning hole is added. preferable. On the other hand, when the distance between the cores exceeds 30 mm, the improvement effect on U% and quality is not seen, and the spinneret size becomes huge, which is not practical for industrial production.

  On the other hand, the cause of frequent yarn breakage and fluff in high-speed spinning with a single yarn decitex of 1.4 or less and 5000 m / min or more is not clear, but in the present invention, polyethylene glycol is used to impart easy dyeability. Because it is copolymerized and heat resistance is inferior to ordinary polyethylene terephthalate, it tends to cause viscosity spots, catalysts, and aggregates of additives in the polymerization process and spinning process, and the single yarn decitex is 1.4 or less. In the case of high-speed spinning at 5000 m / min or more, it is considered that the yarn is easily affected by fluctuations in viscosity, agglomerates of catalysts, additives, and the like, and the occurrence of yarn breakage and fluffing becomes apparent.

  In order to prevent yarn breakage and fluff, it is necessary to pay close attention to preventing abnormal retention as much as possible in the polymer polymerization stage and spinning process, but it is difficult to completely eliminate the abnormal retention portion. Therefore, as a result of intensive studies to avoid the influence of viscosity fluctuations and aggregates of catalysts and additives, yarn breakage and fluff can be controlled by setting the discharge linear velocity from the polymer nozzle to 20 cm / second or more and 100 cm / second or less. Has been found to be resolved.

  If the spinning hole discharge linear velocity is less than 20 cm / sec, yarn breakage and fluff are likely to occur frequently, and preferably 40 cm / sec or more. When the spinning hole discharge linear velocity exceeds 100 cm / sec, melt fracture tends to occur, which may cause unstable spinning and impossible spinning. Further, when the spinning hole discharge linear velocity is less than 20 cm / second, the fluctuation CV value of a long period of 30 to 80 m according to the fineness fluctuation frequency analysis becomes a large value exceeding 0.3%, and the leveling property evaluation by the single-knitted fabric is performed. As a result, band-like dyed spots appear, and high-quality, high-quality easily-dyeable polyester fibers cannot be obtained.

  The polyester fiber in the present invention can be produced using, for example, a spinning device shown in FIG. As the convergence guide composed of the yarn feeding nozzles used in the present invention, the winding device, and other devices necessary for melt spinning, known devices may be used. Further, the finishing oil used in the present invention may be either an emulsion type or a straight type, and its components may be known.

The polyester fiber of the present invention is not particularly limited, but a fiber having a total fineness of 10 to 170 dtex is preferably applied. The form of the fibers may be long fibers or short fibers, and may be uniform or thick in the length direction. And as the form of the yarn in which the fiber is processed, a spun yarn such as a ring spun yarn, an open-end spun yarn, an air jet fine spun yarn, a sweet twisted yarn to a strongly twisted yarn, a false twisted yarn (including POY drawn false twisted yarn) ), Air injection processed yarn, indented processed yarn, knitted knitted yarn, and the like.
The mixed article as used in the present invention is a blend of other fibers such as spandex, cotton, cupra, viscose rayon fiber, protein fiber, etc. within the range not impairing the object of the present invention (silospan, silofil, etc.), entangled mixed fiber (high Different shrinkage mixed yarn with shrink yarn, etc.), cross-twisting, composite false twist (elongation difference false twist, etc.), two-feed air injection processing and the like.

  In the present invention, the mixed polyamide fibers include nylon-4, nylon-6, nylon-66, nylon-7, nylon-12, and dicarboxylic acids such as 1,7-heptanedicarboxylic acid and decamethylenedicarboxylic acid. It can be selected from the group consisting of polyamides obtained from bis (p-aminocyclohexyl) methane and copolymer polyamides of the polyamides. Of these, nylon-6 and nylon-66 are particularly preferred. Also, the polycondensation method is not particularly limited, and a commonly known polyamide polycondensation method, for example, an atmospheric pressure polymerization method often employed for nylon-6 or the like, or a pressure polymerization method employed for nylon-66 or the like. Can be adopted regardless of batch type or continuous type.

  The ratio of the polyester fiber and the polyamide fiber in the mixed article of the present invention is preferably 65% by weight or less for the polyester fiber. The ratio of mixed use is selected according to the form or use of the mixed product. In addition, spandex, cotton, hemp, cupra, viscose rayon, acetate, protein fiber, and the like may be mixed.

  The form of the mixed article of the polyester fiber and the polyamide fiber of the present invention can be a thread form or a fabric form. Examples of yarn forms include blended yarn (blended cotton, fleece blended, sliver blended, core yarn, silo span, silofill, hollow spindle, etc.), entangled blended yarn, twisted yarn, design twisted yarn, covering (single, double), composite temporary Examples of the mixed use include twisting (simultaneous false twisting, first twist false twisting), elongation difference false twisting, phase difference, post-mixing after false twisting, and two-feed (simultaneous feed or feed difference) air jet machining.

  On the other hand, as an example of the form of the fabric, there is a general knitting. For example, in the knitting, the yarns are aligned and fed, or a double knitted fabric (for example, a double circular knitting machine, a double flat knitting machine, a double knitting machine) In a Russell warp knitting machine), there is a method of feeding yarns on the front surface and / or the back surface, respectively. In cross knitting, one is used for warp and the other is used for weft. In warp and / or weft, one to three are alternately arranged by warping or weft insertion, and one of brushed fabric and pile fabric constitutes the ground structure. The other constitutes a raised portion and a pile portion, or is mixed to constitute a ground tissue, a raised portion and the like. In the double woven fabric, the front surface and / or the back surface are configured or mixed, respectively. Further, a combination of these various yarn stages and a combination on the machine may be combined. In particular, sheath-core composite yarns and twisted yarns, which are composed of polyester fibers in the core and polyamide fibers in the sheath, maintain the texture of the polyamide fibers while maintaining dimensional stability, stretchability, and wrinkle resistance It is preferable that the functionality such as can be imparted.

  When dyeing easy-dyeable polyester fibers with disperse dyes when dyeing mixed products of polyester fibers and polyamide fibers of the present invention, any dyeing conditions can be applied as long as the polyester fibers are usually dyed with disperse dyes. The type of dyeing assistant and its use concentration, dyeing pH, dyeing bath ratio, dyeing time, etc. may be appropriately set in consideration of the kind of article to be dyed, the processing apparatus used and the dyeing method. As disperse dyes, use of azo disperse dyes represented by benzeneazo (monoazo, disazo, naphthaleneazo) and heterocyclic azo (thiazoleazo, benzothiazoleazo, quinolineazo, pyridoneazo, imidazoleazo, thiophenazo, etc.) Is preferred for enhancing the color developability of the readily dyeable polyester fiber in atmospheric pressure dyeing, and improving the same colorability and fastness to dyeing with the polyamide fiber.

  In particular, when the dyeing density is low, it is preferable to use a disperse dye having a diffusion index of 3.0 or more because color variation between dyeing batches is reduced. The dyeing of the polyamide fiber can be applied under any conditions in which the polyamide fiber is usually dyed with acid, metal inclusion, reactive dye, etc., and the dyeing method can be a two-bath dyeing method with a disperse dye, a one-bath two-step dyeing method. What is necessary is just to implement suitably the dyeing | staining method, the one bath dyeing | staining method, etc. In particular, in the case of dyeing in a deep color, the use of a sulfone group-containing metal-containing dye is preferable in terms of one-bath dyeability, color development, same color, and fastness performance.

The dyeing temperature at the time of dyeing is preferably 110 ° C. or lower, and dyeing at 100 ° C. or lower is particularly preferable for improving color reproducibility. The dyeing operation can be carried out by either a batch method or a continuous method using an apparatus such as a wins, a jigger, a beam dyeing machine, or a liquid dyeing machine. In addition to the dip dyeing, a padding dyeing method and a printing method can be used. As post-treatment after dyeing, reduction cleaning using a reducing agent, Fix treatment, and the like are performed.
The resulting mixed dyeing product increases the dyeing rate of disperse dyes on easily dyeable polyester fibers, has high color developability even if the single yarn decitex is small, and has the same colorability as polyamide fibers and has a good appearance. A dyed product is obtained. In addition, the color variation of each dyeing batch is suppressed and the operation rate of the dyeing machine is improved.

The mixed dyed product may be finished according to a conventional method after post-treatment, but a preferable result can be obtained by setting the final set temperature to be 10 ° C. lower than the preset temperature.
The mixed product of polyester fiber and polyamide fiber of the present invention has a remarkably soft and supple texture, high color development, good color matching, little color variation between dyeing batches, and color reproduction. A dyed product with high properties is obtained, and fastness performance is also good. Specifically, a high commercial value mixed article in which the fastness to washing in the JIS-L-0844 A-2 method is 3 or higher and the fastness to sweat alkali in the JIS-L-0848 method is 3 or higher. Can be obtained.

Examples The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of the characteristic value used by this invention is shown below.
(1) Intrinsic viscosity [η] (dl / g)
The intrinsic viscosity [η] (dl / g) is a value obtained based on the definition of the following formula.
[Η] = lim (ηr−1) / C
C → 0
In the definition, ηr is a value obtained by dividing the viscosity of a polymer diluted in an o-chlorophenol solvent having a purity of 98% or more at 35 ° C. by the viscosity of the solvent measured at the same temperature, and is defined as a relative viscosity. It is what. C is the polymer concentration expressed in g / 100 ml.
(2) Strength / Elongation Measured using a tensile tester manufactured by Orientec Co., Ltd. under the conditions of a yarn length of 20 cm and a tensile speed of 20 cm / min.

(3) Fineness variation value U%, U% waveform height difference U% was measured at the same time as a fineness variation value chart (graph; Diagram Mass) was obtained by the following method.
・ Measurement device: Evenester (manufactured by Twelvegar Wooster, Wooster Tester UT-4)
Measurement conditions Measurement method: Normal Yarn speed: 100 m / min Disc tension strength (Tension force): 10%
Twist: S twist 10,000 times / min
Measuring thread length: 500m
Scale: ± 10%
・ Fineness fluctuation value U%
The fluctuation chart and displayed fluctuation values were read directly.
・ Fineness fluctuation frequency analysis The fineness fluctuation frequency analysis software attached to the Evenes tester was used to measure 500 m under the above conditions, and the frequency and CV value were read.

(4) Loss tangent Using a Levivibron manufactured by Orientec, the sample weight is about 0.1 mg, the measurement frequency is 110 Hz, the heating rate is 5 ° C./minute, and the measurement is performed in dry air. ), And dynamic viscoelasticity (E ′). From the result, a tan δ-temperature curve was obtained, and the temperature (Tmax) (° C.) at which tan δ showed the maximum value on this curve and the maximum value tan δ max of tan δ at that time were obtained.

(5) Exhaust rate, color developability (K / S) measurement: Evaluation of dyeability Samples were scoured at 70 ° C. for 20 minutes using warm water containing 2 g / liter of score roll 400 using yarn as a knitted fabric. Then, it was dried with a tumbler drier, and then heat-set at 180 ° C. for 30 seconds using a pin tenter was used.
The dye is Sumikaron Blue S-3RF (trade name, manufactured by Sumika Chemtex Co., Ltd.), 5% by weight based on the fabric, and Nikka Sun Salt 7000 (Nikka Chemical Co., Ltd., product) as a dispersant. Name) 0.5 g / liter, acetic acid 0.25 ml / liter, sodium acetate 1.0 g / liter was added to adjust the pH to 5 to obtain a dyeing solution. After dyeing at 95 ° C. for 60 minutes in a dye bath having a bath ratio of 25, the exhaustion rate was determined. The exhaustion rate was determined by substituting the absorbance of the dye stock solution with A and the absorbance a of the dyed solution after dyeing from a spectrophotometer and substituting it into the following equation. As the absorbance, a value at 580 nm, which is the maximum absorption wavelength of the dye, was adopted.
Exhaust rate = (A−a) / A × 100 (%)

The color developability was evaluated using K / S. This value was determined from the Kubelka-Munk equation shown below by measuring the spectral reflectance R of the dyed sample fabric. Larger values indicate higher color developability (higher surface concentration), that is, better color development. The value at 580 nm, which is the maximum absorption wavelength of the dye, was adopted.
^{K / S = (1-R} ) 2 / 2R

(6) Evaluation of spinnability The number of yarn breakage when spinning with one spindle for 24 hours was evaluated as follows.
The case where the number of yarn breaks was 1 or less was marked with ◯, 1 to 3 times with △, and the case with more than 3 times with x.
(7) Evaluation of leveling property The sample was a knitted fabric of yarn and scoured at 70 ° C. for 15 minutes using warm water containing 2 g / liter of score roll 400, and the dye was Foron Navy S-GL (Clariant Japan). (Trade name) manufactured by Co., Ltd. was used at 3% by weight based on the fabric, and as a dispersant, Nikka Sun Salt 7000 (trade name, manufactured by Nikka Chemical Co., Ltd.) 0.5 g / liter, 0.25 ml of acetic acid / Liter and 1.0 g / liter of sodium acetate were added to adjust the pH to 5 to obtain a dyeing solution. After dyeing with a boil for 30 minutes in a dyeing bath having a bath ratio of 25 times, the leveling property was determined by the following method. Three veteran judges were evaluated on a 10-point scale and determined as follows.
○: Level equality is good at 8 or more. Δ: Slightly poor at 6-7.

(8) Texture evaluation The fabric was relatively evaluated according to the following criteria based on the feel of the inspector (30 persons).
◎: Extremely soft and very supple sensation ○: Soft and supple sensation is good △: Soft and supple sensation is slightly inferior ×: Soft and supple sensation is not good (9) Measurement of color development L value of dyed product The color density of the surface of the dyed fabric was measured for L value in the Lab color system using a spectrocolorimeter (manufactured by Kollmorgen, model Macbeth MS-2020). The lower the L value, the higher the color developability.

(10) Same color property The lightness difference between easy-dyeing polyester fiber and polyamide fiber is small, and those with little hue difference, chroma difference, and irritation are considered good, and grade 5 (good) to grade 1 (inferior) Judged.
(11) Color difference between dyeing batches: Color blur evaluation 10 batches of mixed goods are repeated as one batch, and 10 batches of each batch are represented as representatives, and the color difference between 10 batches is represented by a spectrocolorimeter (Kollmorgen). Manufactured, model Macbeth MS-2020), and the average value was used.

(12) Fastness to washing The mixed dyed product was evaluated according to JIS-L-0844 A-2 method. However, the detergent was used at 1 g / liter of Attack (trade name, manufactured by Kao Corporation). The change color of the test piece and the degree of contamination of the attached white cloth piece were judged by comparing with the gray scale for change color and the gray scale for contamination, respectively.
(13) Fastness to sweat alkali The mixed dyed product was evaluated using an alkaline artificial sweat according to the JIS-L-0848 method. The change color of the test piece and the degree of contamination of the attached white cloth piece were judged by comparing with the gray scale for change color and the gray scale for contamination, respectively.

[Example 1, Comparative Example 1]
100 parts of dimethyl terephthalate (hereinafter referred to as DMT), 76 parts of ethylene glycol and 0.04 part of manganese acetate tetrahydrate salt as a transesterification catalyst were charged and heated from 150 ° C to 240 ° C for 3 hours. Then, transesterification was carried out while distilling methanol. Next, 0.04 part of trimethyl phosphate as a stabilizer, 0.05 part of antimony trioxide as a polymerization catalyst, and 0.4 part of titanium dioxide as a matting agent were added, and then polyethylene having a molecular weight and an addition amount shown in Table 1 were added. Glycol and Irganox 245 (manufactured by Ciba Geigy) as a heat stabilizer are added to the polyethylene glycol to 3% and mixed and added. Thereafter, a polycondensation reaction was carried out at normal pressure over 30 minutes and transferred to a polymerization tank. After completion of the transfer, the pressure was gradually reduced and a polycondensation reaction was performed at a vacuum degree of 0.5 Torr and 275 ° C. to obtain a modified polyester having an intrinsic viscosity [η] = 0.73. Using these polymers, a circular array with 36 spinning holes (24 on the outer layer, 10.5 mm between the cores, 12 on the inner layer, 18.3 mm between the cores) drilled to a diameter of 0.17Φ Using a spinning nozzle, high-speed spinning was performed at a spinning temperature of 280 ° C., a discharge linear speed of 43, 2 cm / sec, and a winding speed of 5800 m / min, to obtain 44 dtex / 36 filament fibers. Table 1 shows the Tmax, strength, elongation, color developability, and spinnability evaluation results of the easily dyeable polyester fibers obtained.

The dyeability of the readily dyeable polyester fiber of the present invention with respect to the disperse dye can be evaluated by comparing the dyeability of a polyester fiber (Tmax 136 ° C) spun by a normal method at 130 ° C for 60 minutes. The dye exhaust rate of the polyester fiber spun by the usual method with respect to the disperse dye was 94% and the K / S value was 24.
This yarn and nylon-6 fiber 44 dtex / 34 filament yarn were knitted, and a double-sided reversible knitted knitted fabric of a surface polyester and a back polyamide was knitted by a conventional method. The mixing ratio of the polyester fiber was 50%.

The obtained knitted fabric was scoured and relaxed at 80 ° C., pre-set at 180 ° C., and dyed under the following dyeing conditions.
Dyeing conditions Dye: Dianics Yellow AC-E 0.42% omf
(Diffusion index 3.9)
Dianics Red AC-E 0.30% omf
(Diffusion index 4.8)
Dianics Blue AC-E 0.09% omf
(Diffusion index 5.2)
(All dyes are manufactured by Dystar)
Dispersing leveling agent: Nikka Sun Salt RM-340 (manufactured by Nikka Chemical Co., Ltd.)
0.5 g / liter Acetic acid: 0.5 cc / liter Sodium acetate: 1 g / liter SR-1801M Conch (Takamatsu Yushi Co., Ltd.) 4% omf
Bath ratio: 1:20
Dyeing temperature, time: 95 ° C, 30 minutes

After completion of dyeing, soaping at 60 ° C. for 15 minutes in a nonionic detergent 0.5 g / liter bath, washing with water, and finishing with a dry heat set at 150 ° C. for 30 seconds. Table 1 shows the results of the finished dyeing, such as texture, same color, color difference between dyeing batches, fastness to washing, and fastness to sweat alkali.
From the results shown in Table 1, the mixed products obtained in Example 1 of the present invention all have a soft and supple texture compared to Comparative Example 1, have no irritation, and have the same color characteristics. It can be seen that a dyed product with high reproducibility can be obtained, and a mixed product with high commercial value with good fastness performance can be obtained.

[Example 2, Comparative Example 2]
The polyester yarns of 44 dtex / 36 filaments produced in Example 1 and nylon-6 yarns of 44 dtex / 34 filaments were interlaced (air pressure 0.3 MPa) to give 70 pieces / m entanglement. Next, a twisted yarn (A) with a twist of 1200 T / m (twisting factor 14199) in the S direction by a double twister and a twisted yarn (B) in the Z direction are produced in the same manner, and twisted at 60 ° C. for 40 minutes with a vacuum setter. A stop set was made.
A 28 gauge circular knitted smooth was produced while alternately feeding the obtained twisted yarns (A) and (B).

The obtained knitted fabric was dyed under the following conditions after applying the same scouring relaxation and preset as in Example 1.
Dyeing conditions Dye: Dianics Black SR (200) 6, 3% omf
(Dystar)
Aizen Opal Black new 3% omf
(Hodogaya Chemical Co., Ltd., monosulfonate type metal-containing dye)
Dispersing leveling agent: Nikka Sun Salt RM-340 (manufactured by Nikka Chemical Co., Ltd.)
0.5 g / liter Acetic acid: 0.5 cc / liter Sodium acetate: 1 g / liter SR-1801M Conch (manufactured by Takamatsu Yushi Co., Ltd.): 6% omf
Bath ratio: 1:20
Dyeing temperature, time: 98 ° C, 50 minutes

After the dyeing is completed, the dyeing residual liquid is discharged from the dyeing machine, water is added to the dyeing machine, the temperature is raised to 70 ° C., and the following chemicals are added thereto to prepare a reducing cleaning bath having the following concentration. Reductive washing was performed at 10 ° C. for 10 minutes.
Thiourea dioxide 1 g / liter Caustic soda 1 g / liter Bisnole UP-10 (manufactured by Yushi Kogyo Co., Ltd.) 0.5 g / liter After this reduction cleaning, the remaining liquid is discharged and the dyed product is rinsed with warm water and water. Then, it was finished with a dry heat set at 150 ° C. for 30 seconds.
Table 2 shows the results of the finished dyed product, such as the texture, the same color, the color difference between dyeing batches, the fastness to washing, and the fastness to sweat alkali.

[Comparative Example 3]
For comparison, two nylon-6 fibers 44 dtex / 34 filaments were combined, and a 28-gauge smooth knitted fabric was prepared in the same manner as in Example 2. The scouring was performed by a conventional method, black dyed with a metal-containing dye, and fixed. After finishing, it was finished with a dry heat set at 150 ° C. for 30 seconds. Table 2 shows the evaluation results of the texture of the finished dyeing, the fastness to washing, and the fastness to sweat alkali.
From the results of Table 2, the mixed products according to Example 2 of the present invention all have a soft and supple texture as compared with Comparative Example 2, and have the same color, color reproducibility for each dyeing batch, and fastness. It can be seen that the performance is also good. Moreover, almost the same texture as the polyamide fiber is obtained.

  The mixed article of the present invention can be suitably used particularly in the inner field.

The example of the cross-sectional schematic diagram of the spinneret in the spinning of the polyester fiber used by this invention is shown. The example of the land part plane schematic diagram of the spinning nozzle in spinning of the polyester fiber used by this invention is shown. The example of the spinning production process of the polyester fiber used by this invention is shown. The example of the frequency analysis chart by U% of the polyester fiber used by this invention and an evening tester is shown.

Claims (3)

  It is a mixed product of polyester fiber and polyamide fiber, and the polyester fiber is a polyester obtained by copolymerizing polyethylene terephthalate with 3 to 6% by weight of polyethylene glycol having a molecular weight of 300 to 2000, and 90% by weight or more is composed of ethylene terephthalate repeating units. A polyester fiber comprising polyethylene terephthalate, having a single yarn decitex of 1.4 or less, and a temperature (Tmax) at which the maximum mechanical loss tangent (tan δ) at a measurement frequency of 110 Hz is 85 ° C. or more and 105 ° C. or less. And mixed products of polyamide fiber.   The polyester fiber has a fineness variation value U% of 1.0% or less and a maximum coefficient of variation CV value of 10 to 80 m by a fineness variation frequency analysis is 0.3% or less (however, the fineness variation value U% Is measured over a yarn length of 500 m). The mixed article of polyester fiber and polyamide fiber according to claim 1.   The fastness to washing in the JIS-L-0844 A-2 method is grade 3 or higher, and the fastness to sweat alkali in the JIS-L-0848 method is grade 3 or higher, according to claim 1 or 2. A mix of polyester and polyamide fibers.

Images