JP2006336136A - Blended product of polyester fiber and protein fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blended product of polyester fiber and protein fiber, having especially soft and pliant touch feeling, high in color developability, good in homochromaticity, slight in color variation for each dyeing batch, affording dyed products of high color reproducibility, and also high in color fastness performance. <P>SOLUTION: The blended product of polyester fiber and protein fiber is provided. In this product, the polyester fiber consists of a polyester obtained by copolymerizing 3-6 wt.% of a polyethylene glycol 300-2,000 in molecular weight with polyethylene terephthalate, wherein the polyester comprises a polyethylene terephthalate greater than 90 wt.% of which is composed of ethylene terephthalate recurring units. The polyester fiber is ≤1.4 dtex in single filament fineness and 85-105°C in the temperature(Tmax) at which the dynamic loss tangent(tanδ) at a measurement frequency of 110 Hz is maximum. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  Fabrics made of protein fibers, such as wool and silk, can be dyed at normal pressure, have good dyeability, and are excellent in texture and color, but have poor bulkiness, raw yarn strength, wash and wear properties, It lacks functionality such as pleating, dimensional stability, yellowing, insect repellent and fungicide. For this reason, mixing these polyester fibers excellent in functionality lacking in protein fibers to compensate for these drawbacks has been performed.

  Polyester fibers can compensate for the shortcomings of protein fibers, but when dyed at 95-105 ° C, which is the normal dyeing temperature of protein fibers, due to the difficulty of dyeing polyester fibers, the color development of polyester fibers is extremely low. The same color with cannot be obtained. On the other hand, when dyeing at a high temperature of 130 to 135 ° C., which is a normal polyester fiber dyeing temperature, it is easy to obtain the same color as protein fiber, but under such conditions, protein fiber becomes brittle and physical properties such as strength and elongation are large. In addition to being lowered, the texture is not only impaired, but also problems such as large yellowing occur. In addition, when dyeing is carried out using a carrier agent under normal pressure at a lower dyeing temperature, contamination by disperse dyes on protein fibers increases, dyeing fastness decreases, and it is difficult to remove the carrier in the fibers. In addition, there are problems such as a decrease in working environment due to carrier odor.

  Therefore, as a normal-pressure dyeable polyester fiber that can be dyed in a temperature range that does not cause embrittlement of protein fibers, a method for producing a cationic dye-dyeable polyester fiber in which 5 mol% or more of sodium sulfoisophthalic acid is copolymerized is disclosed in Patent Literature 1 and 2. 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 dyeing property 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 in the light color system cannot be obtained. 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. There is a problem that protein fiber embrittlement is inevitable and soft and supple texture cannot be obtained.

Therefore, at present, dyeing conditions that find a compromise from the balance between the color development properties of the polyester fibers and the physical properties of the protein fibers are used for the mixed products of polyester fibers and protein fibers, and the polyester fibers are dyed with disperse dyes. Has been done. However, when dyed with disperse dyes, protein fibers are contaminated with disperse dyes, and it is difficult to control the contamination. Therefore, there is a problem that color blur at the time of dyeing is large and the same color as polyester fibers is poor. Moreover, there is a problem that the dyeing fastness of the dyed mixed fabric is lowered, the color developability of the polyester fiber is low, and there is a defect called irritation, and only the dyed product with poor quality is obtained. In addition, 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 protein fibers. In fact, only a dyed product with a lower quality is obtained.
Japanese Patent Publication No. 61-17939 JP-A-61-34022 Japanese Patent No. 2870769 Japanese Patent Publication No. 01-15610 JP 59-59911 A

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

  As a result of diligent research on polyester fibers to be mixed with protein fibers, the present inventor has obtained 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 out that a fabric in which a spun polyester fiber is mixed with protein 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 protein 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. The temperature (Tmax) at which the mechanical loss tangent (tan δ) is maximum at a measurement frequency of 110 Hz is 85 ° C. or higher and 105 ° C. or lower. Mixed polyester fiber and protein fiber.
(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 protein 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 protein fiber as described in (2).

  Polyester terephthalate copolymerized with 3 to 6% by weight of polyethylene glycol having a molecular weight of 300 to 2000, a single yarn decitex having a polyester of 1.4 or less spun at a winding speed of 5000 m / min or more, and a dyeable polyester fiber and a protein fiber. When mixed, the color of polyester fibers is high, the same color is good, the color reproducibility and dyeing fastness in 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 product of polyester fiber and protein 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, and the polymer composition becomes unstable. 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, the polyester fiber has a softer texture than the polyester fiber obtained by the conventional method, and further, the crystallization is suppressed by copolymerizing polyethylene glycol, which is further softer. 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 an unprecedented soft and supple texture that is required by the present invention, but also to increase the dyeability and high color development even when the single yarn decitex is reduced. Since the amount of disperse dye contamination is reduced and the degree of coloration of protein fibers can be controlled to 60 or less, 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 preferable because the effect of improving the dyeing is small, dyeing at a higher temperature is required, and the problem of embrittlement of the protein 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 thin by making the fineness of the fiber, the dyeability of the fabric tends to lighten. 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 using a normal method or a straight-roll method, it is difficult to obtain a remarkably soft and suppleness as a texture when mixed with protein 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. Accordingly, there is very little fluctuation in the longitudinal direction of the fiber fineness, there is no specific frequency fluctuation accompanying the longitudinal direction of the fiber, and the CV value is very small as 0.3% or less, and the fineness is very small in the longitudinal direction. It is stable and 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 one-piece 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 easily dyeable 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 mixture of other fibers such as spandex, cotton, cupra, viscose rayon fiber, polyamide fiber, acrylic fiber, etc. within the range that does not impair the object of the present invention (silospan, silofil, etc.) It can be by means of mixing such as fine yarn (different shrinkage mixed yarn with high shrinkage yarn, etc.), cross twist, composite false twist (elongation difference false twist, etc.), two-feed air jet processing and the like.

In the present invention, the mixed protein fiber is a fiber appropriately selected from animal fibers represented by wool, mohair, and cashmere and silk fibers represented by rabbit yarn and wild silk yarn.
In conventional wool fabrics, wool has been scaled with chlorine gas or chlorine compounds for the purpose of being hard to shrink even when wet treated, increasing glossiness, and facilitating dyeing. In the composite with the polyester fiber, there is a problem that the irritation is further promoted. However, if it is a mixed product of the easily dyeable polyester fiber of the present invention and the wool fabric, there is no irritation and the same color is good.

  The polyester fiber and protein fiber in the mixed article of the present invention preferably have a polyester fiber content of approximately 65% by weight or less. 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, acrylic fiber, and the like may be mixed.

  The form of the mixed article of the polyester fiber and the protein fiber of the present invention can be a thread form or a cloth 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 the knit, there is a method in which one is used for the warp and the other is used for the weft. In the warp and / or weft, both are alternately arranged by warping or weft insertion. Furthermore, in the raised fabric and the pile fabric, one side constitutes the ground structure, and the other constitutes the ground portion, the pile portion, or the ground structure, the raised portion, etc. There are configurations or mixed configurations.

  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 protein fibers in the sheath, maintain the texture of the protein fibers, while maintaining dimensional stability, stretchability, and wrinkle resistance It is preferable that it can provide functionality such as.

When dyeing easily-dyeable polyester fibers with a disperse dye in dyeing a mixed product of polyester fiber and protein fiber of the present invention, any dyeing condition can be applied as long as the polyester fiber is usually dyed with a disperse dye. 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.) However, it is preferable from the viewpoint of enhancing the color developability of the readily dyeable polyester fiber under normal pressure dyeing, reducing the contamination of the protein fiber, and increasing the same color and fastness of dyeing. 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.

In addition, protein fiber dyeing can be applied under any conditions in which protein fiber is usually dyed with acid, metal inclusion, chromium, reactive dye, etc., and dyeing method can be two-bath dyeing method with disperse dye, one bath A two-stage dyeing method, a one-bath dyeing method, or the like may be appropriately performed.
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, soaping treatment, and the like, which are usually performed, are performed.

The resulting mixed dyed product increases the dyeing rate of disperse dyes on easily dyeable polyester fibers, has high color developability even with a small single yarn decitex, and has the same colorability as protein fibers, making it a good-looking mix 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 polyester fiber and protein fiber mixed product 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)
Intrinsic viscosity [η] (dl / g) is a value determined based on the definition of the following equation.
[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. Is. 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.
As the dye, Sumikaron Blue S-3RF (manufactured by Sumika Chemtex Co., Ltd., trade name) is used in an amount of 5% by weight with respect to the fabric, and as a dispersant, Nikka Sun Salt 7000 (manufactured by Nikka Chemical Co., Ltd., product) 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) Measurement of color developability 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.

(7) 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.

(8) Evaluation of leveling property The sample was subjected to scouring treatment at 70 ° C. for 15 minutes using warm water containing 2 g / liter of score roll 400 using a yarn as a knitted fabric, and the dye was Foron Navy S-GL (Clariant Japan ( (Trade name) manufactured by Co., Ltd., 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, acetic acid 0.25 ml / Liter and sodium acetate 1.0 g / liter 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.

(9) Texture evaluation The fabric was relatively evaluated according to the following criteria based on the feel of the examiner (30 persons).
◎: Extremely soft and very supple feeling ○: Soft, supple feeling is good △: Soft, supple feeling is slightly inferior ×: Soft, supple feeling

(10) Same color properties Little difference in brightness between easy-dyeing polyester fiber and protein fiber, good hue difference, saturation difference, and little irritation. 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.

(14) Contamination of dry cleaning liquid A dry cleaning test is performed on the mixed dyed product in accordance with JIS L-0860, and the dry cleaning liquid and the dirt liquid after the dry cleaning test are placed in a magnetic container (20 m / m × 40 m / m). 8 cc was taken at × 10 m / m), and the degree of color fading was determined by comparing the degree of liquid contamination with the gray scale for contamination. Good ones with little color fading were classified as grade 5, and were sequentially judged as grade 1 (those with large color fading).

(15) Contamination degree of protein fiber in dyed product After dyeing with disperse dye, the fabric is washed with water and dried, protein fiber is extracted from the fabric, and the degree of contamination is determined in accordance with JIS-Z-8730. (Kollmorgen, Macbeth MS-2020) was used and evaluated. The degree of contamination D indicates the difference in the degree of coloration of protein fibers before and after staining, and was determined by the following formula in the Lab color system. The greater the number, the greater the contamination with disperse dyes.
D = (ΔL ² + Δa ² + Δb ² ) ^1/2

[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 [η] = 0.73.

  Using these polymers, a double-circular circular array having a spinning hole 36 (24 holes in the outer layer, 10.5 mm distance between the cores, 12 holes in the inner layer, 18.3 mm distance 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 evaluation results of Tmax, strength, elongation, dyeability, and spinnability of the easily dyeable polyester fiber 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 wool No. 72 single yarn were twisted and twisted at 750 T / M in the Z direction by a conventional method, and the resulting yarn was used for a woven fabric (warp density of 105 yarns / inch, Weft density of 82 yarns / inch) was prepared (mixing rate of easily dyeable polyester fiber was 25%).

Next, this mixed fabric was scoured and washed by a conventional method, subjected to wool scale treatment with chlorine gas, pre-set at 180 ° C., and then subjected to disperse dyeing under the following dyeing conditions.
Dyeing conditions Dye: Disperse Black JSW (150%) 4.0% omf
(Miki Sangyo Co., Ltd., benzeneazo disperse dye)
Auxiliary agent: Demol N (made by Kitahiro Chemical Co., Ltd.) 1 g / liter Bath ratio: 1:15
Dyeing temperature and time: 98 ° C., 45 minutes After 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 65 ° C., and the following chemicals are added to the following concentration. The reduction washing bath was adjusted, and the dyed product was subjected to reduction washing at 65 ° C. for 10 minutes.
Thiourea dioxide: 1 g / liter
Ammonia water (28%): 1 g / liter Amirazine D (Daiichi Kogyo Seiyaku Co., Ltd.): 0.5 g / liter Bath ratio: 1:20

After this reduction cleaning, the remaining liquid was discharged, and the dyed product was sufficiently rinsed with hot water and water, and then the wool side was dyed under the following conditions.
Dyeing conditions Dye: Diamond Black PV (200%) 5% omf
(Dystar Co., Ltd.)
Auxiliary: Acetic acid (40%) 3% omf
Formic acid (40%) 3% omf
Potassium dichromate 1.1% omf
Bath ratio: 1:20
Dyeing temperature, time: 98 ° C., 60 minutes After 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 75 ° C., and amyrazine D is added at 2 g / liter, and soaping is performed for 10 minutes. Processing was carried out. After the treatment, the dyed product was sufficiently rinsed with warm water and water, then dried, and finished by steaming using a full decatetizer by a conventional method.

Table 1 shows the evaluation results of the texture of the finished dyed product, the color development property of the mixed dyed product, the same color, the fastness to washing, the fastness to sweat alkali, the contamination of the dry cleaning liquid, and the contamination degree of the wool fibers.
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 high color developability, no irritation, and the same color. It can be seen that a dyed product having a good color reproducibility, a high color reproducibility, a fastness performance and a high commercial value can be obtained.

[Example 2, Comparative Example 2]
Each of the 44 dtex / 36 f polyester raw yarns produced in Example 1 was double-covered in the normal silk yarn 44 by a conventional method to produce a covering yarn. This covering yarn was subjected to silk scouring treatment by a conventional method to obtain a 190 dtex yarn (mixing rate of easily dyeable polyester fiber was 23%). Tendon knitted fabric was produced with 24GG using the obtained yarn.

Each obtained knitted fabric was relaxed and scoured by a conventional method, and then dyed under the following conditions.
Dyeing conditions Dye: Kayalon Polyester Yellow BRL-S 2.47% omf
Kayalon polyester rubin 3GL-S (150) 1.24% omf
Kayalon Polyester Navy Blue 2GN-SF (200)
0.16% omf
Kayakaran Yellow GL (143) 0.75% omf
Kayaka Rambordeax BL 1.22% omf
Kayaka Langley BL (167) 0.04% omf
(Manufactured by Nippon Kayaku Colors Co., Ltd., for each dye concentration, disperse dye is the ratio to the polyester weight, and the acid dye is the ratio to the silk weight)
Auxiliary agent: Nikka Sun Salt RM-340 (manufactured by Nikka Chemical Co., Ltd.)
0.5g / liter
Acetic acid 0.5cc / liter
Sodium acetate 1g / liter
SR-1801M Conch (Takamatsu Yushi Co., Ltd.) 3% omf
Bath ratio: 1:20
Dyeing temperature, time: 95 ° C, 30 minutes

After dyeing, soaping was performed at 70 ° C. for 15 minutes in a non-ionic detergent 1 g / liter bath, washed with water, and finished with a dry heat set at 150 ° C. for 30 seconds.
Table 2 shows the evaluation results of the texture of the finished dyed product, the colorability of the mixed dyed product, the same color, the color difference between dyeing batches, the fastness to washing, and the fastness to sweat alkali.
From the results of Table 2, the mixed products obtained in Example 2 of the present invention all have a much softer and more supple texture than Comparative Example 2, have high color developability and good color matching. It can be seen that a dyed product with little color variation between dyeing batches and high color reproducibility can be obtained, and a mixed product with good fastness performance and high commercial value can be obtained.

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

The example of the cross-sectional conceptual diagram of the spinning nozzle in spinning of the polyester fiber used by this invention is shown. The example of the plane conceptual 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)

  Polyester fibers and protein fibers are mixed products, and polyester fibers are polyesters obtained by copolymerizing polyethylene terephthalate with 3 to 6% by weight of polyethylene glycol having a molecular weight of 300 to 2000, and more than 90% by weight of polyethylene comprising ethylene terephthalate repeating units. A polyester fiber comprising terephthalate, having a single yarn decitex of 1.4 or less, and a temperature (Tmax) at which a mechanical loss tangent (tan δ) at a measurement frequency of 110 Hz is maximum is 85 ° C. or more and 105 ° C. or less; Mixed products with protein fiber.   The polyester fiber has a fineness variation value U% of 1.0% or less and a maximum value of the coefficient of variation CV in a period of 10 to 80 m according to the 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 protein 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 mixed product of polyester fiber and protein fiber.

Images