JP2005299046A - Mixed product of polyester fiber and protein fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mixed dyed product having a soft and flexible feeling and also having high color development, and providing good color uniformity and excellent color fastness by mixing a modified polyethylene terephthalate with a protein fiber. <P>SOLUTION: The subject mixed product is obtained by mixing the easily dyeable polyester fiber comprising a polyester obtained by copolymerizing 3-8 wt.% polyethylene glycol having 300-2,000 molecular weigh with a polyethylene terephthalate and containing ≥90 wt.% ethylene terephthalate repeating unit, having a W-shaped cross section of a single fiber, satisfying the condition (1): 2≤ovality≤4, and having the temperature (Tmax) exhibiting the maximum of a dynamic loss tangent (tanδ) at 110 Hz measure frequency within the range of the condition (2): 85°C≤(Tmax)≤105°C, with the protein fiber. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a mixed article of polyester fiber and protein fiber. More specifically, by mixing specific easily-dyeable polyester, the protein fiber can be used to maximize its original texture and physical properties without damaging the protein fiber, and the polyester fiber that combines the functionality of the polyester and protein fiber can be used together. The present invention relates to a fabric dyeing product.

Fabrics made from natural protein fibers, such as wool and silk, can be dyed at normal pressure, have good dyeability and excellent texture and color, but have poor bulkiness and yarn strength and wash and wear properties. It lacks functionality such as pleatability, dimensional stability, yellowing, insect repellent and fungicide. For this reason, mixing these polyesters 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 under the same conditions as protein fibers, polyester fibers have a very low color developability due to the difficulty of polyester fibers, and are therefore the same color as protein fibers. 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 fibers, but under these conditions, protein fibers become brittle and have large physical properties such as strength and elongation. In addition to being lowered, the texture is not only impaired, but also problems such as large yellowing occur. In addition, when dyeing with a carrier agent under normal pressure, contamination by protein-dispersed dyes increases, dyeing fastness decreases, and it is difficult to remove the carrier in the fiber. Problems such as lowering of the level occur.

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 dyeable polyester fiber obtained by copolymerization of 5 mol% or more of sodium sulfoisophthalic acid is disclosed in Patent Document 1. 2. However, although the dyeability is improved, the 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, a soft and supple texture cannot be obtained when using the raw yarn, the raw yarn is prone to yellowing, and sharpness is obtained in a light-colored system. There are problems such as not.

Furthermore, Patent Documents 4 and 5 disclose methods for producing easily dyeable polyester fibers in which the structure inside the fibers 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, under the present circumstances, dyeing conditions that have found a compromise from the balance between the color developability of the polyester fiber and the physical properties of the protein fiber are employed. However, when dyed with a disperse dye, the protein fiber is excessively contaminated by the disperse dye. Since the stainability cannot be controlled, there are problems such as large color blurring at the time of dyeing and poor color matching with polyester fibers. In addition, the dyed mixed fabric has a problem that the fastness of dyeing decreases due to the large contamination of the disperse dye to the protein fiber, and the color development of the polyester fiber is low. The actual situation is not obtained.

Japanese Patent Publication No. 61-17939 JP-A-61-34022 Japanese Patent No. 2870769 Japanese Patent Publication No. 1-15610 JP 59-59911 A

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

As a result of earnest research on polyester fibers to be mixed with protein fibers, the present inventor has found that a polyester obtained by copolymerizing polyethylene terephthalate with 3 to 8% by weight of polyethylene glycol having a molecular weight of 300 to 2000 is wound 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 a protein-based fiber solves the above-mentioned problems and further studying it, the present invention has been made.
That is, the present invention is a polyester obtained by copolymerizing polyethylene terephthalate with 3 to 8% by weight of polyethylene glycol having a molecular weight of 300 to 2000, 90% by weight or more of polyethylene terephthalate composed of ethylene terephthalate repeating units, and the cross-sectional shape of a single yarn is W A temperature (Tmax) that is a polyester fiber that satisfies the following condition (1) and has the maximum mechanical loss tangent (tan δ) at a measurement frequency of 110 Hz is in the range indicated by (2) below. This is a mixed dyed product of easily dyeable polyester fiber and protein fiber.
(1) 2 ≦ Flatness ≦ 4
(2) 85 ° C. ≦ (Tmax) ≦ 105 ° C.

  Easy-dyeable polyester fibers and protein fibers obtained by spinning polyester having a W-shaped cross section of polyethylene terephthalate with 3 to 8% by weight of polyethylene glycol having a molecular weight of 300 to 2000 and spinning at a winding speed of 5000 m / min or more. By mixing the polyester fiber, it is possible to obtain a mixed dyeing product having high color developability of the polyester fiber, good color matching, high dyeing fastness, soft and supple texture.

The present invention will be described in detail below.
Polyethylene glycol used as a copolymerization component in the present invention causes an appropriate disturbance in the amorphous structure of the fiber and contributes to an improvement in dyeability.
When the molecular weight of polyethylene glycol is less than 300, the peak temperature (hereinafter referred to as Tmax) of the mechanical loss tangent (tan δ) obtained from the dynamic viscoelasticity measurement referred to in the present invention is 106 ° C. or higher and is mixed with protein fibers. Soft and supple as the texture when you do it. In addition, the color developability of the polyester fiber is low, and the same color as the protein fiber cannot be obtained. Moreover, 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 is 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, which not only results in poor spinnability but also undesirably deteriorates the dyeing fastness and light resistance. .

Further, when the copolymerization amount of polyethylene glycol is less than 3% by weight, Tmax becomes 106 ° C. or higher, and softness and flexibility as a texture when mixed with protein fibers cannot be obtained. Moreover, the color developability of the polyester fiber is low, and the same color as the protein fiber is poor. On the other hand, when it exceeds 8% by weight, Tmax is less than 85 ° C., and softness and flexibility as a texture when mixed with protein fiber cannot be obtained. Further, although the dyeability is sufficient, the color tone of the polymer is deteriorated, and at a winding speed of 5000 m / min or more, yarn breakage and fluff are frequently generated, and spinning stability becomes poor and production becomes difficult. In addition, the filament produced is not preferable because light fastness and dyeing fastness deteriorate.
The easily dyeable polyester fiber of the present invention needs to have a W-shaped cross section of a single yarn and a flatness of 2.0 or more and 4.0 or less. This is because a soft and supple fabric with excellent texture can be obtained in this range. Moreover, it is because the color developability in normal pressure dyeing improves. When the flatness is less than 2.0, the specific surface area approximates that of a round cross-section yarn, so that a soft texture cannot be obtained, the dye exhaustion rate in atmospheric dyeing is slow, and the color developability is insufficient. On the other hand, when the flatness exceeds 4.0, it becomes close to a mere flat yarn, and the texture of the fabric becomes paper-like, which is not preferable because it gives an irritating gloss. A preferred range of flatness is in the range of 2.5 to 3.5.

In this invention, it is preferable that the opening angle of each recessed part of a W-shaped cross section is 100-150 degree | times. The opening angle means the sharpness of the cross-sectional shape. The smaller the angle, the sharper the cross-section, and the larger the angle, the slower. When the opening angle is less than 100 degrees, deformation of the W cross section is large during drawing false twisting, and many of the grooves of the W cross section shape are crushed, a soft texture cannot be obtained, and color development is insufficient. . On the other hand, even if the opening angle exceeds 150 degrees, the texture and color developability are insufficient.
Polyester fibers are highly atypically modified to improve texture and dyeability, and the single yarn cross section is changed to a Y cross section, cross-shaped cross section, H cross section, star cross section, etc. Although the dyeability is improved, a fatal defect that the fabric has a hard texture becomes obvious. Also, there is a method of having three or more recesses, but the texture and dyeing properties are improved as in the W cross section, but the increase in the recesses decreases the discharge linear velocity of the spinning nozzle and lowers the spinning stability. It is not preferable. In the present invention, it has been found that a soft and supple texture can be obtained by making the cross-sectional shape of the single yarn into a W-shaped cross section, color development is improved, and a polyester fiber excellent in spinning stability can be obtained.
The easily dyeable polyester fiber of the present invention needs to have a loss tangent peak temperature (Tmax) determined by dynamic viscoelasticity measurement of 85 to 105 ° C. In this range, not only can a soft and supple texture similar to the nylon required by the present invention be ensured, but also the dyeing property is improved, the amount of disperse dyes on protein fibers is reduced, and the degree of contamination is controlled to 60 or less. The same color and fastness to dyeing can be obtained. Tmax corresponds to the mobility of molecules in the amorphous part. The smaller this value, the easier the dye enters the amorphous part and the higher the dyeability. If Tmax is less than 85 ° C, there is a problem that the mechanical properties and heat resistance of the raw yarn are lowered. On the other hand, if Tmax exceeds 105 ° C, the dyeability is lowered and dyeing at a higher temperature is required. The problem of fiber embrittlement occurs. A particularly preferable range of Tmax is 90 to 100 ° C.
Although not as important as Tmax, the loss tangent value (tan δmax) at Tmax is preferably in the range of 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.

Next, the manufacturing method of the easily dyeable polyester fiber of this invention is described.
The polyester fiber as used in the present invention is at least 90% of the structural unit is ethylene terephthalate, and may be copolymerized with other components of 5 mol% or less in addition to the polyethylene glycol component. 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 described above, 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 contained as necessary.
A well-known method can be employ | adopted for the polymerization method of the polymer which comprises the easily dyeable polyester fiber of this 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 easily dyeable polyester fiber of the present invention can be obtained only by a high-speed spinning method in which spinning is performed at a winding speed of 5000 m / min or more. Yarns obtained at a winding speed of 5000 m / min or less are stretched in the weaving and knitting process, causing frequent spotting and deterioration in the quality of the fabric. On the other hand, the loss tangent peak temperature (Tmax) obtained from the measurement of dynamic viscoelasticity is out of the range of 85 to 105 ° C. even if the copolymerized polyester is fiberized by a normal method or a straight-roll method, and protein fibers and It is soft and soft as a texture when mixed. 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-roll 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 soft and supple texture, it has been clarified that yarn breakage and fluff frequently occur when the single yarn shape is made into a W cross section and the yarn is produced by the high speed spinning method. In order to avoid this situation, the inventors have conducted intensive research and as a result, as shown in FIG. 1 and FIG. It has also been found that high-quality polyester fibers with few defects such as yarn breakage and knurls during spinning can be obtained. The cause of frequent yarn breakage and fluff is not clear, but when the single yarn shape is a W cross section and the shape of the spout land portion is a perfect circle, abnormal stagnation occurs in the land portion, and there is a decrease in viscosity due to thermal degradation of the polymer. It is thought that thread breakage and fluff frequently occurred in the filament. In particular, in the case of high-speed spinning at 5000 m / min or more, since it is easily affected by fluctuations in the viscosity of the polymer, aggregation of the catalyst and additives, etc., it is necessary to pay close attention in the polymer polymerization stage and the spinning process. Particularly in the case of the present invention, polyethylene glycol is copolymerized to impart easy dyeability, and heat resistance is usually inferior to that of polyethylene terephthalate, so it is necessary to prevent abnormal stagnation as much as possible in the polymerization process and spinning process. is there.
As shown in FIG. 2, the elliptical shape of the spout land portion needs to have a ratio of a long side and a short side of a rectangle circumscribing the ellipse in a range of 1.2 to 3.5. When the ratio of the long side to the short side is less than 1.2 or exceeds 3.5, a high-quality polyester fiber having few defects such as yarn breakage and fluffing that is the target of the present invention cannot be obtained. The cause is not clear, but if the ratio of the long side to the short side is less than 1.2 or exceeds 3.5, the shape of the nozzle and the land part become imbalanced, resulting in a long polymer stay in the land part. It is presumed that the polymer viscosity-decreasing material due to long-term residence is mixed into the filament, so that yarn breakage and fluff are generated.

The easily dyeable polyester fiber of the present invention can be produced using, for example, a spinning device shown in FIG. As the convergence guide, the winding device, and other devices necessary for melt spinning used in the present invention, known devices can 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 in its single yarn decitex, but it is 0.1 to 5 decitex, more preferably 0.5 to 3 decitex, and although not particularly limited, the total decitex is 10 to 10. A fiber at 340 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. As the form of the yarn on 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 multifilament raw yarn having a single yarn decitex of about 0.1 to 5 dtex (extra fine) Thread), sweet twisted yarn or strong twisted yarn, false twisted yarn (including POY stretched false twisted yarn), air jet yarn, indented 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, etc. within the range not impairing the object of the present invention (silospan, silofil, etc.), entangled mixed fiber ( Different shrinkage mixed yarn with high shrinkage yarn, etc.), cross-twisting, composite false twisting (elongation difference false twisting, etc.), mixed feed means such as 2-feed air jet processing.
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 addition, in woolen fabrics, wool is scaled with chlorine gas or chlorine compounds for the purpose of preventing shrinkage, increasing gloss, and facilitating dyeing even when wet treatment is performed. In the composite with the polyester fiber, there is a problem that the irritation is further promoted. However, when the easily dyeable polyester of the present invention is used, there is no irritation and the same color property is obtained.

The ratio of easily dyeable polyester fiber to protein fiber in the mixed dyed product of the present invention is approximately 65% by weight or less for easily dyeable 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 fiber, and the like may be mixed in the protein fiber as the remaining mixed component.
The composite means of easily dyeable polyester fiber and protein fiber according to the present invention can be blended at the yarn stage by blending (mixed cotton, fleece blended, sliver blended, core yarn, silospan, silofil, hollow spindle, etc.), entangled blended fiber , Cross twist, design twist yarn, covering (single, double), composite false twist (simultaneous false twist, pre-twist false false twist), elongation difference false twist, phase difference, post-mixing after false twisting, two feeds (simultaneous feed) And feed difference) There are means such as air injection processing, and as a means to combine on the machine, there is a general knitting machine. For example, in knitting, the two are aligned and fed, or double knitted fabric (For example, in a double circular knitting machine, a double flat knitting machine, a double raschel warp knitting machine), there is a method in which yarns are supplied or drawn together on the front surface and / or the back surface. In cross knitting, one is used for warp and the other for easy yarn. In warp and / or weft, both are alternately arranged by warping or weft insertion, and in brushed fabric or pile fabric, one constitutes the ground structure. On the other hand, the other portion 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, the sheath-core composite yarn and the twisted yarn that are combined so that the easily dyeable polyester fiber is disposed in the core portion and the protein fiber is disposed in the sheath portion, while maintaining the texture of the protein fiber, dimensional stability, stretchability, Functionality such as anti-wrinkle property can also be imparted, which is preferable.

  Next, in dyeing a mixture of easily dyeable polyester fiber and protein fiber of the present invention, when dyeing easily dyeable polyester fiber with a disperse dye, the dyeing condition is usually that the polyester fiber is dyed with disperse dye. Any type of dyeing assistant and its 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 in atmospheric dyeing of readily dyeable polyester fibers, reducing the contamination of protein fibers, 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 among dyeing batches is reduced. In addition, protein fibers can be dyed under any conditions where protein fibers are usually dyed with acid, metal, chromium, reactive dyes, etc. A two-stage dyeing method or a one-bath dyeing method may be appropriately performed.

The dyeing temperature at the time of dyeing is preferably 100 ° C. or less, and the dyeing operation can be carried out by 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.
The resulting mixed dyed product increases the dyeing rate of disperse dyes on easily dyeable polyester fibers, reduces waste of dyes, has high color development, and has good color matching with protein fibers. 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.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the 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 formula, ηr is a value obtained by dividing the viscosity at 35 ° C. of a diluted polymer solution dissolved in an o-chlorophenol solvent having a purity of 98% or more by the viscosity of the solvent measured at the same temperature. Is defined. 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) Flatness Flatness was calculated | required by ratio of the long side A and the short side B of the circumscribed rectangle of the single yarn cross section of a fiber by following Formula.
Flatness = long side A / short side B
(4) Loss tangent Using a Levibron manufactured by Orientec Co., Ltd., measuring a sample weight of about 0.1 mg, a measurement frequency of 110 Hz, a heating rate of 5 ° C./min, in dry air, and measuring the mechanical loss tangent at each temperature ( tan δ), and dynamic viscoelasticity (E ′). From the result, a tan δ-temperature curve is obtained, and the temperature (° C.) at which tan δ exhibits the maximum value on this curve and the maximum value tan δ max of tan δ at that time are obtained.

(5) Exhaust rate, color development (K / S) measurement: Evaluation of dyeability Samples were smelted 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 based on 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
Incidentally, the exhaust rate after dyeing regular polyester fibers (56 dtex / 24f) at 130 ° C. for 60 minutes under the above conditions was 94% and the K / S value was 21.
(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) Texture evaluation The fabric was relatively evaluated according to the following criteria based on the feel of the inspector (30 persons).
◎: Soft, supple feeling is very good ○: Soft, supple feeling is good △: Soft, supple feeling is slightly inferior ×: Soft, supple feeling is not good (9) Same color property Easy dye polyester fiber and protein fiber Those having little brightness difference, less hue difference, saturation difference, and illness were considered good, and were judged in five grades from grade 5 (good) to grade 1 (inferior).
(10) 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.

(11) Contamination of dry cleaning liquid For mixed dyed products, a dry cleaning test is carried out according to JIS-L-0860, and the dry cleaning liquid and the dirt liquid after the dry cleaning test are placed in a magnetic container (20 mm x 40 mm x 10 mm). 8 cc was taken, and the degree of color fading was judged 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).
(12) Contamination of protein fibers in the dyed product Protein fibers are extracted from the fabric, and the degree of contamination is evaluated using a spectrocolorimeter (manufactured by Kollmorgen, model Macbeth MS-2020) in accordance with JIS-Z-8730. did. 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 and mixed and added to 3% of polyethylene glycol. 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 spinneret having an ellipse shape (long side / short side ratio of 2.0) and drilled in a W shape and having 30 spinnerets, a spinning temperature of 280 High-speed spinning was performed at a temperature of 6000 m / min and a fiber of 56 dtex / 30 filaments having a W cross section as a single yarn cross section was obtained. Table 1 shows the Tmax, flatness, strength, elongation, dyeability, and spinnability evaluation results of the easily dyeable polyester fibers obtained.
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 100 yarns / inch, A weft density of 80 / inch was prepared (mixing rate of readily dyeable polyester fiber was 30%).

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%) (Miki Sangyo Co., Ltd., benzeneazo-based disperse dye)
3.5% omf
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 condition Dye: Diamond black PV (200%) (manufactured by Daistar Co., Ltd.) 5% omf
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 completion of the dyeing, the dyeing residual liquid was discharged from the dyeing machine, water was added to the dyeing machine, the temperature was raised to 75 ° C., and amyrazine D; 2 g / liter was added, and a soaping treatment was performed for 10 minutes. 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 colorability of the mixed dyed product, the same color, the fastness to sweat alkali, the contamination of the dry cleaning liquid, and the contamination 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 good color matching. In addition, it can be seen that a mixed product having a high commercial value with good fastness performance can be obtained.

[Example 2, Comparative Example 2]
Each of the 56 dtex / 30 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 205 dtex yarn (mixing rate of easily dyeable polyester fiber was 28%). 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 2.06% omf
Kayalon polyester rubin 3GL-S (150) 1.03% omf
Kayalon Polyester Navy Blue 2GN-SF (200)
0.13% omf
Kayakaran Yellow GL (143) 0.72% omf
Kayaka Rambordeax BL 1.17% omf
Kayaka Langley BL (167) 0.04% omf
(Nippon Kayaku Co., Ltd., for each dye concentration, disperse dye is the ratio to the polyester weight, 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 and time: 95 ° C., 30 minutes After dyeing, soaping was performed at 70 ° C. for 15 minutes in a nonionic 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 same color of the mixed dyed product, and the fastness to washing.

  From the results of Table 2, the mixed products obtained in Example 2 of the present invention all have a soft and supple texture, high color developability, good color matching, and fastness as compared with Comparative Example 2. It can be seen that a mixed product with good product 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 schematic diagram of the spinneret in spinning | fiber-formation of the easily dyeable polyester fiber used by this invention is shown. The example of the land part top view schematic diagram of the spinning nozzle in spinning of the easily dyeable polyester fiber used by this invention is shown. The example of the spinning production process of the easily dyeable polyester fiber used by this invention is shown.

Claims (1)

Polyester obtained by copolymerizing polyethylene terephthalate with 3 to 8% by weight of polyethylene glycol having a molecular weight of 300 to 2000, 90% by weight or more is made of polyethylene terephthalate consisting of ethylene terephthalate repeating units, and the cross-sectional shape of the single yarn is W-shaped. The temperature (Tmax) at which the mechanical loss tangent (tan δ) reaches the maximum at a measurement frequency of 110 Hz is in the range indicated by the following (2). A mixed product of dyeable polyester fiber and protein fiber.
(1) 2 ≦ Flatness ≦ 4
(2) 85 ° C. ≦ (Tmax) ≦ 105 ° C.

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