JPH0987927A - Conjugate fiber having high luster and high colorability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a conjugate fiber high colorability and high luster at the stage of fiber without carrying out modification and post processing of a polymer. SOLUTION: In a sheath-core type conjugate fiber comprising a polyester as a core component A and a polymethylpentene as a sheath component B, this conjugate fiber in which a degree of exhaustion of the sheath component B with a disperse and/or cationic dye is <=20% degree of exhaustion of the core component A with the dye and is substantially <=0.08% owf and a surface area ratio R[B/(A+B)] of the sheath component B to the cross section of the conjugate fiber is 0.1-0.3, is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite fiber which has a very excellent coloring property and has a high gloss, and its field of application is suitable for general clothing, sports clothing, water wear or short business. Material can be provided.

[0002]

2. Description of the Related Art For many years, many studies have been made to impart high coloring properties to fibers. Examples of the dye include an easily dyeable fiber in which dye molecules are improved and the crystallinity of the polymer is lowered to easily adsorb dye molecules, or a cation or anion dyeable fiber in which a group reactive with the dye is introduced into the polymer. In particular, the most widely used polyester at present has a problem in color developability, and many studies have been made. In recent years, a technique different from these techniques, that is, a technique for imparting unevenness of submicron order to the surface of the fiber to give a high coloring property has been established, and has come to be used industrially. In addition, a technique for improving the color developability by coating a resin on the fiber surface by post-processing or imparting irregularities to the fiber surface by low temperature plasma treatment has been put into practical use. On the other hand, as a method for imparting a high color-developing property, a method which is not so efficient as to select a dye or to optimize the cross-sectional shape of the fiber has not been proposed.

[0003]

As described above, the improvement of the color developability of polyester fibers has become an important issue.
If the polymer is modified so that it is easily dyeable or reactive dyeable, it will lead to a decrease in yarn-forming property and fiber performance.
In addition, the method of giving unevenness to the fiber surface is effective for coloring, but there is a problem that "Atari (collapsed unevenness and tectal phenomenon)" occurs in the iron in the processing process and finishing process, and the glossiness remarkably decreases. was there. Further, in the method by post-processing, the processing steps are limited and the durability such as washing is not always sufficient. However, an object of the present invention is to provide a fiber which has high coloring properties and high glossiness at the fiber stage and can solve the above-mentioned problems without modification or post-processing of the polymer. is there.

[0004]

According to the present invention, the above objects are achieved by dispersing and / or cationic dye in a core-sheath type composite fiber in which the core component A is polyester and the sheath component B is polymethylpentene. The dyeing rate of the sheath component B is 20% or less of the dyeing rate of the core component A by the dye, and is substantially 0.08% owf or less, and the sheath component B occupying the cross section of the conjugate fiber. Area ratio R [B / (A + B)]
It is achieved by providing a conjugate fiber having a value of 0.1 to 0.3.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester, which is the core component A of the conjugate fiber of the present invention, means terephthalic acid as the main dicarboxylic acid component and at least one alkylene selected from ethylene glycol, trimethylene glycol and tetramethylene glycol. A polyester containing glycol as a main glycol component is preferable, and the third component may be copolymerized within a range not impairing the object of the present invention.

As the third component which can be copolymerized, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,
4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl isopropylidene dicarboxylic acid, 1,2-diphenoxyethane-4 ', 4 "-dicarboxylic acid, anthracene dicarboxylic acid, 2,5-pyridinedicarboxylic acid, diphenoxy ketone Aromatic dicarboxylic acids such as dicarboxylic acid, 5-sodium sulfoisophthalic acid, dimethyl 5-sodium sulfoisophthalate, 5-tetrabutylphosphonium sulfoisophthalic acid; fats such as malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid Group dicarboxylic acids; alicyclic dicarboxylic acids such as decalin dicarboxylic acid and cyclohexanedicarboxylic acid; hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, hydroxypropionic acid and hydroxyacrylic acid; Forming derivatives derived from carboxylic acids, such as ε over caprolactone aliphatic lactone,
Trimethylene glycol, tetramethylene glycol,
Hexamethylene glycol, neopentyl glycol,
Aliphatic diols such as diethylene glycol and polyethylene glycol; hydroquinone catechol, naphthalene diol, resorcin, bisphenol A, ethylene oxide adduct of bisphenol A, bisphenol S,
Aromatic diols such as ethylene oxide adducts of bisphenol S; aliphatic diols such as cyclohexanedimethanol can be mentioned. These 3rd components may be copolymerized by 1 type (s) or 2 or more types.

Further, in the polyester, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid, and tricarballylic acid within the range where the polyester is substantially linear; glycerin, trimethylolethane, and trimethylol. A polyhydric alcohol such as propane or pentaerythritol may be contained.

In the present invention, a polyester in which 80 mol% or more of the repeating units are ethylene terephthalate units or butylene terephthalate units is preferable, and 5-sodium sulfo is preferable from the viewpoint of vividness of color of the dyed product. Polyethylene terephthalate copolymerized with isophthalic acid or polybutylene terephthalate copolymerized with 5-sodium sulfoisophthalic acid is preferable. The copolymerization amount of 5-sodium sulfoisophthalic acid is preferably in the range of 1 to 10 mol%.

The above polyester may be added to the above-mentioned polyester, if necessary, within a range not impairing the present invention.
Additives such as optical brighteners, matting agents, antistatic agents, flame retardants, flame retardant auxiliaries, lubricants, colorants, plasticizers and inorganic fillers may be added.

The above polyester preferably has an intrinsic viscosity [measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 50/50)] in the range of 0.45 to 0.85. The intrinsic viscosity of the polyester is 0.
If it is less than 45, the strength of the obtained fiber will be low and it will not be practical. On the other hand, when the intrinsic viscosity of the polyester exceeds 0.85, the melt viscosity becomes too high,
The spinnability and spinnability are poor, which is not preferable.

The other sheath component B, polymethylpentene, is a polymer obtained by polymerization of 4-methylpentene-1, and has a melting point of 220 to 245 ° C. Such polymethylpentene may be a copolymer of another polymer or a blend of other polymers within a range that does not impair the polymer performance. Also,
If necessary, within the range not impairing the present invention, an antioxidant,
Additives such as an ultraviolet absorber, a fluorescent whitening agent, a matting agent, an antistatic agent, a flame retardant, a flame retardant auxiliary agent, a lubricant, a colorant, a plasticizer, and an inorganic filler may be blended.

In the composite fiber of the present invention, the composite ratio of the core component A and the sheath component B can be arbitrarily set within the range where the effect of the present invention is not lost, but the sheath component B occupying the fiber cross section of the composite fiber. The area ratio R = B / (A + B) is preferably 0.1 to 0.3. When R is less than 0.1, the sheath component B
In some cases, the core component A is partially exposed on the fiber surface, or the sheath component B is peeled off due to friction or wear. On the other hand, when R exceeds 0.3, the core component A
In some cases, the desired dye cannot be obtained because the dyeing rate of the dye is small. If the dyeing time is extended or a curing agent for swelling the sheath component B is added, a slight dyeing effect can be obtained, but the physical properties of the fiber are deteriorated, and the processing steps are considerably complicated. The cross-sectional area ratio can be obtained from a micrograph of the fiber cross-section, but the core component A and the sheath component B during spinning
It is also possible to set by adjusting the volume ratio of the discharge amounts of

In the conjugate fiber of the present invention, the polyester as the core component A and the polymethylpentene as the sheath component B are separately melted and introduced into the spinning pack portion, and a core-sheath structure is formed by a usual method. A stream is formed and spun from the nozzle. In order to improve the spinnability, it is desirable that the polyester as the core component A and the polymethylpentene as the sheath component B have almost the same melt viscosity. The spun filament yarn is
At a predetermined speed, for example 10-6000 m / min,
After refueling, wind up on the package. Next, the wound yarn is drawn in a usual manner so that the desired elongation and strength can be obtained. This drawing may be carried out continuously after the spun yarn is taken up and not wound up. Alternatively, a method may be adopted in which the desired fiber physical properties are obtained all at once at a high speed of 4000 m / min or more. When the fiber diameter exceeds 100 μm, it is desirable to spin at a low speed, cool in a water bath and draw at a draw ratio of 3 to 6 times. If the fiber diameter is 100 μm or less, 1000
It is desirable to carry out spinning at a speed of up to 6000 m / min, and then draw at a draw ratio of 60 to 90% of the cutting draw ratio, and heat treatment may be carried out for the purpose of controlling the shrinkage ratio and the like.

The resulting conjugate fiber is dispersed and / or dyed with a cationic dye at any subsequent stage. When a disperse dye or a polyester copolymerized with 5-sodium sulfoisophthalic acid is used as the core component A, when dyeing with a cationic dye, the core component A is dyed by these dyes and the polymethylpentene as the sheath component B is dyed. Is hardly stained. However, the dyed composite fiber can exhibit sufficient color developability because of the properties such as transparency and low refractive index of the polymethylpentene that is the sheath component B. The disperse dye and the cationic dye can be mixed and used.

In order to satisfy all of the coloring property, light resistance and washing fastness of the composite fiber dyed product of the present invention, the dyeing rate of the sheath component B is 20% or less, preferably 10% of the dyeing rate of the core component A. %
Hereafter, it is important that the content is more preferably 5% or less, and the dyeing rate of the sheath component B is 0.08% owf or less. When the dyeing rate of the sheath component B with respect to the core component exceeds 20%, the dye in the sheath component B is discolored by light irradiation or washing and the dyeing fastness is remarkably lowered.

The composite fiber of the present invention can control the hue from a light color to a dark color depending on the concentration of the dye used, and is therefore useful in various applications.

The term "dyeing ratio" as used in the present invention is a value representing the amount of dye dyed to the polymer of the core component A or the sheath component B as a percentage.

Normally, when light is incident on a fiber, it is reflected on the surface of the fiber, scattered, or refracted to enter the inside of the fiber. The light that has entered the inside of the fiber becomes colored light if the fiber is colored and comes out of the fiber again, but the surface-reflected light is white light, and if the ratio of the surface-reflected light is large, the fiber is white. The depth is increased and the depth of color is lost.

Generally, the reflectance r at the interface between two kinds of substances having different refractive indexes is shown by the following equation when the incident angle is 0. r = (n ₀ −n ₁ ) ² / (n ₀ + n ₁ ) ² (where n ₀ is the refractive index of the substance below the interface, and n ₁ is the refractive index of the substance above the interface)

Considering the case of a normal fiber, the substance on the boundary surface is air, and the refractive index n ₁ is 1. Therefore, the greater the refractive index n _{0 of the} fiber, the greater the reflectance r and the poorer the color developability of the dyed product. Polyester has a refractive index of about 1.62, which is the largest among general-purpose fibers, and this is considered to be the main reason why the sharpness of color in polyester fibers is not obtained. This can be understood from the fact that it can be dyed with a disperse dye as in the case of polyester fiber, and that the refractive index of acetate, which is a representative fiber of photo-coloring and vivid color, is as small as about 1.51.

In the composite fiber of the present invention, polymethylpentene is used as the sheath component B. Since the polymethylpentene has a very low refractive index of about 1.46, the reflectance of the fiber surface is small and the dyed product The color development and depth of the are increased. In addition to this, in the conjugate fiber of the present invention, as described above, the sheath portion of polymethylpentene is scarcely dyed, and only the core portion of polyester is dyed. When the dyeing density is the same, almost all the dye is dyed to the polyester of the core, the color developability of the polyester is enhanced, and the color developability is almost not hindered by the polymethylpentene of the sheath, and thus the composite fiber is obtained. It becomes a color. Due to these synergistic effects, the conjugate fiber of the present invention is excellent in color developability and color vividness. Further, since the dye is not dyed on the polymethylpentene which is the sheath component B, fading of the dye due to light or the like does not occur, and therefore the dye fastness does not decrease.

The composite fiber of the present invention is a filament or a staple.
It is manufactured in the form of pull or the like and processed into the form of woven fabric, knitted fabric, non-woven fabric, or the like. After that, scouring, dyeing and, if necessary, resin processing are performed. It is also suitable for sports clothing (baseball, tennis, soccer, table tennis uniforms, golf wear, triathlon, etc.), swimwear, women's outerwear, etc., as well as cartes, tablecloths, carpets. Also used for interiors such as tents, stuffed toys, etc.

[0023]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition, the measured value in the examples is a value measured and calculated by the following method, and the cross-sectional area ratio of the core component A and the sheath component B was obtained from the volume ratio of the discharged amount of the polymer. (1) Dyeing ratio (ppm) of core component A After dissolving and removing the sheath component in the composite fiber or its product, the polyester fiber portion as the core component is obtained by washing with water. After weighing a certain amount of the fiber and completely dissolving it in a phenol / tetrachloroethane mixed solution (weight ratio 1/1), the absorbance at the maximum absorption wavelength was measured by a spectrophotometer (type 307, manufactured by Hitachi, Ltd.). To measure. On the other hand, the polyester fiber content similarly taken out from the composite fiber before dyeing or its fiber product is measured in the same manner, and a calibration curve of the dyeing ratio and the absorbance is obtained, and the dyeing amount of the dyed fiber is obtained from this calibration curve. I asked.

(2) Dyeing rate (ppm) of sheath component B A certain amount of the composite fiber or its product is weighed, and then Soxhlet extraction is performed with trichlene to extract the dye from polymethylpentene which is the sheath component. About the extract,
The absorbance at the maximum absorption wavelength is measured with a spectrophotometer (type 307, manufactured by Hitachi, Ltd.). On the other hand, the absorbance of the dye-trichlene solution was measured, the calibration curve of the dye concentration and the absorbance was determined, and the dyed amount of the dyed fiber was determined from this calibration curve.

(3) Chromogenicity (K / S) The spectral reflectance (R) of a product made of composite fiber is measured by a color analyzer (Hitachi 307 type, manufactured by Hitachi Ltd.),
It was determined from the following Kubelka-Munk equation. The larger this value is, the greater the color developability is. K / S = (1−R) ² / 2RR is the reflectance at the maximum absorption wavelength position of the visible reflectance curve of the product. (4) Saturation (%) It is a saturation value determined by JIS Z 8722 (a method for measuring an object color by a 2-degree visual field XYZ system). (5) Gloss (class) Five people visually evaluated and evaluated the following criteria, and show the average value. 5th grade: Very good 4th grade: Good 3rd grade: No problem in practical use 2nd grade: Some luster is seen 1st grade: Almost no luster is seen (6) Dyeing fastness to washing According to JIS L 0844 A test according to the A-2 method was performed. Nylon cloth was used as the white cloth, and the degree of pollution was graded by a staining scale.

(7) Melt viscosity of polymer (poise) It is a value at a shear rate of 1000 sec ^-1 when measured at 300 ° C. by using Toyo Seiki Capillograph 1B type. (8) Melting point of polymer (° C.) This is an endothermic peak temperature determined by DSC of TA-3000 type manufactured by Metra Co. (9) Lightfastness It was evaluated according to the dyeing fastness test method for JIS L 0842 carbon arc lamp (first exposure method).

Example 1 and Comparative Example 1 As core component A, melting point 250 ° C., intrinsic viscosity [η] = 0.
Polyethylene terephthalate of No. 67, polymethylpentene having a melting point of 235 ° C. and a melt viscosity of 1100 poise as a sheath component B, and using a nozzle having a structure shown in FIG. 1 at a temperature of 295 ° C. and a spinning speed of 1000 m / min. Composite spinning was performed and a yarn of 495 denier / 24 filament was obtained. Subsequently, it was brought into contact with a plate at a temperature of 120 ° C. and drawn 3.3 times to obtain a yarn of 150 denier / 24 filament. The cross-sectional shape of the fiber was of the type shown in FIG. 2A, and the cross-sectional area ratio R was 0.18. Using the obtained yarn as warp and weft, an 8-sheet satin woven fabric was prepared, desized and refined,
It was preset at 180 ° C. and dyed under the following conditions.

Dyeing conditions Disperse dye: Dispersol Brill Scarlet D-SF200 Grains 3% owf Dispersant: Diper-TL 1g / l pH adjuster: Acetic acid 0.5cc / l Bath ratio: 50: 1 Temperature: 130 ° C Time: 40 Minute reduction cleaning Hydrosulfide 1g / l Sodium hydroxide 1g / l Amylazine D (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 1g / l Bath ratio: 50: 1 Temperature: 80 ° C Time: 20 minutes

The dyeing rate, color developability, saturation and the like of each component of the composite fiber constituting the dyed product were evaluated and shown in Table 1. Also,
For comparison, only the same polyethylene terephthalate as used in Example 1 was melt-spun and stretched in the same manner as in Example 1 to prepare an 8-satin woven fabric using the stretched yarn as warp and weft. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 1. As is clear from Table 1, the composite fiber of the present invention is superior to the fiber obtained in Comparative Example 1 in dyeing fastness and color development.

Example 2 and Comparative Examples 2 to 3 Stretched yarns were obtained in the same manner as in Example 1 except that the composite ratio of the core component and the sheath component was changed as shown in Table 1 to prepare a woven fabric. Each of the obtained woven fabrics was dyed with a disperse dye, and each of the dyed products was evaluated. The results are shown in Table 1. In Comparative Example 2 having a small amount of sheath component, peeling of the sheath component and fibrils frequently occurred in the weaving process and the like, and the product had no commercial value. On the other hand, in Comparative Example 3 in which the sheath component is large, the dye does not pass through the sheath portion, the polyethylene terephthalate as the core component is not dyed, and the color developability is very poor, and there is a glaring feeling. there were.

Example 3 As core component A, 2.5 mol% of 5-sodium sulfoisophthalic acid was copolymerized, melting point 248 ° C., intrinsic viscosity [η].
The composite fiber was spun in the same manner as in Example 1 except that the polyethylene terephthalate of 0.52 was used under the following conditions, and then a woven fabric was prepared and dyed. The results are shown in Table 1.

Dyeing conditions Cationic dye: Cathilon Brill Red 4GH200 2% owf Auxiliary agent: sodium sulfate 2g / l acetic acid 1% owf sodium acetate 0.5% owf Bath ratio: 50: 1 Temperature: 120 ° C Time: 40 minutes reduction washing Hydrosulfide 1 g / l Ammonia water 1 g / l Amylazine D (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 1 g / l Bath ratio: 50: 1 Temperature: 70 ° C. Time: 20 minutes

Example 4 As core component A, 2.5 mol% of 5-sodium sulfoisophthalic acid was copolymerized, melting point 211 ° C., intrinsic viscosity [η].
Using 0.85 of polybutylene terephthalate, the composite fiber was spun in the same manner as in Example 3 to prepare a woven fabric and dyed. The results are shown in Table 1.

Example 5 In the same manner as in Example 1, except that the cross-sectional shape of the conjugate fiber was changed to the type shown in FIG. 2 (h), the conjugate fiber was spun, a woven fabric was prepared and dyed. The results are shown in Table 1.

[0035]

[Table 1]

[0036]

Industrial Applicability According to the present invention, a fiber having high coloring property, high glossiness at the fiber stage, and excellent light resistance and washing durability without modification or post-processing of the polymer is obtained. can get.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional shape of a nozzle for spinning the conjugate fiber of the present invention.

FIG. 2 is a schematic view showing an example of a cross-sectional shape of the conjugate fiber of the present invention.

[Explanation of symbols]

 A: Core component polymer B: Sheath component polymer

Continued Front Page (72) Inventor Yoshio Kishino 1621 Sakata, Kurashiki, Okayama Prefecture Kuraray Co., Ltd.

Claims (1)

[Claims] 1. A core component A is polyester, and a sheath component B.
In the core-sheath type composite fiber in which is polymethylpentene,
Dispersion and / or the dyeing rate of the sheath component B with the cationic dye is 20% or less of the dyeing rate of the core component A with the dye, which is substantially 0.08% owf, and the crossing of the conjugate fiber. Area ratio R [B / (A +
B)] is 0.1 to 0.3.