JPH06299428A - Combined filament yarn - Google Patents

Abstract

PURPOSE:To provide combined filament yarn consisting of polyamide filaments and polyester filaments composed mainly of ethylene terephthalate unit and having specific boiling water shrinkage and degree of cationic dye exhaustion and giving woven or knit fabric having excellent strength, dyeability and appearance. CONSTITUTION:The combined filament yarn giving woven or knit fabric having excellent strength, dyeability and appearance is produced by the fluid entangling treatment of (A) polyester filaments copolymerized with 1.0-6.0mol% of a glycol of formula I (R1 is 4-20C bivalent hydrocarbon group; 3<=+n<=6), containing 0.5-5.0mol% of 5-sodium sulfoisophthalic acid, terminal-blocked with 0.5-3.0mol% (based on the dicarboxylic acid) of a compound of formula II (Ar is phenyl, etc.; R2 is 1-20C hydrocarbon group; p and q are 0 or 1; A is ester-forming functional group) and having fiber properties satisfying the formula III [DT is breaking strength (g/d); DE is breaking extension (%)], a boiling water shrinkage of formula IV and an exhaustion degree of >=90% calculated by formula V (X and Y are absorbances of the dyeing liquid before and after the dyeing operation, respectively).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mixed yarn for improving the bulge of a woven / knitted fabric and for maintaining the strength of the woven / knitted fabric and producing a woven / knitted fabric having an excellent appearance with excellent dyeability.

[0002]

2. Description of the Related Art Polyamide fibers, unlike polyester fibers, are unlikely to have a difference in shrinkage rate due to heat setting, and thus it is difficult to produce bulges like polyester fiber different-shrink mixed-weave fabrics. Therefore, there is a method of bulging by mixing high shrinkage yarn of polyester fiber and polyamide fiber,
Since ordinary polyester fibers have poor dyeability and can be dyed only by high-pressure dyeing, polyester fibers cannot be sufficiently dyed in the case of a mixed fiber with polyamide fibers, and the appearance is inferior.

As an improvement, JP-A-55-12204
The method of cation dyeing polyester filaments copolymerized with a dicarboxylic acid having a sodium sulfonate group at 120 ° C. or the method of increasing the copolymerization amount of a dicarboxylic acid having a sodium ulphonate group and performing a cation dyeing under normal pressure as in 2 is there. In the case of dyeing at 120 ° C., the polyamide multifilament becomes weak and the strength of the woven or knitted fabric becomes insufficient, and there is a problem that a thin fabric cannot be formed.

In order to solve such a dyeing problem of the polyester component, a method using a cationic dyeable polyester in which an acidic group such as 5-sodium sulfoisophthalic acid is copolymerized has been proposed (Japanese Patent Publication No. 34/34). -104
97). In this case, for dyeing at a pressure of about 100 ° C. under normal pressure without using a carrier, the isophthalic acid component having a metal sulfonate group is 5% of that of the polyester acid component.
It is necessary to contain more than mol%. However, such a polyester having a large amount of isophthalic acid component having a sulfonic acid metal base has a difficulty in sufficiently increasing the degree of polymerization due to the thickening action of the isophthalic acid component,
Even if the degree of polymerization is increased, spinning will be difficult due to the thickening effect. Therefore, in order to obtain sufficient dyeability and spinnability, the degree of polymerization of the copolyester has to be suppressed, and there is a problem that the strength of the obtained fiber becomes low.

Further, in order to make up for the drawbacks of the isophthalic acid component having such a metal sulfonate group while imparting the dyeability under normal pressure, as described in JP-A-57-63325, a high molecular weight compound is used. A method of copolymerizing polyoxyethylene glycol with polyester and a method of copolymerizing another glycol or the like with an isophthalic acid component having a sulfonate metal base have also been proposed. The problem of lower strength than the original strength of the fiber has not been solved. Due to these problems, the strength of the woven or knitted fabric was insufficient, and there was a problem in using it for a thin fabric.

[0006]

DISCLOSURE OF THE INVENTION The present invention eliminates the above drawbacks, improves the bulge of a woven or knitted fabric, and maintains the strength of the woven or knitted fabric to produce a woven or knitted fabric excellent in appearance and excellent in appearance. It is intended to provide a thread.

[0007]

In order to solve the above-mentioned problems, the present invention takes the following means. That is,
The present invention is a mixed filament yarn comprising a polyamide filament and a polyester filament containing ethylene terephthalate as a main repeating component, wherein the polyester filament has physical properties satisfying the following formulas (1) and (2): The mixed fiber is characterized in that the dyeing rate (%) of the cationic dye represented by the formula (3) is 90% or more. DT × DE ^1/2 ≧ 20 (1) where DT is the breaking strength of the fiber (g /
d), DE is the breaking elongation (%) of the fiber. Shrinkage rate of boiling water (%) ≧ 20% (2) Dyeing rate (%) = [(XY) / X] × 100 (3) Further, X is before dyeing. The absorbance of the dyeing solution is and the Y is the absorbance of the dyeing solution after dyeing.

Further, in the present invention, as the polyester component, a special glycol having the general formula 3 is added in an amount of 1.0 to 6.
0 mol% copolymerized, containing 0.5-5.0 mol% of 5-sodium sulfoisophthalic acid residue, and at least a part of the molecular end is 0.5-3.
The mixed fiber according to claim 1, wherein a modified polyester whose end is blocked by a compound represented by generalization 4 which is present at 0 mol% is used.

[0009]

[Chemical 3]

In the chemical formula 3, R1 has 4 to 4 carbon atoms.
20 divalent aliphatic or aromatic hydrocarbon groups,
m and n are arbitrary numbers satisfying 3 ≦ m + n ≦ 6.

[0011]

[Chemical 4]

In the chemical formula 4, Ar is a phenyl or naphthyl ring, P and q are 0 or 1, A is an ester-forming functional group, and R2 is a hydrocarbon group having 1 to 20 carbon atoms.

The present invention will be described in detail below. The polyamide filament used in the present invention may be any polyamide capable of melt spinning, such as nylon 6, nylon 6.
6 is suitable. DT × DE ^1/2, which is a value indicating the fiber physical properties of the polyester filament mixed with the polyamide filament, is an index generally called toughness, and indicates the essential strength of the fiber-forming polymer. In the present invention, since the polyester filament is used as the shrinkage component of the differently contracted mixed fiber, the physical properties of the polyester filament greatly influence the physical properties of the mixed fiber. When the toughness value of this polyester filament is less than 20, the strength as a mixed fiber becomes low, the strength of the woven or knitted fabric is insufficient, and it cannot be used for a thin woven fabric. For the first time, the strength characteristics of the mixed fiber are improved and a mixed fiber having sufficient toughness can be obtained. Further, when the toughness value of this polyester single component is 23 or more, the tenacity is remarkably increased as compared with the conventional cationic dyeable polyester, and therefore it is particularly preferable. In addition, DT is
The breaking strength (g / d) of the fiber, DE is the breaking elongation (%) of the fiber.

When a woven or knitted product is produced as the different-shrinkage mixed yarn, in order to sufficiently bring out the bulge, sufficient bulge is obtained unless the boiling water shrinkage rate of the polyester filament on the high shrink side is 20% or more. Absent. Here, the boiling water shrinkage rate means that when the sample length under a load of 0.1 g / d is L ₀ , the load is removed and the sample is treated in boiling water for 30 minutes, and the length measured again under the same load is L, Boiling water shrinkage (%)
Is boiling water shrinkage (%) = [(L ₀ −L) / L ₀ ] × 10
It is represented by 0. In order to obtain a cationically dyeable polyester filament having a shrinkage of 20% or more at normal pressure, depending on the polymer composition, a filament having a high shrinkage can be obtained only by stretching the yarn without heat setting.
It can also be obtained by drawing a highly oriented yarn spun at a level of up to 4000 m / min without heat setting.

The dyeing ratio of the cationic dye showing the dyeability of the polyester component used in the present invention must be 90% or more because a sufficient dark color cannot be obtained unless it is 90% or more. is there. In addition, the dyeing conditions at the time of dyeing are as follows: Dyecry1 Br. Blue H2
RN (10% owf), auxiliary and concentration are sodium acetate (0.2 g / l), acetic acid (0.2 g / l),
The bath ratio is 1: 100, and the dyeing temperature and time are normal temperature boiling temperature (98 ° C.) × 90 minutes.

The dyeing rate (%) is the dyeing rate (%) =
[(X−Y) / X] × 100, where X is the absorbance of the dyeing solution before dyeing and Y is the absorbance of the dyeing solution after dyeing.

The polyester containing ethylene terephthalate as a main component in the present invention means that 80 mol% or more of the dicarboxylic acid component is terephthalic acid or its ester-forming derivative, and less than 20% of the dicarboxylic acid component. It refers to a polyester obtained by copolymerizing an aromatic, aliphatic, or alicyclic dicarboxylic acid and hydroxycarboxylic acid within the range not degrading the quality of the polyester. Among them, the use of 5-metal sulfoisophthalic acid or its ester-forming derivative in an amount of 0.5 to 5.0 mol% is particularly preferable because the dyeability with a cationic dye is remarkably improved.

As the glycol component of the polyester component used in the present invention, a linear alkylene glycol selected from ethylene glycol, trimethylene glycol, tetramethylene glycol and the like is used in an amount of 80 mol% or more. It is necessary to perform copolymerization so that the glycol shown by 5 is contained in the produced polyester in an amount of 1.0 to 6.0 mol%.

[0019]

[Chemical 5]

In the general formula 5, R1 has 4 to 4 carbon atoms.
It is a divalent aliphatic or aromatic hydrocarbon group of 20 and, among them, an aliphatic hydrocarbon group having a side chain is most preferable. The dyeability of the polyester copolymerized with glycol represented by the general formula 5 becomes extremely large. Also m,
n is an arbitrary number satisfying 3 ≦ m + n ≦ 6, and 3> m +
n causes a problem of distillation during the polycondensation reaction, and m + n
When> 6, the light resistance of the dyed product is significantly reduced. Further, even if the amount of the glycol component is 6.0 mol% or more, the light resistance of the dyed product is remarkably deteriorated, which is not practical.

Further, in the polyester component used in the present invention, at least a part of the molecular terminal is present in the general formula 6 in which 0.5 to 3.0 mol% is present with respect to the dicarboxylic acid component.
It is necessary that the terminal is blocked by the compound represented by, but if it is 3.0 mol% or more, the polymerization time is drastically lengthened, which is not practical.

[0022]

[Chemical 6]

In the formula 6, Ar is a phenyl or naphthyl ring, P and q are 0 or 1, A is an ester-forming functional group, and R2 is a hydrocarbon group having 1 to 20 carbon atoms.

By thus blocking a part of the molecular ends in the copolymerization of polyester, the thickening action during the polycondensation reaction is reduced, and the melt viscosity is controlled within the range in which normal polymerization and spinning are possible. The degree of polymerization of the copolyester produced below can be increased, and since this polyester also has excellent drawability, a high-strength cationic dye-dyeable fiber can be obtained and sufficient strength as a blended yarn can be obtained. is there.

[0025]

【Example】

Examples 1 to 4 and Comparative Examples 1 to 10 Polyesters having the polymer composition shown in Table 1 are spinning temperatures 2
Spinning was performed at 90 ° C. and a spinning speed of 3000 m / min. The obtained undrawn yarn was drawn at a hot roller temperature of 70 ° C. and the heat setting temperature was changed to obtain drawn yarns of 30 denier and 18 filaments having different boiling water shrinkage rates. Further, using nylon 6 having a relative viscosity of 2.60 in 96% concentrated sulfuric acid and spinning at a spinning temperature of 280 ° C. and a spinning speed of 3000 m / min, an undrawn yarn obtained was drawn at a hot roller temperature of 50 ° C. and drawn 180 ℃
A heat-set 30 denier, 36 filament, breaking strength = 5.1 g / d, breaking elongation = 43%, boiling water shrinkage = 8.0% were obtained. The two filaments were entangled with a fluid to obtain a mixed yarn. A woven fabric was made using this mixed fiber, and was subjected to bath dyeing at 98 ° C. with a cationic dye and an acid dye. The results are shown in Table 1. In Table 1, DSN is 5-sodium sulfoisophthalic acid dimethyl ester, * 2
Indicates a sulfonate compound represented by Chemical formula 6, and * 3 indicates a glycol represented by Chemical formula 5.

[0026]

[Table 1]

The measuring methods of Examples and Comparative Examples are as follows. (Intrinsic viscosity of polyester) It was measured at 30 ° C. with a mixed solution of phenol / tetrachloroethane (6: 4 weight ratio). (Relative Viscosity of Polyamide) It was measured using 98% concentrated sulfuric acid. (Dyeing rate) Diacryl Br. Blue H2R-N (Mitsubishi Kasei Co., Ltd.)
(Cationic dye) 10% owf, 0.2 g / 1 of acetic acid and sodium acetate, bath ratio 1: 100, and the sample was dyed for 90 minutes at boiling temperature (98 ° C) under normal pressure, and the absorbance of the dyeing solution before and after dyeing was measured. It was measured and calculated by the following formula. Dyeing rate (%) = {(XY) / X} × 100 (X: absorbance of dyeing solution before dyeing, Y: absorbance of dyeing solution after dyeing) (tensile elongation) "Tensilon" UTM-4L Type tensile tester (manufactured by Toyo Baldwin Co., Ltd.) with a gauge length of 20
The sample was stretched at 0 mm, an initial load of 4 g, and a stretching speed of 200 mm, and the breaking strength (g / d) and breaking elongation (%) of the fiber were obtained from the SS curve drawn at a recording speed of 500 mm / min.
DT × DE ^1/2 was calculated.

From Table 1, the products of Examples 1 to 4 have DT ×
DE ^1/2 is 20 or more, dyeing rate, boiling water shrinkage rate (SHW)
Both satisfied the requirements of the present invention and were satisfactory in terms of bulge, strength and appearance. On the other hand, Comparative Examples 1 to 4 have DT ×
The DE ^1/2 was small and the strength was low. In Comparative Examples 3 to 8, the dyeing rate was low and the appearance was poor. Comparative Examples 9 to 10 had a small boiling water shrinkage and a small bulge. Regarding the bulge, ○ means that there is enough, and × means that it is poor. With respect to strength, ⊚ is sufficient, ∘ is present, and x is poor. Regarding appearance, ◯ is graceful and x is poorly colored.

[0029]

EFFECTS OF THE INVENTION According to the present invention, a drawback of the conventional mixed yarn of polyester and polyamide, that is, the problem that the dyeability is low and the strength is lowered when the dyeability is increased, is solved, and a woven or knitted fabric having a bulge is solved. Can be made.

Claims (2)

[Claims] 1. A mixed filament yarn comprising a polyamide filament and a polyester filament containing ethylene terephthalate as a main repeating component, wherein the polyester filament has physical properties satisfying the following equations (1) and (2): A mixed filament yarn having a dyeing rate (%) of the cationic dye represented by the formula (3) of the polyester filament of 90% or more. DT × DE ^1/2 ≧ 20 (1) where DT is the breaking strength of the fiber (g /
d), DE is the breaking elongation (%) of the fiber. Boiling water shrinkage rate (%) ≧ 20% (2) Dyeing rate (%) = [(X−Y) / X] × 100 (3) where X is dyeing The absorbance of the previous dyeing solution and Y are the absorbance of the dyeing solution after dyeing. 2. As a polyester component, 1.0 to 6.0 mol% of a special glycol represented by the general formula 1 is copolymerized, and 0.5-sodium sulfoisophthalic acid residue is added to 0.5 to 5.
A compound represented by the general formula 2 in which 5.0 mol% is contained and at least a part of the molecular end is present in an amount of 0.5 to 3.0 mol% based on the dicarboxylic acid component. The mixed yarn according to claim 1, wherein a quality polyester is used. [Chemical 1] In Chemical formula 1, R1 is a divalent aliphatic or aromatic hydrocarbon group having 4 to 20 carbon atoms, and m and n are 3 ≦ m.
It is an arbitrary number that satisfies + n ≦ 6. [Chemical 2] In Chemical formula 2, Ar is a phenyl or naphthyl ring, P,
q is 0 or 1, A is an ester-forming functional group, and R2 is a hydrocarbon group having 1 to 20 carbon atoms.