JPH0718055B2 - Basic dye, normal pressure dyeable polyester fiber and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyester fiber which can be dyed with a basic dye in a dark color at atmospheric pressure and a temperature of 95 ° C. or lower, and a method for producing the same, more specifically, Relates to an easily dyeable modified polyester fiber having remarkably improved alkali hydrolysis resistance and a method for producing the same.

[Prior art and its problems]

Conventionally, for the purpose of improving the dyeability and color developability of polyester fibers, it is possible to dye with a basic dye by copolymerizing a metal sulfonate-containing ester-forming component to introduce a metal sulfonate group into the polyester component. It is known that polyester fibers which can be obtained are obtained.

As a method of improving the dyeability of the basic dye-dyeable polyester, a method of polymerizing another third component in addition to the ester-forming component containing a metal sulfonate is known. Isophthalic acid and polyethylene glycol are especially common third components.

By copolymerizing polyethylene glycol with the metal sulfonate-containing ester-forming component, the proportion of the metal sulfonate group is small, but at normal pressure and in a boiling state,
A fiber which can be dyed in a dark color is obtained.

However, it has been impossible to avoid that the obtained fiber has extremely poor alkali hydrolysis resistance.

Alkali weight loss processing, such as making silk material with soft drape by utilizing the moderate alkali hydrolysis of homopolyester, is popular because it satisfies the consumer's needs for high quality products. Has been done to.

However, the present basic dye-dyeable polyester fiber, which has a significantly higher alkali weight loss rate than homopolyester, is (1) prone to a decrease in fineness or uneven fineness (2) is likely to cause a large decrease in strength (3) It is easy to cause problems such as slips and easy breakage of the fabric structure, and it is often difficult or impossible to control the alkali reduction processing.

[Means for solving problems]

In order to solve the above-mentioned drawbacks, the present invention comprises copolymerizing a metal sulfonate group-containing ester-forming component and an easily dyeable polyester improved with polyethylene glycol with a specific component as described in the claims. The present invention provides a fiber having improved alkali hydrolysis resistance and a method for producing the fiber.

The copolymerization ratio of the metal sulfonate group-containing ester forming component (A) of the present invention is 0.8 ≦ (A) ≦ 3.5 mol%,
When it is less than 8, satisfactory dyeing properties cannot be obtained even when a large amount of the component (B) or the component (C) is copolymerized, and when it is more than 3.5, the tackiness during polymerization is large, which is not preferable. Specifically, the component is, for example, 5-sodium sulfoisophthalic acid, potassium sulfoterephthalic acid, sodium sulfonaphthalenedicarboxylic acid, sodium sulfophenyldicarboxylic acid,
Such as dicarboxylic acids and alkyl esters thereof, oxycarboxylic acids such as sodium sulfobenzoic acid and alkyl esters thereof, and dihydroxys such as sodium dihydroethoxybenzenesulfonate, among which 5-sodium sulfoisophthalic acid is particularly preferable. .

Polyethylene glycol (B) is 1.0 ≦ (B) ≦ 10wt
If the ratio is less than 1.0, the expected dyeability is not satisfied if it is less than 1.0, and if it is more than 10, the physical properties such as strength and melting point are deteriorated and it is not practically used. The molecular weight of polyethylene glycol is 400-8
000, preferably 500 to 4000 is suitable.

Further, the component (C) needs to be 2.0 ≦ (C) ≦ 20 mol%.
When it is less than 2.0, the effect of improving the alkali hydrolysis resistance is small, and when it is more than 20, the deterioration of other physical properties is also large, which is not preferable.

As a method for polymerizing the copolymerization component constituting the polyester fiber of the present invention, a known method is used.

That is, the metal sulfonate-containing ester-forming component may be reacted as it is with terephthalic acid and ethylene glycol, or as an ester component such as dimethyl ester, it may be subjected to transesterification with ethylene glycol and then polycondensed. good.

The glycol component can be used in the same way as ethylene glycol. Further, the oxycarboxylic acid component can also be polymerized by the same addition method as that for the metal sulfonate group-containing ester forming component.

The polymer obtained by these methods can be spun into fibers by a known method. That is, as a spinning method, 1) spinning is performed at a winding speed of 1000 to 1500 m / min to obtain an undrawn yarn, and a drawing heat treatment is further performed 3 to 4 times.

2) Spin at a winding speed of 4000 m / min or less, and as POY,
Furthermore, there is a stretching heat treatment at 1.05 to 1.5 times. 3) There is a method of winding at a high speed of 5000 m / min or more.

The method of 3) high-speed spinning of 5000 m / min or more is preferable since productivity can be improved and energy cost can be reduced by omitting the drawing step, and further high-speed spinning can be expected to further improve dyeability. Is.

Also, in general, a metal sulfonate group-containing polyester of 5000
Spinning of m / min or more often causes difficulties due to occurrence of fluff and yarn breakage, but the polyester of the present invention is
The addition of component (C) also has the effect of significantly reducing the occurrence of fluff and yarn breakage.

〔effect〕

The copolyester fiber of the present invention has a feature that it can be sufficiently dyed at a temperature of room temperature of 95 ° C. or less, and also has a high alkali hydrolysis resistance which cannot be obtained by the fiber of this type conventionally. So it was difficult before,
This facilitates alkali weight reduction processing.

As another effect, when the fiber is produced by spinning at a winding speed of 5000 m / min or more, it is impossible to avoid the production of a copolyester of this type in the related art, such as fluff during spinning and yarn breakage. The problem is solved.

Hereinafter, the present invention will be described specifically with reference to Examples.
The evaluation methods of various characteristic values used in the examples of the present invention are as follows.

(Strength, Elongation) Shimadzu Corporation, using Autograph DSC100 type tensile tester,
The initial length is 20 cm and the pulling speed is 20 cm / min.

(Melting point) Perkin Elma Differential Scanning.Calorimete
-1B type, sample 7mg, temperature rising rate 16 ℃ / min N
₍₂₎ Measurement is performed while performing substitution, and the apex of the obtained chart endothermic peak is taken as the melting point.

Cationic dye exhaustion ratio Cationic dye Maxilon Blue 5G (ChibaGeigy) Preparation liquid Sodium acetate 0.5g / l Anhydrous Glauberite 4.0g / l Acidity pH = 4 Bath ratio 1:50 Dye concentration = 5% owt Temperature 95 ℃ After dissolving in the adjustment solution and staining under the above conditions,
Dilute the remaining liquid 70 times with the adjustment liquid and use the Hirama colorimeter to measure 1 cm.
Absorbance (U) was measured at wavelength λ = 655 mμ using a Cholex cell of
From o), define and obtain the exhaustion rate.

(Alkali weight loss) After knitting the fiber with a knitting machine, a surfactant (Score Roll 250,
Kao Atlas) Dissolved in distilled water at a rate of 2.0 g / l, and bath ratio
1: 200, bath temperature 60 ~ 70 ℃ 30 minutes scouring and remove the oil. After scouring, drain the water well and keep it in a temperature-controlled room at a temperature of 23 ° C and a humidity of 65%.
Approximately 5 g (Wo) of the sample after drying for 24 hours was weighed, and the sample was alkali-hydrolyzed with NaOH 5% aqueous solution at a bath ratio of 1:50 for 15 minutes at a liquid temperature in a boiling state, and then washed well with water and dehydrated, Dry under the above conditions, accurately measure the weight (W) after weight reduction,
Calculate by defining the alkali weight loss rate as in the following formula.

[Example] Example 1 2.2 mol% of dimethyl 5-sodium sulfoisophthalate,
The viscosity (ηsp / c) is 0.58 by polymerizing by adding 3.0 wt% of polyethylene glycol having a molecular weight of 600, 5.0 mol% of 1-2 bis (4-carbophenooxy) ethane, and a catalyst as a reaction accelerator, A melt having a melting point of 235 ° C. was obtained.
This was spun at 7,000 m / min using a spinneret of 280 ° C. and 0.23 ^φ × 24H to obtain a fiber of 50 denier single fiber.

This raw yarn was used as a knitted fabric, and after scouring and air-drying, it was dyed by the above method, and the dye exhaustion rate thereof was measured. The dyeability was as expected (shown in Performance Table-1).
Also, the same scouring and air-dried knitted fabric was used, and after alkali treatment by the above method, the alkali weight loss rate was measured.

As a result, almost the expected effect was obtained (shown in Performance Table-1).

Comparative Examples 1-2 Dimethyl 5-sodium sulfoisophthalate and 1-2
Of the three components of bis (4-carbophenooxy) ethane and polyethylene glycol, one or two components were copolymerized, and the performance of the fiber produced by the same method as in Example 1 is shown.
Shown in 1.

Claims (2)

[Claims] 1. A copolymerization ratio of the metal sulfonate group-containing ester forming component (A), polyethylene glycol (B) and 1,2-bis (4-carbophenooxy) ethane (C) is as follows: ), (2) and (3) are satisfied, and a modified polyester fiber having an ethylene terephthalate unit as a main component and easily dyed with a basic dye under normal pressure. (1) Formula 0.8 ≦ (A) ≦ 3.5 mol% (2) Formula 1.0 ≦ (B) ≦ 10.0 wt% (3) Formula 2.0 ≦ (C) ≦ 20.0 mol% 2. A copolymerization ratio of a metal sulfonate group-containing ester forming component (A), polyethylene glycol (B) and 1,2-bis (4-carbophenooxy) ethane (C) is as follows: ), (2) and (3), a polyester having ethylene terephthalate units as a main component is spun at a winding speed of 5000 m / min or more. (1) Formula 0.8 ≦ (A) ≦ 3.5 mol% (2) Formula 1.0 ≦ (B) ≦ 10.0 wt% (3) Formula 2.0 ≦ (C) ≦ 20.0 mol%