JP2809706B2 - Antistatic polyester fiber and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an antistatic polyester fiber and a method for producing the same, and more particularly, to a soft and fibril-resistant soft fiber having a hollow portion communicating along the longitudinal direction of the fiber. The present invention relates to an antistatic polyester fiber having excellent properties and a method for producing the same.

(Prior Art) Polyesters have many excellent properties and are widely used, but on the other hand, have the drawback of easily generating static electricity.

In order to solve this drawback, Japanese Patent Application Laid-Open No. Sho 56-134211 has a hollow portion communicating along the longitudinal direction of a single fiber,
Antistatic polyester fibers containing at most 3% by weight of a polyoxyalkylene glycol and an ionic antistatic agent have been proposed. Furthermore, Japanese Patent Application Laid-Open No. 61-296117 discloses that the slit of the spinning nozzle is specified to improve antistatic and fibril resistance.

However, the antistatic hollow fibers produced by these methods are still not soft enough for recent uses such as lingerie, lining, and dust-free garments, and at the same time, the presence of the hollow portions does not sufficiently suppress the generation of fibrils. Absent.

On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 61-55215 discloses that an undrawn yarn obtained by ultra-high-speed spinning at 5500 m / min or more has an extremely high fibril resistance, but in this range, the Young's modulus is 90%.
0kg / mm is ² or more, this soft feeling needed, such as in lingerie is not far from achieved.

Given that the main applications of antistatic polyesters today are being converted to innerwear such as lingerie, the addition of a soft feel is a very large factor.

(Object of the Invention) It is an object of the present invention to provide a polyester fiber having an unprecedented soft feel, and also having excellent antistatic properties and fibril resistance, and a method for producing the same.

(Constitution) The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, the polyester containing the antistatic agent has a specific structure, so that soft feeling, antistatic properties, and fibril resistance are obtained. They have found that they are satisfactory and have reached the present invention.

That is, the first invention of the present invention is a polyester fiber having a hollow portion communicating along the longitudinal direction of the fiber, the fiber comprising: (a) a polyoxyalkylene glycol having substantially no reactivity with the polyester; (B) An antistatic polyester excellent in softness and excellent in fibril resistance, which contains at most 3% by weight of an ionic antistatic agent with respect to the fiber weight and simultaneously satisfies the following (i) to (v): fiber.

(I) Crystal size of (100) plane (X): 40Å ≦ X ≦ 70
Å (ii) Amorphous orientation (度 na): 0.03 ≦ △ na ≦ 0.09 (iii) Young's modulus (Y): 740 ≦ Y ≦ 850 kg / mm ² (iv) Birefringence (△ n): △ n > 0.05 (v) Thermal stress peak temperature (S _T ): S _T > 90 ° C. Further, the second invention is that the polyester is melt-spun and cooled, and then 3,000 m / min or more and 5500 m / min.
A method for producing a soft and excellent fibril-resistant antistatic polyester fiber, characterized in that the fiber is drawn at a speed of not more than one minute and then drawn without being once wound up under conditions that simultaneously satisfy the following (a) and (b): It is.

(A) y ≧ 0.7x + 1950 (b) 5y ≦ 3x + 16000 Examples of the basic polyester constituting the fiber of the present invention include polyalkylene terephthalate and polyalkylene naphthalate. Among them, the former, in which terephthalic acid is a main acid component and an alkylene glycol component having 2 to 6 carbon atoms, that is, A polyester containing at least one glycol selected from ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, and hexamethylene glycol as a main glycol component. Such a polyester may be produced by any method.For example, in the case of polyethylene terephthalate, a direct esterification reaction of terephthalic acid and ethylene glycol or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is carried out. Either transesterifying ethylene glycol or reacting terephthalic acid with ethylene oxide to produce a glycol ester of terephthalic acid and / or a low polymer thereof, and then heating the product under reduced pressure It is easily produced by a polycondensation reaction until the desired degree of polymerization is reached.

In this polyester, a part of the terephthalic acid component may be replaced by another difunctional carboxylic acid component.
Such carboxylic acids include, for example, isophthalic acid,
Bifunctional aromatic carboxylic acids such as phthalic acid, dibromoterephthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-oxyethoxybenzoic acid, P-oxybenzoic acid, sebacic acid,
Bifunctional aliphatic carboxylic acids such as adipic acid and oxalic acid;
Examples include bifunctional alicyclic carboxylic acids such as 4-cyclohexanedicarboxylic acid. Further, a part of the glycol component may be replaced with another glycol component. Examples of such a glycol component include cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, bisphenol S, 2,2 Aliphatic, alicyclic and aromatic diol compounds such as -bis [3,5-dibromo-4- (2-hydroxyethoxy) phenyl] propane. Further, the above polyester may be blended and melted with a small amount of another polymer as necessary.

The fiber of the present invention can be obtained from a polyester prepared by adding a polyoxyalkylene glycol and an ionic antistatic agent to the polyester described above.

As the polyoxyalkylene glycol, specifically, for example, polyoxyethylene glycol having an average molecular weight of 6,000 or more, preferably 10,000 or more, or mainly oxyethylene units (usually 50% or more), which contains, for example, oxypropylene units Those are preferably used.

Also, the terminal of the polyoxyalkylene glycol may be a hydroxyl group, may be blocked with a non-ester-forming organic group, or may be bonded to another ester-forming organic group by an ether bond, an ester bond, a carbonate bond, or the like. You may. When the terminal is blocked with a non-ester-forming organic group, the average molecular weight of the polyoxyalkylene glycol may be as low as about 800 to 4,000.

The content of the polyoxyalkylene glycol in the polyester is 2% by weight or less, preferably 1% by weight.
It is as follows.

On the other hand, as the ionic antistatic agent used in combination with the above polyoxyalkylene glycol, an anionic antistatic agent, a cationic antistatic agent or a mixture thereof, for example, polyethylene glycol, polybutylene glycol, polyalkyl (or aryl) or alkyl aryl) sulfonic acid metal salts, polyalkyl (or aryl or alkylaryl) amines, polyalkylene oxide addition alkyl (or aryl or alkylaryl) an amine, and the like, anion having inter alia -SO ₃ M General formula among the conductive antistatic agents
A metal salt of an arylalkyl or aralkylsulfonic acid represented by RSO ₃ M is preferably used. Here, M represents an alkali metal and is usually sodium, potassium or lithium, with sodium being particularly preferred. R represents an alkyl group having 8 or more carbon atoms. When the number of carbon atoms in the alkyl group is 7 or less, the compatibility with the polyester is slightly deteriorated. Therefore, usually, those in which R is an alkyl group having 20 to 20 carbon atoms are used, and they are often used as a mixture thereof.

The content of such an alkylsulfonic acid metal salt in the polyester is 1.0% by weight or less based on the weight of the fiber, preferably
0.5% by weight or less.

From the above, the content of the polyoxyalkylene glycol and the ionic antistatic agent, considering the fiber properties,
3% by weight or less, preferably 1.5% by weight or less, based on fiber weight,
It is particularly preferable to add and disperse it in an amount of 1.2% by weight or less. Further, as the lower limit content of polyoxyalkylene glycol and ionic antistatic agent
It is about 0.2% by weight. If the content is less than this, the intended antistatic effect cannot be expected.

In blending the polyoxyalkylene glycol and the ionic antistatic agent into the polyester, any method is adopted, and both can be blended into the polyester simultaneously or in an arbitrary order. That is, at any stage until the spinning of the polyester is completed, for example, before the start of the polycondensation reaction of the polyester, during the polycondensation reaction, at the end of the polycondensation reaction, at the time when the polymer is still in a molten state, in a powder state, In the spinning step or the like, both may be melt-mixed beforehand and added at the same time, may be added in two or more portions, or both may be separately mixed in a polyester before being mixed before molding. Furthermore, when it is added before the middle stage of the polycondensation reaction, it may be added after being dissolved or dispersed in a solvent such as glycol.

The antistatic fiber of the present invention is made of the polyester thus obtained, and satisfies the following fiber properties (i) to (ii) at the same time.

(I) Crystal size of (100) plane X); 40Å ≦ X ≦ 70Å (ii) Degree of orientation in amorphous part (△ na); 0.03 ≦ △ na ≦ 0.09 Meaning of values of (i) and (ii) above The point is that the crystal size is large and the degree of orientation of the amorphous part is low as compared with ordinary polyester fibers for clothing. Therefore, the fiber having such properties has excellent abrasion resistance and greatly reduces fibrillation due to washing or the like.

Here, in the case of a fiber having a crystal size (X) of less than 40 ° or a degree of amorphous part orientation (△ na) of more than 0.09, the entangling property of the amorphous part molecules connecting the crystal and the crystal is reduced, and the wear resistance is reduced. ,
Fibrillation also tends to occur.

On the other hand, in the case of a fiber having a Δna of less than 0.03, the fiber is easily deformed in the weaving and knitting step, so that the quality of the finally obtained woven or knitted fabric is reduced.

Further, the hollow fiber of the present invention simultaneously satisfies the following fiber characteristics (iii) to (v) in addition to the above (i) to (ii), thereby obtaining a woven or knitted fabric having a uniform and soft feel. be able to.

(Iii) Young's modulus (Y): 740 ≦ Y ≦ 850 kg / mm ² (iv) Birefringence (Δn): Δn> 0.05 (v) Thermal stress peak temperature (S _T ): S _T > 90 ° C. in Young's modulus, it exceeds 850 kg / mm ^2, the decrease in softness, woven texture of knitted fabric impaired, △ when n is 0.05 or less, observed orientation uniformity of the fiber structure is decreased, further, if less than S _T is 90 ° C., feeling of woven or knitted fabric obtained becomes hard. That is, in the fiber which does not satisfy the above requirements (iii) to (v), the soft feeling is lowered, the texture of the woven or knitted fabric becomes hard, and the fiber is not suitable for lingerie and lining.

In such fiber properties, Δn is particularly preferably 0.06 to 0.1.
It is preferable 1, S _T is 92-120 ° C..

The antistatic polyester fiber of the present invention is prepared by melt-spinning and cooling polyester, taking it up at a speed of 3000 m / min to 5500 m / min, and satisfying the following magnifications (a) and (b) without being wound up once. And can be obtained by stretching.

(A) y ≧ 0.7x + 1950 (b) 5y ≦ 3x + 16000 where x: take-up speed = 3000-5500 m / min y: stretching speed (m / min) If the spinning speed is less than 3000 m / min, oriented crystallization does not proceed, It is difficult to adjust the crystal size to 40 mm or more, and if it exceeds 5500 m / min, the orientation is too advanced, and it is difficult to suppress the Young's modulus to 800 kg / mm ² or less.

The spinning speed x and the drawing speed y are shown in FIG.
It is necessary that the range is surrounded by four straight lines of 3000, y = 5500, y ≧ 0.7x + 1950, 5y = 3x + 16000. y <0.7x + 19
In the case of 50, since almost no stretching is performed, Δna is less than 0.03, and it is difficult to perform weaving alone.

On the other hand, when 5y> 3x + 16000, the draw ratio is high and Δn
a exceeds 0.09, the fibril resistance is reduced, the Young's modulus is 800 kg / mm ² or more, and the feeling is impaired.

(Effects of the Invention) The antistatic polyester fiber of the present invention has a structure excellent in abrasion resistance in addition to good antistatic properties, so that it has good fibril resistance, and is soft and elegant. Present a match. Therefore, the conventional antistatic polyester fiber can be applied to fields such as lingerie where the hand was hard and could not be developed, and its significance is significant.

(Example) Hereinafter, an example will be described.

The measured values in the examples are measured by the following method.

(1) Charge friction pressure (i) Device and material Rotary drum type friction charge measurement device (Rotary static tester) Oscilloscope Friction cloth Cotton broad 30 /-scouring bleach-free glue finish (ii) Preparation of test piece Roll-in type: 3.8cm × 3.0cm Gold type: 4.0cm × 8.0cm Take 3 pieces each vertically. Furthermore, three cotton broads (30 /-) of friction cloth are sampled at a length of 2.5 cm x 14.0 cm and vertically long.

(Iii) Test operation Humidity control: Leave in a desiccator at 65 ± 2% RH for a day or more.

Measurement room atmosphere: 20 ± 2 ° C, 65 ± 2% RH Sample: Number of stacks: 1 Drum rotation speed: 700 rpm Equilibrium charge time: 1 minute Contact pressure load: 600 g Rotate one test piece face up Attach it to the static rotating drum, and attach one piece of friction cloth to the clips at the lower ends in parallel at the position where it comes into contact with the test piece.
Apply a load of 0 g. Recorder (5cm / min)-rotating drum-
Operate in the order of an oscilloscope, and when the charging equilibrium is reached, the friction band voltage (V) and the extreme values (+,-) are read and expressed as an average value of three sheets. (Up to the 10th integer place) In addition, regarding the relationship between the antistatic effect and the triboelectric voltage, if the latter is about 2000 V (preferably 1000 V) or less, the antistatic effect is exhibited.

(2) Mechanical damage of fibers (fibrils) Using a tetron georgette crepe fabric (white) instead of white cotton cloth set on a test piece stand by stacking two specimens with a JISL0823 friction tester type II, load 500 g The fibril condition after 500 reciprocations is visually rated as fifteenth grade, where no fibrils are generated, and ranked as fourth, third, second, or first grade as the number of fibrils increases. As a result, the practicable range was set to class 3 or higher.

(3) Hand The test piece was touched by hand and evaluated by a five-point scale (5i good to 1i bad) by a sensory test.

(4) Quality Investigate the glossy spots on the fabric in the longitudinal direction,
X, those without gloss spots were evaluated as ○.

(5) Amorphous part orientation degree (△ na) The amorphous part orientation degree (△ na) was obtained from the following equation.

Δna = (Δn−fc · Δnc ⁰ × Xv) / (1−Xv) where Δn; birefringence Xv; crystallinity (density method) fc; crystal part orientation degree (X-ray refraction method) Δnc ⁰ ; intrinsic limit value 0.212 (polyester) (6) Crystal size (X) In the intensity distribution curve measured by the X-ray wide-angle diffraction method, the half-value width of (010) (100) is obtained, and the Scherrer equation is calculated. Was used to calculate the crystal size.

Examples and Comparative Examples Intrinsic viscosity measured in orthochlorophenol at 25 ° C.
98.8% by weight of polyethylene terephthalate of 65, 0.8% by weight of polyoxyethylene glycol having an average molecular weight of 20,000,
Sodium alkyl sulfonate having an average carbon number of 12 to 13 0.4
The polyester consisting of 100% by weight was directly spun and stretched under the conditions shown in Table 1 to obtain a multifilament 50 de / 24 fil having a hollow section and a triangular cross section.

In each of the following filaments, the hollow portion was located substantially at the center of the cross section, and the ratio of the hollow portion to the entire cross-sectional area including the hollow portion was approximately 5%, which was common to all the samples.

After twisting the obtained polyester yarn at 300 T / M, the warp density is set to 350 yarns / in using a sizing dobby loom.
After weaving at 350 rpm, setting is performed at 180 ° C for 1 minute to obtain a greige fabric, which is reduced by about 15% in a 3% aqueous solution of caustic soda (boiling water). Dianix Black-HG-FS) 10% OWF and nonionic dispersant (Meisei Chemical Disper VG) 0.5g / at a bath ratio of 1:50
After dyeing at 130 ° C. for 1 hour, treatment with a neutralizing agent (Bisnhol P-70), washing, air drying, and drying with hot air at 80 ° C. for about 1 hour. Laundry was carried out in an automatic reversing type washing machine, 40 g of commercial synthetic detergent Zab was placed in warm water 20 at 40 ° C., washed for 20 minutes, rinsed with running water for 20 minutes, and evaluated for antistatic properties, fibril resistance, feeling, and quality. The results are shown in Table 1 together with the physical properties of the yarn.

Experimental Example 1 is an example in which the spinning speed is low, orientation crystallization does not occur, the fibril resistance is low, and the Young's modulus is low.

 Experimental examples 2, 7, 9, 12, 13, and 14 are examples of the present invention.

Experimental Examples 4, 5, and 10 are examples in which the draw ratio is high, the orientation of the amorphous portion is advanced, Δna is increased, the Young's modulus is increased, the feel is hard, and a soft feeling cannot be obtained.

Experimental examples 6, 8, and 11 are examples in which the draw ratio is low with respect to the spinning speed, the Young's modulus is small, and the quality is inferior.

Experimental Example 3 is an example in which the spinning speed is high, the Young's modulus is high, and a soft feeling cannot be obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between spinning take-off speed and drawing speed employed in the method of the present invention.

────────────────────────────────────────────────── (5) Int.Cl. ⁶ identification symbol FI D01F 6/92 301 D01F 6/92 301Q (56) Reference JP-A-57-82523 (JP, A) JP-A-61-52515 (JP, A) JP-A-61-55213 (JP, A)

Claims (2)

(57) [Claims] 1. A polyester fiber having a hollow portion communicating along the longitudinal direction of the fiber, the fiber comprising: (a) a polyoxyalkylene glycol having substantially no reactivity with the polyester; A soft antistatic fibril-resistant polyester fiber characterized by containing at most 3% by weight of a conductive antistatic agent with respect to the fiber weight and simultaneously satisfying the following (i) to (v): (I) Crystal size of (100) plane (X): 40Å ≦ X ≦ 70Å (ii) Amorphous part orientation degree (△ na): 0.03 ≦ △ na ≦ 0.09 (iii) Young's modulus (Y): 740 ≦ Y ≦ 850 kg / mm ² (iv) Birefringence (Δn): Δn> 0.05 (v) Thermal stress peak temperature (S _T ): S _T > 90 ° C. 2. The polyester is melt-spun and cooled, and then cooled to 3000 m / m.
Soft, anti-fibril-resistant antistatic polyester characterized in that it is taken up at a speed of at least 5500 m / min and then stretched under conditions that simultaneously satisfy the following (a) and (b) without being once wound up: Fiber manufacturing method. (A) y ≧ 0.7x + 1950 (b) 5y ≦ 3x + 16000