JPH06313273A - Antistatic polyester fabric - Google Patents

Abstract

PURPOSE:To produce the subject easily processable fabric bearing excellent antistaticity, low in the deterioration of physical properties, consisting of such smoothly producible polyester fibers as not to need any complicated spinning technology even in high-speed spinning process. CONSTITUTION:At least a part of this fabric is composed of polyester fibers consisting of 100 pts.wt. of acid component of the polyester and (a) polyethylene glycol 4000-50000 in weight-average molecular weight, (b) an alkali metal salt of alkylsulfonic acid and (c) an alkali metal salt of alkylbenzenesulfonic acid. The components (a), (b) and (c) satisfy the following relationships: 0.5 pts.wt. <=(a) <= 5 pts.wt.; 1.5 pts.wt. <= (b)+(c) <= 5 pts.wt.; and 0.05 pts.wt. <= (b) <=1.0 pts.wt. Besides, the surface of the polyester fibers is covered with a copolymer from terephthalic acid and/or isophtalic acid and polyalkylene glycol and/or alkylene glycol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic polyester cloth, and more particularly to an antistatic polyester cloth having excellent anti-static properties with excellent washing durability.

[0002]

2. Description of the Related Art Polyester fiber cloths, especially polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, and polyester fiber cloths mainly containing these are superior to natural fibers in terms of mechanical strength, durability and functionality. However, since it has a high volume electric resistance and a high surface resistance and is likely to generate static electricity, it has a drawback that various troubles are likely to occur during manufacturing, processing and use. Conventionally, various methods have been proposed for solving such drawbacks. For example, the simplest method is a method of applying an antistatic agent to the fiber surface, but in this case, the antistatic agent is likely to disappear due to the dyeing process or washing, and a permanent antistatic effect cannot be expected. is there.

Permanence of antistatic effect in antistatic fiber cloth is a basic required property, and in order to obtain this property, a method of kneading an antistatic agent into a polymer to modify the polyester itself, for example, Japanese Patent Publication No. 39-5214 discloses a method of incorporating polyoxyalkylene glycol into fibers. However, in order to exert sufficient antistatic property by this method, a large amount of polyoxyalkylene glycol as much as 10% by weight is required, so that the mechanical properties and light resistance of the resulting antistatic polyester fiber are greatly reduced, Can not stand.

Japanese Patent Publication No. 47-11280 discloses that
A method in which polyoxyalkylene glycol and sodium alkylbenzene sulfonate are used in combination and mixed therein, JP-A-53-
Japanese Patent No. 149246 proposes a method in which polyoxyalkylene glycol and sodium alkyl sulfonate are used together and mixed. According to these methods, the amount of polyoxyalkylene glycol used can be reduced, so that an antistatic polyester fiber with less deterioration in physical properties can be obtained. However, although the former method does not increase the pack pressure during spinning and improves the spinnability, it has a problem of poor antistatic durability after dyeing in the processing step and after washing after becoming a product. . In the latter method, the antistatic performance has good durability, but the fibers are markedly colored and the pot pressure rises quickly, so the spinneret replacement cycle is shortened and productivity is reduced, resulting in poor spinnability. It has the disadvantage of being inferior.

As described above, a large number of methods such as a coating method, a kneading method and a composite spinning method have been proposed as an antistatic method. However, a practical level of antistatic effect and its durability, mechanical characteristics, At present, it is not possible to obtain what satisfies the light resistance and the manufacturing cost at the same time. Furthermore, in a high-speed spinning method that does not require a stretching step, it is common to carry out stricter polymer filtration than a normal spinning method,
A fabric using an antistatic polyester fiber that satisfies the pressure increase and the spinnability in the spinning process has not been obtained yet.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art, to have excellent antistatic property, to reduce the deterioration of physical properties, and to perform a complicated spinning technique even when spinning by a high speed spinning method. An object of the present invention is to provide an antistatic polyester fiber cloth which is made of fibers having good spinnability and which is easy to process under conditions without using.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result, have a flexible and good antistatic effect without impairing the excellent properties peculiar to polyester fibers, It has been found that a more excellent antistatic property can be exhibited by applying a specific resin processing agent to the surface of a fabric having at least a part of polyester fibers of a specific composition that enables stable production in a stable manner. It has arrived.

That is, the antistatic polyester cloth according to the present invention has (a) a weight average molecular weight of 4,000 to 50,000 per 100 parts by weight of the acid component constituting the polyester.
Polyethylene glycol, (b) an alkali metal salt of an alkyl sulfonic acid and (c) an alkali metal salt of an alkylbenzene sulfonic acid of the formulas (I) to (III) (units are parts by weight) 0.5 ≦ (a) ≦ 5 ( I) A fabric having polyester fibers at least partly blended so as to satisfy 1.5 ≦ (b) + (c) ≦ 5 (II) 0.05 ≦ (b) ≦ 1.0 (III) The polyester fiber surface is coated with a copolymer of terephthalic acid and / or isophthalic acid and polyalkylene glycol and / or alkylene glycol.

The polyester fiber used in the present invention is
Polyester, (a) Weight average molecular weight 4,000-5
It is obtained by blending 10,000 polyethylene glycol, (b) an alkali metal salt of an alkyl sulfonic acid and (c) an alkali metal salt of an alkylbenzene sulfonic acid at a specific blending ratio, and spinning the mixture by a known method.
The polyester used as the base of the polyester fiber used in the present invention is preferably a polyester having an ethylene terephthalate unit as a main repeating unit, which is obtained by a polycondensation reaction of terephthalic acid and ethylene glycol, but is not limited thereto. For example, as the dicarboxylic acid component other than the terephthalic acid component, for example, an acid component such as isophthalic acid, adipic acid, sebacic acid, or naphthalenedicarboxylic acid may be used, and as the glycol component other than the ethylene glycol component, 1,4- Butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and the like may be used.

There is no particular limitation on the method of blending the above-mentioned components (a), (b) and (c) with the polyester, and at any stage until the formation of the polyester is completed, for example, before starting the polycondensation reaction of the polyester, During the polycondensation reaction, may be blended at the end of the polycondensation reaction, etc., or after producing a normal polyester resin, the resin pellets and components (a), (b),
(c) may be mixed in an extruder. Ingredients (a), (b), (c)
May be blended simultaneously or separately. Among these methods, it is preferable from the viewpoint of dispersibility that these additives are blended at the same time before the start of the polycondensation reaction of the polyester or during the polycondensation reaction.

The polyethylene glycol as the component (a) has a weight average molecular weight of 4,000 to 50,000, particularly 10,
The range of 000 to 30,000 is preferable. When the weight average molecular weight is less than 4,000, the frictional electrification voltage of the obtained fiber is 2
Since it is 000 V or more, it is inferior in antistatic property, and the durability by washing treatment is not sufficient. When the weight average molecular weight exceeds 50,000, the fibers are colored, the number of yarn breaks during spinning is increased, and the spinnability is deteriorated. The blending amount of polyethylene glycol is 0.
A range of 5 to 5 parts by weight, particularly a range of 2.0 to 4 parts by weight is preferable. If the content of polyethylene glycol is less than 0.5 part by weight, a sufficient antistatic effect cannot be obtained, and if it exceeds 5 parts by weight, the light resistance and mechanical properties of the fiber are deteriorated and the coloration of the fiber becomes remarkable.

The alkali metal salt of an alkyl sulfonic acid as the component (b) has a general formula R-SO ₃ M (wherein R is a carbon number of 8 to 10).
20 is an alkyl group, and M is a compound represented by Li, Na or K), specifically, sodium octyl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate, sodium stearyl sulfonate. Etc. The alkali metal salt of alkylbenzene sulfonic acid of the component (c) has the general formula

[Chemical 1] (In the formula, R'is an alkyl group having 8 to 20 carbon atoms, M'is L
i represents a metal atom of Na or K), and specific examples thereof include sodium octylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, and the like.

The blending amount of the component (b) is preferably 0.05 to 1.0 part by weight, particularly 0.3 to 0.7 part by weight, relative to 100 parts by weight of the acid component constituting the polyester. component
If the blending amount of (b) is less than 0.05 parts by weight, sufficient antistatic effect cannot be obtained even if the blending amount of the component (c) is adjusted, and if it exceeds 1.0 parts by weight, the coloring of the fiber is remarkable. However, the pot pressure rises remarkably and the yarn formability deteriorates. Also, the component (b) and the component
The total compounding amount of (c) is 1.5 to 5 parts by weight, especially 2.0 to
A range of 3.0 parts by weight is preferred. If the total amount of the components (b) and (c) is less than 1.5 parts by weight, a sufficient antistatic effect cannot be obtained, and if it exceeds 5.0 parts by weight, the fibers are markedly colored and the spinnability is deteriorated. To do.

A specific amount of the above component (a) in the polyester,
By blending (b) and (c), polyester fibers having excellent spinnability and antistatic properties can be obtained. Although the reason for this is not clear, the presence of the alkali metal salt of alkylbenzene sulfonic acid (b) makes it easier to emulsify and disperse the alkali metal salt of alkyl sulfonic acid (c).
As a result, the compatibility with polyethylene terephthalate (a) is enhanced, and it is considered that problems in the spinning process such as an increase in pack pressure and a decrease in spinnability can be avoided.

The polyester fiber is composed of components (a), (b),
The polyester obtained by blending (c) can be obtained by spinning using a known melt spinning method. In particular, the high-speed spinning method, which does not require a drawing step, improves productivity, reduces cost by omitting a drawing step, improves dyeability, and allows easy knitting and weaving with other types of fibers, thus expanding the range of applications. Is preferred. The winding speed is preferably 5200 m / min or more in order to obtain a highly oriented yarn having sufficient practical characteristics only by the melt spinning process without passing through the drawing process. 5200m /
At a winding speed of not more than a minute, elongation is likely to occur in the weaving / knitting process, and stains and deterioration of fabric quality are likely to occur.
The yarn obtained by the high-speed spinning method has a softer texture than the yarn obtained by the drawing method, and thus is particularly useful for inner fields such as foundations and lingerie.

The polyester fiber obtained by the high speed spinning method has a mechanical loss tangent (ta) at a measurement frequency of 110 Hz.
It is preferable that the temperature (Tmax) at which n δ) shows the maximum and the maximum value [(tan δ) max] of (tan δ) exist in a range satisfying the following formulas (IV) and (V). 0.12 ≤ (tan δ) max ≤ 0.20 (IV) 90 ° C ≤ (Tmax) ≤ 120 ° C (V) (tan δ) max is greater than 0.20 and [(ta
If n δ) max] is lower than 90 ° C, the antistatic performance at the yarn stage will be good, but the antistatic agent will fall off due to repeated high-temperature dyeing in the processing step and repeated washing after the product is finished. The anti-static performance may be easily deteriorated, and the frictional charging voltage of 2000 V may be greatly exceeded. When (tan δ) max is less than 0.12 and (Tmax) is greater than 120 ° C, the antistatic performance level of the yarn is 2000 in terms of friction electrification voltage.
It tends to be lower than V and lower.

Antioxidants such as hindered phenol compounds and phosphite compounds may be added to the polyester fibers, and other additives such as colorants and matting agents may be added as required. Good. The cloth used in the present invention is
It can be obtained by weaving by a known method using the above-mentioned specific polyester fibers in whole or in part. When a part of the above-mentioned specific polyester fiber is used, other materials, for example, ordinary polyester fibers are used as long as the antistatic property is not lost, but the types of other materials and the mixing method are not particularly limited.

The antistatic polyester cloth according to the present invention is
A copolymer of terephthalic acid and / or isophthalic acid (d) and polyalkylene glycol and / or alkylene glycol (e) is attached to the surface of a fabric woven or knitted using at least a part of the above-mentioned specific polyester fiber. It is obtained by processing and forming a resin film. The amount of the copolymer deposited is usually 0.05 to 5.0% by weight, preferably 0.1 to 3.0% by weight.

The alkylene glycol has 2 to 10 carbon atoms such as ethylene glycol and propylene glycol.
Those of are preferably used. Other functional groups such as sulfonic acid groups may be present on isophthalic acid. Above (d)
The mixing ratio of (e) and (e) is not particularly limited. The average molecular weight of the copolymer is preferably 1,000 to 20,000, more preferably 5,000 to 15,000. When the average molecular weight is less than 1,000, the durability of the resin coating is poor, and when it exceeds 20,000, the dispersion stability in an aqueous solution is poor.

Examples of the method for adhering the copolymer to the fiber surface include a dipping method and a pad method, and any of these methods may be used or used in combination. In the adhesion processing, the copolymer is often handled as a resin processing agent dispersed in water. The dipping method is a method in which a cloth and a resin-treating agent are put into a bath and the mixture is kneaded under heat of 80 to 130 ° C., and can be performed at the same time as dyeing. The pad method is to dry the cloth after padding an aqueous solution of the resin processing agent on the cloth.
This is a method of curing under dry heat of 150 to 200 ° C., and it is possible to put together with various other finishing agents for fibers such as softening agents and antifouling agents.

By depositing the copolymer on the surface of the above-mentioned specific polyester cloth and coating the polyester fiber with the copolymer, an excellent antistatic property with washing durability can be obtained. The reason for this is not clear, but since the constituents of the copolymer are similar to the constituents of the fiber, the copolymer is easy to fit on the fiber surface and adheres evenly to coat the polyester fiber. The bleed-out of the alkali metal salt of alkyl sulfonic acid (b) and the alkali metal salt of alkylbenzene sulfonic acid (c) inside the fiber to the fiber surface was suppressed appropriately, and the polyalkylene glycol and alkylene glycol in the copolymer were further suppressed. It is presumed that, in combination with the antistatic function due to, the antistatic property with excellent washing durability is exhibited.

Further, by adhering the copolymer on the surface of the cloth, the flexibility of the cloth is improved, and the water absorption and antifouling properties are also improved. The fabric of the present invention is
Taking advantage of its excellent antistatic properties, low-temperature dyeability, soft texture, water absorption, antifouling properties, etc., it can be used in various fields such as foundation fields, lingerie and other inner fields, and other types of fibers in outer fields. Deployment is possible.

[0023]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. The measured values in the examples are those measured by the following method. (1) Reduced viscosity of polymer: Measured at 35 ° C. using o-chlorophenol as a solvent. (2) Friction electrification voltage: Using a rotary drum type friction electrification voltage measuring device (Kyoto Kaken type rotary static tester), a cotton cloth was used as the friction cloth, and the measurement was performed in an atmosphere of 20 ° C. and 40% RH. 2000V or less (preferably 1000V
Below), it can be said that the antistatic property is good. (3) Mechanical loss tangent (tan δ): Ryovibron (RheoViblon) DDVII-EA type dynamic viscoelasticity measuring device manufactured by Toyo Baldwin Co., Ltd., using a sample about 0.25 g, measuring frequency 110 Hz, heating rate 5 ° C. / Measure tan δ at each temperature in dry air in minutes. tan δ-Temperature curve to tan
δ Peak temperature (Tmax) (° C) and peak height [(tan
δ) max] is obtained. (4) Laundry treatment: Washing was performed at 40 ° C. for 5 minutes using 2 g / l of detergent New Beads (registered trademark, manufactured by Kao Corporation),
Rinse twice for 2 minutes at room temperature. This was repeated 30 times as one cycle.

Examples 1 to 4 and Comparative Examples 1 to 6 (1) Synthesis of Polyester 700 kg of dimethyl terephthalate and 470 kg of ethylene glycol were used as a catalyst with 0.7 kg of calcium acetate as a catalyst while stirring from 140 ° C. to 230 ° C. in a nitrogen stream, The temperature was raised over 2 hours and 30 minutes to complete the transesterification reaction. Next, 0.53 kg of trimethyl phosphate, 1.8 kg of ethylene glycol slurry containing 20% by weight of titanium dioxide and 0.35 kg of antimony (II) trioxide were added to this reaction product, and (a) polyethylene of the compounding amount shown in Table 1 was used. After adding glycol, (b) sodium tetradecyl sulfonate and (c) sodium dodecyl benzene sulfonate respectively, the temperature was raised from 240 ° C to 260 ° C over 1 hour, and then 260 ° C to 280 ° C over 1 hour. The temperature was reduced to 1 mmHg or less while raising the temperature. In this state, polycondensation reaction is performed for 2 hours to obtain a reduced viscosity of 0.7.
Two polymers I and II were obtained. For comparison, a polycondensation reaction was carried out in the same manner except that the components (a), (b), and (c) were not added, to obtain a polymer III composed only of ordinary polyethylene phthalate.

[0025]

[Table 1]

(2) Production of polyester fiber Polymers I, II, and III obtained in (1) were dried by a conventional method, and 20 μm was obtained using a direct winding high-speed spinning device.
Spinning temperature is 290 ° C while passing through a m filter.
With a slit width of 0.11 mm, a slit length of 0.34 mm, and a hole of 12 holes, the spinneret was spun out from a triaxial isometric spinneret, and after cooling and solidification, a finishing agent was applied and at each winding speed shown in Table 2. After winding, 30d / 12f raw yarns I, II and III were obtained.
Table 2 shows the spinning conditions and the physical properties of the obtained fiber.

[0027]

[Table 2]

(3) Manufacture of polyester cloth Using the yarns I, II and III for the front back respectively, 3
A 6-gauge half tricot ground was knitted. After scouring this greige machine and pull-setting at 180 ° C., dyeing and reduction washing were performed under the following conditions to produce polyester cloth I, II,
I got III. [Dyeing] Dye: Sumikaron Black S-BGL (1
5% owf) Acetic acid: 0.2 ml / l Dispersing and leveling agent: Nikkasan Salt RM-340 (1 g / l)
l) Treatment conditions with jet dyeing machine: 100 ° C., 60 minutes [reduction washing] hydrosulfite: 2 g / l sodium carbonate: 2 g / l Surfactant: Sanmor RC-700 (2 g / l) jet dyeing Machine treatment conditions: 80 ° C, 20 minutes

(4) Antistatic treatment of polyester cloth A copolymer obtained by blending terephthalic acid, polyethylene glycol (average molecular weight about 4000) and polypropylene glycol (average molecular weight about 4000) at a molar ratio of 10: 8: 2. A polymer (average molecular weight of about 10,000) was dispersed in water to prepare a processing agent A (copolymer concentration 5% by weight). For comparison, a processing agent B was prepared by dispersing an esterification product (average molecular weight of about 9000) of polyethylene glycol of polyacrylic acid (average molecular weight of about 4000) in water.
(Polymer concentration 5% by weight) was adjusted. The polyester cloths I, II, and III obtained in (3) and the processing agents A and B were subjected to adhesion processing by the combinations and processing methods shown in Table 3, and the friction electrification voltage of the obtained cloth was measured. The results are shown in Table 3. The adhesion processing was performed by the dipping method and pad method shown below. (A) Immersion method: Processing agent A was added to the dyeing bath in an amount of 10% owf. After dyeing, a final set was performed at 160 ° C. (B) Pad method: The cloth was padded in an aqueous solution containing 20% by weight of the processing agent A and squeezed with a mangle so that the pick-up rate of the aqueous solution was 50%. Then, it is dried at 100 ℃, 16
The final set was performed at 0 ° C.

[0030]

[Table 3]

From Table 3, it can be seen that Examples 1 to 4 show excellent washing durability and excellent antistatic performance.
On the other hand, in Comparative Examples 1 and 2 in which no resin-treating agent was attached at the time of dyeing, the wear electrification voltage exceeded 1000 V and decreased to 2000 V or more due to repeated washing. Further, in Comparative Examples 3 and 4 processed with the conventional antistatic agent B and Comparative Examples 5 and 6 in which the fabric using the ordinary yarn III composed only of polyethylene terephthalate was treated with the agent A, antistatic by repeated washing was performed. There is a large decrease in performance.

Example 5 and Comparative Example 7 Using Polymer I according to the spinning conditions of Yarn 1, 50 d /
24f of raw yarn IV was obtained. On the other hand, using the polymer III, a yarn V of 75d / 36f was obtained according to the spinning conditions of the yarn III. A taffeta woven fabric was prepared by using the raw yarn IV as the warp and the raw yarn V as the weft (weaving density: warp 100 / inch, weft 82 /
inch). This greige machine was scoured by a conventional method, preset at 180 ° C., and then dyed and reduced and washed under the same conditions as in Example 1. Terephthalic acid, sodium 5-sulfoisophthalate, polyethylene glycol (average molecular weight about 3000) and ethylene glycol in a molar ratio of 10:
The copolymer (average molecular weight of about 8000) obtained by using in a ratio of 1: 1: 10 was dispersed in water to prepare a processing agent C (copolymer concentration 5% by weight). Using this processing agent C, adhesion processing was performed by the pad method as in Example 1. For comparison, the final set was performed at 160 ° C. without padding with the processing agent C. The frictional electrification voltage of the obtained cloth was measured, and the results are shown in Table 4.

[0033]

[Table 4] From Table 4, it can be seen that Example 5 shows excellent antistatic performance with excellent washing durability, but Comparative Example 7 is inferior in washing durability.

[0034]

The antistatic polyester cloth of the present invention impairs the original excellent properties of the polyester fiber because the surface of the cloth having the specific polyester fiber in at least part thereof is coated with the specific resin processing agent. In addition, it has excellent anti-static performance with excellent washing durability and a soft texture, and is also excellent in water absorption and stain resistance.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location D03D 15/00 A 7199-3B // (C08L 67/02 71:02) 9167-4J

Claims (1)

[Claims] 1. A weight average molecular weight of 4,000 to 50,0 based on 100 parts by weight of the acid component constituting the polyester.
No. 00 polyethylene glycol, (b) an alkali metal salt of an alkyl sulfonic acid and (c) an alkali metal salt of an alkyl benzene sulfonic acid are represented by the formulas (I) to (III) (unit: parts by weight): 0.5 ≦ (a) ≦ 5 (I) At least part of the polyester fiber is blended so as to satisfy 1.5 ≦ (b) + (c) ≦ 5 (II) 0.05 ≦ (b) ≦ 1.0 (III) An antistatic polyester cloth, wherein the surface of the polyester fiber is coated with a copolymer of terephthalic acid and / or isophthalic acid and polyalkylene glycol and / or alkylene glycol.