JPS6364532B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing antistatic fibers, and more specifically to a novel method for producing fibers with excellent antistatic properties from a fiber-forming thermoplastic polymer containing polyoxyalkylene glycol or its derivatives. This relates to a manufacturing method. Synthetic fibers made from fiber-forming thermoplastic polymers, such as polyester, have excellent mechanical strength and durability, but on the other hand, these synthetic fibers have extremely high electrical resistance and are charged with static electricity. It has the fatal drawback of being easy to use. Many various methods have been proposed to prevent this tendency to build up static electricity. However, none of these methods has been able to satisfy all of the requirements at present in terms of cost increase, spinning operation stability, quality stability, antistatic performance and durability, balance with other fiber properties, etc. do not have. For example, in a method in which an antistatic agent is applied on the surface of fibers, part or all of the antistatic agent disappears during washing or dyeing processes, and durable antistatic performance cannot be obtained. In addition, in order to obtain fibers with durable antistatic properties, antistatic agents such as polyoxyalkylene glycols or their derivatives (hereinafter abbreviated as POG) are added to the fiber-forming thermoplastic polymer before spinning. A method of making fibers by incorporating
No. 5214) has also been proposed, but it is possible to simply add an antistatic agent such as POG to a fiber-forming thermoplastic polymer before spinning and melt-spun it by a conventional method.
When trying to obtain antistatic fibers, it is necessary to use a large amount of POG to obtain fibers with practically sufficient antistatic performance.
The large amount of POG impairs the excellent mechanical properties of the fibers made from the fiber-forming thermoplastic polymer, and also extremely deteriorates the light fastness of the dyed fibers obtained. In such a method, most of the commercial value of the fiber is lost in order to obtain an antistatic effect. The method of producing antistatic fibers by simply adding POG to a fiber-forming thermoplastic polymer has the above-mentioned drawbacks. Many methods for producing fibers having certain antistatic properties have been proposed. Among them, there are methods such as adding a third component to POG, methods using static kneading elements, etc., and composite spinning methods, but all of them have advantages and disadvantages, such as increased spinning costs and raw material costs. , unstable operation,
This results in instability of quality, etc., and the current situation is that there is no method for obtaining antistatic fibers that satisfies all of these problems and has practical and commercial value. The present inventors solved the various problems mentioned above,
The present invention was arrived at as a result of intensive research to obtain antistatic fibers that have practical and commercial value. That is, the gist of the present invention is to use a fiber-forming thermoplastic polymer containing 0.5% by weight or more of polyoxyalkylene glycol or a derivative thereof for producing solid fibers having a single spinning hole opening area of 0.2 mm ² or more. Using a spinneret with spinning holes, the opening area S (mm ² ) of the single hole in the spinneret and the discharge amount Q (g/
This is a method for producing antistatic fibers, characterized in that melt spinning is carried out under conditions where the relationship between S≧0.02Q ² +0.2...(1) The fiber-forming thermoplastic polymer in the present invention is
Any thermoplastic polymer can be used as long as it can be formed into fibers by melt spinning, and typical examples include polyester, polyamide,
polystyrene, polyethylene, polypropylene,
Examples include polyether ester, but it goes without saying that the material is not limited to these examples. The present invention particularly relates to the above-mentioned fiber-forming thermoplastic polymers having the general formula (where n is an integer of 2 to 6) It exhibits excellent effects on polyesters mainly composed of repeating units, and polyamides represented by nylon 6, nylon 66, etc. In addition, especially in the case of polyester, the general formula

Excellent effect on basic dye dyeable polyester containing [Formula]. Polyoxyethylene glycol or a derivative thereof (POG) referred to in the present invention is known to be mixed into thermoplastic synthetic fibers to impart antistatic properties, for example, in Japanese Patent Publication No. 39-5214, Japanese Patent Publication No. 57-4724, etc. This term refers to all commonly known substances, such as polyethylene glycol, polypropylene glycol, random or block copolymers of ethylene oxide and propylene oxide, polytetramethylene glycol, and polyethylene glycol. Block copolymers obtained by adding ethylene oxide to tetramethylene glycol, polyoxyalkylene compounds with hydroxyl groups at both ends such as compounds obtained by adding ethylene oxide to neopentyl glycol or bisphenol glycol, monophenoxy polyethylene glycol, nonyl fluoride, etc. Enoxypolyethylene glycol, sodium sulfophenoxypolyethylene glycol, diphenoxypolyethylene glycol, compounds in which 2 moles of monophenoxy polyethylene glycol are bonded with 1 mole of tolylene diisocyanate, etc. One or both ends are ether bonded. Polyethers esterified at one or both ends, such as polyoxyalkylene compounds blocked via polyoxyalkylene compounds, polyethylene glycol laurates, polyethylene glycol phosphates or partially alkali salts thereof, polyethylene glycol phosphonates or partially alkali salts thereof. Compound, block copolymer of polyethylene glycol and polyethylene terephthalate, block copolymer of polytetramethylene glycol and polyethylene terephthalate or polybutylene terephthalate, block copolymer of polyethylene glycol and polyε-capramide, one or both ends Examples include polyethylene glycol which has been cyanoethylated, polyethylene glycol which has the cyano group converted into an amino group, and compounds obtained by adding ethylene oxide to a primary or secondary alkylamine. It goes without saying that the polyether compound referred to in the present invention is not limited to the above specific examples, and may be a single compound or a mixture of two or more of these compounds. In addition, in the above POG, both ends are -OH, -
In the case of a group having active hydrogen such as COOH, -NH2 _{, etc.} , the weight average molecular weight (hereinafter abbreviated as molecular weight) of the POG is preferably 6000 or more. Also, when one end is blocked by a group having active hydrogen and the other end is blocked by a group not having active hydrogen,
The molecular weight of POG is preferably 4000 or more.
Further, when both ends are blocked with a group having no active hydrogen, the molecular weight of POG is preferably 1000 or more. The POG to be used in the present invention may be any POG such as those described above. Furthermore, antioxidants, ultraviolet absorbers, pigments, organic or inorganic ionic compounds, and other additives may be mixed in advance with the POG to be added. If the amount of POG to be added is less than 0.5% by weight, the antistatic performance will be insufficient for practical purposes no matter how the method of the present invention is used. Therefore, the amount of POG added to the fiber-forming thermoplastic polymer in the present invention needs to be 0.5% by weight or more, more preferably 1.0% by weight or more. The upper limit of the POG content is not particularly limited in the present invention, but in general, as the POG content increases, the light fastness of the dyed fiber obtained deteriorates. POG within the range that does not pose a practical problem
It becomes necessary to appropriately set the upper limit of the content. According to the findings of the present inventors, although there are differences depending on the type of POG, the molecular weight of POG, and whether or not a light resistance improver is used together, generally the POG content exceeds about 7% by weight. Since this will result in a noticeable decrease in light resistance, the upper limit of the POG content is usually about 7% by weight. However, the antistatic properties become better as the POG content increases, so in practice, the POG content is determined from both antistatic properties and light resistance depending on the purpose and application. The method of incorporating POG into the fiber-forming thermoplastic polymer is not limited as long as it is before spinning, and as long as it does not adversely affect spinnability etc., it can be added from the polymerization initiation stage of the thermoplastic polymer to just before spinning. It can be at any point in the stage. The present invention uses such a POG-containing fiber-forming thermoplastic polymer by using a spinneret for manufacturing solid fibers having a larger opening area of a single spinning hole than those conventionally generally used, and Melt spinning is carried out under the conditions that the relationship between the opening area S (mm ² ) and the discharge amount Q (g/min) per single hole satisfies the following formula (1), preferably the following formula (2). It has the following characteristics. S≧0.02Q ² +0.2 …(1) S≧0.1Q ² +0.2 …(2) Conventionally, in melt spinning of thermoplastic synthetic fibers,
As a spinneret for producing solid fibers, those having a single hole opening area of approximately 0.03 mm ² to 0.13 mm ² are used, and the output amount per single hole is 0.8 g/ 3.0 g/min, and when a POG-containing fiber-forming thermoplastic polymer is spun under conventional melt spinning conditions to produce antistatic fibers, satisfactory antistatic properties can be obtained as long as a large amount of POG is not included. Performance cannot be obtained, and even if a large amount of POG is contained, the half-life after 20 washes, which will be described later, is
It was not possible to obtain an antistatic fiber with excellent antistatic properties that lasted for 150 seconds or less. However, surprisingly, a solid fiber manufacturing spinneret having a single hole with a single opening area of 0.2 mm ² or more was used, and the opening area of the single hole in the spinneret S (mm ² ) was used.
The thermoplastic polymer containing POG is melt-spun under conditions such that the relationship between Q and the discharge amount Q (g/min) per single hole satisfies the above formula (1), preferably the above formula (2). The present inventors have discovered that by doing so, fibers with surprising durable antistatic performance can be obtained even when the POG content is small. Obtaining an antistatic effect by incorporating POG into a thermoplastic polymer is generally known in the past, but the thermoplastic polymer containing POG is melt-spun under the melt-spinning conditions of the present invention. No literature has been found that describes or teaches that a surprising antistatic property improvement effect can be obtained by using the above method. The present inventors have discovered that by spinning a POG-containing fiber-forming thermoplastic polymer under the above-described spinning conditions, a surprising effect of improving antistatic properties can be obtained with a small amount of POG. The reason and mechanism by which the above effect was produced has not yet been precisely elucidated, but the flow state of the POG-containing fiber-forming thermoplastic polymer within the single spinning hole is a major contributor. I guess. By increasing the opening area of the single spinning hole to 0.2 mm ² or more and performing spinning under conditions where the frictional loss energy due to fluid flow within the single hole is small, the fiber-forming thermoplastic polymer is substantially incompatible with the fiber-forming thermoplastic polymer. The POG of
It is believed that under the spinning conditions of the present invention, fibers are formed in a dispersed state that is extremely effective for improving antistatic properties. In determining the spinning conditions of the present invention, the opening area S of a single spinning hole and the discharge amount Q per single hole are important factors. The opening area S of the single spinning hole of the spinneret for producing solid fibers used in the present invention is not particularly limited as long as it is 0.2 mm ² or more, and may be as large as it is as long as melt spinning is possible. However, in practice, there are restrictions on the fiber denier depending on the purpose and use. Therefore, it is preferable to set it as 0.4-1.5 mm ^<2> . The spinneret in the present invention is for producing solid fibers, and its cross-sectional shape may be not only circular but also non-circular as long as the opening area of the single spinning hole is 0.2 mm ² or more. Examples thereof include, but are not limited to, a triangle, a quadrangle, a polygon larger than that, a cross, a circle, a cross, and a Y-shape. However, those shaped to obtain fibers with hollow portions (hollow fibers) are excluded. Here, in the case of a fiber having a shape to obtain a hollow part, if the melt spinning conditions of the present invention are adopted, it will be difficult to perform melt spinning with good spinning stability. Fibers with excellent properties cannot be stably obtained. The upper and lower limits of the discharge amount Q per single hole in the present invention are not particularly limited, and as long as melt spinning is possible, no matter how large it is as long as it satisfies the above formulas (1) and (2), However small it may be, it is actually limited by the fiber properties and productivity depending on the purpose and use. Therefore 0.1~5
Preferably it is g/min. The winding speed in the present invention is not particularly limited, but
The speed is preferably 500 to 8000 m/min, preferably 1000 to 4000 m/min. The present invention can also be applied when using a spinneret for producing mixed fiber yarn. In this case, the spinneret for producing mixed fiber yarn has a single spinning hole with an opening area of 0.2 mm ² or more,
The number of single holes for producing solid fibers in which the relationship between the opening area S and the discharge amount Q per single hole satisfies the previous formula (1) is at least one hole, preferably for the total number of single holes in the spinneret. Any material may be used as long as it accounts for 5% or more, more preferably 10% or more. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples. In the examples, unless otherwise specified, percentages are percentages by weight, and parts are parts by weight. In addition, charge leakage half-life (hereinafter simply referred to as half-life) and light resistance in Examples were measured by the following methods. (a) Half-life: The half-life was measured using method A (half-life measurement method) of the obtained knitted filament according to JIS-L-1094-1980 (Testing method for electrification of woven and knitted fabrics). . In order to evaluate the durability of the antistatic property, the obtained filament was knitted, subjected to the washing treatment shown below, air-dried, and then used as a sample for the above-mentioned half-life measurement. Washing treatment: Wash the knitted fabric with 0.5g of neutral detergent/aqueous solution at 40℃
Wash in a home washing machine for 20 minutes, dehydrate, rinse under running water at room temperature for 20 minutes, dehydrate again, and rinse with warm water at 40℃ for 5 minutes to dehydrate. The above operation was repeated 20 times, and after air drying, it was used as a sample for a chargeability test. (b) Light resistance; knitting the filament obtained in the same manner as above,
The knitted fabric is treated with Resolin Blue before and after washing.
Dye with FBL (Bayer disperse dye) 1.0% owf, dissolution ratio 1:50 dyeing solution at 130℃ for 60 minutes in a conventional manner, wash with reduction, air dry, and then apply JIS-L-0842.
-1971 (Test method for dyeing fastness to carbon arc lighting), the light resistance was measured. Example 1 Terephthalic acid and ethylene glycol were esterified by a conventional method, and after initial condensation, immediately before completing the polymerization, a hindered phenol antioxidant was added to polyethylene glycol (average molecular weight 20,000). 1,3,5-trimethyl 2,4,6-tris(3,5-ditertiarybutyl-4-hydroxybenzyl)benzene (manufactured by Ciba Geigy, trade name Irganox 1330)
Add 1.0% and melt and mix it so that the POG content is as shown in Table 1,
Polymerization of the POG-containing polyester is completed, and the POG has the intrinsic viscosity [η] (measured at 30°C in a mixed solvent of phenol/tetrachloroethane = 6/4) shown in the same table.
A containing polyester was obtained. Using these polymers, melt spinning was carried out at 290°C under the spinning conditions shown in Table 1, and after the spun yarn was cooled and solidified, the wound yarn was drawn in a conventional manner, and the thus obtained fibers were drawn. The fabric was knitted and its half-life and light resistance before and after washing were evaluated. In this example, the winding speed is experiment number 21.
All speeds were kept constant at 1300m/min except for 600m/min. The results are shown in Table 1.

[Table] From Table 1, it can be seen that the fibers of the comparative examples (experiment numbers 1 and 2) obtained from polyester containing 0.3% POG are inferior in antistatic performance.
On the other hand, the present invention containing 8% POG (experiment number 8)
It can be seen that the antistatic performance is very good.
However, the light resistance is slightly worse. In addition, POG is 8%
Comparing the comparative example containing 0.5% POG (experiment number 7) and the present invention containing 0.5% POG (experiment number 4), the fiber obtained with the present invention has excellent light resistance even with a small amount of POG. It can be seen that it has excellent antistatic performance. In addition, the present invention (experiment ^number 11, 12, 13, 14) have superior antistatic performance compared to the comparative examples (experiment numbers 9 and 10). In addition, when polyester containing 4.0% POG was used, the present invention (experiment numbers 17, 18, 19, 20,
It can be seen that the fibers in Example 21) have superior antistatic performance compared to the fibers in Comparative Examples (Experiment Nos. 15 and 16). In addition, experiment number 6 in Table 1 represents the present invention, and experiment numbers 3 and 5 represent comparative examples.

Claims (1)

[Scope of Claims] 1. A fiber-forming thermoplastic polymer containing 0.5% by weight or more of polyoxyalkylene glycol or a derivative thereof, in which the opening area of a single spinning hole is 0.2%.
Using a spinneret having a spinning hole for producing solid fibers of mm ² or more, the opening area S (mm ² ) of the single hole of the spinneret
A method for producing antistatic fibers, characterized in that melt spinning is carried out under conditions where the relationship between Q and discharge amount per single hole (g/min) satisfies the following formula (1). S≧0.02Q ² +0.2...(1) 2 The method for producing antistatic fibers according to claim 1, wherein the fiber-forming plastic polymer is polyester.