JPH07324219A - Preparation of phosphorescence yarn and yarn prepared by itsmethod - Google Patents

Abstract

PURPOSE: To obtain phosphorescent textile fibers, filaments, yarns, tapes and fibrillated film that have uniform phosphorescent characteristics. CONSTITUTION: A prescribed amount of polymer pellets and a wetting agent are mixed in a mixer to wet the surfaces of the solid pellets almost uniformly, then a powdery solid phosphorescent pigment is added into the mixer in an amount of about 2-15 wt.% and the mixing is continued until the polymer pellets are coated with the pigment almost uniformly. The polymer coated with the pigment is heated and kneaded in an extruder and the melt in which the phosphorescent pigment distributes uniformly is extruded into filaments.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a phosphorescent textile for textiles suitable for the production of textile products.
fiber) and its manufacturing method.

[0002]

2. Description of the Related Art Phosphorescence or luminescence
Synthetic resins or polymer materials having inescence) are used in various fields such as toys, signboards, safety equipment, and clothes. Fluorecent dyes are also used in the manufacture of textile products, including yarns. However, in most cases, the manufacturing method of phosphors and phosphors is completely different, for example, most fluorescent dyes are lighter compounds than the treated synthetic resin, while phosphorescent substances such as zinc sulfide are treated. It is a compound heavier than synthetic resin.

In the luminescent rope described in Warren, US Pat. No. 2,382,355, filaments are made from a resin material containing a suitable luminescent material. In this patent, phosphors (or phosphors) are mixed in powder form with plastics, or at any time before ropes are extruded into filaments or cold rolled during rope manufacturing The substance is dispersed throughout the plastic. In another embodiment, the luminescent material is mixed with a plastic carrier to coat the filaments with a clear or colorless plastic coating thereon. Each filament is molecularly oriented by drawing or die drawing in order to obtain tensile strength.

Schmidling US Patent No.
No. 2,436,182 discloses a phosphorescent molded article molded from a resin material containing a phosphorescent filler mixed in the entire resin.
What is made of this is a rather heavy rigid molded product.
U.S. Pat. No. 2,838,762 to Wadely describes patterned floor coverings and rugs made from phosphor impregnated threads. The phosphorescent yarn is coated with a binder that transmits light.

US Patent No. 4,640,7 to Goguen
No. 97 describes a method for manufacturing phosphorescent polymer materials used in the molding of athlete shoes for athletics and cycling. In this method, an elastomer material containing 20 to 50% by weight of processing oil is heated and kneaded with an extruder, and the kneaded material is molded into pellets (the shoe sole is molded using this pellet), etc. Mix 3 to 30% by weight of the phosphor (along with the other ingredients) into the molten component as uniformly as possible. This patent uses oil as a plasticizer for polymeric materials.

US Pat. No. 4,781,647 to Doane discloses a method of extruding a thermoplastic polymer containing a mixture of phosphor particles. What is extruded in this patent is the size of a doll's hair that glows in the dark. The maximum size of the phosphor particles is stated to be less than half the strand diameter. The strand diameter is 0.015 inches or less, preferably in the range of 0.002 to 0.004 inches, the polymeric material is preferably polyamide, polyester, polyolefin, polyacrylonitrile, polyvinyl chloride and the phosphor is zinc sulfide, cadmium sulfide or calcium sulfide. . The phosphorescent particles are coated with a coupling agent for better mixing.

US Pat. No. 5,13 to Vockel et al.
No. 5,591 discloses a method for producing a phosphorescent fiber-reinforced plastic product in which a phosphor is encapsulated on the surface of a molded product.

As is apparent from the patents of known processes, including the above, many efforts have been made to use phosphorescent materials such as zinc sulphide, but it is not easy to produce a satisfactory product. Absent. For example, polypropylene, nylon, which has properties that can be used commercially in the textile industry,
It has been believed that phosphorescent fibers that can be used as threads such as bulky continuous filaments (BCF) (bulky yarn) of thermoplastic polymers such as polyester are not possible. That is,
The yarns used in these applications have high uniformity of phosphorescence characteristics, color, and other characteristics, and also adversely affect the processability including the dyeing and physical properties of the threads or filaments from which the used phosphor is manufactured. It is necessary not to give.

Although uncertain determination cannot be made, it is considered that a major problem in producing a synthetic yarn containing a phosphor is that the phosphor cannot be sufficiently mixed with the synthetic resin material.
That is, the most widely used commercially available phosphors are relatively heavier than polymers, causing the phosphors to settle. Further, conventionally, a dry phosphor is added by a melt extruder, and in this melt extruder, an auger is generally used for physically stirring and mixing the materials.
However, in the production of ultrafine fibers and filaments, it is clear that even a slight change in the concentration of solid particles will degrade the product properties and interrupt the process.

When producing BCF yarns of thermoplastic polymers on an industrial melt spinning line, it is generally exceptional that the amount of pigments and other foreign matters contained in the solution dyed yarns is about 1% or more. It has been considered that 2-3% is the industrial upper limit for this manufacturing method.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an improved process for making phosphorescent continuous filaments or fibers suitable for use in the textile industry. It is another object of the present invention to provide an improved method of melt spinning phosphorescent yarns or filaments from thermoplastic polymeric materials. Yet another object of the invention is to provide a method for incorporating fine phosphorescent pigments into polymeric materials in fairly high proportions in order to increase their phosphorescence.
Yet another object of the present invention is to provide improved monofilaments, spun, continuous filaments and / or BCF phosphorescent yarns having substantially uniform phosphorescent properties. Yet another object of the present invention is to provide an improved textile fiber or filament produced by the above method.

[0012]

In addition to the above and other objects and advantages, an important feature of the present invention is that the finely divided phosphor is mixed with a thermoplastic polymer prior to spinning to form particles of phosphor powder throughout the polymer. The point is that they are distributed almost uniformly. To do this, use a wetting agent that can coat each pellet of polymer, then add finely ground phosphorescent powder and tumbling or otherwise mix to attach the powder pigment to the outer surface of all pellets almost uniformly. Let Next, the pellets coated with the wetting agent and the phosphorescent powder pigment are placed in a commercially available extruder, the pellets are heated and kneaded, and the filaments are extruded. Since the powdered phosphorescent pigment was evenly deposited on the surface of each pellet, the phosphorescent material can be very evenly distributed throughout the melt. As a result, it is possible to operate industrial melt spinning equipment in the high phosphorous content, producing a very uniform product with suitable properties for use in the textile industry producing commercial high-grade textile products. It can be manufactured.

In the present invention, phosphorescent fibers, filaments,
Yarns, tapes, fibril (split) films or tapes are made from thermoplastic polymer materials. Finely ground phosphorescent pigments are dispersed almost uniformly throughout the melt of the polymeric material and extruded in a melt spinning machine to give the desired phosphorescence, yet with physical properties suitable for use in the textile industry. Manufacture fibers, filament yarns, etc. The phosphor can be milled or powdered commercially available activated zinc sulfide, preferably with an average particle size of about 30 microns or less. The polymers that can be used in the present invention can be commercially extrudable thermoplastic polymers such as nylon, polypropylene or polyester which are widely used in the manufacture of BCF yarns used in the textile industry.

The method of the present invention is applicable to the production of fibers in various forms, such as monofilaments, multifilaments, staple yarns, tapes or fibril films, but is particularly suitable for the production of BCF yarns,
Hereinafter, a method for manufacturing the BCF yarn will be described. However, the present invention is not so limited.

First, the chipped or pelletized polymeric material is placed in a mixer or tumbler (along with any necessary or desired stabilizers, etc.) and a wetting agent (such as a suitable oil compatible with the polymeric material). To pellets. Then tumbling or mixing until the entire outer surface of each pellet is wet. The powdered phosphor is then added in the desired amount and tumbling is continued in the mixer until the powder pigment is evenly attached to each pellet. The material is then introduced into the extruder, the polymer is melted in the same manner as conventional methods, and the phosphor is thoroughly mixed throughout the melt.

Since the pellets are coated with a wetting agent in the present invention, the powdered phosphor is deposited on each pellet as a substantially uniform film regardless of the amount of powder added. The phosphor powder is evenly distributed throughout the extruder feedstock, which can adversely affect the physical properties of individual filaments and cause non-uniform phosphorescence properties in the final product made from the yarn. Concentration of solid particles can be eliminated.

The uniform distribution of fine phosphor particles does not adversely affect the dyeability. That is, the yarn produced by the method of the present invention can be colored by solution dyeing or secondary dyeing, such as Beck dyeing, package dyeing, piece dyeing, continuous dyeing, space dyeing or printing, and can be colored in a single color or multiple colors according to standard dyeing methods. Can be color yarn. The individual fibers or filaments can be solid or hollow and can be of any known shape, such as round, triangular, rectangular, trilobal, square, hexagonal, pentagonal. The multifilament yarn spun from the product of the invention is air entangled, twisted, heat set, twisted or otherwise treated by any of the conventional methods used for multifilament or spun polymer yarns. The yarn can be used to make textiles by taffeta processing, over taffeta processing, weaving, knitting, twisting, melt bonding, flocking, felting, melting, sewing, and other conventional methods. The fabric thus obtained can also be patterned to selectively cover / expose phosphorescent fibers.

Examples of uses of the product of the present invention include carpets, rugs, mats, upholstery cloths, wallpapers, apparel, heavy industry fabrics, ropes, laces, shoelaces, safety equipment,
There is a net etc. Hereinafter, examples of the present invention will be described.
The present invention is not limited to the examples below.

[0019]

EXAMPLE 1 A bulky continuous filament yarn of phosphorescent polypropylene was produced on a carpet mill industrial production line using a small melt spinning line capable of extruding both polypropylene and nylon BCF yarns. . Put the polypropylene pellets used in a tumbling mixer, spray about 0.1% by weight of mineral oil as a wetting agent,
Tumbling was continued until each pellet was coated.
Finely ground or powdered commercially available activated zinc sulfide phosphorescent pigment with an average particle size of about 30 microns was then added to the tumbler, all powdered pigments adhering to the pellet surface, visually observing that each pellet was approximately Continue tumbling until you find a uniform coating.

The melt-spinning line starts with raw polypropylene pellets and runs there until the spinning process is stabilized. At the stabilization point, the pellets fed to the extruder are switched to coated pellets. The spinning process stabilizes quickly, although the line needs to be readjusted slightly. The operation was carried out using a 78-hole and 120-hole spinneret.

First, the yarn was prepared and tested with 1% by weight of phosphor. At 1 wt% loading, the yarn has good physical properties but does not exhibit the desired phosphorescence properties. Then the phosphorescent pigment concentration was increased to 2%, 2.5% and 3%. The product containing 2% had insufficient phosphorescence,
The products containing 2.5% and 3.0% showed very good phosphorescence. Increasing the phosphor content will initially cause process problems, but the equipment can be tuned according to normal line conditioning methods, after which it will have very good performance both in terms of processability and product quality. Become.

Yarns made from products containing 2.5% and 3% phosphorescent pigment exhibited the following physical properties: Denier 2233 Break strength 3500-3700 g Tenacity 1.59 g per denier Elongation 36.7% Natural crimp 2.83% Annealed Crimp 8.74% Shrink 2.03% The physical properties of these yarns are always typical and identical to conventional polypropylene BCF yarns. The phosphorescent pigment did not decompose even at the melt spinning temperature of 490 ° F., there was no evidence of deterioration, and the processability of the entire process was good.

Example 2 It was confirmed that a nylon BCF yarn having phosphorescent properties could be extruded using the same equipment as above. 78 holes and 120
A hole spinneret was used. Nylon is generally considered to be more reactive than polypropylene, so known stabilizers were added. Nylon chips and additives (stabilizer pellets) were mixed, mineral oil was added as a wetting agent, and the surface of the polymer and stabilizer pellets was completely wetted by a tumbling / mixing operation. Then the phosphorescent pigment was added by the method described above. Since nylon pellets are highly hygroscopic, the amount of wetting agent used at the beginning of operation should be increased to 0.63%. Increasing the amount of wetting agent delayed the moisture absorption of nylon chips, improving the viscosity and processability of the compound with a large amount of additive.

At the beginning of the experiment, the system was run with only nylon pellets, and when the system was stabilized the system was switched to a wet pellet / stabilizer system and at the re-stabilized stage it contained 3% by weight of phosphorescent pigment. Replaced with blend. The phosphorescent pigment loading was increased to 4%, 5%, 7% and 10%. Even if the blending ratio of the phosphorescent pigment was 10%, the overall processability was good with a slight adjustment. Next, the compounding ratio of the phosphorescent pigment was increased to 15%. At this compounding ratio, the filament broke, so the test was completed with a sample of the product containing 15% phosphorescent material. Adjusting the process conditions should allow nylon to contain 15% by weight of phosphorescent material to operate well, but this compounding level seems to be close to the practical upper limit for high speed industrial operation. The properties of the yarn samples obtained are summarized in Table 1. The values shown in this table are average results of three samples. The results of the three samples were surprisingly consistent.

[0025]

[Table 1]

Example 3 In order to increase the proportion of phosphorescent pigment in polypropylene and to reduce the denier of the filaments to a size suitable for processing on known staple yarn spinning machines, the above-mentioned 2
It was tested using the same equipment as in the two examples. For spinning on known staple yarn spinning machines, the filament denier of extruded staple fibers usually must be 25 or less. The cross section is trilobal
Both 78 and 120 hole spinnerets were run for both the and delta (triangle) fibers.

For polypropylene pellets, the procedure was the same as above, except that the amount of wetting agent was increased to about 0.2% by weight. That is, the line was first stabilized with normal resin and then again with resin pellets coated with a wetting agent.
First, we added phosphorescent pigment to the wet pellets at a level of 3.0% to run it, then weighed 4.0% and 5.0%.
%, And finally increased to 7.0%. Adjustment of process conditions was necessary to increase the pigment concentration to 5.0%. Five.
The results were good even at a concentration of 0%.

When the compounding ratio was 7.0%, the compound deteriorated and the workability deteriorated, so the test was completed after obtaining the sample. In the case of polypropylene fiber, when the concentration exceeds 5.0%, it is considered necessary to use a dispersant to improve processability. The physical properties of the yarns obtained from a representative sample of this test are quite satisfactory. Although the filament denier was smaller than the above and the phosphorescent pigment loading was increased from the above (Example 1), the physical properties were comparable to those obtained at 3.0% concentration. The results are shown in [Table 2].

[0029]

[Table 2]

The values obtained were tested under normal operating specifications, 4
It is the same as the dispersion level in one sample. It is believed that the results of this processability and the physical properties obtained in this test are significantly improved over the above (Example 1). This test produces a filament denier of 17, which allows the present invention to extrude phosphorescent fibers into a filament denier suitable for processing into staple yarns on known staple yarn spinning machines. It was confirmed. It has also been shown that the present invention is also suitable for producing nonwovens by continuous melting.

Fabrication properties of the nylon and polypropylene phosphorescent yarn samples prepared in Example 3 were evaluated on twist-processed and heat-set yarn and final textile manufacturing machines. The results of the twisting, heat-setting, taffeta and finishing machine processing tests were almost the same as those of the corresponding yarns made by the phosphorescent solution dyeing method, and no substantial adverse effects or adverse properties were found. .
Performance tests are also carried out on the yarns according to the invention and the fabrics produced therefrom in independent, reliable test laboratories to determine light fastness, accelerated weathering resistance, flammability, abrasion resistance, abrasion simulation tests, electrostatic properties. , Chemical resistance and phosphorescence retention characteristics were measured. All test results were good. The performance of both nylon and polypropylene BCF yarns prepared in the above examples was shown to be similar to the corresponding solution dyed yarns with significantly lower concentrations of non-phosphorescent pigment. The yarns of the present invention have a very high concentration of phosphorescent pigment with no evidence of significant degradation of the performance of the textile fiber or fabric.

Although the above embodiment shows a preferred embodiment of the present invention, the present invention is not limited to the above embodiment. For example, other thermoplastic materials such as filament yarns used in the textile industry and polyesters (PET, PBT) normally used in the production of staple yarns can be used. Also, various wetting agents that are compatible with the polymer used can be used, and further known stabilizers, such as oxidation known in the art,
Stabilizers that reduce heat, chemicals, UV degradation, etc. can be used.

The weights of the yarns shown in Examples 1, 2 and 3 above are expressed in denier of the complete yarn, but the procedure is 78
It should be pointed out that this was done using an extrusion head with holes and 120 holes. A more meaningful indication of the extruded filament size would be denier per filament. In this regard, experience gained from operation to date shows that filament denier achievable with both nylon and polypropylene is in the range of about 5-100, while the preferred denier per filament is about 10-60. Is in the range. Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and all embodiments which are obvious to those skilled in the art to be included in the spirit and the scope of the present invention are not limited to the present invention. included.

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Claims (28)

[Claims] 1. A synthetic fiber filament for a woven fabric from a thermoplastic polymer, which comprises supplying a polymer in pellet form to an extruder, heating and kneading the polymer in the extruder, and extruding the obtained melt into a filament or fiber form. The method of melt spinning of claim 1, wherein a predetermined amount of polymer pellets and a wetting agent are mixed in a mixer to wet the surface of the solid pellets almost uniformly, Add the solid phosphorescent pigment, continue mixing until the polymer pellets are almost uniformly coated with the pigment, heat and knead the pigment-coated polymer with an extruder, and melt the phosphorescent pigment uniformly distributed into filaments. A method characterized by extruding. 2. The method of claim 1, wherein the phosphorescent pigment is zinc sulfide. 3. The method of claim 2 wherein the polymer is selected from polypropylene, nylon and polyester. 4. The method of claim 1 wherein the polymer is nylon and about 3 to 12% by weight of zinc sulfide is added to the polymer during the step of adding the solid phosphorescent pigment. 5. An oil compatible with nylon is added as a wetting agent in an amount of about 3 to 5% at the step of adding the wetting agent.
The method described in. 6. The method of claim 5, wherein the wetting agent is mineral oil. 7. The method of claim 6 wherein the zinc sulfide has an average particle size of about 30 microns or less. 8. The method of claim 1 wherein the polymer is polypropylene and about 2-5% by weight zinc sulfide is added to the polymer during the step of adding the phosphorescent pigment. 9. The method according to claim 8, wherein the step of adding the wetting agent comprises adding about 0.1 to 3% of an oil compatible with polypropylene as the wetting agent. 10. The method of claim 9 wherein the wetting agent is mineral oil. 11. The method of claim 10, wherein the zinc sulfide has an average particle size of about 30 microns or less. 12. The spun yarn is formed by simultaneously melt spinning a plurality of filaments in the step of extruding the melt.
The method described in. 13. The yarn is a bulky continuous filament (BCF).
13. The method of claim 12, which is a yarn. 14. A phosphorescent synthetic filament for textiles made by the method of claim 1 wherein the denier is in the range of about 5-100. 15. The filament of claim 14 wherein the thermoplastic polymer is polypropylene, the synthetic textile filament comprises about 2 to 7 wt% phosphor and the denier of the filament is in the range of about 10-60. 16. The filament of claim 15 wherein the phosphor is present in an amount of about 3-5% by weight and the phosphor has an average particle size of about 30 microns or less. 17. The thermoplastic polymer is nylon,
15. The average particle size of the phosphor is less than about 30 microns.
Filament. 18. The filament of claim 17, wherein the phosphor is present in an amount of about 3-10% by weight. 19. The filament of claim 18, wherein the denier of the filament is in the range of about 10-60. 20. A phosphorescent synthetic textile yarn made by the method of claim 12 wherein the filament denier of the yarn is in the range of about 5-100. 21. The yarn of claim 20 wherein the thermoplastic polymer is polypropylene, the filament of the yarn comprises about 2 to 7% by weight phosphor and the denier of the filament is in the range of about 10-60. 22. The yarn of claim 21, wherein the phosphor is present in an amount of about 3-5% by weight and the phosphor has an average particle size of about 30 microns or less. 23. The thermoplastic polymer is nylon
21. The yarn of claim 20, wherein the phosphor has an average particle size of about 30 microns. 24. The yarn of claim 23, wherein the phosphor is present in an amount of about 3-10%. 25. A phosphorescent spun polymer fabric yarn comprising a phosphorescent pigment in an amount of about 2-5% by weight dispersed substantially uniformly throughout the filament of the yarn, the filament denier of the yarn being in the range of about 5-100. And the phosphorescent pigment is a finely ground solid having an average particle size of about 30 microns or less. 26. The yarn of claim 25, wherein the filament denier is in the range of about 10-60. 27. The yarn of claim 26 in which the polymer is nylon and the pigment is present in the range of about 3-12% by weight. 28. The yarn of claim 26, wherein the polymer is polypropylene and the phosphor is present in an amount of about 3-5% by weight.