TWI418676B - Fibers having infrared absorption ability, fabrication methods thereof and fabrics containing the same - Google Patents

Description

Fiber with infrared absorbing function, its preparation method and textile

The present invention relates to a fibrous material, and more particularly to a fibrous material having an infrared absorbing function.

In general, natural or synthetic fibers are required to achieve a better warming effect, and it is generally necessary to use a fabric having a high warp density or to increase the thickness of the fabric, but these methods may deteriorate the gas permeability of the finished textile product and increase the weight.

In addition, animal down can be used as a filling in the finished textile product, or artificial hollow or porous fiber can be used to make the finished textile product to achieve the effect of keeping warm and lightweight. However, such textile products have high bulkiness and cause inconvenience to the user's activities.

Accordingly, there is a need in the industry for a fibrous material that can provide thermal insulation to the fibers and the textiles they make, while at the same time having a lightweight and avoiding excessive bulkiness of the textile product to overcome the above disadvantages.

At present, people have used zirconia powder to add and disperse in the fiber to prepare textiles, which have excellent infrared absorption performance (infrared energy can be converted into heat energy, which causes the temperature of the textile to rise to achieve warmth), but because the textile is dark black. And the price is very expensive, which leads to a very limited application. Therefore, the development of light color and low-infrared absorbing infrared functional textiles is currently the focus.

Zinc oxide is a semiconductor material with an energy gap of 3.37 eV at room temperature. As the size of the zinc oxide powder decreases, the band gap increases gradually. To enhance its electrical or optical properties, Elements of Groups IIIA through VA are typically doped. Zinc oxide or zinc oxide doped with Group IIIA to VA elements is commonly used in industries related to the semiconductor industry, such as conductive materials, piezoelectric materials, gas detectors or solar cells.

Embodiments of the present invention provide a fiber having an infrared absorbing function, the fiber comprising a fiber body, and a powder having an infrared absorbing function, which is added and dispersed inside the fiber body.

Further, an embodiment of the present invention provides a textile having an infrared absorbing function, which comprises a fiber having an infrared absorbing function as described above.

In addition, an embodiment of the present invention further provides a method for manufacturing a fiber having an infrared absorbing function, comprising: providing a powder having an infrared absorbing function, providing at least one monomer to be blended with the powder, and polymerizing the monomer. A composite material in which at least one polymer is blended with the powder is formed, and the composite material is processed by spinning to form a fiber having an infrared absorbing function, wherein the powder is added and dispersed inside the fiber.

In another embodiment, a method for manufacturing a fiber having an infrared absorbing function is provided, the method comprising: providing a powder having an infrared absorbing function, providing at least one polymer mixed with the powder to form a polymer and the powder The body blended composite material, and the composite material is processed by spinning to form a fiber having an infrared absorbing function, wherein the powder is added and dispersed inside the fiber.

The textile made by adding the powder having the function of absorbing infrared rays of the present invention has a color change of about 2% with respect to the textile having no powder added. This performance is far superior to textiles with added zirconia powder (with infrared absorption), the color change is very obvious, and the average visible light reflectance difference can reach more than 40%.

In order to make the above objects, features, and advantages of the present invention more comprehensible, the following detailed description is made in conjunction with the accompanying drawings.

The invention utilizes the powder with the function of absorbing infrared rays to be dispersed and dispersed in the interior of the fiber main body, so that the fiber has the function of absorbing infrared rays, and the textile made of the fiber also has the function of absorbing infrared rays, thereby achieving the absorption of infrared rays by the textile and The effect of keeping warm, while maintaining the advantages of lightweight textiles and avoiding the disadvantages of excessive fluffiness of textiles.

In an embodiment of the present invention, the powder having the function of absorbing infrared rays may be a metal oxide powder doped with one or more metal elements of Group IIIA to Group VA, or may be doped with the aforementioned Group IIIA to A combination of a metal oxide powder of a metal element of Group VA.

In one embodiment, the powder having the function of absorbing infrared rays may be zinc oxide (ZnO) powder doped with gallium (Ga), aluminum (Al) or a combination of the foregoing elements, or zinc oxide doped with different elements as described above. In combination with the powder, the zinc oxide powder having a doping element has an absorption ability for infrared rays having a wavelength of about 780 nm or more. The zinc oxide powder may have a particle size of between about 10 nm and 200 nm, preferably less than 100 nm. In one embodiment, in the zinc oxide powder having a doping element, the weight percentage of the doping element is about 0.1 to 20 weight percent (wt%) based on the total weight of the zinc and the doping element.

The method of doping gallium (Ga) or aluminum (Al) in the zinc oxide powder can be:

(1) Mixing the nitrate or sulfate of zinc with the chloride or sulfate of the doping element (including gallium or aluminum) at a concentration of 0.5 ml/L to 5.0 ml/L, and adding the doping element. The molar amount is 0.1 mol% to 10.0 mol% of the total molar amount of zinc and doping elements.

(2) The mixed salt solution and the ammonium hydrogencarbonate solution disposed in the step (1) are added dropwise to the water, and the temperature is kept at 40 ° C and the pH is controlled at 7.0 to 7.5 while stirring vigorously. That is, a uniformly doped white basic zinc carbonate precipitate is obtained.

(3) The precipitate is dried by washing and separating, and the obtained powder is sintered under a mixture of hydrogen and argon, and the sintering temperature is 400 ° C to 700 ° C for 30 minutes to 60 minutes, and the final blend is obtained after sintering. A zinc oxide powder of gallium or aluminum.

According to an embodiment of the present invention, one or more zinc oxide (ZnO) powders doped with gallium (Ga), aluminum (Al) or a combination of the foregoing may be blended in one or more monomers, Next, the monomer is polymerized to form a composite material of the polymer and the above powder, and then the composite material is processed by a spinning process to form a fiber having an infrared absorbing function. In one embodiment, the monomer may be a combination of adipic acid/hexamethylenediamine, caprolactam, a combination of ethylene glycol/terephthalic acid, ethylene and propylene, and the polymerization thereof is high. The molecule may be polyethylene, polypropylene, polyamide, polyester or a combination of the foregoing, and the fibers formed may be polyethylene fibers, polypropylene fibers, polyamide fibers, polyester fibers or a combination thereof, and have the above The powder is added and dispersed inside the fiber so that the fiber has a function of absorbing infrared rays.

According to another embodiment of the present invention, one or more zinc oxide (ZnO) powders doped with gallium (Ga), aluminum (Al) or a combination of the foregoing may be directly mixed with one or more polymers. (blending), forming a composite material of the polymer and the above powder, and then processing the composite material by a spinning process to form a fiber having an infrared absorbing function. In this embodiment, the polymer may be polyethylene, polypropylene, polyamide, polyester or a combination thereof, and the fibers formed may be polyethylene fibers, polypropylene fibers, polyamide fibers, polyester. The fiber or a combination of the foregoing, and having the above powder blended inside the fiber, so that the fiber has a function of absorbing infrared rays.

In the embodiment of the present invention, in the fiber having an infrared absorbing function, the powder accounts for about 0.1 to 10.0% by weight (wt%) based on the total weight of the fiber and the powder.

In addition, the above-mentioned fiber having infrared absorbing function can also have other functions through selection of a monomer material, a polymer material or a fiber material, such as anti-ultraviolet rays, antibacterial, antistatic, cationic dyeable, high ammonia low temperature dyeable, and irregular Cross-section moisture wicking or hollow warmth and other functions.

In the embodiment of the present invention, the above-mentioned fiber having the function of absorbing infrared rays can be separately made into a textile or mixed with other fibers to form a textile, and the finished product made of the textile can absorb infrared rays, thereby having a warming effect.

Hereinafter, each of the examples and comparative examples will be described to describe a method for producing a fiber having an infrared absorbing function and a textile thereof according to the present invention and characteristics thereof:

[Example 1]

The gallium-doped zinc oxide powder (doped amount of gallium is 1.0 wt% of the total weight of zinc and gallium) is added to water to mix and mix (concentration: 25 wt%) and added to the internal temperature of 70 ° C to 80 ° C. In the caprolactam monomer, the amount of the gallium-doped zinc oxide powder is 0.5 wt% (relative to the total weight of the gallium-doped zinc oxide powder and the caprolactam monomer). Then, stirring at a temperature of 190 ° C ~ 200 ° C for 6 hours, then pressure relief (about 30 minutes), and then warming to 230 ° C ~ 240 ° C, stirring for 18 hours, this time has been caprolactam single The polymer is polymerized into a polyamide, and the polyamine compound containing gallium-doped zinc oxide powder is compounded by a spinning and false twisting project (spinning temperature 260 ° C, winding speed 4500 m/min, oil loading 0.5 opu). The false twist was made into a polyamide fiber of 70d/24f size and woven into a knitted fabric having a basis weight of 150g/m2.

The average reflectance of the knitted fabric of Example 1 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were 68% and 65%, as listed in Table 1.

[Example 2-4]

The knitted fabrics of Examples 2-4 were prepared in the same manner as in Example 1, except that the doping amount of the gallium element and the addition amount of the gallium-doped zinc oxide powder were different as listed in Table 1.

Similarly, the average reflectance of the knitted fabric of Examples 2-4 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer. As listed in Table 1.

[Comparative Example 1]

The caprolactam monomer was polymerized into a polyamide, and the polyamidamine fiber was converted into a polyamide fiber of 70 d/24 f size by spinning and false twisting, and woven into a basis weight of 150 g/m ^{2 .} Knitted fabric.

The average reflectance of the knitted fabric of Comparative Example 1 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were measured using an integrating sphere spectrophotometer, and the results were 70% and 40%, as listed in Table 1.

[Comparative Example 2]

The zirconia powder having a particle diameter of about 100 nm is added to water and mixed with water (concentration: 25 wt%) and added to a caprolactam monomer at a temperature of 70 ° C to 80 ° C, wherein the amount of the zirconium carbide powder is 0.5 wt% (relative to the total weight of the zirconium carbide and caprolactam monomers). Then, stirring at a temperature of 190 ° C ~ 200 ° C for 6 hours, then pressure relief (about 30 minutes), and then warming to 230 ° C ~ 240 ° C, stirring for 18 hours, this time has been caprolactam single The polymer is polymerized into a polyamide, and the polytheneamine complex containing zirconia powder is made into a spinning and false twisting project (spinning temperature: 260 ° C, winding speed: 4500 m/min, oil loading: 0.5 opu). A polyamide fiber of 70d/24f size was woven into a knitted fabric having a basis weight of 150 g/m ² .

The average reflectance of the knitted fabric of Comparative Example 2 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were respectively 25% and 60%, as listed in Table 1.

[Embodiment 5]

The aluminum-doped zinc oxide powder (the doping amount of aluminum is 0.8 wt% of the total weight of zinc and aluminum) is first mixed with a trimethylolethane or a polyvinyl pyrrolidone dispersant (amount of powder) 20 wt% to 100 wt% of the body is pulverized and dispersed in a jet mill, and then directly mixed with polypropylene, wherein the weight ratio of the aluminum-doped zinc oxide powder is 1.5 wt% (relative to Aluminum-doped zinc oxide powder and polypropylene total weight), containing zinc-doped zinc oxide powder in spinning and false twisting engineering (spinning temperature 250 ° C, coiling speed 2500 m / min, oil loading 1.0opu) The polypropylene composite false twisted into a 60d/24f polypropylene fiber and woven into a knitted fabric having a basis weight of 120 g/m ² .

The average reflectance of the knitted fabric of Example 5 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were respectively 65% and 64%, as listed in Table 2.

[Example 6-8]

The knitted fabrics of Examples 6-8 were prepared in the same manner as in Example 5, except that the doping amount of the aluminum element and the addition amount of the aluminum-doped zinc oxide powder were different as listed in Table 2.

Similarly, the average reflectance of the knitted fabric of Examples 6-8 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer. As listed in Table 2.

[Comparative Example 3]

The polypropylene false twist was made into a 60d/24f polypropylene fiber by a spinning and false twisting process, and then woven into a knitted fabric having a basis weight of 120 g/m ² .

The average reflectance of the knitted fabric of Comparative Example 3 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were respectively 60%. 45%, as listed in Table 2.

[Comparative Example 4]

The zirconium carbide powder having a particle diameter of 100 nm is firstly dispersed in a jet mill with a dispersing agent such as Trimethylolethane or Polyvinyl pyrrolidone (in an amount of 20 wt% to 100 wt% of the powder). Crushing and dispersing, and then directly blended with polypropylene, wherein the weight ratio of zirconium carbide powder is 1.5 wt% (relative to the total weight of zirconium carbide powder and polypropylene), in the spinning and false twisting project ( The spinning temperature is 250 ° C, the winding speed is 2500 m/min, and the oil loading is 1.0 pu.) The polypropylene composite containing the zirconia powder is made into a 60 d/24 f polypropylene fiber and woven into a basis weight of 120 g/m ^{2 .} Knitted fabric.

The average reflectance of the knitted fabric of Comparative Example 4 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were respectively 8% and 72%, as listed in Table 2.

[Embodiment 9]

The aluminum-doped zinc oxide powder (the doping amount of aluminum is 0.8 wt% of the total weight of zinc and aluminum) is first mixed with a dispersing agent such as Trimethylolethane or Polyvinyl pyrrolidone (the amount is 20 wt% to 100 wt% of the powder is pulverized and dispersed in a jet mill, and then directly mixed with polypropylene, wherein the weight ratio of the aluminum-doped zinc oxide powder is 1.5 wt% (relative For the doping of aluminum-doped zinc oxide powder and polypropylene, the spinning and false twisting engineering (spinning temperature 250 ° C, coiling speed 2500 m / min, oil loading 1.0opu) will contain the oxidation of doped aluminum The polypropylene composite false twist of zinc powder becomes a polypropylene fiber of 50d/36f size.

Next, the 50d/36f polypropylene fiber and the 75d/96f polyester fiber were interwoven into a knitted fabric having a basis weight of 170 g/m ² at a ratio of 1:1 yarn.

The average reflectance of the knitted fabric of Example 9 in the visible light wavelength range of 400 nm to 780 nm and the average absorption rate in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were 74% and 61%.

Next, the knitted fabric of Example 9 was cut into a cuff, and the temperature rise test of the thermal dummy wearing the cuff was performed according to the test method ASTM F1291 of the thermal insulation property of the garment, and the knitting of Example 9 was performed after 15 minutes of irradiation. The temperature rise of the cloth was 4.0 °C.

[Comparative Example 5]

Polypropylene false twist was made into a 50d/36f polypropylene fiber by spinning and false twisting. Next, the 50d/36f polypropylene fiber and the 75d/96f polyester fiber were interwoven into a knitted fabric having a basis weight of 170 g/m ² at a ratio of 1:1 yarn.

The average reflectance of the knitted fabric of Comparative Example 5 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were respectively 75% and 40%.

Next, the knitted fabric of Comparative Example 5 was cut into a cuff, and the thermal temperature dummy test was carried out according to the test method ASTM F1291 of the thermal insulation performance of the clothing. After 15 minutes of irradiation, the knitting of Comparative Example 5 was carried out. The temperature rise of the cloth was 1.9 °C.

[Embodiment 10]

The esterification reaction is carried out by using monomeric terephthalic acid and ethylene glycol. The monomer feed molar ratio is terephthalic acid: ethylene glycol = 100: 110~200, the reaction temperature is 260 ° C ~ 280 ° C, and the reaction pressure is 100 kpa~300kpa, the reaction residence time is 1.5~4.0 hours. The addition of the gallium-doped zinc oxide powder (the doping amount of gallium is 1.0 wt% of the total weight of zinc and gallium) is selected before the esterification reaction. When the esterified raw material is beaten and mixed, 0.5 wt% of the gallium-doped zinc oxide powder is added to the esterification raw material, and the esterification process is started. The precondensation and polycondensation reactions are carried out under a negative pressure, the reaction temperature is controlled to be 270 ° C to 285 ° C, and the residence time of the reactant is controlled to be 1.0 to 3.0 hours. The degree of vacuum of the precondensation reaction is controlled from 1.0 kpa to 2.0 kpa, and the degree of vacuum of the polycondensation reaction is controlled from 0.1 kpa to 0.2 kpa. The polycondensation catalyst is ethylene glycol ruthenium, and the amount is determined by the weight of the monomeric terephthalic acid, and is controlled by cesium ions, and is controlled to be 120 mg/kg to 300 mg/kg. After the polycondensation reaction is completed, a polyester polymer composite is obtained. The polyester composite containing the gallium-doped zinc oxide powder was made into a 74d/48f polyester fiber by a spinning and false twisting process, and woven into a knitted fabric having a basis weight of 175 g/m ² .

The average reflectance of the knitted fabric of Example 10 in the visible light wavelength range of 400 nm to 780 nm and the average absorption rate in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were respectively 72% and 61%, as listed in Table 3.

[Example 11-13]

The knitted fabrics of Examples 11-13 were prepared in the same manner as in Example 10, except that the doping amount of the gallium element and the addition amount of the gallium-doped zinc oxide powder were different, as listed in Table 3.

Similarly, the average reflectance of the knitted fabric of Examples 11-13 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer. As listed in Table 3.

[Comparative Example 6]

The polyester polymer false twist was made into a 75d/48f polyester fiber by a spinning and false twisting process, and then woven into a knitted fabric having a basis weight of 175 g/m ² .

The average reflectance of the knitted fabric of Comparative Example 6 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were 74% and 44%, as listed in Table 3.

[Comparative Example 7]

The zirconium carbide powder having a particle diameter of 100 nm is firstly dispersed in a jet mill with a dispersing agent such as Trimethylolethane or Polyvinyl pyrrolidone (in an amount of 20 wt% to 100 wt% of the powder). Crushing and dispersing, and then directly blending with polyester, wherein the weight ratio of zirconium carbide powder is 1.5 wt% (relative to the total weight of zirconium carbide powder and polyester), and the spinning and false twisting project will be The polypropylene composite false-twist containing zirconia powder was a 75d/48f polyester fiber and woven into a knitted fabric having a basis weight of 175 g/m ² .

The average reflectance of the knitted fabric of Comparative Example 7 in the visible light wavelength range of 400 nm to 780 nm and the average absorption ratio in the infrared wavelength range of 780 to 2500 nm were tested using an integrating sphere spectrophotometer, and the results were respectively 25% and 61%, as listed in Table 3.

From the comparison results of the average infrared absorption rate and the degree of temperature rise of the knitted fabrics of the above respective examples and comparative examples, it is understood that the knitted fabric made of the zinc oxide powder containing the doping element has infrared absorption properties. A knitted fabric made of fibers other than powder. Moreover, the average visible light reflectance difference between the examples and the knitted fabric of the comparative example containing no powder was very small, indicating that the addition of the zinc oxide powder containing the doping element did not affect the color of the textile. However, the comparative visible light reflectance of the textile of the comparative example in which the zirconia powder was added was significantly lower than that of the textile of the example, indicating that the zirconium carbide seriously affects the color of the textile, and thus the color application of the textile for clothing has been severely restricted.

Further, a knitted fabric made of a fiber containing a doped element of zinc oxide powder has a higher temperature rise than a knitted fabric made of a fiber containing no powder.

Therefore, it can be seen from the above results that the present invention uses a powder having an infrared absorbing function to be added and dispersed in the interior of the fiber main body, so that the fiber and the textile produced therefrom can have a high infrared absorbing ability and can be preferably obtained. The warmth effect.

Although the present invention has been disclosed in its preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

Claims (15)

A fiber having an infrared absorbing function, comprising: a fiber body; and a powder having an infrared absorbing function, which is added and dispersed in the interior of the fiber body, wherein the powder comprises gallium, aluminum or a combination of the foregoing elements. A zinc powder, or a combination of the aforementioned zinc oxide powders having doping elements. The fiber having an infrared absorbing function as described in claim 1, wherein the doping element is 0.1 to 20% by weight with respect to the total weight of the zinc and the doping element in the zinc oxide powder. The fiber having an infrared absorbing function as described in claim 1, wherein the powder accounts for 0.1 to 10% by weight. The fiber having an infrared absorbing function as described in claim 1, wherein the fiber body comprises polyethylene fiber, polypropylene fiber, polyamide fiber, polyester fiber or a combination thereof. A textile having an infrared absorbing function, comprising the fiber having an infrared absorbing function as described in claim 1 of the patent application. A textile having an infrared absorbing function as described in claim 5, further comprising at least one fiber blended with the fiber having an infrared absorbing function. A textile having an infrared absorbing function as described in claim 6, wherein the fiber and the infrared absorbing fiber comprise polyethylene fiber, polypropylene fiber, polyamide fiber, polyester fiber, cotton fiber, and enamel. Tantalum fiber or acetate fiber, or modified fiber mainly composed of the above fiber. A method for manufacturing a fiber having an infrared absorbing function, comprising: Providing a powder having an infrared absorbing function; providing at least one monomer mixed with the powder; polymerizing the monomer to form a composite material in which at least one polymer is mixed with the powder: and spinning the composite material Engineering to form a fiber having an infrared absorbing function, wherein the powder is added and dispersed inside the fiber, and the powder includes zinc oxide powder doped with gallium, aluminum or a combination of the foregoing elements, or the foregoing doped A combination of elemental zinc oxide powders. The method for producing a fiber having an infrared absorbing function according to claim 8, wherein the doping element is 0.1 to 20% by weight with respect to the total weight of zinc and the doping element in the zinc oxide powder. . The method for producing a fiber having an infrared absorbing function according to claim 8, wherein the monomer comprises a combination of adipic acid/hexamethylenediamine, caprolactam, ethylene glycol/p-benzoic acid A combination of formic acid, ethylene and propylene. The method for producing a fiber having an infrared absorbing function according to claim 8, wherein the polymer comprises polyethylene, polypropylene, polyamine, polyester or a modified polymer mainly composed of the polymer. And the fiber comprises polyethylene fiber, polypropylene fiber, polyamide fiber, polyester fiber or modified fiber mainly composed of the foregoing fiber. The method for producing a fiber having an infrared absorbing function according to claim 8, wherein the powder has an infrared absorbing function, and the powder accounts for 0.1 to 10% by weight. A method for manufacturing a fiber having an infrared absorbing function, comprising: providing a powder having an infrared absorbing function; providing at least one polymer mixed with the powder to form a composite of the polymer and the powder And processing the composite material by a spinning process to form a fiber having an infrared absorbing function, wherein the powder is blended into the interior of the fiber, and the powder comprises doped gallium, aluminum or a combination of the foregoing elements. A zinc oxide powder, or a combination of the foregoing zinc oxide powders having doping elements. The method for producing a fiber having an infrared absorbing function according to claim 13, wherein the powder has an infrared absorbing function of 0.1 to 10% by weight. The method for producing a fiber having an infrared absorbing function according to claim 13, wherein the polymer comprises polyethylene, polypropylene, polyamide, polyester or the combination thereof, and the fiber comprises polyethylene fiber. Polypropylene fiber, polyamide fiber, polyester fiber or modified fiber mainly composed of the foregoing fiber.