KR20120026825A - Ultra violet shielding polyamide compositions and fibers produced therefrom - Google Patents

Abstract

PURPOSE: An ultra violet shielding polyamide composition and a fiber manufactured therefrom capable of improving ultraviolet blocking property and quick-drying characteristic are provided to improve spinning workability and ultraviolet blocking property which does not damaged by washing. CONSTITUTION: An ultra violet shielding polyamide composition comprises 0.01-5 parts by weight of polyethylene-based ionomer and 0.01-5 parts by weight of inorganic particle based on 100.0 parts by weight of polyamide resin. The inorganic particle has average particle diameter of 50-900 nm and refractive index of 1.8 or greater. A difference of refraction index between polyamide resin and the inorganic particle is 0.3-1.7. The polyamide resin is more than one which is selected from a group consisting of crystalline aliphatic polyamide, amorphous copolyamide, and aromatic polyamide.

Description

 Ultraviolet shielding polyamide compositions and fibers produced therefrom}

 The present invention relates to sunscreen polyamide compositions and fibers made therefrom. More specifically, the polyamide composition exhibits excellent UV blocking properties without damage to UV rays even after washing, and has excellent dyeing performance due to its excellent transparency. And to fibers made therefrom.

     In addition, the present invention relates to a polyamide fiber having excellent sweat absorption and quick drying property as well as UV protection.

Recently, due to the destruction of the ozone layer in the air, the possibility of damage of ultraviolet rays increases, and a lot of technologies for manufacturing ultraviolet ray shielding fibers for protecting the human body from ultraviolet rays have been developed.

     In particular, as the activation of leisure sports increases the amount of time spent in the outdoors exposed to a lot of ultraviolet rays, the necessity of a fiber for leisure sports clothing with excellent UV protection. Representative methods for manufacturing such garments include post-processing methods for coating or laminating organic sunscreens on fabrics, etc. This method is expensive to manufacture and may cause environmental problems due to the use of solvents. There is a disadvantage that is sharply lowered.

     As a method of improving such disadvantages, there is a method of manufacturing a fiber by melting and spinning a synthetic resin such as polyamide obtained by mixing and dispersing an inorganic particle sunscreen such as titanium dioxide and zinc oxide in the polymerization by several percent by weight or more. This method has the great advantage of permanently excellent UV protection without damage to UV protection even after several washings, but due to the aggregation of undispersed inorganic particles, the frequency of trimming during the spinning process is extremely high. Since the inorganic particles are added in excess, the texture of the fibers is poor and there is a problem in that the bright dyeing is difficult due to the opacity. Especially in the case of leisure sports clothing which is essential to UV protection, primary colors and bright dyeing clothes are preferred, and the appearance of textiles and clothing corresponding thereto is anticipated.

     In other words, the inorganic particle-based sunscreen agent, which is advantageous for the appearance of permanent sunscreen, is prescribed, but it causes highly dispersed state of the inorganic particles, so that trimming is extremely suppressed. The emergence of new technologies for the production of synthetic fibers, such as the novel polyamides expressed, is very urgent.

     In addition, the fiber for leisure sports clothing not only requires the above-mentioned permanent UV protection, but also absorbs sweat well and easily dry the absorbed sweat. There is also an urgent need for the emergence of new technologies for the production of polyamide fibers that exhibit both fast drying and the like.

In order to solve the above problems, the present inventors have led to the present invention as a result of intensive studies. That is, the present invention has a polyamide resin composition exhibiting excellent dye-blocking property due to transparency while at the same time exhibiting excellent UV-blocking property without damaging the UV-blocking property even when washing with trimming having extremely suppressed spinning workability. And fibers made therefrom.

     In addition, the present invention is to provide a polyamide fiber having excellent permanent UV protection and vivid dyeing, while also exhibiting excellent sweat absorption and quick drying.

In order to solve the above object, the present invention is a polyethylene ionomer 0.01 to 5 parts by weight, an average particle diameter of 50 to 900nm, a refractive index of 1.8 or more and a refractive index difference of 0.3 to 1.7 with respect to 100 parts by weight of polyamide resin When providing a sunscreen polyamide resin composition comprising 0.01 to 5 parts by weight of inorganic particles, surprisingly semi-permanently exerts excellent UV protection, while at the same time significantly lower transparency and trimming rate (radiation workability) Remarkable improvement), dyeing property and excellent sweat absorption and quick drying can be produced simultaneously.

     In another aspect, the present invention provides a sunscreen polyamide fiber characterized in that the resin composition is obtained by melt spinning.

     In another aspect, the present invention is to provide a sunscreen sweat-absorbing quick-drying polyamide fibers, characterized in that the resin composition is obtained by spinning through a mold having a release cross-section.

     An important object of the present invention is to secure permanent UV protection. Therefore, the use of inorganic sunscreens instead of organic sunscreens is advantageously adopted. The reason for this is not clear, but in the composition of the present invention, the dispersion properties are significantly improved and at the same time, the average particle diameter is 50 to 900 nm and the refractive index is 1.8 or more, preferably 1.8 to 3.5, and the difference between the polyamide resin and the refractive index is 0.3 or more. In the case of using inorganic particles, preferably 0.3 to 1.7, this UV blocking effect was very excellent.

     Another important purpose is to dramatically improve the transparency of the resin composition for clear dyeing expression compared to the prior art. In general, when several weight percent of the micro-size inorganic particles are added to the polyamide resin, it becomes an opaque resin composition of 90% or more on a haze basis, and when the fiber is manufactured by melt spinning, vivid dyeability cannot be expressed.

     In order to overcome this problem, a nano-size inorganic particle having a refractive index of 0.3 or more difference with respect to a polyamide resin, a so-called nano inorganic particle, was introduced, and a polyethylene-based ionomer having a carboxylic acid group and a metal carboxylate group contained 100 weight of polyamide. When used together with 0.01 to 5 parts by weight, it was possible to produce a significantly improved fiber that satisfies all physical properties such as transparency, sweat absorption and fast drying properties without impairing the UV blocking properties of the present invention.

     In the present invention, the polyamide resin includes polyamide 3, polyamide 4, polyamide 6, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6 Crystalline aliphatic polyamides such as, 10 and the like, amorphous copolyamides such as terephthalic acid and copolymers of isophthalic acid and hexamethylenediamine (eg, Grivory-ems Grivory G21), aromatic polyamides such as polymethyyleneadipamide, etc. (Eg, Mitsubishi Gas Chemical Company Nylon-MXD6) and the like, but are not necessarily limited thereto.

     In the present invention, the polyethylene ionomer is a carboxylic acid group-containing polyethylene copolymer neutralized with metal ions, more specifically, 10 to 80% by weight of the carboxylic acid content of the carboxylic acid group-containing polyethylene copolymer is converted into metal ions. If the neutralization degree is less than 10% by weight, there is a fear that the dispersibility of the inorganic particles is lowered, and when the degree of neutralization exceeds 80% by weight, compatibility with the polyamide resin may be lowered.

     The carboxylic acid group-containing polyethylene-based copolymer is a polyethylene-based copolymer having a carboxylic acid content of 3 to 50% by weight, and when the carboxylic acid content is less than 3% by weight, the dispersibility to inorganic particles may be deteriorated and 50% by weight. If exceeded, the rigidity of the resin itself is weak, which may result in a decrease in the mechanical properties of the polyamide resin composition. The carboxylic acid group-containing polyethylene copolymer is specifically methacrylic acid or acrylic acid-containing polyethylene copolymer, such as methacrylic acid-ethylene copolymer, acrylic acid-ethylene copolymer, methacrylic acid-methyl methacrylate-ethylene copolymer , Acrylic acid-methyl acrylate-ethylene copolymer, and the like, and more specific examples thereof include DucPont Nucrel 0403, a methacrylic acid-ethylene copolymer, and Exoron Mobil Escor 6000, USA, an acrylic acid-ethylene copolymer. Escor AT310 of ExxonMobil, Inc. which is an ethylene copolymer, etc. are mentioned.

     The metal of the metal ion is one or two or more selected from the group consisting of alkali metals such as lithium, sodium, potassium, cesium, alkali metals such as magnesium, calcium, barium, and transition metals such as iron, copper and zinc, and double lithium, sodium, zinc This is more preferable.

     As a more specific example of the polyethylene-based ionomer, SurPoin of DuPont, an ionomer having a copolymer structure of methacrylic acid neutralized with metal ions and ethylene, and an copolymer having a copolymer structure of acrylic acid neutralized with metal ions and ethylene Iotek from ExxonMobil, an ionomer, and the like, are not limited thereto.

     The polyethylene ionomer of the present invention is added 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight based on 100 parts by weight of polyamide. When the amount of the polyethylene-based ionomer is less than 0.01 parts by weight, it is difficult to express highly dispersible and desired compatibility with polyamide resin for the desired nano-inorganic particles, and when it exceeds 5 parts by weight, the rigidity is inferior and the polyethylene-based ionomer Due to the high price, the economy may be inferior.

     In the present invention, the inorganic particles include, but are not limited to, titanium dioxide, zinc oxide, cerium oxide, zirconium dioxide, chromium trioxide, copper oxide, iron trioxide, nickel oxide, and the like. In particular, double titanium oxide, zinc oxide, cerium oxide and the like are more preferable.

     In particular, in the present invention, the refractive index of the inorganic particles is preferably 1.8 or more, preferably 1.8 to 3.5. If the refractive index of the inorganic particles is less than 1.8, it is not easy to express the sunscreen effect by surface reflection or scattering, and in order to obtain a desired sunscreen effect, an excessive amount of inorganic particles should be added to the polyamide resin. Is difficult. On the other hand, when the refractive index of the inorganic particles is too high, it is difficult to secure the desired transparency (clear dyeing) due to the extreme surface reflection or scattering, and inorganic particles having a difference in refractive index of 0.3 to 1.7 and preferably 0.4 to 1.5 from polyamide resin are preferable. . In other words, when the difference between the refractive index and the polyamide resin is less than 0.3, it is not easy to express the sunscreen effect due to surface reflection or scattering, whereas when the difference between the polyamide resin and the refractive index is more than 1.7, the surface reflection or scattering is severe and thus the desired transparency (clear Dyeability) is difficult to achieve and it is difficult to achieve the object of the present invention.

     The form of the inorganic particles may be any of spherical, needle-like, and plate-shaped, but a spherical shape is preferable, and an average particle diameter is preferably 10 to 900 nm, more preferably 100 to 600 nm. If the average particle size is less than 10nm, the particle size is so small that scattering hardly occurs, so that the effect of UV blocking may be lowered. If it exceeds 900nm, transparency is impaired and it is difficult to secure desired vivid dyeability.

     The inorganic particles of the present invention is added 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight based on 100 parts by weight of polyamide resin. When the added amount of the inorganic particles is less than 0.01 parts by weight, it is difficult to secure the desired UV blocking properties, and when it exceeds 5 parts by weight, it may be difficult to secure vivid dyeability due to transparency damage.

     The polyamide resin composition prepared in the present invention may further include conventional additives such as antioxidants, heat stabilizers, pigments, optical brighteners, antibacterial agents, deodorants, flame retardants, antistatic agents, etc. in a range that does not impair the object of the present invention. It can mix | blend it.

In the present invention, with respect to 100 parts by weight of the polyamide resin, 0.01 to 5 parts by weight of polyethylene ionomer, average particle diameter of 50 to 900nm, refractive index of 1.8 or more, inorganic particles 0.01 ~ 1.7 of the refractive index difference between the polyamide resin and 0.01 ~ By mixing 5 parts by weight in an appropriate ratio it can be prepared in the form of a compound pellet by injecting into a hopper of the kneader such as a single screw extruder, a twin screw extruder, mixing rolls, balbaric mixer, kneader and melt kneading.

     In addition, the polyamide resin composition is a mixture of 30 to 70% by weight polyethylene ionomer 30 to 70% by weight, an average particle diameter of 50 to 900nm, a refractive index of 1.8 or more, and a polyamide resin and an inorganic particle having a refractive index difference of 0.3 to 1.7. After mixing and entering into the hopper of the kneader, melt-kneading and dispersing to prepare a pellet-shaped inorganic particle masterbatch (A), the polyamide resin, polyethylene ionomer, inorganic particle masterbatch (A) by drive landing It may be obtained by mixing or by mixing the mixture into the hopper of the kneader and melt kneading to prepare a pellet form.

The present invention also provides a sunscreen polyamide fiber obtained by the fiber manufacturing method by a conventional melt spinning the polyamide resin composition.

     For example, in consideration of the characteristics of the matrix polyamide resin, the UV-protective polyamide resin composition pellets according to the present invention are appropriately dried, introduced into a hopper of an extruder, melt-extruded, spun through a mold of a constant shape, cooled and heat-set, Ultraviolet-resistant polyamide fibers can be prepared by stretching and post-processing.

     In addition, the present invention, by changing the shape of the detention during the process of manufacturing the fiber using the polyamide resin composition, as well as circular, square, triangular, Y-type, W-type, wang-type, island-in-the-sea, split type such as various shapes It provides a sunscreen absorbent quick-drying polyamide fiber obtained by spinning through the excitation detention.

The UV-protective polyamide fibers having the release cross-section not only exert UV protection, but also form a passage that acts as a capillary tube when the fibers (filaments) come into contact with each other. While being physically bonded to the surface, it can be easily discharged by deformation force such as torsion, so as to exhibit so-called quick drying property which causes rapid drying. In particular, in the present invention, the market for leisure sports apparel fibers, which are the main targets of the present invention, require permanent UV protection, and also have a great demand for quick-drying moisture absorption.

 As described above, the polyamide resin composition according to the present invention and the fiber produced therefrom have extremely suppressed spinning action while trimming and exfoliate permanently without damaging the UV blocking property even after washing. Due to its transparency, it is vividly dyed, and when it is spin processed into a sectional cross-section yarn, it is also a breakthrough in sweat absorption and dryness. It is expected to be very useful for clothing, especially leisure sports clothing.

 Hereinafter, the present invention will be described in more detail with reference to Examples, which are intended only for understanding the constitution and effects of the present invention and are not intended to limit the scope of the present invention.

     UV protection, transparency, radioworkability, absorbency and dryness of the sunscreen polyamide resin composition and fibers of the present invention were evaluated by the following test methods.

1. UV protection

     In consideration of the fact that it is difficult to evaluate the UV protection property by the fiber (filament) itself, a sample resin is used to produce a film having a thickness of 20 μm (3 denier fiber diameter level), and the UV-VIS Spectrometer is used in the UV region for the sample film. UV protection (%) was assessed as a percentage of the amount not permeable.

2. Haze

     Transparency, which can be a measure of vivid dyeability, was evaluated as blurring. The hazemeter (%) was measured using a hazemeter according to ASTM D1004 for a film sample having a thickness of 20 μm (3 denier fiber diameter level) used in the evaluation of the UV protection property.

3. Radio workability

     The radioworkability was evaluated as the frequency of trimming during spinning. In the measurement results, ◎ (excellent) indicates the case of less than one time / day, ○ (good) indicates the case of one time / day, △ (normal) indicates the case of 23 times / day, and X (defect) four times. It represents the case of / day or more.

4. Absorbent

     It measured based on the Wicking Test published in KS K0815.5.27. In other words, the sample fabric (filament) using a 32 gauge interlock double-sided circular knitting machine was woven and then cut it into 2.5 cm wide by 20 cm long to prepare a fabric sample. One part of the fabric sample was immersed in water for 2.5 cm, left for 10 minutes, and the average value was obtained by measuring the height (mm) of moisture absorbed in the fabric sample three times. In the measurement results, ◎ (excellent) indicates the case of 150 mm / 10 minutes or more, ○ (good) indicates the case of 100 150 mm / 10 minutes, △ (normal) indicates the case of 50 100 mm / 10 minutes, and X (bad) indicates 50 mm / The case of less than 10 minutes is shown.

5. Dryability

     It evaluated using the fabric sample produced for the absorbency evaluation. That is, after dropping 0.05cc of water into the fabric sample, the time taken for complete drying was measured and set as the drying speed. In the measurement results, ◎ (excellent) indicates a case of less than 20 minutes, ○ (good) indicates a case of 2035 minutes, △ (normal) indicates a case of 3550 minutes, and X (bad) indicates a case of exceeding 50 minutes. .

     Example 1

Polyamide 6 (PA-A) (refractive index 1.55) having a relative viscosity of 2.5 was prepared as a polyamide resin, and a polyethylene ionomer had a melt viscosity of 0.9 g / 10 min and was neutralized with sodium ions (neutralization 60%). DuPont's Surlyn 8920 (PEI-A), an ionomer that is a copolymer of acrylic acid (15% by weight) and ethylene, was prepared. Rutile type dioxide with an index of refraction of 2.76 and an average particle diameter of 300 nm was prepared. Titanium (TiO ₂ -A) was prepared. The mixture prepared by mixing the prepared raw materials at a blending ratio of 100 parts by weight of PA-A, 0.1 parts by weight of PEI-A, and 1.0 parts by weight of TiO ₂ -A was kneaded and dispersed in a L / D 42, 90Φ twin screw extruder under conditions of a cylinder temperature of 260 ° C. To obtain a polyamide resin composition (A) in the form of pellets.

     The obtained polyamide resin composition (A) pellets were dried to a moisture content of 0.05% by weight or less and introduced into an extruder hopper and melt-extruded to prepare a spinning solution. The spinning solution is spun through a circular spinneret with a spinneret at a spinning temperature of 260 ° C and a spinning speed of 4,000m / min, cooled by blowing air at 20 ° C at a wind speed of 0.5m / min, and undergoing heat setting and stretching. After that, 3 denier polyamide fibers (A) were obtained. The obtained polyamide resin composition (A) was prepared using a heating press to produce a film having a thickness of 20 μm (3 denier fiber diameter level), and the UV protection and cloudiness were measured, and the polyamide resin composition (A) was used to spin the polyamide fiber. The radioworkability was evaluated as the frequency of trimming during spinning during (A). The results are shown in Table 1.

     [Example 2]

The polyamide resin was prepared in the same manner as in Example 1 except that the mixture prepared by mixing the raw material prepared in Example 1 with 100 parts by weight of PA-A, 0.5 parts by weight of PEI-A, and 1.0 parts by weight of TiO ₂ -A was used. A pellet of the composition (B) was obtained and was then used in the same manner as in Example 1 to obtain 3denier polyamide fibers (B). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Example 3

The polyamide resin was prepared in the same manner as in Example 1 except that the mixture prepared by mixing the raw materials prepared in Example 1 with 100 parts by weight of PA-A, 1.0 parts by weight of PEI-A, and 1.0 parts by weight of TiO ₂ -A was used. A pellet of the composition (C) was obtained and was then used in the same manner as in Example 1 to obtain 3denier polyamide fibers (C). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Example 4

The polyamide resin was prepared in the same manner as in Example 1 except that the mixture prepared by mixing the raw material prepared in Example 1 with 100 parts by weight of PA-A, 1.5 parts by weight of PEI-A, and 4.0 parts by weight of TiO ₂ -A was used. A pellet of the composition (D) was obtained and was then used in the same manner as in Example 1 to obtain 3denier polyamide fibers (D). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Example 5

A mixture of 50 wt% PEI-A and 50 wt% TiO ₂ -A, which are the raw materials prepared in Example 1, was kneaded and dispersed in a L / D 42, 90Φ twin screw extruder under a cylinder temperature of 200 ° C. In the form, an inorganic particle masterbatch (A) was obtained. Pellet-based PA-A, PEI-A and inorganic master bezel (A) were dry-branded and mixed and adjusted to a blending ratio of 100 parts by weight of PA-A, 1.0 parts by weight of PEI-A, and 3.0 parts by weight of TiO ₂ -A to polyamide resin. A pellet of the composition (E) was obtained and used in the same manner as in Example 1 to obtain 3denier polyamide fibers (E). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     [Example 6]

Polyethylene-based ionomer, DuPont's Surlyn, a copolymer of methacrylic acid (35% by weight) and ethylene (65% by weight) neutralized with zinc ions (neutrality of 37%) with a melt viscosity of 5.0 g / 10 min 9950 (PEI-B) was prepared, and an inorganic particle masterbatch (B) having a blending ratio of 50 wt% of PEI-B and 50 wt% of TiO ₂ -A was prepared in the same manner as in Example 5. Pellet-based PA-A, PEI-B and inorganic masterbatches (B) were dry-branded and mixed and adjusted to a blending ratio of 100 parts by weight of PA-A, 0.1 parts by weight of PEI-B, and 0.05 parts by weight of TiO ₂ -A to form polyamide resin. A pellet of the composition (F) was obtained and was also used in the same manner as in Example 1 to obtain 3denier polyamide fibers (F). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Example 7

     As the inorganic particles, zinc oxide (ZnO-A) having a refractive index of 2.01 and an average particle diameter of 500 nm was prepared. According to the same method as in Example 5, an inorganic particle masterbatch (C) having a blending ratio of 50 wt% of PEI-B and 50 wt% of ZnO-A was obtained. Pellet-based PA-A, PEI-B and inorganic masterbatches (C) were dry-branded and mixed and adjusted to a blending ratio of 100 parts by weight of PA-A, 1.0 parts by weight of PEI-B, and 2.0 parts by weight of ZnO-A to form a polyamide resin composition. (G) A pellet was obtained and was used in the same manner as in Example 1 to obtain 3denier polyamide fiber (G). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Comparative Example 1

As inorganic particles, rutile titanium dioxide (TiO ₂ -B) having a refractive index of 2.76 and an average particle diameter of 2,500 nm was prepared. A polyamide resin composition (H) pellet was obtained in the same manner as in Example 1, except that 100 parts by weight of PA-A and a mixture of TiO ₂ -B 3.0 parts by weight were used. The same procedure was followed to obtain 3 denier polyamide fibers (H). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Comparative Example 2

A polyamide resin composition (I) pellet was obtained in the same manner as in Example 1 except that the mixture obtained by mixing the raw material obtained in Example 1 with 100 parts by weight of PA-A and 1.0 parts by weight of TiO ₂ -A was used. This was carried out in the same manner as in Example 1 to obtain 3 denier polyamide fibers (I). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Comparative Example 3

As inorganic particles, calcium carbonate (CaCO ₃ -A) having a refractive index of 1.58 and an average particle diameter of 40 nm was prepared. A polyamide resin composition (J) pellet was obtained in the same manner as in Example 1, except that 100 parts by weight of PA-A and a mixture of CaCO ₃ -A 1.0 parts by weight were used. The same procedure was followed to obtain 3 denier polyamide fibers (J). UV protection, cloudiness and radioworkability were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

     Example 8

From the raw material obtained in Example 6, dry blending of the PA-A, PEI-B and the inorganic masterbatch (B) in the pellet state, the blending ratio of 100 parts by weight of PA-A, 0.7 parts by weight of PEI-B, 1.5 parts by weight of TiO ₂ -A The mixture was adjusted to obtain a polyamide resin composition (K) pellet.

     The obtained polyamide resin composition (K) pellets were dried to a moisture content of 0.05% by weight or less and introduced into an extruder hopper and melt-extruded to prepare a spinning solution. The prepared spinning solution was carried out in the same manner as in Example 1 except that the spinneret having a Y-shaped cross-section shown in Fig. 1 (a) was obtained to obtain 3denier polyamide fibers (K). In the same manner as in Example 1, UV protection, cloudiness and emissivity were evaluated, and the absorbency and dryness of the fiber were evaluated and the results are shown in Table 1.

     Example 9

     As a polyamide resin, a polyamide 6,6 (PA-B) pellet having a relative viscosity of 40 was prepared. Mix and adjust the inorganic masterbatch (C) obtained in Example 7 and PA-B and PEI-B in pellet form by blending ratio of 100 parts by weight of PA-B, 1.0 parts by weight of PEI-B, and 2.0 parts by weight of ZnO-A 2.0 parts by weight. To obtain a polyamide resin composition (L) pellet.

     The obtained polyamide resin composition (L) pellets were dried to a moisture content of 0.05% by weight or less, charged into an extruder hopper, and melt-extruded to prepare a spinning solution. 3denier polyamide fibers (L) were obtained in the same manner as in Example 1 except that the prepared spinning solution was passed through a spinneret having a wang cross-sectional structure shown in Fig. 1 (b) and the spinning temperature was adjusted to 305 ° C. . In the same manner as in Example 1, UV protection, cloudiness and emissivity were evaluated, and the absorbency and dryness of the fiber were evaluated and the results are shown in Table 1.

     [Comparative Example 4]

The same method as in Example 1 except that PA-B prepared in Example 9 and TiO ₂ -B prepared in Comparative Example 1 were used in a mixture of 100 parts by weight of PA-B and 2.0 parts by weight of TiO ₂ -B. The polyamide resin composition (M) pellets were obtained, and the same procedure as in Example 1 was used to obtain 3 denier polyamide fibers (M). In the same manner as in Example 1, UV protection, cloudiness and emissivity were evaluated, and the absorbency and dryness of the fiber were evaluated and the results are shown in Table 1.

In Example 13, the same inorganic particles were contained, but as the polyethylene-based ionomer content was increased, it was found that the UV protection, transparency, and radiation workability tended to be excellent. Example 4 having a high content of inorganic particles can be seen that it exhibits perfect UV protection while maintaining good transparency and radiation workability. Comparing Example 5 and Example 4, which is a case where a polyamide resin composition is prepared by using inorganic particles as a master batch, Example 5 exhibits perfect UV protection while having less inorganic content than Example 4, while providing transparency. And it can be seen that the spinning workability is more excellent.

     As can be seen in Examples 6 and 7, even when the metal ion of polyethylene ionomer is changed from sodium ion to zinc ion, it exhibits excellent UV protection, transparency, and radio workability, and it is 1.8 or more even if the inorganic particles are changed from titanium dioxide to zinc oxide. When the refractive index difference between the polyamide resin and the high refractive index is 0.3 to 1.7 and the average particle diameter is 50 to 900 nm, it can be seen that it exhibits excellent UV protection, transparency, and radiation workability.

     In particular, when compared with Comparative Example 1 using inorganic particles having an average particle diameter of 900 nm or more without using the polyethylene ionomer according to Example 5 and the present invention, Comparative Example 1 exhibited some degree of UV protection, but the transparency and radiation work It can be seen that the sex is extremely poor. In addition, the polyamide resin and the refractive index difference is in the range of 0.3 to 1.7 and has a high refractive index of 1.8 or more, and titanium dioxide inorganic particles having an average particle diameter of 50 to 900 nm are used, but a smaller amount is used than Comparative Example 1 and no polyethylene ionomer is used. In Comparative Example 2 not shown, it can be seen that the poor in all aspects of UV protection, transparency, radiation workability.

     In addition, as in Example 17, a polyethylene-based ionomer was used, and an inorganic particle having an average particle diameter of 50 to 900 nm, but having a refractive index lower than 1.8 and a difference in refractive index with a polyamide resin, was not in the range of 0.3 to 1.7. In Comparative Example 3 using calcium it can be seen that the transparency and radiation workability is good but the desired UV protection.

The fibers of Examples 8 and 9 obtained by using the polyamide resin composition according to the present invention and spun through a mold having a heteromorphic cross section such as Y-type, 王 -type, rather than circular cross-section mold, are characterized by UV protection, transparency, It can be seen that not only the spinning workability is excellent, but also the absorption and drying properties, that is, the sweat-absorbing quick drying property. In particular, the difference can be clearly seen when comparing the fiber of Comparative Example 4 obtained by spinning a simple composition with the polyamide resin and the inorganic particles according to the prior art through a circular cross section detention.

Claims (16)

0.01 to 5 parts by weight of polyethylene ionomer, average particle diameter of 50 to 900 nm, refractive index of 1.8 or more, and 0.01 to 5 parts by weight of inorganic particles having a refractive index difference of 0.3 to 1.7 with respect to 100 parts by weight of polyamide resin. UV-blocking polyamide resin composition, characterized in that. The method of claim 1,
The polyamide resin is a sunscreen polyamide resin composition, characterized in that at least one selected from the group consisting of crystalline aliphatic polyamide, amorphous copolyamide, aromatic polyamide. The method of claim 2,
The crystalline aliphatic polyamide resin is polyamide 3, polyamide 4, polyamide 6, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6, A sunscreen polyamide resin composition, characterized in that at least one selected from the group consisting of 10. The method of claim 1,
The polyethylene ionomer is a sunscreen polyamide resin composition, characterized in that the carboxylic acid group-containing polyethylene copolymer neutralized with metal ions. The method of claim 4, wherein
The polyethylene ionomer is a UV-blocking polyamide resin composition, characterized in that the carboxylic acid content of the carboxylic acid group-containing polyethylene copolymer is 10 to 80% by weight neutralized with metal ions. The method of claim 4, wherein
The metal is an ultraviolet blocking polyamide resin composition, characterized in that at least one selected from the group consisting of alkali metal, alkaline earth metal, transition metal. The method of claim 4, wherein
The carboxylic acid group-containing polyethylene copolymer is a sunscreen polyamide resin composition, characterized in that the methacrylic acid or acrylic acid-containing polyethylene copolymer.


The method of claim 4, wherein
The carboxylic acid group-containing polyethylene copolymer is a sunscreen polyamide resin composition, characterized in that the carboxylic acid content of 3 to 50% by weight. The method of claim 1,
The inorganic particles are at least one sunscreen polyamide resin composition selected from the group consisting of titanium dioxide, zinc oxide, cerium oxide, zirconium dioxide, chromium trioxide, copper oxide, iron trioxide, nickel oxide. The method of claim 1,
The inorganic particles are at least one UV-blocking polyamide resin composition selected from the group consisting of titanium dioxide, zinc oxide, cerium oxide. The method of claim 1,
UV-blocking polyamide resin composition, characterized in that the inorganic particles are titanium dioxide.


The method of claim 1,
UV-blocking polyamide resin composition, characterized in that the inorganic particles are zinc oxide.      0.01 to 5 parts by weight of polyethylene ionomer, average particle diameter of 50 to 900 nm, refractive index of 1.8 or more, and mixing of polyimide resin with 0.01 to 5 parts by weight of inorganic particles having a difference in refractive index of 0.3 to 1.7 with respect to 100 parts by weight of polyamide resin A method for producing a sunscreen polyamide resin composition, which is introduced into a hopper of a group and melt-kneaded to obtain a pellet. a) 30 to 70 wt% polyethylene ionomer, 50 to 900 nm average particle diameter, 1.8 or more refractive index, and a mixture of polyamide resin and 30 to 70 wt% composition having a refractive index difference of 0.3 to 1.7 Preparing an inorganic particle masterbatch (A) in pellet form by pouring into a hopper and melt kneading;
b) mixing the polyamide resin, polyethylene ionomer, and inorganic particle master batch (A) by dry blending, or mixing the mixture into a hopper of a kneader and melt kneading to prepare a resin composition in pellet form;
Method for producing a sunscreen polyamide resin composition comprising a.      A sunscreen polyamide fiber characterized in that the resin composition according to claim 1 is obtained by melt spinning. 15. The ultraviolet blocking sweat-absorbing quick-drying polyamide fiber according to claim 1 to 14, wherein the resin composition according to claim 1 is obtained by spinning through a mold having a deformed section.