Black special-shaped fine denier polyamide 6 cool-feeling fiber master batch, and preparation method and application thereof

Abstract

The application discloses a black special-shaped fine denier polyamide 6 cool feeling fiber master batch and a preparation method and application thereof, and belongs to the technical field of new materials. The black color is prepared by selecting three or more than three color dyes and using the color mixing principle, the absorption rate of the black color to near infrared rays is far less than that of carbon black in a conventional black master batch, and the infrared reflection capacity of polyamide 6 black master spinning fiber is greatly improved. The preferred inorganic filler can improve the spinning capacity of polyamide 6 and the infrared reflectivity of the master batch spinning fiber at the same time, and the application in summer outdoor polyamide 6 textiles has low heat absorption and temperature rise and excellent cool feeling effect.

Description

Technical Field

[0001] This invention belongs to the field of fiber masterbatch technology, specifically relating to a black irregular fine denier polyamide 6 cooling fiber masterbatch, its preparation method, and its application. Background Technology

[0002] In recent years, with the increasing attention people pay to comfort and health, the demand for cooling fiber materials has also been growing. Polyamide 6 cooling fiber masterbatch has become a research hotspot in the field of cooling fiber materials due to its special structure and material properties. This fiber masterbatch not only has good moisture absorption and perspiration wicking properties, but also has a noticeable cooling sensation to the touch, making it a promising material for summer clothing, bedding and outdoor sports equipment.

[0003] TWI698563B discloses a heat-insulating dark-colored cooling fiber and the textiles made from it. It utilizes two or more materials selected from nano-Fe, Cu, Ni, Co, or Cr to achieve high near-infrared reflectance and heat insulation properties in the textile fiber. Compared to ordinary black fabrics, it provides approximately 12°C of heat insulation, with a near-infrared reflectance of 50-80%. While the black fabric prepared by this patent exhibits excellent heat insulation and infrared reflectance, the nanoparticles used are chromium and iron compounds with a particle size of 300-1800 nm. Because they are inorganic pigments, their coloring power is low; a concentration of 5% is required in the fiber to achieve a certain level of blackness. Such a high content of inorganic filler is difficult to disperse in the polyamide 6 polymer system, easily causing cobweb-like strands in fine denier or shaped polyamide 6 yarns, affecting subsequent drafting / texturing and weaving processes, resulting in a poor fabric hand feel.

[0004] CN112501708B discloses a cooling fiber and its preparation method. The method involves melt-blending bamboo fiber particles and cooling functional powder into polyamide 6 chips, followed by spinning through a shaped spinneret to obtain a cross-shaped cooling polyamide 6 fiber. Its Q-max can reach 0.416, exhibiting a noticeable cooling sensation upon contact and significant antibacterial effects. The bamboo fiber particles used in this patent have a particle size of 100μm to 300μm, which is relatively coarse and only suitable for low-speed spinning of coarse denier polyamide 6 fibers. Furthermore, due to the use of thermally conductive fillers such as jade, its use in outdoor textiles would actually result in a warmer effect. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0006] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0007] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a black irregular fine denier polyamide 6 cooling fiber masterbatch.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution: the masterbatch, by weight parts, comprises,

[0009] 1-30 parts of inorganic nanofiller, 35-60 parts of polyamide 6 resin, 1-30 parts of composite pigments and dyes, and 1-5 parts of dispersant;

[0010] The composite dye is a black dye obtained by compounding three or more of the following: Solvent Red 179, Pigment Red 214, Solvent Red 135, Pigment Orange 68, Pigment Yellow 95, Pigment Yellow 196, Solvent Yellow 157, Pigment Green 7, Pigment Blue 15:3, Pigment Blue 60, Solvent Blue 104, and Solvent Violet 13.

[0011] As a preferred embodiment of the black irregular fine denier polyamide 6 cooling fiber masterbatch of the present invention, wherein the inorganic nanofiller includes one or more of nano zinc oxide, titanium dioxide, and barium sulfate.

[0012] As a preferred embodiment of the black irregular fine denier polyamide 6 cooling fiber masterbatch of the present invention, wherein the dispersant includes one or more of vinyl acetate copolymer, ethylene bis-stearamide, and oxidized polyethylene wax.

[0013] Another objective of this invention is to provide a method for preparing a black, irregularly shaped, fine-denier polyamide 6 cooling fiber masterbatch.

[0014] To solve the above-mentioned technical problems, the present invention provides the following technical solution: including,

[0015] Inorganic nanopowder, composite dyes and dispersants are premixed at low speed and thoroughly moistened before being added to polyamide 6 resin for high-speed mixing. The blended material is then fed into the feed hopper of a twin-screw extruder for extrusion granulation to obtain polyamide 6 cooling fiber masterbatch.

[0016] In a preferred embodiment of the preparation method of the black irregular fine denier polyamide 6 cooling fiber masterbatch of the present invention, the low-speed premixing is performed at a speed of 450~550 rpm for 3~7 min.

[0017] In a preferred embodiment of the preparation method of the black irregular fine denier polyamide 6 cooling fiber masterbatch of the present invention, the high-speed mixing is performed at a speed of 900~1100 rpm for 8~12 min.

[0018] In a preferred embodiment of the preparation method of the black irregular fine denier polyamide 6 cooling fiber masterbatch of the present invention, wherein: in the extrusion granulation, the maximum extrusion temperature is set to 260~280℃.

[0019] Another object of the present invention is to provide a cooling fiber using the aforementioned black profiled fine denier polyamide 6 cooling fiber masterbatch.

[0020] As a preferred embodiment of the cooling fiber of the present invention, the amount of black irregular fine denier polyamide 6 cooling fiber masterbatch added in the cooling fiber is 5~7wt%.

[0021] As a preferred embodiment of the cooling fiber of the present invention, the content of inorganic nanofiller in the cooling fiber is <2wt%.

[0022] Beneficial effects of this invention:

[0023] This invention uses a combination of three or more pigments and dyes to create black using color mixing principles. The black produced by this method has a much lower absorption rate of near-infrared light than carbon black in conventional black masterbatches, which greatly improves the infrared reflectivity of polyamide 6 black masterbatch spun fibers.

[0024] The preferred inorganic filler of this invention can improve the spinning ability of polyamide 6 while increasing the infrared reflectivity of the masterbatch spun fibers. When applied to outdoor polyamide 6 textiles in summer, it has low heat absorption and temperature rise, and has an excellent cooling effect. Attached Figure Description

[0025] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0026] Figure 1 This is a simulation diagram of sunlight exposure testing according to the present invention, wherein 1) is the placement position of the temperature probe of the simulation testing device, 2) is the placement position of the test cloth sample during the simulation, and 3) is the irradiation position of the infrared lamp. Detailed Implementation

[0027] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0028] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0029] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0030] Unless otherwise specified, all raw materials used in this invention are commercially available in the field. The polyamide 6 resin used has a melting point of 215~225℃ and a relative viscosity of 2.46±0.05.

[0031] Example 1

[0032] 1) Weigh the raw materials according to the following formula:

[0033] 12.8 parts solvent red 179, 5.7 parts pigment green 7, 5.4 parts pigment blue 15:3, 25 parts inorganic nanofiller (5 parts nano zinc oxide, 20 parts nano titanium dioxide), 2.5 parts dispersant (vinyl acetate copolymer), 48.6 parts polyamide 6 resin;

[0034] Preparation of masterbatch: Solvent Red 179, Pigment Green 7, Pigment Blue 15:3, nano zinc oxide, nano titanium oxide, and vinyl acetate copolymer were mixed at a low speed of 500 rpm for 5 min, and then polyamide 6 resin was added and mixed at a high speed of 1000 rpm for 10 min.

[0035] The mixed material is added to the hopper of a twin-screw extruder. The screw speed is set to 250 rpm, and the maximum screw temperature is set to 270℃ for extrusion granulation. The masterbatch filtration pressure is 0.6 MPa / g.cm. 2 Black irregular fine denier polyamide 6 cooling fiber masterbatch was obtained.

[0036] Spinning: Adding the obtained black profiled fine denier polyamide 6 cooling fiber masterbatch at an addition rate of 5wt% to the polyamide spinning system can spin 75D / 72f "cross" shaped filaments.

[0037] Example 2

[0038] The difference between this embodiment and Embodiment 1 is that the 20 parts of nano-titanium dioxide in the inorganic nanofiller in Embodiment 1 are replaced with 20 parts of nano-barium sulfate. All other process steps and parameters are the same as in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0039] Comparative Example 1

[0040] The difference between this comparative example and Example 1 is that no inorganic nanofiller is added, the amount of polyamide 6 resin is adjusted to 73.6 parts, and the remaining process parameters are the same as in Example 1. The masterbatch of this example is obtained and spun to obtain cool-feeling fibers.

[0041] Comparative Example 2

[0042] The difference between this comparative example and Example 1 is that, instead of using composite pigments to color the black masterbatch, conventional carbon black was used directly as the dye to obtain the masterbatch of this comparative example, which was then spun to obtain cool-feeling fibers.

[0043] Reference Figure 1 The fibers of the example and the comparative example were irradiated with a 100W infrared lamp for 5 minutes to observe the temperature rise and evaluate the spinning performance. The results are shown in Table 1.

[0044] Table 1

[0045]

[0046] As can be seen from Table 1, the absorption rate of black near-infrared rays produced by the present invention using the color-tuning principle is much lower than that of carbon black in conventional black masterbatch, which greatly improves the infrared reflectivity of polyamide 6 black masterbatch spun fibers. The added inorganic filler can improve the spinning ability of polyamide 6 while improving the infrared reflectivity of masterbatch spun fibers. When applied to outdoor polyamide 6 textiles in summer, it has low heat absorption and temperature rise, and has an excellent cooling effect.

[0047] Example 3

[0048] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 25 parts of nano zinc oxide, while the other process parameters are the same as those in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0049] Example 4

[0050] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 25 parts of nano titanium dioxide, while the other process steps and parameters are the same as in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0051] Example 5

[0052] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 25 parts of nano barium sulfate, while the other process parameters are the same as those in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0053] Example 6

[0054] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 10 parts of nano zinc oxide and 15 parts of nano titanium dioxide. The remaining process steps and parameters are the same as those in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0055] Example 7

[0056] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 20 parts of nano zinc oxide and 5 parts of nano titanium dioxide. The remaining process parameters are the same as those in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0057] Example 8

[0058] The difference between this embodiment and Example 1 is that the inorganic nanofiller in the formulation of Example 1 is adjusted to 10 parts of nano zinc oxide and 15 parts of nano barium sulfate. The remaining process parameters are the same as those in Example 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0059] Example 9

[0060] The difference between this embodiment and Example 1 is that the inorganic nanofiller in the formulation of Example 1 is adjusted to 20 parts of nano zinc oxide and 5 parts of nano barium sulfate. The remaining process parameters are the same as those in Example 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0061] Example 10

[0062] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 5 parts of nano titanium dioxide and 20 parts of nano barium sulfate. The remaining process steps and parameters are the same as those in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0063] Example 11

[0064] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 10 parts of nano titanium dioxide and 15 parts of nano barium sulfate. The remaining process parameters are the same as those in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0065] Example 12

[0066] The difference between this embodiment and Embodiment 1 is that the inorganic nanofiller in the formulation of Embodiment 1 is adjusted to 20 parts of nano titanium dioxide and 5 parts of nano barium sulfate. The remaining process steps and parameters are the same as those in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0067] Following the aforementioned method, the fibers of Examples 3-12 were irradiated with a 100W infrared lamp for 5 minutes. The temperature rise was observed and the spinning performance was evaluated. The results are shown in Table 2, compared with Examples 1 and 2.

[0068] Table 2

[0069]

[0070] As can be seen from Table 2, adjusting the formulation of inorganic fillers has a significant impact on the infrared reflection effect and spinnability of fibers. In particular, the fibers prepared by the schemes in Examples 3 and 6-9 have poor spinnability and are not suitable for actual production applications.

[0071] Furthermore, different types of fillers and their proportions can also cause differences in the infrared reflection effect of fibers. This is because there are mutual adsorption, aggregation and stacking effects between composite inorganic fillers and other matrices. These interactions affect the dispersibility and stability of fillers in polyamide 6 resin, which in turn affects the infrared reflection performance of fibers and ultimately affects the performance of cool-feeling fibers. In the compounding scheme of the present invention, the fibers obtained all have good infrared reflection effects.

[0072] Example 13

[0073] The difference between this embodiment and Embodiment 1 is that the proportions of inorganic nanofillers in the masterbatch formula are adjusted to 15, 20, 30, and 35, respectively. The remaining process parameters are the same as in Embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0074] The fiber prepared in this example was irradiated with a 100W infrared lamp for 5 minutes according to the aforementioned method. The temperature rise was observed and the spinning performance was evaluated. The results were compared with those of Example 1 (25 parts of inorganic nanofiller). The results are shown in the table.

[0075] Table 3

[0076]

[0077] Example 14

[0078] The difference between this embodiment and embodiment 2 is that the proportions of inorganic nanofillers in the masterbatch formula are adjusted to 15, 20, 30, and 35, respectively. The remaining process parameters are the same as in embodiment 1. The masterbatch of this embodiment is obtained and spun to obtain cool-feeling fibers.

[0079] The fibers prepared in the example were irradiated with a 100W infrared lamp for 5 minutes according to the aforementioned method. The temperature rise was observed and the spinning performance was evaluated. The results were compared with those of Example 2 (25 parts of inorganic nanofiller). The results are shown in the table.

[0080] Table 4

[0081]

[0082] As can be seen from the above embodiments, the masterbatch obtained under the formulations of Embodiments 1 and 2 of the present invention has good spinnability, and the spun fibers have excellent infrared reflectivity. As can be seen from the results in Tables 3 and 4, the amount of inorganic nanofiller added under the same compound system has a significant impact on the spinnability of the masterbatch and the infrared reflectivity of the fibers. In the scheme of the present invention, only a low amount of inorganic filler is needed to obtain fibers with good infrared reflectivity. At this time, the masterbatch still has good spinnability. However, when the amount is greater than 30 parts, the spinnability of the masterbatch deteriorates and it is not suitable for practical application.

[0083] In summary, the black pigment formulated by this invention using color mixing principles has a much lower absorption rate of near-infrared rays than carbon black in conventional black masterbatches, greatly improving the infrared reflectivity of polyamide 6 black masterbatch spun fibers. At the same time, the inorganic filler preferred in this invention can improve the infrared reflectivity of masterbatch spun fibers while enhancing the spinning ability of polyamide 6. When applied to outdoor polyamide 6 textiles in summer, it has low heat absorption and temperature rise, resulting in excellent cooling effect.

[0084] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A black, irregularly shaped, fine-denier polyamide 6 cooling fiber masterbatch, characterized in that: The masterbatch, by weight parts, includes, 1-30 parts of inorganic nanofiller, 35-60 parts of polyamide 6 resin, 1-30 parts of composite pigments and dyes, and 1-5 parts of dispersant; The inorganic nanofiller is selected from one or more of nano zinc oxide, titanium dioxide, and barium sulfate, and when nano zinc oxide is selected as the inorganic nanofiller, its amount is 5 parts. The composite dye is a black dye obtained by compounding three or more of the following: Solvent Red 179, Pigment Red 214, Solvent Red 135, Pigment Orange 68, Pigment Yellow 95, Pigment Yellow 196, Solvent Yellow 157, Pigment Green 7, Pigment Blue 15:3, Pigment Blue 60, Solvent Blue 104, and Solvent Violet 13.

2. The black irregular fine denier polyamide 6 cooling fiber masterbatch as described in claim 1, characterized in that: The dispersant includes one or more of vinyl acetate copolymer, ethylene bis-stearamide, and oxidized polyethylene wax.

3. The method for preparing black irregular fine denier polyamide 6 cooling fiber masterbatch as described in any one of claims 1 to 2, characterized in that: include, Inorganic nanopowder, composite dyes and dispersants are premixed at low speed and fully wetted and mixed, then polyamide 6 resin is added and mixed at high speed. The blended material is fed into the feed hopper of a twin-screw extruder for extrusion granulation to obtain polyamide 6 cooling fiber masterbatch.

4. The method for preparing the black irregular fine denier polyamide 6 cooling fiber masterbatch as described in claim 3, characterized in that: The low-speed premixing is performed at a speed of 450~550 rpm for 3~7 minutes.

5. The method for preparing the black irregular fine denier polyamide 6 cooling fiber masterbatch as described in claim 3, characterized in that: The high-speed mixing is performed at a speed of 900~1100 rpm for 8~12 minutes.

6. The method for preparing the black irregular fine denier polyamide 6 cooling fiber masterbatch as described in claim 3, characterized in that: In the extrusion granulation, the maximum extrusion temperature is set to 260~280℃.

7. A cooling fiber using the black profiled fine denier polyamide 6 cooling fiber masterbatch as described in any one of claims 1 to 2.

8. The cooling fiber as described in claim 7, characterized in that: The amount of black irregular fine denier polyamide 6 cooling fiber masterbatch added to the cooling fiber is 5~7wt%.

9. The cooling fiber as described in claim 7 or 8, characterized in that: The inorganic nanofiller content in the cooling fiber is <2wt%.

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