Manufacturing method for in-cylinder fluorine-free water-repellent yarn with reduced adhesion and yellowing

Abstract

This invention provides a method for manufacturing a fluorine-free water-repellent yarn package with reduced adhesion and yellowing, comprising the following steps in sequence: a yarn preparation step, a yarn impregnation step, and a heating step. The method involves subjecting the entire yarn package, composed of wound yarns, to a single-process water-repellent treatment in a vat to form a fluorine-free water-repellent yarn package. The fluorine-free water-repellent yarn in this package will not exhibit yellowing, will not stick together, and preferably can be subsequently dyed.

Description

Manufacturing method for in-cylinder fluorine-free water-repellent yarn with reduced adhesion and yellowing This invention relates to a method for manufacturing a water-repellent yarn, specifically a method for manufacturing a fluorine-free water-repellent yarn by subjecting a whole yarn bobbin, which is composed of wound yarns, to a single-process water-repellent treatment in a vat, thereby forming a fluorine-free water-repellent yarn bobbin. The fluorine-free water-repellent yarn bobbin does not exhibit yellowing, the fluorine-free water-repellent yarns do not stick together, and preferably, the fluorine-free water-repellent yarn can be subsequently dyed. This method reduces adhesion and yellowing in a vat-processed fluorine-free water-repellent yarn bobbin. Currently known water-repellent fabrics are typically produced by applying a water-repellent treatment (such as screen printing, roller printing, and pressure absorption) to the yarn or fabric after the dyeing process. This water-repellent treatment involves applying a water-repellent agent to the dyed yarn or fabric. Water-repellent agents can be categorized into fluorinated and fluorine-free agents. Of these, fluorine-free water-repellent yarns or fabrics made using fluorine-free agents best meet environmental protection requirements. Republic of China Invention Patent Publication No. 201912733 (hereinafter referred to as Document 1) proposes a fluorine-free water-repellent agent and a fluorine-free water-repellent yarn. Document 1 first prepares a fluorine-free water-repellent composition formed by a polyamine-based silicone compound and an acrylic-based fluorine-free water-repellent agent, and then mixes the fluorine-free water-repellent composition with a spinning oil, a chemical fiber oil, or a cotton oil during the spinning process to obtain a fluorine-free water-repellent yarn. However, the first literature has the following problems: (1) When the fluorine-free water-repellent composition attached to the yarn is uneven, the amine groups in the polyamine-siloxane compound are prone to yellowing. Therefore, the appearance of the fluorine-free water-repellent yarn with excessive fluorine-free water-repellent composition will show obvious yellowing or yellowing phenomenon; (2) When the fluorine-free water-repellent composition attached to the yarn is uneven, excessive attachment will easily cause the fluorine-free water-repellent yarn to stick together, which is not conducive to subsequent processing. For example, it will cause yarn breakage when the yarn is unwinding. In addition, the fluorine-free water-repellent composition will destroy the lubrication effect of spinning oil, chemical fiber oil, and cotton oil, which will easily cause the yarn to break. Damaged yarn breaks, thus it cannot be wound into a cone or the yarn breaks when the cone is unwinding, resulting in poor subsequent processing efficiency; (3) Although Literature 1 claims that it can make textiles from fluorine-free water-repellent yarn and then dye and finish them to achieve water-repellent effect, it only provides water-repellent effect and has no experimental results to prove that its fluorine-free water-repellent yarn has good dyeing effect. In fact, Literature 1 dyes the fluorine-free water-repellent layer rather than dyes the fiber. Therefore, the fluorine-free water-repellent layer after dyeing in Literature 1 cannot pass the tests of water wash fastness and water fastness. Therefore, it does not provide relevant test results of dyeing fastness. Furthermore, the fluorine-free water-repellent agent described in Reference 1 forms a fluorine-free water-repellent layer on the surface of the yarn, which is claimed not to affect the fabric's feel. However, in reality, the feel and hand feel recognized by the textile industry are not the same. Excellent water-repellent fabrics formed from fluorine-free water-repellent yarns require not only a soft hand feel, but also that their water repellency, wash fastness to color, and water fastness to color meet the set standard values ​​after washing tests. For water-repellent fabrics to simultaneously possess good softness, water repellency, wash fastness to color, and water fastness to color, in addition to considerations of yarn and fabric structure design, the water repellency treatment and dyeing process conditions must also be taken into account. Therefore, the object of the present invention is to provide a method for manufacturing a fluorine-free water-repellent yarn in a vat with reduced adhesion and yellowing. The method involves performing a single water-repellent process on the entire yarn package, which is composed of wound yarns, in a vat to form a fluorine-free water-repellent yarn package composed of wound fluorine-free water-repellent yarns. The fluorine-free water-repellent yarn package does not exhibit yellowing, the fluorine-free water-repellent yarns do not stick together, and preferably, the fluorine-free water-repellent yarns can be dyed subsequently. Based on the above-mentioned objective, a method for manufacturing dyeable, fluorine-free, water-repellent yarn is provided, comprising the following steps: a yarn preparation step: preparing a yarn, the yarn being wound around a bobbin having a hollow interior to form a bobbin, the bobbin having a plurality of through holes penetrating an outer surface and an inner surface of the bobbin, the plurality of through holes being spaced apart and arranged in a ring around the circumference of the bobbin, the yarn being wound around the outer surface of the bobbin and covering the plurality of through holes; a yarn impregnation step: placing the bobbin in a sealable vat. Inside the body, a fluorine-free water-repellent composition is supplied by a supply device through the hollow interior of the body and through the plurality of through holes, so that the fluorine-free water-repellent composition wets the yarn to form a wetted yarn and the fluorine-free water-repellent composition flows out of the yarn package, and the fluorine-free water-repellent composition flowing out of the yarn package flows back into the supply device to supply the fluorine-free water-repellent composition to form a composition cycle; a heating step: using a heating device and a heating process to heat the fluorine-free water-repellent composition so that the wetted yarn forms a dyeable fluorine-free water-repellent yarn. The inner surface of one of the cylindrical bodies has a guide notch at its lower edge, and the inner surface of the cylindrical body has a groove communicating with the guide notch. The groove extends along a direction of extension of the cylindrical body. The supply device includes a motor and an inlet pipe and an outlet pipe connected to the motor. The outlet pipe supplies the fluorine-free water-repellent component through the cylindrical body and through the plurality of through holes. The fluorine-free water-repellent component flowing out of the yarn package flows back into the inlet pipe to supply the fluorine-free water-repellent component again, forming a circulation of the component. The outlet pipe... The system has a plurality of water outlets, and the outer surface of the water outlet pipe has a protrusion. The cylindrical system is fitted onto the outer surface of the water outlet pipe with the hollow interior. The protrusion slides into the groove through the guide notch. The plurality of water outlets correspond to the plurality of through holes. The fluoride-free water-repellent composition flows through the plurality of water outlets and the plurality of through holes. Furthermore, the position of the yarn and / or the yarn in the cylinder is higher than the liquid level of the fluoride-free water-repellent composition, so that the yarn and / or the yarn will not be immersed in the fluoride-free water-repellent composition. Based on the above technical features, the cylinder has a top that closes the top of the cylinder or closes one end of the hollow interior; and the top of the water outlet pipe abuts against the top of the cylinder. Based on the above technical features, the pH value of the fluoride-free water-repellent composition is between 5 and 8. Based on the above technical features, the fluorine-free water-repellent composition is composed of acrylic-based fluorine-free water-repellent agent and water / or additives. Assuming the fluorine-free water-repellent composition is 100wt%, the acrylic-based fluorine-free water-repellent agent is 1.0wt%~1.5wt%, and the remainder is water and / or additives. Based on the above technical features, the additive is an acid used to adjust the pH value of the fluoride-free water-repellent composition. Based on the above technical features, the acid is glacial acetic acid or citric acid. Based on the aforementioned technical features, the heating process involves heating the fluorine-free water-repellent component from 30°C to 90°C at a heating rate between 0.5°C / min and 3°C / min, and then holding the temperature for between 30 and 50 minutes, while the internal pressure of the cylinder is between 2 kg / cm². 2 Up to 3.5 kg / cm 2 between. Based on the above technical features, the yarn is composed of at least one synthetic fiber, which is a long fiber, and the fluorine-free water-repellent component forms a fluorine-free water-repellent layer on the surface of the synthetic fiber, which does not cover the entire surface of the synthetic fiber. According to the above technical features, a dyeing step is performed after the heating step. The dyeing step involves applying a dye to a section of the synthetic fiber that is not covered by the fluorine-free water-repellent layer, and the dye is not applied to the fluorine-free water-repellent layer. The present invention provides a method for manufacturing a fluorine-free water-repellent yarn in a vat with reduced adhesion and yellowing by water-repellent treatment using a fluorine-free water-repellent composition. The dyeable fluorine-free water-repellent yarn produced is suitable for both "yarn dyed" (commonly referred to as pre-dyeing) and "piece dye" (commonly referred to as post-dyeing) processes. To facilitate the understanding of the technical content, features, and effects of this invention by examiners, the presentation of embodiments and comparative examples will provide a clearer explanation; however, this invention is not limited to these embodiments. Furthermore, the use of "between... and..." or "~" in this specification and / or the claims scope indicates that the numerical range encompasses the range described before and after as a lower and upper limit value; the use of "wt%" in this specification and / or the claims scope refers to a weight percentage. Referring to Figure 1, this invention first provides a method for manufacturing a fluorine-free water-repellent yarn with reduced adhesion and yellowing in a vat, comprising at least the following steps in sequence: a yarn preparation step, a yarn impregnation step, and a heating step. The dyeable fluorine-free water-repellent yarn obtained by this method can be woven into a dyeable fluorine-free water-repellent fabric and then dyed in a dyeing step. It exhibits good soft hand feel, water repellency, wash fastness, and water fastness. Please refer to Figure 2. The yarn preparation step involves preparing a yarn 1, which is wound around a bobbin 21 having a hollow interior 22 to form a bobbin 2. The bobbin 21 has a plurality of through holes 213 penetrating an outer surface 211 and an inner surface 212. These through holes 213 are spaced apart and arranged in a ring around the circumference of the bobbin 21. The yarn 1 is wound around the outer surface 211 of the bobbin 21 and covers the plurality of through holes 213. The yarn 1 can be colored yarn or undyed yarn. It should be noted that the winding thickness of the yarn 1 in the upper, middle and lower parts of the yarn package 2 is approximately the same. The package body 21 may have a top 23, which closes the top end of the package body 21, or the top 23 closes one end of the hollow interior 22. A guide notch 24 may be provided on the lower edge of the inner surface of the package body 21, and a groove 25 communicating with the guide notch 24 is provided on the inner surface of the package body 21. The groove 25 extends along an extension direction of the package body 21. Please refer to Figures 2 and 3 simultaneously. The impregnation step involves placing the yarn bobbin 2 inside a sealable cylinder 3 (also known as a pressure vessel), and supplying a fluorine-free water-repellent component W through the hollow interior 22 of the cylinder 21 and through the plurality of through holes 213, so that the fluorine-free water-repellent component W impregnates the yarn 1 to form an impregnated yarn 11. The fluorine-free water-repellent component W flows out of the yarn bobbin 2 and then flows back into the supply device 4 to supply the fluorine-free water-repellent component W again, thus forming a component cycle P. The supply device 4 includes a motor 41 and an inlet pipe 42 and an outlet pipe 43 connected to the motor 41. The outlet pipe 43 supplies the fluorine-free water-repellent component W through the hollow interior 22 of the cylinder 21, through the plurality of through holes 213, and the fluorine-free water-repellent component W flowing out of the yarn package 2 flows back into the inlet pipe 42 to supply the fluorine-free water-repellent component W again, thus forming the component circulation P. In other words, the motor 41, the inlet pipe 42, the outlet pipe 43, and the interior of the cylinder 3 together form a passage for the fluorine-free water-repellent component W to form the component circulation P. It is particularly noteworthy that the outlet pipe 43 has a plurality of outlets 432, and the top 431 of the outlet pipe 43 abuts against the top 23 of the cylinder. Please refer to area A and its enlarged view in Figure 3; the outer surface of the outlet pipe 43 further has a protrusion 433. The cylindrical body 21 is fitted tightly or with only a small gap to the outer surface of the water outlet pipe 43 through the hollow interior 22. When the protrusion 433 slides into the groove 25 guided by the guide notch 24, it achieves lateral positioning; and the top 431 of the water outlet pipe abuts against the top 23 of the cylindrical body to achieve longitudinal (the extending direction) positioning. When lateral and longitudinal positioning are achieved, at least a portion of the plurality of water outlets 432 correspond to the plurality of through holes 213, thereby allowing the fluoride-free water-repellent composition W to flow through the plurality of through holes 213 and the plurality of water outlets 432. Preferably, each water outlet 432 corresponds to one through hole 213. Please refer to Figures 3, 4, and 5 simultaneously. The heating step utilizes a heating device 5 and a heating process Q to heat the fluorine-free water-repellent component W, causing the impregnated yarn 11 to form a dyeable fluorine-free water-repellent yarn 12. This dyeable fluorine-free water-repellent yarn 12 is also wound around the bobbin 21 to form a dyeable fluorine-free water-repellent bobbin 2', as shown in Figure 6. The heating device 5 can be, for example, a heat exchanger located inside the cylinder 3, which receives hot steam from an external boiler and heats the fluorine-free water-repellent component W via heat exchange. Specifically, the yarn 1 is composed of at least one synthetic fiber 1'; preferably, the yarn 1 is composed of a plurality of synthetic fibers 1'. The synthetic fiber 1' is a long fiber. The fluorine-free water-repellent component W is attached to the surface of the synthetic fiber 1' and then heated through the heating process Q. A subsequent yarn drying step dries the fluorine-free water-repellent component W, for example, by using contact drying air, hot air, or a hot plate to cause moisture loss and form a fluorine-free water-repellent layer W'. This fluorine-free water-repellent layer W' does not cover the entire surface of the synthetic fiber 1'. In other words, the dyeable fluorine-free water-repellent yarn 12 includes the yarn 1 and the fluorine-free water-repellent layer W' attached to the surface of the yarn 1. As shown in Figure 4, the heating process Q heats the fluorine-free water-repellent component W from an initial temperature to a target temperature at a heating rate and holds it at the target temperature for a holding time. The cylinder contains a cylinder pressure. Preferably, the heating rate is between 0.5°C / min and 3°C / min, the initial temperature is 30°C, the target temperature is 90°C, the holding time is between 30 minutes and 50 minutes, and the cylinder pressure is between 2 kg / cm². 2 Up to 3.5 kg / cm 2 In other words, the heating process Q heats the fluoride-free water-repellent component W from 75°C to 90°C at a heating rate between 0.5°C / min and 3°C / min, and then holds the temperature at 90°C for a time between 30 and 50 minutes, while the internal pressure of the cylinder is between 2 kg / cm². 2 Up to 3.5 kg / cm 2 between. It should be noted that the fluorine-free water-repellent composition W wets the yarn 1 but does not soak it. More specifically, the position of the yarn package 2 and / or the yarn 1 in the tank 3 is higher than the liquid level of the fluorine-free water-repellent composition W. Therefore, the yarn package 2 and / or the yarn 1 will not be soaked in the fluorine-free water-repellent composition W, so that the fluorine-free water-repellent composition W adheres to the inner, middle and outer layers of the yarn 1 of the yarn package 2 in a predetermined amount, and ensures that the inner, middle and outer layers are heated evenly. Specifically, referring again to Figure 5, the dyeable fluorine-free water-repellent yarn 12 includes the yarn 1 and the fluorine-free water-repellent layer W' attached to the surface of the yarn 1. The fluorine-free water-repellent layer W' does not cover the entire surface S of the synthetic fiber 1'. More specifically, the fluorine-free water-repellent layer W' only covers the covered surface S1 of the synthetic fiber 1', leaving an uncovered surface S2 of the synthetic fiber 1'. The covered surface S1 and the uncovered surface S2 form the entire surface S of the synthetic fiber 1'. The uncovered surface S2 is used for subsequent dyeing. The fluorine-free water-repellent composition W is an emulsion solution composed of an acrylic-based fluorine-free water-repellent agent and water / or additives. Based on 100 wt% of the fluorine-free water-repellent composition, the acrylic-based fluorine-free water-repellent agent comprises 1.0 wt% to 1.5 wt%, with the remainder being water and / or additives. The acrylic-based fluorine-free water-repellent agent contains an acrylic-based fluorine-free water-repellent polymer and an emulsifier. The additive may be an acid to adjust the pH value (acidity / alkalinity) of the fluorine-free water-repellent composition, ensuring that the adjusted pH value is between 5 and 8. For example, the acid may be glacial acetic acid or citric acid. <Preparation of Fluorine-Free Water-Repellent Components> Commercially available acrylic-based fluorine-free water-repellent agents (such as the DAIKIN UNIDYNE XF series of fluorine-free water-repellent agents) are used. These are emulsion solutions formed from at least acrylic-based fluorine-free water-repellent polymers, emulsifiers, and water. Glacial acetic acid is used as an additive. Water is added to adjust the fluorine-free water-repellent composition used in the examples and comparative examples in Table 1 below. Assuming the fluorine-free water-repellent composition of the present invention is 100 wt%, the acrylic-based fluorine-free water-repellent agent (acrylic-based fluorine-free water-repellent polymer and emulsifier) ​​is 1.0 wt%, and the remainder is water and glacial acetic acid, wherein the glacial acetic acid is used to adjust the pH value of the fluorine-free water-repellent composition. <Evaluation of Fluoride-Free Water-Repellent Components> <pH value between 5 and 8> The dyeable fluorine-free water-repellent yarn was manufactured using the fluorine-free water-repellent composition of the examples and comparative examples described in Table 1 below, through the aforementioned method for manufacturing fluorine-free water-repellent yarns with reduced adhesion and yellowing in a vat. The results of yellowing detection, inter-yarn adhesion detection, and residual liquid turbidity detection of the inner, middle, and outer layers of the dyeable fluorine-free water-repellent yarn 2' were evaluated. The yarn used was polyester fiber PET 155D / 144T, with a winding thickness of 9 cm, and the inner, middle, and outer layers corresponding to 3 cm, 3 cm, and 3 cm respectively. The heating rate was between 0.5°C / min, the initial temperature was 30°C, the target temperature was 90°C, the holding time was 30 minutes, and the vat pressure was between 2 kg / cm². 2In this process, visual inspection reveals that yellowing of the color indicates a failure marked as "X," while no yellowing indicates a pass marked as "O." Yellowing that is acceptable is marked as "△." When the dyeable fluorine-free water-repellent yarn 2' is rewinded, yarn adhesion indicates a failure marked as "X," while no adhesion indicates a pass marked as "O." Adhesion that is acceptable is marked as "△." After performing the above-described method for manufacturing fluorine-free water-repellent yarn in a vat to reduce adhesion and yellowing, the residual turbidity of the aforementioned vat is tested using a commercially available TURBIQUANT 1100T turbidity meter to represent the degree of absorption of the fluorine-free water-repellent components. Since this can be used as an indirect indicator of the water-repellent effect of the dyeable fluorine-free water-repellent yarn, a value below 100 is considered acceptable marked as "O," and a value above 100 is considered unacceptable marked as "X." In Table 1, the same embodiment or comparative example is subjected to the aforementioned three tests: yellowing phenomenon detection, yarn adhesion phenomenon detection, and residual liquid turbidity detection. If any "X" appears in the test results, it is marked as "X" in the "Overall Evaluation Result" column of Table 1, indicating that this embodiment or comparative example does not meet the requirements of the present invention; if any "△" appears in the test results, it is marked as "△" in the "Overall Evaluation Result" column of Table 1, indicating that this embodiment or comparative example meets the requirements of the present invention; if any "O" appears in all test results, it is marked as "O" in the "Overall Evaluation Result" column of Table 1, indicating that this embodiment fully meets the requirements of the present invention. Table 1 As shown in Table 1, the dyeable fluorine-free water-repellent yarn produced using a fluorine-free water-repellent composition with a pH value between 5 and 8 (Examples 1-4) under the aforementioned method for manufacturing fluorine-free water-repellent yarns in a vat with reduced adhesion and yellowing exhibits good overall evaluation results and meets the requirements of this invention. However, Comparative Examples 1 and 2, which used pH values ​​of 4 and 9 respectively, showed unsatisfactory overall evaluation results and did not meet the requirements of this invention. Clearly, the pH value of the fluorine-free water-repellent composition is a crucial factor affecting the quality of the dyeable fluorine-free water-repellent yarn; moreover, only fluorine-free water-repellent compositions with a specific pH range (pH value between 5 and 8) can ensure that the dyeable fluorine-free water-repellent yarn achieves the good overall evaluation results required by this invention. Furthermore, Table 1 shows that by detecting the yellowing phenomenon and inter-yarn adhesion of the inner, middle, and outer layers of the dyeable fluorine-free water-repellent yarn in the dyeable fluorine-free water-repellent package yarn, it can be found that a fluorine-free water-repellent composition with a specific pH range (pH value between 5 and 8) can make the dyeable fluorine-free water-repellent yarn in the inner, middle, and outer layers of the dyeable fluorine-free water-repellent package yarn have better consistency. In particular, the fluorine-free water-repellent composition of Example 3 has a pH value of 7, and its inner, middle, and outer layers have the best consistency, thus meeting the requirements of the present invention. Moreover, its residual turbidity is the lowest among all examples and comparative examples, so Example 3 is the best example. However, in contrast, Comparative Examples 1 and 2, which use pH values ​​of 4 and 9 respectively, do not have consistency in their inner, middle, and outer layers, thus not meeting the requirements of the present invention. Next, the dyeable fluorine-free water-repellent yarns produced in the comparative examples and examples in Table 1 (application comparative examples and application examples) were used to weave the inner, middle, and outer layers of the dyeable fluorine-free water-repellent yarn 2' into a dyeable fluorine-free water-repellent fabric (fabric application comparative examples and fabric application examples) using a weaving process. The initial water repellency of the dyeable fluorine-free water-repellent fabric was tested according to the AATCC 22-2017 water repellency test specification. Then, the fabric was washed 20 times according to the AATCC 135-2018 washing test specification, and the water repellency of the dyeable fluorine-free water-repellent fabric was tested according to the AATCC 22-2017 water repellency test specification. The results are recorded in Table 2 below, which is the water repellency fastness. In Table 2, the same fabric application example or the same fabric application comparative example were subjected to the aforementioned initial water repellency test and wash water repellency test. If any value in the test result is less than 80, it is marked as "X" in the "Water Repellency Evaluation Result" column of Table 2, indicating that it does not meet the requirements of the present invention; if all test results are greater than or equal to 80, it is marked as "O" in the "Water Repellency Evaluation Result" column of Table 2, indicating that this example fully meets the requirements of the present invention. Table 2 As shown in Table 2, similar to Table 1, the dyeable fluorine-free water-repellent yarn produced using fluorine-free water-repellent compositions with pH values ​​between 5 and 8 (Examples 1-4) under the aforementioned method for manufacturing fluorine-free water-repellent yarns in a vat with reduced adhesion and yellowing exhibits good water repellency evaluation results and meets the requirements of this invention. However, Comparative Examples 1 and 2, using pH values ​​of 4 and 9 respectively, have unsatisfactory water repellency evaluation results and do not meet the requirements of this invention. Clearly, the pH value of the fluorine-free water-repellent composition is a crucial factor affecting the quality of dyeable fluorine-free water-repellent yarn; moreover, only fluorine-free water-repellent compositions with a specific pH range (pH value between 5 and 8) can ensure that the dyeable fluorine-free water-repellent yarn achieves the water repellency evaluation results required by this invention. Furthermore, Table 2 shows that by testing the initial water repellency and water fastness (washing water repellency) of the inner, middle, and outer layers of the dyeable fluorine-free water-repellent yarn, it can be found that fluorine-free water-repellent components with a specific pH range (pH value between 5 and 8) can make the dyeable fluorine-free water-repellent yarn of the inner, middle, and outer layers of the dyeable fluorine-free water-repellent yarn have better consistency. In particular, the fluorine-free water-repellent component of Example 3 has a pH value of 7, and its inner, middle, and outer layers have the best consistency, thus meeting the requirements of the present invention. Therefore, Example 3 is the best example. However, in contrast, Comparative Examples 1 and 2, which use pH values ​​of 4 and 9 respectively, do not have consistency in their inner, middle, and outer layers, thus not meeting the requirements of the present invention. <The amount of acrylic-based fluorine-free water-repellent agent is 1.0wt%~1.5wt%> Table 3 The preparation, manufacturing, and evaluation of Comparative Example 3, Application Comparative Example 3, and Fabric Application Comparative Example 3' in Table 3 above followed the comparative examples, application comparative examples, and fabric application comparative examples in Tables 1 and 2 above, and therefore will not be repeated. As can be seen from Table 3, the fluorine-free water-repellent compositions of Examples 3', 3, and 3 all have a pH value of 7. The difference lies in the amount of acrylic-based fluorine-free water-repellent agent used, which are 1.5 wt%, 1.0 wt%, and 0.5 wt%, respectively. Only Comparative Example 3 does not meet the requirements for initial water repellency and water fastness of the present invention. Therefore, an amount of acrylic-based fluorine-free water-repellent agent of 1.0 wt% to 1.5 wt% can obtain the initial water repellency and water fastness that meet the requirements of the present invention. <Hand Feel Test> Table 4 The fabric application examples in Table 4 above refer to the inner layer of the corresponding dyeable, fluorine-free, water-repellent yarn 2'. The hand feel assessment method involved five people assigning scores of 1 to 5, which were then averaged. An average score of 4.5 or higher indicates a soft hand feel (marked "O"), 3.5 to 4.4 indicates a firm but acceptable hand feel (marked "△"), and below 3.4 indicates a firm and unacceptable hand feel (marked "X"). Table 4 shows that all fabric application examples of the present invention exhibit a soft hand feel, meeting the requirements of the present invention. <Staining test> Next, the dyeable fluorine-free water-repellent fabrics of Comparative Examples 1'~2' and Examples 1'~4' in Table 2 were dyed using a single dyeing step, and their wash fastness and water fastness were tested after dyeing. This dyeing step used a 2% concentration of disperse dye (S-type) for polyester fibers, a dyeing temperature of 135 degrees Celsius, and a holding time of 40 minutes. The color fastness was tested according to the ISO 105 C06 B1S (Color Fastness to Washing) and ISO 150 E01 (Color Fastness to Water) standards, respectively. The test results are recorded in Table 5 below. In Table 5, the same fabric application example is subjected to the aforementioned water fastness to dyeing (also known as water fastness) and water fastness to dyeing (also known as wash fastness) tests. If any of the test results is less than 4, it is marked as "X" in the "Dyeing Evaluation Result" column of Table 5, indicating that it does not meet the requirements of the present invention; if all test results are greater than or equal to 4, it is marked as "O" in the "Dyeing Evaluation Result" column of Table 5, indicating that this example fully meets the requirements of the present invention. Table 5 As can be seen from Table 5, the dyeing evaluation results of the fabric application examples of the present invention all have good wash fastness and water fastness, thus meeting the requirements of the present invention. Specifically, referring to Figure 7, after the dyeable fluorine-free water-repellent fabric is dyed using this dyeing step, the dye D is applied to the interior and / or the uncovered surface S2 of the synthetic fiber 1' in the dyeable fluorine-free water-repellent yarn 12. In other words, this dyeing step involves applying the dye to the section of the synthetic fiber that is not covered by the fluorine-free water-repellent layer, and the dye does not apply to the fluorine-free water-repellent layer. The dyeing is achieved by bonding to the yarn through a physical or chemical reaction. Similarly, the dyeable fluorine-free water-repellent yarn 12 can be dyed in this dyeing step before being woven into a dyeable fluorine-free water-repellent fabric. The dye D is applied to the interior and / or the uncovered surface S2 of the synthetic fiber 1' in the dyeable fluorine-free water-repellent yarn 12. In other words, the dyeing step applies the dye to the section of the synthetic fiber without the fluorine-free water-repellent layer covering the surface, and the dye does not apply to the fluorine-free water-repellent layer. In summary, the present invention provides a method for manufacturing in-bottle fluorine-free water-repellent yarn with reduced adhesion and yellowing by water-repellent treatment using fluorine-free water-repellent components, and a method for manufacturing dyeable fluorine-free water-repellent fabrics. The dyeable fluorine-free water-repellent yarns and dyeable fluorine-free water-repellent fabrics produced are suitable for "yarn dyed" (commonly referred to as pre-dyeing) and "piece dye" (commonly referred to as post-dyeing) processes, and have good soft hand feel, water repellency, wash fastness, and water fastness. However, the above description is merely an embodiment of the present invention and should not be construed as limiting the scope of the present invention. Any simple equivalent changes and modifications made in accordance with the scope of the patent application and the contents of the patent specification shall still fall within the scope of the patent of the present invention. 1: Yarn 1': Synthetic Fiber 11: Impregnated Yarn 12: Dyeable Fluorine-Free Water-Repellent Yarn 2: Bundle Yarn 2': Dyeable Fluorine-Free Water-Repellent Bundle Yarn 21: Bundle Body 211: Outer Surface 212: Inner Surface 213: Through Hole 22: Hollow Interior 23: Top of Bundle Body 24: Guide Notch 25: Slide Groove 3: Cylinder Body 4: Supply Device 41: Motor 42: Inlet Pipe 43: Outlet Pipe 431: Top of Outlet Pipe 432: Outlet 433: Protrusion 5: Heating Device D: Dye P: Composition Circulation Q: Heating Process S: All Surfaces S1: Covered Surface S2: Uncovered Surface W: Fluorine-Free Water-Repellent Composition W': Fluorine-Free Water-Repellent Layer Other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, wherein: Figure 1 is a flowchart of the manufacturing method of the in-cylinder fluorine-free water-repellent yarn with reduced adhesion and yellowing according to the present invention. Figure 2 is a structural schematic diagram of the yarn of the present invention. Figure 3 is a schematic diagram of the operation of the yarn of the present invention set in the cylinder and an enlarged view of region A. Figure 4 is a schematic diagram of the heating process of the present invention. Figure 5 is a structural schematic diagram of the fluorine-free water-repellent yarn of the present invention. Figure 6 is a structural schematic diagram of the dyeable fluorine-free water-repellent yarn of the present invention. Figure 7 is a structural schematic diagram of the dyeing of the dyeable fluorine-free water-repellent yarn of the present invention.

Claims

1. A method for manufacturing a fluorine-free water-repellent bobbin with reduced adhesion and yellowing, comprising at least the following steps: a yarn preparation step: preparing a yarn (1), the yarn (1) being wound around a bobbin (21) having a hollow interior (22) to form a bobbin (2), the bobbin (21) having a plurality of through holes (213) penetrating an outer surface (211) and an inner surface (212) of the bobbin (21), the plurality of through holes (213) being spaced apart and arranged in a ring around the circumference of the bobbin (21), the yarn (1) being wound around the outer surface (211) of the bobbin (21) and covering the plurality of through holes (213); A yarn impregnation step: The yarn cone (2) is placed inside a sealable cylinder (3), and a fluorine-free water-repellent composition (W) is supplied by a supply device (4) through the hollow interior (22) of the cylinder (21) and through the plurality of through holes (213), so that the fluorine-free water-repellent composition (W) impregnates the yarn (1) to form an impregnated yarn (11), and the fluorine-free water-repellent composition (W) flows out of the yarn cone (2), and the fluorine-free water-repellent composition (W) flowing out of the yarn cone (2) flows back into the supply device (4) to supply the fluorine-free water-repellent composition (W) to form a composition circulation (P); and a heating step: The fluorine-free water-repellent composition (W) is heated by a heating device (5) and a heating process (Q) so that the impregnated yarn (11) forms a dyeable fluorine-free water-repellent yarn (12); wherein, A guide notch (24) is provided on the lower edge of one inner surface of the cylinder (21), and a groove (25) communicating with the guide notch (24) is provided on the inner surface of the cylinder (21). The groove (25) extends along an extension direction of the cylinder (21). The supply device (4) includes a motor (41) and an inlet pipe (42) and an outlet pipe (43) respectively connected to the motor (41). The outlet pipe (43) supplies the fluoride-free water-repellent composition (W) to flow through the cylinder (21) through the plurality of through holes (213). The fluoride-free water-repellent composition (W) flowing out of the yarn package (2) flows back into the inlet pipe (42) to supply the fluoride-free water-repellent composition (W) again, thus forming a composition circulation (P). The outlet pipe (43) is equipped with There are multiple water outlets (432), and the outer surface of the water outlet pipe (43) has a protrusion (433). The cylinder (21) is fitted onto the outer surface of the water outlet pipe (43) with the hollow interior (22). The protrusion (433) slides into the groove (25) by the guide notch (24). The multiple water outlets (432) correspond to the multiple through holes (213) respectively. The fluoride-free water-repellent composition (W) flows through the multiple water outlets (432) and the multiple through holes (213). Moreover, the position of the yarn (2) and / or the yarn (1) in the cylinder (3) is higher than the liquid level of the fluoride-free water-repellent composition (W) so that the yarn (2) and / or the yarn (1) will not be immersed in the fluoride-free water-repellent composition (W). The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 1, wherein... The cylinder (21) has a top (23) which closes the top of the cylinder (21) or closes one end of the hollow interior (22); and the top (431) of the outlet pipe (43) abuts against the top (23) of the cylinder. The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 2, wherein... The pH value of this fluoride-free water-repellent component (W) is between 5 and 8. The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 3, wherein... The fluorine-free water-repellent composition (W) is composed of acrylic-based fluorine-free water-repellent agent and water / or additives. Assuming the fluorine-free water-repellent composition (W) is 100 wt%, the acrylic-based fluorine-free water-repellent agent is 1.0 wt% to 1.5 wt%, and the remainder is water and / or additives. The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 4, wherein... The additive is an acid used to adjust the pH of the fluoride-free water-repellent composition. The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 5, wherein... The acid is either glacial acetic acid or citric acid. The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 6, wherein... The heating process (Q) involves heating the fluorine-free water-repellent component from 30°C to 90°C at a heating rate between 0.5°C / min and 3°C / min, and then holding the temperature for a duration between 30 minutes and 50 minutes. The internal pressure of the cylinder (3) is between 2 kg / cm². 2 Up to 3.5 kg / cm 2 between. The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 7, wherein... The yarn (1) is composed of at least one synthetic fiber (1'), which is a long fiber. The fluorine-free water-repellent component (W) is attached to the surface of the synthetic fiber (1') to form a fluorine-free water-repellent layer (W'), which does not cover the entire surface of the synthetic fiber (1'). The method for manufacturing in-cylinder fluoride-free water-repellent yarn with reduced adhesion and yellowing as described in claim 8, wherein... Following the heating step, a dyeing step is performed, in which a dye (D) is applied to a section of the synthetic fiber (1') that is not covered by the fluorine-free water-repellent layer (W'), and the dye (D) is not applied to the fluorine-free water-repellent layer (W').

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