TWI827447B - Manufacturing method of dyeable fluorine-free water-repellent yarn and fabric - Google Patents

Abstract

The invention provides a method for manufacturing dyeable fluorine-free water-repellent yarn, which includes in sequence: a yarn preparation step, a yarn soaking step and a temperature-raising heating step. A dyeable fluorine-free water-repellent yarn prepared by the method of manufacturing the dyeable fluorine-free water-repellent yarn is then woven into a dyeable fluorine-free water-repellent fabric and then dyed in a dyeing step, which has Good soft hand feel, water-repellent fastness, wash-resistant dye fastness and water-resistant dye fastness.

Description

Manufacturing method of dyeable fluorine-free water-repellent yarn and fabric

The present invention relates to a method for manufacturing dyeable water-repellent yarns and fabrics. In particular, it refers to a dyeable water-repellent yarn and fabrics that can be selectively dyed separately after being treated with a fluorine-free water-repellent agent. Method for manufacturing dyed fluorine-free water-repellent yarn and dyeable fluorine-free water-repellent fabric.

The currently known water-repellent fabrics with water-repellent properties are usually made by subjecting the yarn or fabric to water-repellent treatment (such as screen printing, roller and pressure suction methods) after the dyeing process. Water treatment is to treat dyed yarn or fabric with water-repellent agent. The types of water-repellent agents can be divided into fluorine-containing water-repellent agents or fluorine-free water-repellent agents. Among the two, fluorine-free water-repellent fabrics made by using fluorine-free water-repellent agents are the most environmentally friendly.

However, even if a conventional fluorine-free water-repellent agent and the above-mentioned water-repellent treatment are applied, it still cannot get rid of the restrictions on the above-mentioned process sequence caused by the requirement of dyeing reliability. For example, if contrary to the traditional process sequence, the yarn or fabric is first treated with fluorine-free water-repellent treatment and then dyed, there will be a problem that the yarn or fabric cannot be dyed and does not have dyeability, or there will be no fluorine-free water-repellent agent. Due to the alkali treatment in the dyeing process, it will peel off in the dye vat and temporarily adhere to the wall of the dye vat, thus affecting the dyeing quality of the next batch of yarn or fabric. A typical example is the Republic of China Invention Patent Announcement No. I718683 (hereinafter referred to as Document 1), which is restricted to dyeing the yarn before using a fluorine-free water-repellent agent for water-repellent treatment.

Furthermore, the problem existing in Document 1 also includes the evaluation of the feel of water-repellent fabrics. Document 1: In order to make the water-repellent fabric pass the washing test, a bridging agent is added to the fluorine-free water-repellent agent, which makes the water-repellent fabric feel harder (more stiff), which in turn reduces the value of the water-repellent fabric. . Although the fluorine-free water-repellent agent proposed by the Republic of China Invention Patent Publication No. 201912733 (hereinafter referred to as Document 2) uses a general-purpose bridging agent and claims not to affect the touch of the fabric, it provides a tactile feel rather than solving the problem of Document 1. The use of bridging agents causes the problem of a harder feel.

In addition, the fluorine-free water-repellent agent provided in Document 2 forms a fluorine-free water-repellent layer on the surface of the yarn. However, in addition to having a soft hand feel, excellent water-repellent fabrics must also meet set standard values for water-repellent fastness, wash-resistant dyeing fastness, and water-resistant dyeing fastness after washing tests. If a water-repellent fabric wants to have a good soft hand feel, water-repellent fastness, washing and dyeing fastness, and water-resistant dyeing fastness at the same time, in addition to the considerations of yarn and fabric weave design, it must also consider the water-repellent treatment and Dyeing process conditions. The water-repellent treatment provided in Document 2 is a traditional pressure-suction drying process. Although it states that the yarn can be dyed after the water-repellent treatment, it is actually dyed on the fluorine-free water-repellent layer instead of dyeing the fiber. Therefore, The dyed fluorine-free water-repellent layer in Document 2 cannot pass the test of washable dye fastness and water fastness, so it does not provide relevant dye fastness test results.

Therefore, the object of the present invention is to provide a method for producing dyeable fluorine-free water-repellent yarns by subjecting undyed yarns, dyed yarns, undyed fabrics or dyed fabrics to a fluorine-free water-repellent composition. Method and manufacturing method of dyeable fluorine-free water-repellent fabric, and can be selectively dyed separately, and the dyeable fluorine-free water-repellent fabric produced according to the above method has good soft hand feel, water-repellent fastness, and durability. Washing dye fastness and water resistant dye fastness.

Based on the above object of the invention, a method for manufacturing dyeable fluorine-free water-repellent yarn is provided, which includes in sequence: a yarn preparation step: preparing a yarn, which is wound around a cylinder with a hollow interior. A tube of yarn is formed. The tube is provided with a plurality of through holes penetrating an outer surface and an inner surface of the tube. The plurality of through holes are arranged at intervals and are arranged in a ring around the circumference of the tube. , the yarn is wound around the outer surface of the cylinder and covers the plurality of through holes; a step of soaking the yarn: placing the yarn inside a sealable cylinder and supplying it with a supply device A fluorine-free water-repellent composition flows from the hollow interior of the cylinder through the plurality of through holes, and the fluorine-free water-repellent composition infiltrates the yarn to form a soaked yarn and the fluorine-free water-repellent composition flows Out of the package yarn, the fluorine-free water-repellent composition flowing out of the package yarn flows 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 The temperature-raising process heats the fluorine-free water-repellent composition, so that the soaked yarn forms a dyeable fluorine-free water-repellent yarn.

According to the above technical features, the position of the yarn package and/or the yarn in the cylinder is higher than the liquid level of the fluorine-free water-repellent composition, so that the package yarn and/or the yarn The thread will not be soaked in the fluorine-free water-repellent composition.

According to the above technical characteristics, the pH value of the fluorine-free water-repellent composition is between 5 and 8.

According to the above technical characteristics, the fluorine-free water-repellent composition is composed of an acrylic-based fluorine-free water-repellent agent and water/or additives. Based on 100wt% of the fluorine-free water-repellent composition, the acrylic water-repellent composition is The fluorine-free water-repellent agent is 1.0wt%~1.5wt%, and the rest is water and/or additives.

According to the above technical features, the additive is an acid to adjust the pH value of the fluorine-free water-repellent composition.

According to the above technical characteristics, the acid is glacial acetic acid or citric acid.

According to the above technical characteristics, the heating process is to heat the fluorine-free water-repellent composition from 30°C to 90°C at a heating rate between 0.5°C/min and 3°C/min and then heat it at a temperature between 30°C and 30°C. The temperature is maintained for a temperature holding time of between 1 minute and 50 minutes, and the internal pressure of the cylinder is between 2 kg/cm ² and 3.5 kg/cm ² .

According to the above technical features, the yarn is composed of at least one synthetic fiber, the synthetic fiber is a long fiber, and the fluorine-free water-repellent composition forms a fluorine-free water-repellent layer on the surface of the synthetic fiber, The fluorine-free water-repellent layer 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 is to dye a dye on the section of the synthetic fiber that is not covered with the fluorine-free water-repellent layer, and The dye does not stain the fluorine-free water-repellent layer.

The invention also provides a method for manufacturing a dyeable fluorine-free water-repellent fabric, which involves weaving the dyeable fluorine-free water-repellent yarn produced by the above-mentioned method for manufacturing a dyeable fluorine-free water-repellent fabric into a dyeable fluorine-free water-repellent fabric. After the fluorine-free water-repellent fabric is produced, a dyeing step is performed. The dyeing step is to dye a dye on the section of the synthetic fiber that is not covered with the fluorine-free water-repellent layer, and the dye is not dyed on the surface of the synthetic fiber. Fluorine-free water-repellent layer.

The present invention provides a method for manufacturing dyeable fluorine-free water-repellent yarns and a method for manufacturing dyeable fluorine-free water-repellent fabrics that are treated with a fluorine-free water-repellent composition. The dyeable fluorine-free water-repellent fabrics produced therefrom Yarns and dyeable fluorine-free water-repellent fabrics are suitable for "yarn dyed" (commonly called first dyeing) and "piece dye" (commonly called post-dyed) processes, and have good soft hand feel, water-repellent fastness, Washing Dye Fastness and Water Dye Fastness.

In order to make it easier for the examiner to understand the technical content, features and effects of the present invention, examples and comparative examples are presented to make it more clear, but the present invention is not limited by these examples. In addition, the use of "between... to..." or "~" in this specification and/or the scope of the patent application to indicate a numerical range refers to a range that covers the values recorded before and after as the lower limit and upper limit. ; The use of "wt%" in this specification and/or the patent application scope refers to the weight percentage.

Please refer to Figure 1. First of all, the present invention provides a method for manufacturing dyeable fluorine-free water-repellent yarn, which at least includes in sequence: a yarn preparation step, a yarn soaking step and a heating step. A dyeable fluorine-free water-repellent yarn prepared by the method of manufacturing the dyeable fluorine-free water-repellent yarn can be woven into a dyeable fluorine-free water-repellent fabric and then dyed in a dyeing step, which has Good soft hand feel, water-repellent fastness, wash-resistant dye fastness and water-resistant dye fastness.

Please refer to Figure 2, in which the yarn preparation step is to prepare a yarn 1. The yarn 1 is wound around a cylinder 21 having a hollow interior 22 to form a cylinder 2. The cylinder 21 is provided with a penetrating The cylinder has a plurality of through holes 213 on an outer surface 211 and an inner surface 212. The plurality of through holes 213 are spaced apart and arranged in a ring around the cylinder 21. The yarn 1 is It is wrapped around the outer surface 211 of the cylinder 21 and covers the plurality of through holes 213 . The yarn 1 may be colored yarn or undyed yarn.

Please refer to Figure 2 and Figure 3 at the same time. In the step of soaking the yarn, the yarn package 2 is placed inside a sealable cylinder 3 (also called a pressure vessel), and a supply device 4 supplies a fluorine-free The water-repellent composition W flows from the hollow interior 22 of the barrel 21 through the plurality of through holes 213, and the fluorine-free water-repellent composition W infiltrates the yarn 1 to form a wetted yarn 11 and the fluorine-free water-repellent composition W flows through the through holes 213. The water-repellent composition W flows out of the package yarn 2, and the fluorine-free water-repellent composition W flowing out of the package yarn 2 flows into the supply device 4 to re-supply the fluorine-free water-repellent composition W to form a composition cycle P. The supply device 4 includes a motor 41 and a water inlet pipe 42 and a water outlet pipe 43 respectively connected to the motor 41 , and the water outlet pipe 43 supplies the fluorine-free water-repellent composition W from the hollow interior 22 of the cylinder 21 The fluorine-free water-repellent composition W flowing out of the package yarn 2 flows through the plurality of through holes 213 and then flows into the water inlet pipe 42 to re-supply the fluorine-free water-repellent composition W to form the composition cycle P. In other words, the motor 41 , the water inlet pipe 42 , the water outlet pipe 43 and the inside of the cylinder 3 jointly form a passage for the fluorine-free water-repellent composition W to form the composition circulation P.

Please refer to Figures 3, 4 and 5 at the same time. The temperature-raising heating step uses a heating device 5 and a temperature-raising process Q to heat the fluorine-free water-repellent composition W, so that the impregnated yarn 11 forms a dyeable Fluorine-free water-repellent yarn 12, the dyeable fluorine-free water-repellent yarn 12 is also wound around the barrel 21 to form a dyeable fluorine-free water-repellent yarn 2', as shown in Figure 6. The heating device 5 may be, for example, a heat exchanger disposed inside the cylinder 3 , which provides hot steam from an external boiler and heats the fluorine-free water-repellent composition W through the principle of 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, and the fluorine-free water-repellent composition W is attached to the surface of the synthetic fiber 1' and heated through the heating process Q, and then dried (for example, exposed to dry wind, hot air or hot plate) to allow moisture to escape to form a fluorine-free water-repellent layer W', and the 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 is to heat the fluorine-free water-repellent composition W from a starting temperature to a target temperature at a heating rate and then maintain the temperature at the target temperature for a holding time, and There is a cylinder pressure inside the cylinder. Preferably, the heating rate is between 0.5°C/min and 3°C/min, the starting temperature is 30°C, the target temperature is 90°C, and the temperature holding time is between 30 minutes and 50 minutes. time, the cylinder pressure is between 2 kg/cm ² and 3.5 kg/cm ² . In other words, the temperature-raising process Q is to heat the fluorine-free water-repellent composition W from 75°C to 90°C at a temperature-raising rate between 0.5°C/min and 3°C/min, and then heat it for between 30 minutes and 50 minutes. The temperature holding time is 90°C, and the pressure inside the cylinder is between 2 kg/cm ² and 3.5 kg/cm ² .

Specifically, the fluorine-free water-repellent composition W wets the yarn 1 but does not soak the yarn 1. More specifically, the package yarn 2 and/or the yarn 1 in the cylinder 3 The position is higher than the liquid level of the fluorine-free water-repellent composition W, so the package yarn 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 The water composition W adheres to the yarn 1 in the inner, middle and outer layers of the package yarn 2 in a predetermined amount, and ensures that the inner, middle and outer layers are heated evenly.

In particular, please refer to Figure 5 again. 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' Layer W' does not cover an entire surface S of the synthetic fiber 1'. In more detail, the fluorine-free water-repellent layer W' only covers a covered surface S1 of the synthetic fiber 1', leaving an uncovered surface S2 of the synthetic fiber 1', and the covered surface S1 and the covered surface S2 are left. The uncovered surface S2 forms 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 the fluorine-free water-repellent composition being 100wt%, the acrylic-based fluorine-free water-repellent composition The water-repellent agent is 1.0wt%~1.5wt%, and the rest is water and/or additives. The acrylic-based fluorine-free water-repellent agent includes an acrylic-based fluorine-free water-repellent polymer and an emulsifier. The additive can be An acid is used to adjust the pH value (acid-base value) of the fluorine-free water-repellent composition, so that the pH value of the fluorine-free water-repellent composition after adjusting the 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 composition＞

Take a commercially available acrylic-based fluorine-free water-repellent agent (such as DAIKIN UNIDYNE XF non-fluorine-based water-repellent agent series), which is an emulsified solution composed of at least an acrylic-based fluorine-free water-repellent polymer, an emulsifier and water. Glacial acetic acid is used as an additive, and water is added to prepare the fluorine-free water-repellent composition used in the embodiments and comparative examples described in Table 1 below, so that the fluorine-free water-repellent composition of the present invention is 100wt%, and the acrylic system is fluorine-free. The fluorine water-repellent agent (acrylic-based fluorine-free water-repellent polymer and emulsifier) is 1.0wt%, and the rest is water and glacial acetic acid. The glacial acetic acid is used to adjust the pH value of the fluorine-free water-repellent composition.

＜Evaluation of fluorine-free water-repellent composition＞

＜pH value between 5 and 8＞

The dyeable fluorine-free water-repellent yarn was produced using the above-mentioned manufacturing method of the dyeable fluorine-free water-repellent yarn using the fluorine-free water-repellent compositions of the Examples and Comparative Examples described in Table 1 below, and the dyeable fluorine-free water-repellent yarn was evaluated. The results of yellowing phenomenon detection, inter-yarn viscosity detection and residual liquid turbidity detection of the dyeable fluorine-free water-repellent yarn in the inner, middle and outer layers of the water cone yarn 2', the yarn of the cone yarn used It is polyester fiber PET 155D/144T. The winding thickness of the yarn is 9 cm. The inner, middle and outer layers are 3 cm, 3 cm and 3 cm respectively. The heating rate is between 0.5℃/min and the starting temperature. is 30°C, the target temperature is 90°C, the temperature holding time is 30 minutes, and the cylinder pressure is between 2 kg/cm ² . Among them, if the color is yellowed by visual inspection, the unqualified mark is marked as "X"; otherwise, if there is no yellowing, the qualified mark is "O"; if the color is yellowed but acceptable, it is marked as "△"; Fluorine water-repellent yarn 2' performs rewinding operation. If the yarns are not sticky, the unqualified mark is "X". On the contrary, if there is no stickiness between the yarns, the qualified mark is "O". The stickiness between the yarns is acceptable but marked as "O". "△". After implementing the above manufacturing method of dyeable fluorine-free water-repellent yarn, use a commercially available turbidity meter TURBIQUANT 1100T to test the residual liquid turbidity of the aforementioned cylinder to represent the degree of absorption of the fluorine-free water-repellent composition, because it can be used as a dyeable fluorine-free water-repellent yarn. The water-repellent effect of dyed fluorine-free water-repellent yarn is indirectly judged. If the value is below 100, it will be marked as "O", and if it is above 100, it will be marked as "X". In Table 1, the same example or the same comparative example is subjected to the aforementioned three tests of yellowing phenomenon detection, inter-yarn stickiness phenomenon detection, and residual liquid turbidity detection. If any "X" appears in the test results, then The "overall evaluation result" column in Table 1 is marked with " The "Evaluation Result" column is marked as "△", which means that this embodiment or comparative example meets the requirements of the present invention; if "O" appears in all test results, the "Overall Evaluation Result" column in Table 1 is marked as "O" means that this embodiment fully meets the requirements of the present invention.

Table 1 Fluorine-free water-repellent composition number pH value Dyeable fluorine-free water-repellent yarn number Yellowing phenomenon detection Detection of stickiness between yarns Residual liquid turbidity detection Overall assessment results inner layer middle level Outer layer inner layer middle level Outer layer Comparative example 1 4 Application comparison example 1 X O O X O O 140 X X Example 1 5 Application Example 1 △ O O △ O O 90 O △ Example 2 6 Application Example 2 △ O O △ O O 90 O △ Example 3 7 Application Example 3 O O O O O O 70 O O Example 4 8 Application Example 4 △ O O △ O O 90 O △ Comparative example 2 9 Application comparison example 2 X O O X O O -- -- X

It can be seen from Table 1 that the fluorine-free water-repellent composition (Examples 1 to 4) with a pH value between 5 and 8 is used to produce the dyeable fluorine-free water-repellent yarn according to the aforementioned manufacturing method. The dyeable fluorine-free water-repellent yarn has good overall evaluation results and meets the requirements of the present invention; however, comparative examples 1 and 2 using pH values 4 and 9 respectively have unsatisfactory overall evaluation results and do not meet the requirements of the present invention. Meet the requirements of the present invention. Obviously, the pH value of the fluorine-free water-repellent composition is an important factor affecting the quality of the dyeable fluorine-free water-repellent yarn; moreover, the fluorine-free water-repellent yarn with a specific pH value range (pH value between 5 and 8) Only with a water composition can the dyeable fluorine-free water-repellent yarn have good overall evaluation result quality that meets the requirements of the present invention. In addition, in Table 1, by detecting the yellowing phenomenon of the dyeable fluorine-free water-repellent yarn in the inner, middle and outer layers of the dyeable fluorine-free water-repellent yarn and the viscosity phenomenon between the yarns, it can also be found that the dye has a specific pH. The fluorine-free water-repellent composition in the pH range (pH value between 5 and 8) can make the inner, middle and outer layers of the dyeable fluorine-free water-repellent yarn of the dyeable fluorine-free water-repellent yarn have better consistency. properties, especially 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, so it meets the requirements of the present invention, and its residual liquid turbidity is the same as that of all examples. and the lowest among the comparative examples, so Example 3 is the best example; however, in contrast, Comparative Examples 1 and 2 using pH values of 4 and 9 respectively have inconsistent inner, middle and outer layers, so they do not meet this requirement. invention requirements.

Next, use the dyeable fluorine-free water-repellent yarns produced by the comparative examples and examples in Table 1 (application comparative examples and application examples), and use the inner, middle and outer layers of the dyeable fluorine-free water-repellent yarn 2' respectively. A dyeable fluorine-free water-repellent fabric (fabric application comparison example and fabric application example) was woven using a weaving process, and the initial repellency of the dyeable fluorine-free water-repellent fabric was tested according to the AATCC 22-2017 water repellent test specification. Water content; then wash it 20 times according to the AATCC 135-2018 water repellent test specification, and then test the water repellency resistance of the dyeable fluorine-free water repellent fabric according to the AATCC 22-2017 water repellent test specification, and record it in Table 2 below. It is water repellent fastness. In Table 2, the same fabric application example or the same fabric application comparative example is subjected to the aforementioned initial water repellency test and washing resistance water repellency test. If any of the values in the test results is less than 80, then " The "Water Repellency Evaluation Result" column is marked with "X", which means it does not meet the requirements of the present invention; if all test results are greater than or equal to 80, then the "Water Repellency Evaluation Result" column in Table 2 is marked with "O" means that this embodiment fully meets the requirements of the present invention.

Table 2 Fluorine-free water-repellent composition number pH value Dyeable fluorine-free water-repellent yarn number Dyeable fluorine-free water-repellent fabric number Initial water repellency Washing and water repellency (water repellency) Water repellency evaluation results inner layer middle level Outer layer inner layer middle level Outer layer Comparative example 1 4 Application comparison example 1 Fabric Application Comparative Example 1 90 70 70 70 50 50 X Example 1 5 Application Example 1 Fabric Application Example 1 90 90 90 80 85 80 O Example 2 6 Application Example 2 Fabric Application Example 2 95 95 95 90 90 85 O Example 3 7 Application Example 3 Fabric Application Example 3 95 95 95 90 90 90 O Example 4 8 Application Example 4 Fabric Application Example 4 90 90 90 90 85 80 O Comparative example 2 9 Application comparison example 2 Fabric Application Comparative Example 2 90 70 70 80 50 50 X

It can be seen from Table 2 that, similar to Table 1, using a fluorine-free water-repellent composition (Examples 1 to 4) with a pH value between 5 and 8 is used in the aforementioned manufacturing method of dyeable fluorine-free water-repellent yarn. The dyeable fluorine-free water-repellent yarn produced below has good water-repellent evaluation results and meets the requirements of the present invention; however, comparative examples 1 and 2 using pH values 4 and 9 respectively are not satisfactory. Qualified water repellency evaluation results do not meet the requirements of the present invention. Obviously, the pH value of the fluorine-free water-repellent composition is an important factor affecting the quality of the dyeable fluorine-free water-repellent yarn; moreover, the fluorine-free water-repellent yarn with a specific pH value range (pH value between 5 and 8) Only with a water composition can the dyeable fluorine-free water-repellent yarn have the water-repellent evaluation result quality that meets the requirements of the present invention. In addition, in Table 2, through the initial water repellency test and washing water repellency (water repellency fastness) test of the inner, middle and outer layers of the dyeable fluorine-free water-repellent yarn, it can also be found that the yarn has a specific pH value range (pH The fluorine-free water-repellent composition (value between 5 and 8) can make the inner, middle and outer layers of the dyeable fluorine-free water-repellent yarn of the dyeable fluorine-free water-repellent yarn have better consistency, especially 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, so it meets the requirements of the present invention. Therefore, Example 3 is the best example; however, relatively, Comparative Examples 1 and 2 with pH values of 4 and 9 were used respectively. The inner, middle and outer layers were not consistent and therefore did not meet the requirements of the present invention.

<The amount of acrylic-based fluorine-free water-repellent agent is 1.0wt%~1.5wt%>

table 3 Fluorine-free water-repellent composition number pH value Amount of acrylic-based fluorine-free water-repellent agent Dyeable fluorine-free water-repellent yarn number Dyeable fluorine-free water-repellent fabric number Initial water repellency Washing and water repellency (water repellency) Water repellency evaluation results inner layer middle level Outer layer inner layer middle level Outer layer Example 3' 7 1.5wt% Application Example 3 Fabric Application Example 3 95 95 95 90 90 90 O Example 3 7 1.0wt% Application Example 3 Fabric Application Example 3 95 95 95 90 90 90 O Comparative example 3 7 0.5wt% Application comparative example 3 Fabric Application Comparative Example 3 90 70 70 80 50 50 X

The preparation, production and evaluation of Comparative Example 3, Application Comparative Example 3 and Fabric Application Comparative Example 3' in Table 3 above are based on the Comparative Examples, Application Comparative Examples and Fabric Application Comparative Examples in Table 1 and Table 2, and therefore are not Again. It can be seen from Table 3 that the fluorine-free water-repellent compositions of Example 3', Example 3 and Comparative Example 3 all have a pH value of 7, and the difference lies in the amount of acrylic-based fluorine-free water-repellent agent used. They are 1.5wt%, 1.0wt% and 0.5wt% respectively, and only Comparative Example 3 does not meet the requirements of the initial water repellency and water repellency fastness of the present invention. Therefore, the amount of acrylic-based fluorine-free water-repellent agent is 1.0wt%~1.5wt% to obtain the initial water-repellent degree and water-repellent fastness consistent with the present invention.

＜Feel test＞

Table 4 Fluorine-free water-repellent composition number pH value Dyeable fluorine-free water-repellent yarn number Dyeable fluorine-free water-repellent fabric number Feel evaluation results Example 1 5 Application Example 1 Fabric Application Example 1 O Example 2 6 Application Example 2 Fabric Application Example 2 O Example 3 7 Application Example 3 Fabric Application Example 3 O Example 4 8 Application Example 4 Fabric Application Example 4 O

The fabric application examples in the above Table 4 are the inner layers of the corresponding dyeable fluorine-free water-repellent tube yarn 2'. The hand feeling evaluation method is to have 5 people give scores from 1 to 5 points respectively and then average the average scores. A score of 4.5 or above indicates a soft feel and is marked as "O", a score of 3.5 to 4.4 indicates a firm feel but is acceptable and is marked as "△", and a score of 3.4 or below indicates a firm feel and is unacceptable and is marked as "X". It can be seen from Table 4 that the fabric application examples of the present invention all have evaluation results of soft hand feel and meet the requirements of the present invention.

＜Dyeing test＞

Next, the dyeable fluorine-free water-repellent fabrics of Fabric Application Comparative Examples 1' to 2' and Fabric Application Examples 1' to 4' in Table 2 were dyed in one dyeing step, and their water resistance after dyeing was tested. Dye fastness and water fastness. In this dyeing step, the concentration of disperse dye (S type) for polyester fiber is 2%, the dyeing temperature is 135 degrees, and the temperature is maintained for 40 minutes. Among them, the dyeing was first tested according to the test specification ISO 105 C06 B1S (Color Fastness to Washing, color fastness to water) and the test specification ISO 150 E01 (Color Fastness to Water, color fastness to water). Fastness. The above test results are recorded in Table 5 described below. In Table 5, the same fabric application example is subjected to the aforementioned water fastness test (also called water fastness) and water fastness test (also called wash fastness). If any of the values in the test results appears If less than 4, the "Dyeing Evaluation Result" column in Table 5 will be marked as " The “Verification Result” column is marked “O”, which means that this embodiment fully meets the requirements of the present invention.

table 5 Fluorine-free water-repellent composition number pH value Dyeable fluorine-free water-repellent yarn number Dyeable fluorine-free water-repellent fabric number Washing fastness Water fastness Dyeing evaluation results inner layer middle level Outer layer inner layer middle level Outer layer Example 1 5 Application Example 1 Fabric Application Example 1' 4 4 4 4 4 4 O Example 2 6 Application Example 2 Fabric Application Example 2' 4 4 4 4 4 4 O Example 3 7 Application Example 3 Fabric Application Example 3' 4 4 4 4 4 4 O Example 4 8 Application Example 4 Fabric Application Example 4' 4 4 4 4 4 4 O

It can be seen from Table 5 that the dyeing evaluation results of the fabric application examples of the present invention all have good washing fastness and water fastness, and therefore meet the requirements of the present invention.

Specifically, please refer to Figure 7. After the dyeable fluorine-free water-repellent fabric is dyed in this dyeing step, the dye D passes through the uncovered surface of the synthetic fiber 1' in the dyeable fluorine-free water-repellent yarn 12. S2 is dyed on the interior of the synthetic fiber 1' and/or the uncovered surface S2. In other words, the dyeing step is to dye the section of the synthetic fiber that is not covered with the fluorine-free water-repellent layer, and the dye is not dyed to the fluorine-free water-repellent layer. Wherein, the dyeing is combined with the yarn through a physical or chemical reaction.

Similarly, the dyeable fluorine-free water-repellent yarn 12 can also be dyed through the dyeing step and then woven into a dyeable fluorine-free water-repellent fabric, wherein the dye D passes through the dyeable fluorine-free water-repellent yarn 12 The uncovered surface S2 of the synthetic fiber 1' is dyed on the interior of the synthetic fiber 1' and/or the uncovered surface S2. In other words, the dyeing step is to dye the section of the synthetic fiber that is not covered with the fluorine-free water-repellent layer, and the dye is not dyed to the fluorine-free water-repellent layer.

In summary, the present invention provides a method for manufacturing dyeable fluorine-free water-repellent yarns and a method for manufacturing dyeable fluorine-free water-repellent fabrics that are treated with a fluorine-free water-repellent composition. Dyed fluorine-free water-repellent yarns and dyeable fluorine-free water-repellent fabrics are suitable for "yarn dyed" (commonly called first dyeing) and "piece dye" (commonly called post-dyed) processes, and have a good soft feel. , water-repellent fastness, wash-resistant dye fastness and water-resistant dye fastness.

However, the above are only examples of the present invention, and should not be used to limit the scope of the present invention. All simple equivalent changes and modifications made based on the patent scope of the present invention and the content of the patent specification are still within the scope of the present invention. Within the scope covered by the patent of this invention.

1: yarn

1’:Synthetic fiber

11: Soak yarn

12: Dyeable fluorine-free water-repellent yarn

2: Cone yarn

2’: Dyeable fluorine-free water-repellent yarn

21:Cylinder

211:Outer surface

212:Inner surface

213:Through hole

22: Hollow interior

3:Cylinder

4: Supply device

41: Motor

42:Inlet pipe

43: Outlet pipe

5:Heating device

D:Dye

P: composition cycle

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, in which: Figure 1 is a flow chart of the manufacturing method of the dyeable fluorine-free water-repellent yarn of the present invention. Figure 2 is a schematic structural diagram of the package yarn of the present invention. Figure 3 is a schematic diagram of the operation of the package yarn installed in the cylinder according to the present invention. Figure 4 is a schematic diagram of the heating process of the present invention. Figure 5 is a schematic structural diagram of the fluorine-free water-repellent composition of the present invention. Figure 6 is a schematic structural diagram of the dyeable fluorine-free water-repellent yarn of the present invention. Figure 7 is a schematic structural diagram of dyeing dyeable fluorine-free water-repellent yarn with the dye of the present invention.

Claims (9)

A method for manufacturing dyeable fluorine-free water-repellent yarn, which at least includes in sequence: a yarn preparation step: preparing a yarn (1), and the yarn (1) is wound around a yarn having a hollow interior (22) A cylinder (21) is used to form a cylinder of yarn (2). The cylinder (21) is provided with a plurality of through holes (211) and an inner surface (212) penetrating the cylinder (21). 213), the plurality of through holes (213) are arranged at intervals and are arranged in a ring around the circumference of the cylinder (21), and the yarn (1) is wound around the outer surface of the cylinder (21) The surface (211) is covered with the plurality of through holes (213); a step of soaking the yarn: placing the package yarn (2) inside a sealable cylinder (3), and using a supply device (4 ) supplies a fluorine-free water-repellent composition (W) from the hollow interior (22) of the cylinder (21) to flow through the plurality of through holes (213), and allows the fluorine-free water-repellent composition (W) to infiltrate The yarn (1) forms a soaked yarn (11) and the fluorine-free water-repellent composition (W) flows out of the package yarn (2), and the fluorine-free water-repellent composition (W) flows out of the package yarn (2). W) then flows into the supply device (4) to supply the fluorine-free water-repellent composition (W) to form a composition cycle (P); a temperature-raising heating step: using a heating device (5) and a temperature-raising process ( Q) Heating the fluorine-free water-repellent composition (W) so that the soaked yarn (11) forms a dyeable fluorine-free water-repellent yarn (12); wherein, the fluorine-free water-repellent composition (W) in the cylinder (3) The position of the package yarn (2) and/or the yarn (1) is higher than the liquid level of the fluorine-free water-repellent composition (W), so that the package yarn (2) and/or the yarn (1) ) will not be soaked in the fluorine-free water-repellent composition (W). The manufacturing method of dyeable fluorine-free water-repellent yarn as described in claim 1, wherein the pH value of the fluorine-free water-repellent composition (W) is between 5 and 8. The manufacturing method of dyeable fluorine-free water-repellent yarn as described in claim 2, wherein the fluorine-free water-repellent composition (W) is composed of an acrylic-based fluorine-free water-repellent agent and water/or additives, Taking the fluorine-free water-repellent composition (W) as 100wt%, the acrylic-based fluorine-free water-repellent agent is 1.0wt%~1.5wt%, and the rest is water and/or additives. The manufacturing method of dyeable fluorine-free water-repellent yarn as described in claim 3, wherein the additive is an acid to adjust the pH value of the fluorine-free water-repellent composition. The manufacturing method of dyeable fluorine-free water-repellent yarn as described in claim 4, wherein the acid is glacial acetic acid or citric acid. The manufacturing method of dyeable fluorine-free water-repellent yarn as described in claim 5, wherein the temperature-raising process (Q) is to heat the fluorine-free water-repellent yarn at a heating rate between 0.5°C/min and 3°C/min. After the water composition is heated from 30°C to 90°C, the temperature is maintained for a holding time of between 30 minutes and 50 minutes, and the internal pressure of the cylinder (3) is between 2kg/ ^cm2 and 3.5 kg/cm ² . The manufacturing method of dyeable fluorine-free water-repellent yarn as described in claim 6, wherein the yarn (1) is composed of at least one synthetic fiber (1'), and the synthetic fiber (1') is long Fiber, the fluorine-free water-repellent composition (W) forms a fluorine-free water-repellent layer (W') on the surface of the synthetic fiber (1'), and the fluorine-free water-repellent layer (W') does not cover the synthetic fiber (1') all surfaces. The manufacturing method of dyeable fluorine-free water-repellent yarn as described in claim 7, wherein a dyeing step is followed by the heating step, and the dyeing step The step is to dye a dye (D) on the section of the synthetic fiber (1') that is not covered with the fluorine-free water-repellent layer (W'), and the dye (D) is not dyed on the surface of the fluorine-free water-repellent layer (W'). Fluorine water-repellent layer (W'). A method of manufacturing a dyeable fluorine-free water-repellent fabric, which is to weave the dyeable fluorine-free water-repellent yarn (12) prepared by the method of manufacturing a dyeable fluorine-free water-repellent fabric as described in claim 7 into a fabric. After the fluorine-free water-repellent fabric can be dyed, a dyeing step is carried out. The dyeing step is to dye a dye (D) on the synthetic fiber (1') that is not covered with the fluorine-free water-repellent layer (W'). section of the surface, and the dye (D) does not stain the fluorine-free water-repellent layer (W').