Processing method of fluoride-free DWR waterproof zipper

Abstract

The invention relates to the field of zipper processing, in particular to a processing method of a fluoride-free DWR waterproof zipper, which sequentially adopts four steps of pretreatment, padding treatment, drying treatment and heat treatment to carry out waterproof processing on the zipper, the fluorine-free DWR waterproof zipper prepared by matching paraffin, polyether modified silicone oil, carbodiimide, nano silicon dioxide dispersion liquid, fatty alcohol-polyoxyethylene ether and diethylene glycol monobutyl ether has the following advantages that 1, the fluorine-free DWR waterproof zipper meets the limitation requirements of Europe and America regulations and various standards on fluorine element, 2, the waterproof grade meets the grade 4.5 or above of standards such as AATCC / ISO / GB / T and the like, and the fluorine-free DWR waterproof zipper has a good waterproof effect. 3, the washing resistance can reach more than 20 times of washing and drying tests; 4, the phenomenon of white grasping in the market is avoided; and 5, the anti-siphon performance can reach 10H without climbing.

Description

Technical Field

[0001] The invention relates to the field of zipper processing, and in particular to a processing method of a fluorine-free DWR waterproof zipper. Background Art

[0002] As consumers pay more and more attention to environmental protection and health, fluorine-free waterproof technology is gradually favored by the market. As one of the application products, the market demand for fluorine-free waterproof zippers is also gradually growing. Especially in the fields of outdoor products, sporting goods and high-end clothing, fluorine-free waterproof zippers are highly praised for their good waterproof performance and environmental protection characteristics. According to market research reports, the scale of the global and Chinese waterproof zipper markets is constantly expanding, and it is predicted that it will maintain a stable annual compound growth rate in the next few years. Although the specific market size data for fluorine-free waterproof zippers may be difficult to obtain, it is foreseeable that with the continuous advancement of technology and the expansion of application fields, the fluorine-free waterproof zipper processing market will usher in a broader development space.

[0003] The existing fluorine-free waterproof zipper has poor water-washing resistance, so the waterproof zipper cannot be widely used. Summary of the invention

[0004] The purpose of the present invention is to provide a method for processing a fluorine-free DWR waterproof zipper, wherein the waterproof zipper processed by the method has good water washing resistance.

[0005] In order to achieve the above-mentioned purpose, the present invention specifically adopts the following technical scheme: a method for processing a fluorine-free DWR waterproof zipper, comprising the following steps: Step (1) pre-treatment: placing the assembled zipper in a degreasing agent for pre-treatment; Step (2) padding treatment: immersing the stacked zippers in a prepared waterproof agent by rolling them with a roller, wherein the waterproof agent mainly comprises water-based polyurethane and polyacrylic acid emulsion; Step (3) Drying: Drying the assembled zippers after dipping and rolling through a constant temperature drying device; Step (4) heat treatment: the dried assembled zippers are placed in a constant temperature infrared device for heat treatment.

[0006] Preferably, the degreasing agent in step (1) is prepared by mixing 8%-10% alkyl glycoside (APG), 2%-5% saponin, 3%-5% sodium bicarbonate, 2%-3% sodium citrate, 20%-25% ethanol, and the remainder deionized water.

[0007] Preferably, the pretreatment time in step (1) is 10-15 minutes.

[0008] Preferably, the waterproofing agent in step (2) comprises the following raw materials in percentage by weight: Waterborne polyurethane: 25 - 35% Polyacrylate emulsion: 8 - 15% Paraffin wax: 15 - 20% Polyether-modified silicone oil: 5 - 10% Carbodiimide: 4 - 8% Nano-silica dispersion: 2 - 4% Fatty alcohol polyoxyethylene ether (AEO-9): 0.3 - 0.8% Diethylene glycol butyl ether (DGB): 2 - 5% Defoamer: 0.2 - 0.5% Deionized water: the balance.

[0009] Preferably, the waterborne polyurethane resin is an aliphatic waterborne polyurethane with a solid content of 45 - 55%, and the waterborne polyurethane resin of model AH-1618 produced by Anhui Dawei Huatai New Material Technology Co., Ltd. can be used.

[0010] Preferably, the polyacrylate emulsion uses Dow Tianba Tianba 2012 polyacrylate emulsion.

[0011] Preferably, the defoamer uses TEGO 810.

[0012] Preferably, the preparation method of the waterproof agent in step (2) includes the following steps: Preferably, in step (A), the polyacrylate emulsion is added to the waterborne polyurethane and stirred at 30 - 35°C for 10 - 20 minutes; Preferably, in step (B), paraffin wax and polyether-modified silicone oil are continuously added, stirred for 20 - 40 minutes, then fatty alcohol polyoxyethylene ether and defoamer are added, and stirred for 10 - 20 minutes; Preferably, in step (C), after the nano- dispersion liquid is stirred evenly, the carbodiimide cross-linking agent diluted with deionized water to a mass concentration of 10% is added dropwise; Preferably, in step (D), diethylene glycol butyl ether is finally added, stirred for 10 - 20 minutes, and then adjusted to the required viscosity with deionized water.

[0013] Preferably, the preparation method of the nano- dispersion liquid is: nano- and deionized water are configured into a suspension with a mass concentration of 5 - 10%, and then 0.5 - 1% of nano-silane coupling agent KH-550 based on the weight of the suspension is added and dispersed evenly under ultrasonic conditions to obtain nano- dispersion liquid, wherein the silica uses silica with a particle size of 10 - 30 nm and 70 - 90 nm in a mass ratio of 1 - 3:1.

[0014] Preferably, the padding treatment time in step (2) is 30 - 40 minutes, and the liquor pickup rate is 40 - 45%.

[0015] Preferably, the temperature of the drying treatment in step (3) is 145 - 155 °C, and the drying time is 30 - 60 minutes.

[0016] Preferably, the temperature of the heat treatment in step (3) is 68 - 72 °C, and the heat treatment time is 2 - 3 hours.

[0017] The beneficial effects of the present invention are as follows: The present invention sequentially uses four steps of pretreatment, padding treatment, drying treatment, and heat treatment to perform waterproof processing on the zipper. When performing the padding treatment, a fluorine-free DWR waterproof zipper prepared by using waterborne polyurethane and polyacrylate emulsion as the main body, and cooperating with paraffin, polyether-modified silicone oil, carbodiimide, nano-silica dispersion, fatty alcohol polyoxyethylene ether, and diethylene glycol butyl ether has the following advantages: 1. It meets the regulatory requirements of Europe and the United States and various standards for fluorine elements; 2. The waterproof grade meets the standards of AATCC / ISO / GB / T and other standards above level 4.5; 3. The washability can reach more than 20 times of washing and drying tests; 4. There is no phenomenon of white marks when grabbed by hand as seen in the market; 5. The anti-siphon performance can reach no climbing within 10H. Detailed Embodiments

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below.

[0019] Embodiment 1

[0020] To achieve the above objectives, the present invention specifically adopts the following technical solutions: A processing method for a fluorine-free DWR waterproof zipper, comprising the following steps: Step (1) Pretreatment: Put the packaged zipper into a degreasing agent for pretreatment; Step (2) Padding treatment: Immerse the packaged zipper into the prepared waterproof agent and perform padding by roller rolling; Step (3) Drying treatment: Dry the padded packaged zipper through a constant-temperature drying device; Step (4) Heat treatment: Place the dried packaged zipper in a constant-temperature infrared device for heat treatment.

[0021] Among them, the degreasing agent in step (1) is prepared by mixing 8% alkyl polyglycoside (APG), 2% saponin, 3% sodium bicarbonate, 2% sodium citrate, 20% ethanol, and the balance deionized water.

[0022] Among them, the pretreatment time in step (1) is 10 minutes.

[0023] Among them, the waterproofing agent in step (2) is composed of raw materials in the following weight percentages: Waterborne polyurethane 25% Polyacrylic acid emulsion 15% Paraffin wax 15% Polyether-modified silicone oil 5% Carbodiimide 4% Nano-silica dispersion 2% Fatty alcohol polyoxyethylene ether (AEO-9) 0.3% Diethylene glycol butyl ether (DGB) 2% Defoaming agent 0.2% Deionized water balance.

[0024] Among them, the preparation method of the waterproofing agent in step (2) includes the following steps: Among them, in step (A), polyacrylic acid emulsion is added to waterborne polyurethane and stirred at 30 °C for 10 minutes; Among them, in step (B), paraffin wax and polyether-modified silicone oil are continuously added, stirred for 20 minutes, then fatty alcohol polyoxyethylene ether and defoaming agent are added, and stirred for 10 minutes; Among them, in step (C), nano- After the dispersion is stirred evenly, a carbodiimide cross-linking agent diluted to 10% mass concentration with deionized water is added dropwise; Among them, in step (D), diethylene glycol butyl ether is finally added, stirred for 10 minutes, and then adjusted to the required viscosity with deionized water.

[0025] Among them, nano- The preparation method of the dispersion is: nano- and deionized water are configured into a suspension with a mass concentration of 5%, and then 0.5% of nano-silane coupling agent KH-550 based on the weight of the suspension is added and dispersed evenly under ultrasonic conditions to obtain nano- dispersion.

[0026] Among them, the padding treatment time in step (2) is 30 minutes, and the liquor ratio is 40%.

[0027] Among them, the temperature of the drying treatment in step (3) is 145 °C, and the drying time is 30 minutes.

[0028] Among them, the temperature of the heat treatment in step (3) is 68 °C, and the heat treatment time is 2 hours.

[0029] Example 2

[0030] To achieve the above object, the present invention specifically adopts the following technical solutions: A processing method of a fluorine-free DWR waterproof zipper, comprising the following steps: Step (1) Pretreatment: Put the packaged zipper into a degreasing agent for pretreatment; Step (2) Padding treatment: Immerse the packaged zipper into the prepared waterproof agent and pad it by roller; Step (3) Drying treatment: Dry the padded packaged zipper through a constant temperature drying device; Step (4) Heat treatment: Place the dried packaged zipper in a constant temperature infrared device for heat treatment.

[0031] Among them, in step (1), the degreasing agent is composed of 9% alkyl polyglycoside (APG), 3% saponin, 4% sodium bicarbonate, 2% sodium citrate, 22% ethanol, and the balance deionized water.

[0032] Among them, in step (1), the pretreatment time is 12 minutes.

[0033] Among them, the waterproof agent in step (2) is composed of the following raw materials in weight percentages: Waterborne polyurethane 30% Polyacrylate emulsion 12% Paraffin wax 18% Polyether modified silicone oil 8% Carbodiimide 6% Nano-silica dispersion 3% Fatty alcohol polyoxyethylene ether (AEO-9) 0.6% Diethylene glycol butyl ether (DGB) 4% Defoamer 0.3% Deionized water The balance.

[0034] Among them, the preparation method of the waterproof agent in step (2) includes the following steps: Among them, in step (A), add polyacrylate emulsion to waterborne polyurethane and stir at 32 °C for 15 minutes; Among them, in step (B), continue to add paraffin wax and polyether modified silicone oil, stir for 30 minutes, then add fatty alcohol polyoxyethylene ether and defoamer, and stir for 15 minutes; Among them, in step (C), after adding the nano- dispersion and stirring evenly, dropwise add the carbodiimide crosslinking agent diluted with deionized water to a mass concentration of 10%; Among them, in step (D), finally add diethylene glycol butyl ether, stir for 15 minutes, and adjust to the required viscosity with deionized water.

[0035] Among them, the preparation method of the nano- dispersion is: Put the nano- It is configured into a suspension with a mass concentration of 8% with deionized water, and then 0.8% of nano-silane coupling agent KH-550 based on the weight of the suspension is added and dispersed evenly under ultrasonic conditions to obtain nano- dispersion liquid.

[0036] Among them, in step (2), the padding treatment time is 35 minutes and the liquor pickup is 42%.

[0037] Among them, in step (3), the drying treatment temperature is 150 °C and the drying time is 45 minutes.

[0038] Among them, in step (3), the heat treatment temperature is 70 °C and the heat treatment time is 2 hours.

[0039] Example 3

[0040] In order to achieve the above object, the present invention specifically adopts the following technical solutions: A processing method of a fluorine-free DWR waterproof zipper, comprising the following steps: Step (1) Pretreatment: Put the packaged zipper into a degreasing agent for pretreatment; Step (2) Padding treatment: Immerse the packaged zipper into the prepared waterproof agent and pad it by roller rolling; Step (3) Drying treatment: Dry the padded packaged zipper through a constant temperature drying device; Step (4) Heat treatment: Place the dried packaged zipper in a constant temperature infrared device for heat treatment.

[0041] Among them, in step (1), the degreasing agent is composed of 10% alkyl polyglycoside (APG), 5% saponin, 5% sodium bicarbonate, 3% sodium citrate, 25% ethanol, and the balance of deionized water.

[0042] Among them, in step (1), the pretreatment time is 15 minutes.

[0043] Among them, the waterproof agent in step (2) is composed of the following raw materials in weight percentages: Waterborne polyurethane 35% Polyacrylate emulsion 8 Paraffin wax 20% Polyether modified silicone oil 10% Carbodiimide 8% Nano-silica dispersion liquid 4% Fatty alcohol polyoxyethylene ether (AEO-9) 0.8% Diethylene glycol butyl ether (DGB) 5% Defoaming agent 0.5% Deionized water balance.

[0044] Among them, the preparation method of the waterproof agent in step (2) includes the following steps: Among them, in step (A), polyacrylate emulsion is added to aqueous polyurethane and stirred at 35 °C for 20 minutes; Among them, in step (B), paraffin and polyether-modified silicone oil are continuously added, stirred for 40 minutes, and then fatty alcohol polyoxyethylene ether and defoaming agent are added and stirred for 20 minutes; Among them, in step (C), nano After the dispersion is stirred evenly, a carbodiimide cross-linking agent diluted to a mass concentration of 10% with deionized water is added dropwise; Among them, in step (D), diethylene glycol butyl ether is finally added, stirred for 20 minutes, and then adjusted to the required viscosity with deionized water.

[0045] Among them, nano The preparation method of the dispersion is as follows: nano and deionized water are configured into a suspension with a mass concentration of 10%, and then 1% of nano-silane coupling agent KH-550 based on the weight of the suspension is added and dispersed evenly under ultrasonic conditions to obtain nano dispersion.

[0046] Among them, the padding treatment time in step (2) is 40 minutes, and the liquor pickup is 45%.

[0047] Among them, the temperature of the drying treatment in step (3) is 155 °C, and the drying time is 60 minutes.

[0048] Among them, the temperature of the heat treatment in step (3) is 72 °C, and the heat treatment time is 3 hours.

[0049] Example 4

[0050] The difference between this example and Example 2 is that: among them, the silica is a mixture of 10-30 nm silica and 70-90 nm silica with a mass ratio of 2:1, and the influence of different particle size combinations on the waterproof performance is studied.

[0051] Example 5

[0052] The difference between this example and Example 2 is that: the nano dispersion is further modified: nano and deionized water are configured into a suspension with a mass concentration of 8%, and then 0.8% of nano-silane coupling agent KH-550 based on the weight of the suspension is added and dispersed evenly under ultrasonic conditions to obtain nano dispersion, then 4% of carbon nanotubes based on the weight of the nano dispersion is added and ultrasonically dispersed for another 10 min, and finally 0.2% of dispersant TNWDIS based on the mass of the carbon nanotubes is added and ultrasonically dispersed evenly to obtain the modified nano Dispersion liquid.

[0053] Comparative Example 1 The difference between this example and Example 2 is that: the formulation of the pretreatment of the present invention is not adopted, and only an aqueous solution of ethanol is used for cleaning.

[0054] Comparative Example 2 The difference between this example and Example 2 is that: polyacrylic acid emulsion is not adopted.

[0055] Comparative Example 3 The difference between this example and Example 2 is that: nano- Dispersion liquid.

[0056] Experimental data

[0057] It can be seen from the experiments that the various performances of Examples 1-3 of the present invention are all good. In particular, in Example 4, the particle size of nano-silica is adjusted. The nano-silica with a large particle size can interact with the waterproof film formed by the polymer to jointly build a strong waterproof system, effectively resisting the erosion of moisture. The nano-silica with a smaller particle size can penetrate into the tiny pores on the surface of the material, making the material structure more dense and further enhancing its waterproof and wash-resistant performances.

[0058] In Example 5, the nano- Dispersion liquid was further modified. The addition of carbon nanotubes can not only form a waterproof film with the polymer, but also cooperate with nano-silica. The nano-silica is in the micron level, while the radial size of the carbon nanotubes is in the nanometer order of magnitude and the axial size is in the micron order of magnitude. The cooperation between the micron level and the nano level makes part of the nano-silica adhere to the carbon nanotubes, forming a stable core-shell structure and further enhancing its waterproof and wash-resistant performances.

[0059] In Comparative Example 1, since the formulation of the pretreatment of the present invention is not adopted, the penetration force and adhesion on the surface of the zipper decrease. During the padding process, the waterproof potion cannot be well combined with the surface of the zipper, resulting in a decrease in waterproof and wash-resistant performances. In Comparative Example 2, since polyacrylic acid emulsion is not adopted, the simple waterborne polyurethane base film causes a decrease in waterproof performance. In Comparative Example 3, since nano- Dispersion liquid is not adopted, lacking the supporting effect of physical waterproofing on the polymer base film, resulting in a decrease in waterproof and wash-resistant performances.

[0060] In the description of this specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0061] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and what is described in the above embodiments and the specification only illustrates the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A method for processing a fluorine-free DWR waterproof zipper, characterized in that: The following steps are involved: Step (1) pre-treatment: placing the assembled zipper in a degreasing agent for pre-treatment; Step (2) padding treatment: immersing the stacked zippers in a prepared waterproof agent by rolling them with a roller, wherein the waterproof agent mainly comprises water-based polyurethane and polyacrylic acid emulsion; Step (3) Drying: Drying the assembled zippers after dipping and rolling through a constant temperature drying device; Step (4) heat treatment: the dried assembled zippers are placed in a constant temperature infrared device for heat treatment.

2. The method for processing a fluorine-free DWR waterproof zipper according to claim 1, characterized in that: In step (1), the degreasing agent is prepared by mixing 8%-10% alkyl glycoside (APG), 2%-5% saponin, 3%-5% sodium bicarbonate, 2%-3% sodium citrate, 20%-25% ethanol, and the balance deionized water.

3. The method for processing a washable fluorine-free DWR waterproof zipper according to claim 1, characterized in that: The pre-treatment time in step (1) is 10-15 minutes.

4. The method for processing a fluorine-free DWR waterproof zipper according to claim 1, characterized in that: The waterproofing agent in step (2) is composed of the following raw materials in weight percentage: Waterborne polyurethane 25-35% Polyacrylic acid emulsion 8-15% Paraffin 15-20% Polyether modified silicone oil 5-10% Carbodiimide 4-8% Nano-silicon dioxide dispersion 2-4% Fatty alcohol polyoxyethylene ether (AEO-9) 0.3-0.8% Diethylene glycol butyl ether (DGB) 2-5% Defoamer 0.2-0.5% Deionized water balance.

5. The method for processing a fluorine-free DWR waterproof zipper according to claim 4, characterized in that: The method for preparing the waterproof agent in step (2) comprises the following steps: Step (A) adding polyacrylic acid emulsion to waterborne polyurethane and stirring at 30-35° C. for 10-20 minutes; Step (B): continue to add paraffin wax and polyether-modified silicone oil, stir for 20-40 minutes, then add fatty alcohol polyoxyethylene ether and defoamer, and stir for 10-20 minutes; Step (C) Nano- After the dispersion is stirred evenly, a carbodiimide crosslinker diluted with deionized water to a concentration of 10% by mass is added dropwise; In step (D), diethylene glycol butyl ether is added, stirred for 10-20 minutes, and then adjusted to the desired viscosity with deionized water.

6. The method for processing a fluorine-free DWR waterproof zipper according to claim 5, characterized in that: nanometer The preparation method of the dispersion is as follows: and deionized water to prepare a suspension with a mass concentration of 5-10%, and then add 0.5-1% of the weight of the suspension nano-silane coupling agent KH-550 to disperse evenly under ultrasonic conditions to obtain nano- Dispersion.

7. The method for processing a fluorine-free DWR waterproof zipper according to claim 1, characterized in that: The padding treatment time in step (2) is 30-40 minutes, and the liquid carrying rate is 40-45%.

8. The method for processing a fluorine-free DWR waterproof zipper according to claim 1, characterized in that: The drying temperature in step (3) is 145-155° C. and the drying time is 30-60 minutes.

9. The method for processing a fluorine-free DWR waterproof zipper according to claim 1, characterized in that: The heat treatment temperature in step (3) is 68-72° C. and the heat treatment time is 2-3 hours.

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