Real silk three-proofing finishing agent as well as preparation method and application thereof

Abstract

The invention relates to a real silk three-proofing finishing agent and a preparation method and application thereof.The finishing agent is a silicon-fluorine-containing acrylic emulsion and is of a core-shell structure with a shell structure and a core structure, the shell structure is formed by polymerizing 40-55 wt% of perfluorohexyl ethyl acrylate, 20-40 wt% of vinyltriethoxysilane, 15-20 wt% of 2-ethylhexyl acrylate and an emulsifier, and the emulsifier is an emulsifier. The core structure is formed by polymerizing 40 to 60 weight percent of methyl methacrylate, 30 to 60 weight percent of 2-ethylhexyl acrylate and an emulsifier. The finishing agent disclosed by the invention can realize low-temperature three-proofing finishing on real silk fabrics, ensures water and oil repellency, improves flexibility, reduces emulsifier residues after finishing of the silk fabrics, and meets the hand feeling requirements of the silk fabrics.

Description

Technical Field

[0001] The invention relates to the field of textiles, and in particular to a silk three-proof finishing agent and a low-temperature finishing process thereof. Background Art

[0002] At present, the market demand for textiles with water-repellent, oil-repellent and easy-to-clean functions is growing rapidly, and textiles are required to maintain their original air permeability, moisture permeability, whiteness and physical and mechanical strength after "three-proof" finishing. The key and difficulty of research in this field is to give fabrics "three-proof" functions through three-proof finishing agents, maintain high water resistance and maintain the original fabric style.

[0003] The three-proof finishing is to apply a finishing agent with low surface energy on the fabric, firmly attach to the fiber or form a chemical bond with it, change the composition of the fiber surface layer, reduce the surface energy of the fabric, make the critical surface tension of the fabric much smaller than the surface tension of liquids such as water or oil, and no longer be wetted by water and oil, making it difficult for water and oil to spread on the surface of the fabric and then wet the fabric. After finishing, the fabric should still maintain good air permeability and moisture permeability, and not affect the feel and style of the fabric.

[0004] Silk is a natural protein fiber with many excellent wearing properties, such as soft luster, smooth touch, moisture absorption and breathability, lightness and elegance, good drape performance, etc. In today's advocacy of environmental protection, health and comfort, silk fabrics are favored by the market as ecological textiles. In order to meet the requirements of personalized, novel and functional fabrics, it is imperative to develop multifunctional "three-proof" silk fabrics. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems existing in the prior art and provide a silk three-proof finishing agent and a low-temperature finishing process thereof, wherein the finishing agent can achieve low-temperature three-proof finishing on silk fabrics.

[0006] In order to achieve the above technical objectives and the above technical effects, the present invention is implemented through the following technical solutions: A three-proof finishing agent for silk, which is a silicone-fluorine-containing acrylic emulsion and a core-shell structure having a shell structure and a core structure, wherein the shell structure is polymerized by 40-55wt% of perfluorohexylethyl acrylate, 20-40wt% of vinyl triethoxysilane, 15-20wt% of isooctyl acrylate, and an emulsifier, and the core structure is polymerized by 40-60wt% of methyl methacrylate, 30-60wt% of isooctyl acrylate, and an emulsifier.

[0007] Furthermore, the emulsifier is a polymerizable emulsifier DNS-86, and the amount used is 1 to 3 wt % of the total weight of the monomers.

[0008] Furthermore, the mass ratio of the shell structure to the core structure is 1-2:3-4.

[0009] A method for preparing a silk triple-proof finishing agent, the preparation method comprising the following specific steps: Step S1: at room temperature, a certain ratio of monomers for shell structure is uniformly stirred at high speed in an aqueous solution with an emulsifier added, and then emulsified at a speed of 8000 to 10000 r / min for 5 to 8 minutes using a high shear dispersing emulsifier to obtain a shell structure monomer emulsion; Step S2: stirring a core structure monomer mixture of a certain ratio in a polymerizable emulsifier aqueous solution at high speed to obtain a core structure monomer emulsion; Step S3: taking out 1 / 3 of the core structure monomer emulsion and adding it into a three-necked flask equipped with a constant pressure funnel, a thermometer and nitrogen protection as a seed emulsion, adding a pre-prepared 1 / 3 initiator aqueous solution, slowly stirring evenly in a water bath and heating to 70-75° C., after the system shows blue light at a constant temperature, dripping the remaining core structure monomer emulsion into the system, maintaining a drip rate of 1 drop / s, and after the dripping is completed, adding 1 / 3 of the initiator aqueous solution and reacting at a constant temperature for 20-30 minutes to prepare a core structure emulsion; Step S4: adding the shell monomer emulsion to the core structure emulsion at a dripping rate of 1 drop / 2s at a constant temperature, then heating the system to 75-80°C, adding the remaining 1 / 3 of the initiator aqueous solution, reacting for 40-60 minutes, cooling the prepared emulsion to room temperature, and filtering to obtain a core-shell finishing agent emulsion.

[0010] Furthermore, the initiator is potassium persulfate, and the amount used is 1wt% of the total amount of monomers.

[0011] A silk triple-proof finishing agent is used for low-temperature finishing of silk fabrics. The silk fabrics are treated with 50-100 g / L of the silk triple-proof finishing agent by double dipping and double padding, and then pre-baked and baked at 100-110° C. for 2-5 minutes.

[0012] Furthermore, the rolling ratio is 75% to 80%, and the pre-baking is performed at 80 to 100° C. for 2 to 4 minutes.

[0013] The beneficial effects of the present invention are: 1. The present invention adopts copolymerization of perfluorohexyl ethyl acrylate and vinyl triethoxy silane to prepare a silk triple-proof finishing agent, which overcomes the environmental impact of PFOA produced by conventional perfluoroalkyl chains. The use of perfluorohexyl ethyl acrylate and vinyl triethoxy silane avoids the adverse effects of PFOA and ensures that the water- and oil-repellent properties meet the standards.

[0014] 2. The vinyl triethoxysilane copolymer monomer used in the present invention has an effect of improving the softness of silk fabrics. The reactivity of the ethoxy group and the active groups in the polymerizable emulsifier DNS-86 help to achieve low-temperature finishing of silk, avoiding the adverse effects of high-temperature baking on silk.

[0015] 3. The presence of the emulsifier causes the emulsifier to migrate to the film surface during the process of water evaporation and film formation, which greatly affects the water resistance and stain resistance of the film. The present invention adopts a polymerizable emulsifier to reduce the emulsifier residue after silk fabric finishing and meet the hand feel requirements of silk fabric. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a test diagram of the water contact angle of silk after low-temperature finishing of silk using the silk triple-proof finishing agent of the present invention. DETAILED DESCRIPTION

[0017] The present invention will be described in detail below with reference to the accompanying drawings and in combination with embodiments.

[0018] The invention provides a three-proof finishing agent for silk. The finishing agent is a silicone-fluorine-containing acrylic emulsion and is a core-shell structure having a shell structure and a core structure. The shell structure is polymerized by 40-55wt% of perfluorohexylethyl acrylate, 20-40wt% of vinyl triethoxysilane, 15-20wt% of isooctyl acrylate and an emulsifier, and the core structure is polymerized by 40-60wt% of methyl methacrylate, 30-60wt% of isooctyl acrylate and an emulsifier.

[0019] The emulsifier is a polymerizable emulsifier DNS-86, and the amount used is 1-3 wt % of the total weight of the monomers. The mass ratio of the shell structure to the core structure is 1-2:3-4.

[0020] The present invention provides a method for preparing a silk three-proof finishing agent, and the preparation method comprises the following specific steps: Step S1: at room temperature, a certain ratio of monomers for shell structure is uniformly stirred at high speed in an aqueous solution with an emulsifier added, and then emulsified at a speed of 8000 to 10000 r / min for 5 to 8 minutes using a high shear dispersing emulsifier to obtain a shell structure monomer emulsion; Step S2: stirring a core structure monomer mixture of a certain ratio in a polymerizable emulsifier aqueous solution at high speed to obtain a core structure monomer emulsion; Step S3: taking out 1 / 3 of the core structure monomer emulsion and adding it into a three-necked flask equipped with a constant pressure funnel, a thermometer and nitrogen protection as a seed emulsion, adding a pre-prepared 1 / 3 initiator aqueous solution, slowly stirring evenly in a water bath and heating to 70-75° C., after the system shows blue light at a constant temperature, dripping the remaining core structure monomer emulsion into the system, maintaining a drip rate of 1 drop / s, and after the dripping is completed, adding 1 / 3 of the initiator aqueous solution and reacting at a constant temperature for 20-30 minutes to prepare a core structure emulsion; Step S4: adding the shell monomer emulsion to the core structure emulsion at a dripping rate of 1 drop / 2s at a constant temperature, then heating the system to 75-80°C, adding the remaining 1 / 3 of the initiator aqueous solution, reacting for 40-60 minutes, cooling the prepared emulsion to room temperature, and filtering to obtain a core-shell finishing agent emulsion.

[0021] The initiator is potassium persulfate, and the amount used is 1wt% of the total amount of monomers.

[0022] The invention provides a low-temperature finishing application of a silk triple-proof finishing agent on silk fabrics. The silk fabrics are treated with 50-100 g / L of the silk triple-proof finishing agent by double dipping and double padding, and then pre-baked and baked at 100-110° C. for 2-5 minutes.

[0023] The rolling rate is 75% to 80%, and the pre-baking is carried out at 80 to 100°C for 2 to 4 minutes.

[0024] The monomer raw materials used in the low-temperature three-proof finishing agent of the present invention are all commercially available, and the initiator and emulsifier are also commercially available. Unless otherwise specified, all other raw material components are commercially available commodities well known to those skilled in the art.

[0025] The water and oil repellency was tested according to AATCC118-2009 standard. The contact angle test was conducted by CA500S contact angle tester, and the average value was taken for 5 measurements. The durability test was conducted by washing the product at room temperature for 25 minutes at a standard setting in a household washing machine with 2g / L soap powder and a bath ratio of 1:30, then dehydrating the product, washing it with clean water for 2 minutes, drying it, and drying it at 80℃ for 30 minutes to test its water and oil repellency.

[0026] The mechanical stability test method of the emulsion is to run the prepared emulsion on a centrifuge at 2000r / min for 30min and observe the emulsion stratification and precipitation phenomena.

[0027] The emulsion dilution stability test method is to dilute the prepared emulsion with distilled water to a solid content of 4%, seal it and let it stand for 72 hours, and observe the emulsion stratification and precipitation phenomena.

[0028] Example 1 A three-proof finishing agent for silk, the finishing agent is a silicone-fluorine-containing acrylic emulsion, the finishing agent is a core-shell structure having a shell structure and a core structure, the shell structure is polymerized by 40wt% of perfluorohexylethyl acrylate, 40wt% of vinyl triethoxysilane, 20wt% of isooctyl acrylate, and 1wt% of the total weight of a polymerizable emulsifier DNS-86, the core structure is polymerized by 60wt% of methyl methacrylate, 30wt% of isooctyl acrylate, and 1wt% of the total weight of a polymerizable emulsifier; the mass ratio of the shell structure to the core structure is 1:3.

[0029] The preparation method of the above-mentioned silk three-proof finishing agent is as follows: Step S1: at room temperature, a certain ratio of monomers for shell structure is uniformly stirred at high speed in an aqueous solution with an emulsifier added, and then emulsified at a speed of 8000 r / min for 8 minutes using a high shear dispersing emulsifier to obtain a shell structure monomer emulsion; Step S2: stirring a core structure monomer mixture of a certain ratio in a polymerizable emulsifier aqueous solution at high speed to obtain a core structure monomer emulsion; Step S3: taking out 1 / 3 of the core structure monomer emulsion and adding it into a three-necked flask equipped with a constant pressure funnel, a thermometer and nitrogen protection as a seed emulsion, adding a pre-prepared 1 / 3 KPS initiator aqueous solution, slowly stirring evenly in a water bath and heating to 70° C., after the system shows blue light at a constant temperature, dripping the remaining core structure monomer emulsion into the system, maintaining a drip rate of 1 drop / s, and after the dripping is completed, adding 1 / 3 of the KPS initiator aqueous solution and reacting at a constant temperature for 25 minutes to prepare a core structure emulsion; Step S4: adding the shell monomer emulsion to the core structure emulsion at a constant temperature at a rate of 1 drop / 2s, then heating the system to 75°C, adding the remaining 1 / 3 KPS initiator aqueous solution, reacting for 45 minutes, cooling the prepared emulsion to room temperature, filtering and obtaining a core-shell finishing agent emulsion, wherein the amount of KPS initiator is 1wt% of the total amount of monomers.

[0030] The prepared silk triple-proof finishing agent has a milky white and delicate appearance, is translucent and has a blue glow, and contains very little gel. The mechanical stability, dilution stability and storage stability of the prepared emulsion are relatively stable, and no precipitation occurs after the emulsion is placed for 3 months.

[0031] The low-temperature finishing process of the above-mentioned silk triple-proof finishing agent when applied to silk fabrics comprises the following steps: The silk fabric was treated with the above 60g / L silk three-proof finishing agent by two dipping and two padding, with a rolling rate of 80%, pre-baked at 90℃ for 2min and baked at 110℃ for 2min. Figure 1As shown, the water contact angle of the obtained triple-proof finished silk fabric is maintained at about 136°, and the water contact angle is still maintained above 130° after washing 30 times.

[0032] Embodiment 2: A three-proof finishing agent for silk, the finishing agent is a silicone-fluorine-containing acrylic emulsion, the finishing agent is a core-shell structure having a shell structure and a core structure, the shell structure is polymerized by 55wt% of perfluorohexylethyl acrylate, 20wt% of vinyl triethoxysilane, 15wt% of isooctyl acrylate, and 1wt% of the total weight of a polymerizable emulsifier DNS-86, the core structure is polymerized by 50wt% of methyl methacrylate, 30wt% of isooctyl acrylate, and 1wt% of the total weight of a polymerizable emulsifier; the mass ratio of the shell structure to the core structure is 2:4.

[0033] The preparation method of the above-mentioned silk three-proof finishing agent is as follows: Step S1: at room temperature, a certain ratio of monomers for shell structure is uniformly stirred at high speed in an aqueous solution with an emulsifier added, and then emulsified at a speed of 10000 r / min for 5 minutes using a high shear dispersing emulsifier to obtain a shell structure monomer emulsion; Step S2: stirring a core structure monomer mixture of a certain ratio in a polymerizable emulsifier aqueous solution at high speed to obtain a core structure monomer emulsion; Step S3: taking out 1 / 3 of the core structure monomer emulsion and adding it into a three-necked flask equipped with a constant pressure funnel, a thermometer and nitrogen protection as a seed emulsion, adding a pre-prepared 1 / 3 KPS initiator aqueous solution, slowly stirring evenly in a water bath and heating to 75° C., after the system shows blue light at a constant temperature, dripping the remaining core structure monomer emulsion into the system, maintaining a drip rate of 1 drop / s, and after the dripping is completed, adding 1 / 3 of the KPS initiator aqueous solution and reacting at a constant temperature for 20 minutes to prepare a core structure emulsion; Step S4: adding the shell monomer emulsion to the core structure emulsion at a constant temperature at a dripping rate of 1 drop / 2s, then heating the system to 80°C, adding the remaining 1 / 3 KPS initiator aqueous solution, reacting for 40 minutes, cooling the prepared emulsion to room temperature, and filtering to obtain a core-shell finishing agent emulsion, wherein the amount of potassium persulfate KPS initiator is 1wt% of the total amount of monomers.

[0034] The prepared silk triple-proof finishing agent has a milky white and delicate appearance, is translucent and has a blue glow, and contains very little gel. The mechanical stability, dilution stability and storage stability of the emulsion are relatively stable, and no precipitation occurs after the emulsion is placed for 3 months.

[0035] The low-temperature finishing process of the above-mentioned silk triple-proof finishing agent when applied to silk fabrics comprises the following steps: The silk fabric was treated with the above-mentioned 80g / L silk triple-proof finishing agent by double dipping and double rolling, with a rolling rate of 80%, and pre-baked at 80°C for 3min and baked at 100°C for 3min. The obtained triple-proof finished silk fabric had excellent triple-proof properties. The water contact angle of the obtained triple-proof finished silk fabric was maintained at about 136°, and the water contact angle was still maintained above 130° after washing 30 times.

[0036] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A silk three-proof finishing agent, characterized in that: The finishing agent is a silicone-fluorine-containing acrylic emulsion, and is a core-shell structure having a shell structure and a core structure. The shell structure is polymerized by 40-55wt% of perfluorohexylethyl acrylate, 20-40wt% of vinyl triethoxysilane, 15-20wt% of isooctyl acrylate, and an emulsifier, and the core structure is polymerized by 40-60wt% of methyl methacrylate, 30-60wt% of isooctyl acrylate, and an emulsifier.

2. The silk three-proof finishing agent according to claim 1, characterized in that: The emulsifier is a polymerizable emulsifier DNS-86, and the amount used is 1 to 3 wt % of the total weight of the monomers.

3. The silk three-proof finishing agent according to claim 2, characterized in that: The mass ratio of the shell structure to the core structure is 1-2:3-4.

4. A method for preparing the silk triple-proof finishing agent according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following specific steps: Step S1: at room temperature, a certain ratio of monomers for shell structure is uniformly stirred at high speed in an aqueous solution with an emulsifier added, and then emulsified at a speed of 8000 to 10000 r / min for 5 to 8 minutes using a high shear dispersing emulsifier to obtain a shell structure monomer emulsion; Step S2: stirring a core structure monomer mixture of a certain ratio in a polymerizable emulsifier aqueous solution at high speed to obtain a core structure monomer emulsion; Step S3: taking out 1 / 3 of the core structure monomer emulsion and adding it into a three-necked flask equipped with a constant pressure funnel, a thermometer and nitrogen protection as a seed emulsion, adding a pre-prepared 1 / 3 initiator aqueous solution, slowly stirring evenly in a water bath and heating to 70-75° C., after the system shows blue light at a constant temperature, dripping the remaining core structure monomer emulsion into the system, maintaining a drip rate of 1 drop / s, and after the dripping is completed, adding 1 / 3 of the initiator aqueous solution and reacting at a constant temperature for 20-30 minutes to prepare a core structure emulsion; Step S4: adding the shell monomer emulsion to the core structure emulsion at a dripping rate of 1 drop / 2s at a constant temperature, then heating the system to 75-80°C, adding the remaining 1 / 3 of the initiator aqueous solution, reacting for 40-60 minutes, cooling the prepared emulsion to room temperature, and filtering to obtain a core-shell finishing agent emulsion.

5. The preparation method according to claim 4, characterized in that: The initiator is potassium persulfate, and the amount used is 1wt% of the total amount of monomers.

6. A method for low-temperature finishing of silk fabrics using the silk triple-proof finishing agent according to any one of claims 1 to 3 or the silk triple-proof finishing agent obtained by the preparation method according to any one of claims 4 to 5, characterized in that: The silk fabric is treated with 50-100 g / L of the silk three-proof finishing agent by two dipping and two padding, and then pre-baked and baked at 100-110° C. for 2-5 minutes.

7. The use according to claim 6, characterized in that: The rolling rate is 75% to 80%, and the pre-baking is carried out at 80 to 100°C for 2 to 4 minutes.

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