Preparation method and application of fluorosilicone modified polyacrylate emulsion for washing-free printing of liquid disperse dye

Abstract

The invention belongs to the technical field of printing and dyeing materials, and particularly relates to a preparation method and application of a fluorine-silicon modified polyacrylate emulsion for washing-free printing of a liquid disperse dye. The invention provides a preparation method of a fluorosilicone modified polyacrylate emulsion (FMP). The invention also provides application of the fluorine-silicon modified polyacrylate emulsion prepared by the method. The fluorine-silicon modified polyacrylate emulsion is mixed with a liquid disperse dye and the like to prepare printing paste, and the printing paste is used for washing-free printing of fabrics (terylene). According to the present invention, by using the excellent light aging resistance endowed by acrylonitrile, the hydrophobic wear resistance brought by the fluorosilicone chain segment and the no reduction cleaning of the printed fabric, the washing-free printing of the polyester fabric is achieved, the color fastness to sunlight of the printed fabric is improved, and the water resource consumption and the environmental protection cost in the printing and dyeing industry are reduced.

Description

Technical Field

[0001] This invention belongs to the field of printing and dyeing materials technology, specifically relating to a method for preparing and applying a fluorosilicone-modified polyacrylate emulsion for waterless printing with liquid disperse dyes. Background Technology

[0002] Disperse dyes, as the core coloring agents for printing on synthetic fibers (especially polyester), are widely used in the textile printing and dyeing industry. Traditional disperse dye printing processes require a complete process of "printing-baking-soaping-multiple washing-drying," consuming as much as 300-500 tons of water per 10,000 meters of printed polyester fabric. Moreover, the wastewater from washing has a high concentration of residual dyes and auxiliaries, and wastewater treatment costs account for 15%-20% of the total printing and dyeing costs. This not only causes serious waste of water resources but also increases the environmental burden on enterprises, which is seriously contrary to the current green and low-carbon transformation goals of the textile industry.

[0003] Waterless printing technology utilizes a short "printing-pre-baking-cure" process, leveraging the film-forming properties of adhesives to encapsulate unfixed dyes and combining this with the heat-freezing properties of disperse dyes to achieve zero emissions during the washing process. This represents a key technological direction for solving the problems of high pollution and high water consumption in traditional printing. The adhesive, as the core functional component of waterless printing pastes, directly determines the colorfastness, color yield, and hand feel of the printed fabric.

[0004] Polyacrylate emulsions have become the mainstream adhesive in the field of waterless printing due to their simple preparation process, excellent film-forming properties, and low cost. However, existing products have three major technical defects: 1. Poor water resistance of the film: It is prone to swelling in a wet environment, which leads to dye migration, resulting in the wet rubbing color fastness of printed fabrics being generally only grade 3, which is difficult to meet the use requirements of high-end textiles. 2. Lack of UV protection: It cannot inhibit the damage of ultraviolet rays to the dye conjugated system, resulting in high fading rate and insufficient weather resistance of printed fabrics after long-term sun exposure; 3. Limited effect of single modification: Single modification (such as only silicone modification) is difficult to achieve the multi-functional integration of "wear resistance, sun resistance and color locking", and cannot meet the performance requirements of high-end textiles.

[0005] To address the aforementioned issues, there is an urgent need in this field to develop an adhesive that combines high-efficiency color locking, abrasion resistance, water resistance, and UV protection to promote the industrial application of waterless printing technology and help the printing and dyeing industry achieve a green and low-carbon transformation. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a method for preparing and applying a fluorosilicone modified polyacrylate emulsion for waterless printing of liquid disperse dyes.

[0007] To address the above problems, this invention provides a method for preparing a fluorosilicone-modified polyacrylate emulsion (FMP), comprising the following steps: 1) Preparation of the oil phase: Butyl acrylate (BA), acrylonitrile (AN), acrylic acid (AA) and vinyl-terminated fluorinated polysiloxane (DVFS) were added to a co-emulsifier and mixed uniformly to prepare an oil phase; The mass ratio of butyl acrylate: acrylonitrile: acrylic acid: vinyl-terminated fluorinated polysiloxane is 15~16:9~10:0.6~1:2.6~3; Note: Butyl acrylate, acrylonitrile, acrylic acid, and vinyl-terminated fluorinated polysiloxane are the four monomers. 2) Dissolve the composite emulsifier and N-hydroxymethylacrylamide (NMA) in deionized water to prepare an aqueous phase; 3) According to the mass ratio of N-hydroxymethylacrylamide: (butyl acrylate + acrylonitrile + acrylic acid + vinyl-terminated fluorinated polysiloxane) = 1.9~2.1:28~29; The aqueous and oil phases are mixed to form an emulsion, which is then ultrasonically treated in an ice bath (ultrasonic cell disruptor) to obtain a fine emulsion (a milky white, stable fine emulsion). 4) Set the mass ratio of ammonium persulfate to N-hydroxymethylacrylamide to 0.3:1.9~2.1; prepare an ammonium persulfate aqueous solution with a mass concentration of (3±0.5)%, and name it APS aqueous solution; Take 1 / 3 of the fine emulsion and heat it to 78±0.5℃ under stirring. Then add 1 / 3 of the APS aqueous solution. When the temperature stabilizes at 78±0.5℃ and the emulsion turns blue (indicating the formation of seed latex particles), raise the temperature to 80±0.5℃. Under the conditions of keeping warm (80±0.5℃) and stirring, add dropwise (dropwise time is 2±0.5 h) the remaining 2 / 3 of the fine emulsion and the remaining 2 / 3 of the APS solution. After the dropwise addition is complete, continue to react under the conditions of keeping warm (80±0.5℃) and stirring for 60±5 min. After the reaction is complete, the mixture is allowed to cool naturally to room temperature. The pH is then adjusted to neutral by adding 25-28% ammonia solution. The mixture is then filtered (using a 300-mesh nylon filter to remove a small amount of gel particles) to obtain a fluorosilicone modified polyacrylate emulsion (a milky white FMP emulsion).

[0008] An improvement to the preparation method of the fluorosilicone modified polyacrylate emulsion (FMP) of the present invention: The co-emulsifier is hexadecane (HD); The mass ratio of n-hexadecane to (butyl acrylate + acrylonitrile + acrylic acid + vinyl-terminated fluorinated polysiloxane) is 1.5:28~29.

[0009] As a further improvement to the preparation method of the fluorosilicone modified polyacrylate emulsion (FMP) of the present invention: The composite emulsifier is prepared by mixing sodium dodecyl sulfate (SDS): fatty alcohol polyoxyethylene ether (O-10): propylene oxypropyl alkylphenol polyether ammonium sulfate (V-20S) in a mass ratio of 2.4~2.6:1.6~1.8:1.6~1.8. 5.6-6.2 g of composite emulsifier and 1.9-2.1 g of N-hydroxymethylacrylamide (NMA) were dissolved in 100 g of deionized water to prepare an aqueous phase.

[0010] As a further improvement to the preparation method of the fluorosilicone modified polyacrylate emulsion (FMP) of the present invention: The stirring speed in step 4) is 300±50 r / min.

[0011] As a further improvement to the preparation method of the fluorosilicone modified polyacrylate emulsion (FMP) of the present invention: The mass ratio of N-hydroxymethylacrylamide: butyl acrylate: acrylonitrile: acrylic acid: terminal vinyl fluorinated polysiloxane is 2:15.4:9.6:0.8:2.8.

[0012] As a further improvement to the preparation method of the fluorosilicone modified polyacrylate emulsion (FMP) of the present invention: The mass ratio of sodium dodecyl sulfate (SDS): fatty alcohol polyoxyethylene ether (O-10): propylene oxypropyl alkylphenol polyether ammonium sulfate (V-20S) is 2.5:1.7:1.7.

[0013] As a further improvement to the preparation method of the fluorosilicone modified polyacrylate emulsion (FMP) of the present invention, the preparation method of the vinyl-terminated fluorinated polysiloxane (DVFS) includes the following steps: ① Under an inert gas atmosphere (including nitrogen), octamethylcyclotetrasiloxane (D4) and 1,3-divinyltetramethyldisiloxane (DVMS, i.e., C8H) are reacted. 18 OSi2) is mixed evenly until it becomes transparent; The molar ratio of octamethylcyclotetrasiloxane (D4): 1,3-divinyltetramethyldisiloxane is 5:1. ② Heat the product obtained in step ① to 65±5℃ and keep it at that temperature for 30±10 min. Under stirring conditions, add trifluoromethanesulfonic acid as a catalyst and stir evenly. Then add methyltrifluoropropylcyclotrisiloxane and keep it at 65±5℃ for 6±0.5 h. The molar ratio of methyltrifluoropropylcyclotrisiloxane (D3F) to octamethylcyclotetrasiloxane (D4) is 1:2. The amount of trifluoromethanesulfonic acid used is 0.1% of the total mass of (octamethylcyclotetrasiloxane + 1,3-divinyltetramethyldisiloxane + methyltrifluoropropylcyclotrisiloxane); ③ After the reaction product obtained in step ② is cooled (naturally cooled to room temperature), the pH is adjusted to neutral (anhydrous sodium carbonate powder is added and the pH is adjusted to 7.0 by stirring). Continue stirring (30±10 min) to neutralize the residual catalyst; filter using filter paper (standardized filter paper to remove salt impurities from the system); ④ Purify the filtrate (transfer to a vacuum oven, set the temperature to 60℃ and the vacuum degree to -0.095MPa, and purify for 2 hours to remove low-boiling substances) to obtain colorless and transparent vinyl-terminated fluorinated polysiloxane (DVFS).

[0014] The present invention also provides the application of the fluorosilicone modified polyacrylate emulsion prepared by the above method: it is mixed with liquid disperse dyes to prepare printing paste (printing paste) for waterless printing on fabrics (polyester).

[0015] That is, the present invention also provides the application of the above-mentioned fluorosilicone modified polyacrylate emulsion in waterless printing of polyester with liquid disperse dyes.

[0016] While existing fluorosilicone-modified polyacrylates have solved the defects of traditional polyacrylates, such as "hot stickiness and cold brittleness" and poor hand feel and stiffness of printed fabrics, they lack ultraviolet absorption capabilities. This means that when printed fabrics are used outdoors or in sunlight for extended periods, the dye conjugated system is easily damaged, resulting in loss of color development and fading. Some acrylates use styrene as a comonomer; although the benzene ring's large π-conjugated system can absorb 250-280nm ultraviolet light, it still exhibits colorfastness. However, the excited state of the benzene ring is unstable and easily triggers photo-oxidation reactions leading to polymer degradation. In contrast, this invention uses acrylonitrile as the polymerizing monomer, whose π electrons in the cyano carbon-nitrogen triple bond can absorb ultraviolet energy to undergo photo-oxidation. and The acrylonitrile-containing polyacrylate copolymer (such as the fluorosilicone-modified polyacrylate of this invention) is a more suitable choice than styrene-containing polyacrylate for long-term use in outdoor or sun-exposed environments. It can absorb energy and then convert it into heat energy through intramolecular vibration and rotation, reducing the damage of ultraviolet rays to the polymer backbone.

[0017] This invention addresses the technical problems of poor water resistance, lack of UV protection, and insufficient color fastness of printed fabrics in existing adhesive films through a synergistic modification strategy of "fluorine-silicone segments + cyano groups".

[0018] This invention achieves uniform copolymerization of monomers through a fine emulsion polymerization method, ensuring the colloidal stability and structural uniformity of the emulsion. The process is simple, highly reproducible, and easy for industrial production. The synthesis route (synthesis route of fluorosilicone-modified polyacrylate) is as follows:

[0019] In this invention: 1. Innovation in modification strategies: This invention is the first to propose a synergistic modification strategy of "fluorinated silicon segments + cyano groups". Fluorinated silicon segments (DVFS) endow the film with high hydrophobicity and abrasion resistance, while cyano groups (introduced into the polymer from the monomer acrylonitrile) provide excellent UV protection. This solves the problem of existing adhesives having "excellent single properties but insufficient overall performance". The film (medium-wave ultraviolet light, wavelength 280-315nm) has a UVB transmittance of only 0.28%, a dry rubbing color fastness of 4-5, a wet rubbing color fastness of 3-4, and a sun fading rate of 1.10% and a water washing fading rate of 1.1%, demonstrating leading overall performance. 2. Stable and controllable process: FMP emulsions were prepared using a fine emulsion polymerization method. Ultrasonic dispersion and seed polymerization were used to ensure uniform copolymerization of monomers. The emulsions had an average particle size of 80-90 nm, a PDI of ≤0.2, and excellent colloidal stability, which could meet the storage and transportation requirements in industrial production. 3. Significantly environmentally friendly and economical: When applied to waterless printing with liquid disperse dyes, high-performance printing can be achieved without a water washing process, while reducing wastewater treatment costs, which is in line with green printing and dyeing and the "dual carbon" goal; 4. Broad prospects for industrialization: The preparation process is simple, the raw materials are readily available, and the cost is controllable. No adjustments are required to existing printing equipment during application. It can directly replace traditional adhesives and is suitable for printing on various fibers such as polyester and nylon, resulting in significant economic and environmental benefits.

[0020] In summary, this invention places no special requirements on the polyester fabric to be printed, only requiring that it be a white polyester fabric after degreasing. This invention utilizes the excellent light aging resistance imparted by acrylonitrile and the hydrophobic and abrasion-resistant properties provided by fluorosilicone segments, eliminating the need for reduction washing of the printed fabric, thus achieving waterless printing on polyester fabrics, improving the lightfastness of the printed fabrics, and reducing water consumption and environmental costs in the printing and dyeing industry. The waterless printing method for polyester fabrics provided by this invention has the following advantages: (1) Printed fabrics do not require reduction washing, resulting in less wastewater discharge; (2) The printed area feels soft to the touch and does not harden; (3) The printed fabrics have excellent color fastness in all aspects. Attached Figure Description

[0021] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0022] Figure 1 Infrared spectra of DVFS and FMP; Figure 2 This is a particle size distribution diagram of FMP; Figure 3 The K / S diagram of the printed fabric before and after washing; Figure 3 middle: A is the K / S diagram of the printed fabric before and after washing with liquid disperse orange 288 dye; B is the K / S diagram of the printed fabric before and after washing with Liquid Disperse Red 167 dye; C is the K / S diagram of the printed fabric before and after washing with Liquid Disperse Blue 79 dye; Figure 4 The K / S diagram of the printed fabric before and after sun exposure; Figure 4 middle: A is the K / S diagram of printed fabrics before and after exposure using liquid disperse orange 288 dye; B is the K / S diagram of printed fabrics before and after exposure using Liquid Disperse Red 167 dye; C is the K / S diagram of printed fabrics before and after exposure using liquid disperse blue 79 dye. Detailed Implementation

[0023] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0024] Example 1: Preparation of vinyl-terminated fluorinated polysiloxanes (DVFS): 1) Set up a 250mL three-necked flask reaction apparatus, equip it with a mechanical stirrer, thermometer, reflux condenser, and connect a nitrogen protection device to ensure that the apparatus is sealed and leak-free.

[0025] 2) Under a nitrogen atmosphere, add 0.1 mol of octamethylcyclotetrasiloxane (D4) and 0.02 mol of 1,3-divinyltetramethyldisiloxane (DVMS, i.e., C8H4) to a three-necked flask. 18 OSi2), turn on the stirrer, set the speed to 300 r / min, and mix until the system is transparent.

[0026] 3) Heat to 65℃ and hold for 30 min to stabilize the system temperature; add trifluoromethanesulfonic acid (CF3O3H) as a catalyst and stir for 10 min to ensure uniform dispersion of the catalyst; slowly add 0.05 mol methyltrifluoropropylcyclotrisiloxane (D3F) and maintain the reaction at 65℃ for 6 h, stirring continuously during the process to ensure complete reaction.

[0027] The amount of trifluoromethanesulfonic acid used is 0.1% of the total mass of D4, DVMS and D3F.

[0028] 4) After the reaction is complete, allow it to cool naturally to room temperature, add anhydrous sodium carbonate powder, stir to adjust the pH to 7.0, and continue stirring for 30 minutes to neutralize the residual catalyst; filter with filter paper (standard qualitative filter paper) to remove salt impurities from the system.

[0029] 5) Transfer the filtrate to a vacuum oven, set the temperature to 60℃ and the vacuum degree to -0.095MPa, and purify for 2 hours to remove low-boiling substances, to obtain colorless and transparent vinyl-terminated fluorinated polysiloxane (DVFS).

[0030] 6) The number-average molecular weight of DVFS was determined using gel permeation chromatography (tetrahydrofuran as the mobile phase and polystyrene as the standard); the double bond value was determined by iodometric titration.

[0031] The number-average molecular weight of DVFS is 7488; the double bond value is 0.4 mmol / g.

[0032] Example 2: Preparation of fluorosilicone modified polyacrylate emulsion (FMP): 1) Weigh 15.4g of BA (butyl acrylate), 9.6g of AN (acrylonitrile), 0.8g of AA (acrylic acid), 2.8g of DVFS (vinyl-terminated fluorinated polysiloxane), and 1.5g of co-emulsifier HD (n-hexadecane) into a beaker and stir evenly with a magnetic stirrer to prepare the oil phase; The composite emulsifier consists of 2.5 g of SDS (sodium dodecyl sulfate), 1.7 g of O-10 (fatty alcohol polyoxyethylene ether), and 1.7 g of V-20S (propylene oxypropyl alkylphenol polyether ammonium sulfate). An aqueous phase was prepared by dissolving 2 g of the composite emulsifier and NMA (N-hydroxymethylacrylamide) in 100 g of deionized water.

[0033] The aqueous and oil phases were mixed together and stirred for 30 minutes to form an emulsion. The emulsion was then placed in an ice bath and subjected to conventional ultrasonic treatment for 20 minutes using an ultrasonic cell disruptor to form a milky white, stable fine emulsion. 2) Prepare 10g of APS (ammonium persulfate) aqueous solution with a mass fraction of 3%; Transfer 1 / 3 of the fine emulsion obtained in step 1) above to a 250 mL four-necked flask, turn on mechanical stirring (300 r / min), stir and heat to 78°C. Then add 1 / 3 of the APS aqueous solution, wait for the temperature to stabilize and the emulsion to turn blue (indicating the formation of seed latex particles); raise the temperature to 80°C, stir at 300 r / min, and under the conditions of keeping warm (80°C) and stirring, add the remaining 2 / 3 of the fine emulsion and the remaining 2 / 3 of the APS solution dropwise to the four-necked flask at a uniform rate over 2 h using a peristaltic pump; after the dropwise addition is complete, continue to react under the conditions of keeping warm (80°C) and stirring for 60 min; after the reaction is completed, allow the latex produced by polymerization to cool naturally to room temperature, add ammonia water (concentration of about 25-28%) to adjust the pH to neutral, filter through a 300-mesh nylon filter to remove a small amount of gel particles, and obtain a milky white FMP emulsion.

[0034] The infrared spectra of the DVFS obtained in Example 1 and the FMP obtained in Example 2 are as follows: Figure 1 As shown.

[0035] The following experiments were conducted using the FMP emulsion obtained in Example 2.

[0036] Experiment 1-1: Printing application of 5% FMP (Disperse Orange 288): 1. Prepare 50g of printing paste: The mixture consisted of 3% Dispersible Orange 288, 3% PTF thickener, 5% FMP emulsion prepared in Example 2, and 89% deionized water by mass fraction. The mixture was stirred in the following order: "deionized water + PTF → FMP emulsion → Dispersible Orange 288" for a total stirring time of 45 min at 800 r / min. The mixture was then filtered through a 40-mesh filter and allowed to stand for 10 min to defoam.

[0037] 2. Select 80g / m 2 Oil-free white polyester plain weave woven fabric was cut into 4cm×20cm samples and equilibrated for 24 hours at 20℃±1℃ and 65%±2% relative humidity.

[0038] 3. Apply approximately 1g of printing paste to the fabric using a magnetic rod printing machine at room temperature; Magnetic rod printing machine parameters: 10mm diameter magnetic rod, pressure 0.3MPa, printing speed 10cm / s, uniform printing of color paste.

[0039] 4. After printing, the fabric is pre-dried at 80℃ for 5 minutes, then baked at 180℃ for 3 minutes, and then naturally cooled to room temperature.

[0040] Experiments 1-2: Printing application of 10% FMP (Disperse Orange 288): Printing pigment formula: Liquid Dispersible Orange 288 3%, Thickener PTF 3%, FMP emulsion 10%, Deionized water 84%.

[0041] The rest is the same as Experiment 1-1.

[0042] Experiments 1-3: Printing applications of 15% FMP (Disperse Orange 288): Printing pigment formulation: Liquid Dispersible Orange 288 3%, Thickener PTF 3%, FMP emulsion 15%, Deionized water 79%.

[0043] The rest is the same as Experiment 1-1.

[0044] Experiments 1-4, FMP usage 0%, i.e., printing applications without binder (Dispersion Orange 288): Liquid Dispersion Orange 288 3%, Thickener PTF 3%, Deionized Water 94%.

[0045] The rest is the same as Experiment 1-1.

[0046] Experiment 2-1: Printing application of 5% FMP (Disperse Red 167): Printing pigment formula: Liquid Dispersible Red 167 3%, Thickener PTF 3%, FMP emulsion 5%, Deionized water 89%.

[0047] The rest is the same as Experiment 1-1.

[0048] Experiment 2-2: Printing application of 10% FMP (Disperse Red 167): Printing pigment formula: Liquid Dispersible Red 167 3%, Thickener PTF 3%, FMP emulsion 10%, Deionized water 84%.

[0049] The rest is the same as Experiment 1-1.

[0050] Experiments 2-3: Printing application of 15% FMP (Disperse Red 167): Printing pigment formula: Liquid Dispersible Red 167 3%, Thickener PTF 3%, FMP emulsion 15%, Deionized water 79%.

[0051] The rest is the same as Experiment 1-1.

[0052] Experiments 2-4, FMP usage 0%, i.e., printing applications without binder (Dispersion Red 167): Printing pigment formula: Liquid Dispersible Red 167 3%, Thickener PTF 3%, Deionized Water 94%.

[0053] The rest is the same as Experiment 1-1.

[0054] Experiment 3-1: Printing application of 5% FMP (Disperse Blue 79): Printing pigment formula: Liquid Dispersible Blue 79 3%, Thickener PTF 3%, FMP Emulsion 5%, Deionized Water 89%.

[0055] The rest is the same as Experiment 1-1.

[0056] Experiment 3-2: Printing application of 10% FMP (Disperse Blue 79): Printing pigment formula: Liquid Dispersible Blue 79 3%, Thickener PTF 3%, FMP Emulsion 10%, Deionized Water 84%.

[0057] The rest is the same as Experiment 1-1.

[0058] Experiment 3-3: Printing application of 15% FMP (Disperse Blue 79): Printing pigment formula: 79.3% liquid dispersible blue, 3% thickener PTF, 15% FMP emulsion, and 79% deionized water.

[0059] The rest is the same as Experiment 1-1.

[0060] Experiments 3-4, FMP usage 0%, i.e., printing applications without binder (Disperse Blue 79): Printing pigment formula: 79.3% liquid dispersible blue, 3% thickener PTF, 94% deionized water.

[0061] The rest is the same as Experiment 1-1.

[0062] The fabric obtained from the above experiments was subjected to the following performance tests: Color fastness to rubbing: Test the color fastness to dry and wet rubbing according to GB / T 3920-2008 (the rubbing medium is standard white cloth, the wet moisture content is 100%, and the rating is 1-5). The results are shown in Table 1 below.

[0063] Table 1

[0064] Comparative Example 1: In Example 2, “AN (acrylonitrile) 9.6g, DVFS (terminated vinyl fluorinated polysiloxane) 2.8g” was replaced with “12.4g methyl methacrylate (MMA)”, and the rest was the same as in Example 2, to obtain PA emulsion.

[0065] Comparative Example 2: Replace “AN (acrylonitrile) 9.6g” in Example 2 with “styrene 9.6g”, and keep the rest the same as in Example 2 to obtain silicone-acrylic emulsion (SAE).

[0066] Comparative Experiment 1-1: Printing Application of PA Adhesive (Dispersion Orange 288, 10% dosage): In Experiments 1-2, “FMP emulsion (prepared in Example 2)” was changed to “PA emulsion (prepared in Comparative Example 1)”, while the amount remained unchanged at 10%, and the rest was the same as in Experiments 1-2.

[0067] Comparative experiments 1-2: Printing applications of MCH-206 commercial adhesive (Dispersion Orange 288, 10% dosage): Replace “FMP emulsion” in Experiment 1-2 with “commercial adhesive MCH-206”, keep the amount unchanged at 10%, and the rest is the same as in Experiment 1-2.

[0068] Comparative experiments 1-3: Printing applications of SAE adhesive (Dispersion Orange 288, 10% dosage): In Experiments 1-2, “FMP emulsion (prepared in Example 2)” was changed to “SAE emulsion (prepared in Comparative Example 2)”, while the amount remained unchanged at 10%, and the rest was the same as in Experiments 1-2.

[0069] Comparative Experiment 2-1: Printing Application of PA Adhesive (Dispersion Red 167, 10% dosage): In Experiment 2-2, “FMP emulsion (prepared in Example 2)” was changed to “PA emulsion (prepared in Comparative Example 1)”, while the amount remained unchanged at 10%, and the rest was the same as in Experiment 2-2.

[0070] Comparative Experiment 2-2: Printing application of MCH-206 commercial adhesive (Dispersion Red 167, 10% dosage): Replace “FMP emulsion” in Experiment 2-2 with “commercial adhesive MCH-206”, keep the amount unchanged at 10%, and the rest is the same as in Experiment 2-2.

[0071] Comparative Experiment 3-1: Printing Application of PA Adhesive (Disperse Blue 79, 10% dosage): In Experiment 3-2, “FMP emulsion (prepared in Example 2)” was changed to “PA emulsion (prepared in Comparative Example 1)”, while the amount remained unchanged at 10%, and the rest was the same as in Experiment 3-2.

[0072] Comparative Experiment 3-2: Printing application of MCH-206 commercial adhesive (Disperse Blue 79, 10% dosage): Replace “FMP emulsion” in Experiment 3-2 with “commercial adhesive MCH-206”, keep the amount unchanged at 10%, and the rest is the same as in Experiment 3-2.

[0073] The color fastness to rubbing was tested in the above comparative experiments.

[0074] The washing fastness and light fastness were also tested in some experiments and in all comparative experiments: Colorfastness to washing: Tested according to ISO 105-C04:2010, calculate the fading rate (fading rate % = (K / S0 - K / S)). t ) / K / S0×100%, where K / S0 is the value before washing, and K / S t (Value after washing); Lightfastness: According to GB / T 8427-2019, after 100 hours of xenon arc lamp irradiation, the K / S values ​​before and after sunlight exposure were measured using a Datacolor 2100 colorimeter, and the fading rate was calculated; Fading rate % = (K / S0 - K / S) t ) / K / S0×100%, where K / S0 is the value before washing, and K / S t (Value after washing).

[0075] The results are compared in Table 2 below.

[0076] Table 2

[0077] In summary, this invention utilizes a fine emulsion polymerization method to prepare a fluorosilicone-modified polyacrylate emulsion (FMP emulsion) for waterless printing of liquid disperse dyes. One of the core invention points addresses the problems of existing fluorosilicone-modified polyacrylates lacking UV absorption capabilities and the susceptibility of some acrylates containing styrene comonomers to photo-oxidative degradation. By selecting acrylonitrile as the polymerizing monomer, the π electrons of its cyano carbon-nitrogen triple bond can absorb UV energy and generate... and The process involves molecular transitions, converting energy into heat through intramolecular vibrations and rotations, thus reducing the damage of ultraviolet light to the polymer backbone and dye conjugated system. Experimental data shows that fabrics printed with this emulsion (using three dyes: Disperse Orange 288, Disperse Red 167, and Disperse Blue 79) exhibit a lightfastness fading rate of only 1.9%-2.9%, far superior to the 4.1%-5.8% of commercial adhesive MCH-206, the 5.6%-8.4% of PA adhesives without acrylonitrile and fluorosilicone segments, and the 6.7%-10.7% of adhesive-free samples. Simultaneously, the film exhibits UV resistance... With a transmittance of only 0.28%, it achieves a dry rubbing color fastness of 4-5 and a wet rubbing color fastness of 3-4. The color fading rate after washing is as low as 1.1%-2.8%. The emulsion has an average particle size of 80-90nm and a PDI ≤ 0.2, exhibiting excellent colloidal stability. When applied to waterless printing on fibers such as polyester, it can achieve high-performance printing without the need for a washing process, solving the problems of high water consumption and high pollution in traditional printing. It also takes into account the functions of efficient color locking, abrasion resistance, water resistance, and UV protection. Moreover, the preparation process is simple and can directly replace traditional adhesives, showing good prospects for industrialization.

[0078] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A method for preparing fluorosilicone-modified polyacrylate emulsion, characterized in that... Includes the following steps: 1) Preparation of the oil phase: 2) Dissolve the composite emulsifier and N-hydroxymethylacrylamide in deionized water to prepare an aqueous phase; 3) After mixing the aqueous phase and the oil phase to form an emulsion, ultrasonic treatment is performed to obtain a fine emulsion; 4) Preparation of fluorosilicone modified polyacrylate emulsion using fine emulsion.

2. The method for preparing the fluorosilicone-modified polyacrylate emulsion according to claim 1, characterized in that: 1) Preparation of the oil phase: Butyl acrylate, acrylonitrile, acrylic acid and vinyl-terminated fluorinated polysiloxane were added to a co-emulsifier and mixed evenly to prepare an oil phase; The mass ratio of butyl acrylate: acrylonitrile: acrylic acid: vinyl-terminated fluorinated polysiloxane is 15~16:9~10:0.6~1:2.6~3; Note: Butyl acrylate, acrylonitrile, acrylic acid, and vinyl-terminated fluorinated polysiloxane are the four monomers. 2) Dissolve the composite emulsifier and N-hydroxymethylacrylamide in deionized water to prepare an aqueous phase; 3) According to the mass ratio of N-hydroxymethylacrylamide: (butyl acrylate + acrylonitrile + acrylic acid + vinyl-terminated fluorinated polysiloxane) = 1.9~2.1:28~29; The aqueous and oil phases are mixed to form an emulsion, which is then ultrasonically treated in an ice bath to obtain a fine emulsion. 4) Set the mass ratio of ammonium persulfate to N-hydroxymethylacrylamide to 0.3:1.9~2.1; prepare an ammonium persulfate aqueous solution with a mass concentration of (3±0.5)%, and name it APS aqueous solution; Take 1 / 3 of the fine emulsion and heat it to 78±0.5℃ under stirring. Then add 1 / 3 of the APS aqueous solution. When the temperature stabilizes at 78±0.5℃ and the emulsion turns blue, raise the temperature to 80±0.5℃. Under the conditions of heat preservation and stirring, add the remaining 2 / 3 of the fine emulsion and the remaining 2 / 3 of the APS solution dropwise. After the addition is complete, continue to react under the conditions of heat preservation and stirring for 60±5 min. After the reaction was complete, the mixture was allowed to cool naturally to room temperature, the pH was adjusted to neutral, and the mixture was filtered to obtain a fluorosilicone modified polyacrylate emulsion.

3. The method for preparing the fluorosilicone-modified polyacrylate emulsion according to claim 2, characterized in that: The co-emulsifier is n-hexadecane, wherein the mass ratio of n-hexadecane to (butyl acrylate + acrylonitrile + acrylic acid + vinyl-terminated fluorinated polysiloxane) is 1.5:28~29.

4. The method for preparing the fluorosilicone-modified polyacrylate emulsion according to claim 2 or 3, characterized in that: The composite emulsifier is prepared by mixing sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether, and propylene oxypropyl alkylphenol polyether ammonium sulfate in a mass ratio of 2.4~2.6:1.6~1.8:1.6~1.

8. 5.6-6.2 g of composite emulsifier and 1.9-2.1 g of N-hydroxymethylacrylamide were dissolved in 100 g of deionized water to prepare an aqueous phase.

5. The method for preparing the fluorosilicone-modified polyacrylate emulsion according to claim 4, characterized in that: The stirring speed in step 4) is 300±50 r / min.

6. The method for preparing the fluorosilicone-modified polyacrylate emulsion according to claim 5, characterized in that: The mass ratio of N-hydroxymethylacrylamide: butyl acrylate: acrylonitrile: acrylic acid: terminal vinyl fluorinated polysiloxane is 2:15.4:9.6:0.8:2.

8.

7. The method for preparing the fluorosilicone-modified polyacrylate emulsion according to claim 6, characterized in that: The mass ratio of sodium dodecyl sulfate: fatty alcohol polyoxyethylene ether: propylene oxypropyl alkylphenol polyether ammonium sulfate is 2.5:1.7:1.

7.

8. The method for preparing the fluorosilicone-modified polyacrylate emulsion according to any one of claims 1 to 7, characterized in that... The preparation method of vinyl-terminated fluorinated polysiloxane includes the following steps: ① Under an inert gas atmosphere, octamethylcyclotetrasiloxane and 1,3-divinyltetramethyldisiloxane are mixed evenly until the mixture becomes transparent; The molar ratio of octamethylcyclotetrasiloxane to 1,3-divinyltetramethyldisiloxane is 5:

1. ② Heat the product obtained in step ① to 65±5℃ and keep it at that temperature for 30±10 min. Under stirring conditions, add trifluoromethanesulfonic acid as a catalyst and stir evenly. Then add methyltrifluoropropylcyclotrisiloxane and keep it at 65±5℃ for 6±0.5 h. The molar ratio of methyltrifluoropropylcyclotrisiloxane to octamethylcyclotetrasiloxane is 1:

2. The amount of trifluoromethanesulfonic acid used is 0.1% of the total mass of (octamethylcyclotetrasiloxane + 1,3-divinyltetramethyldisiloxane + methyltrifluoropropylcyclotrisiloxane); ③ After cooling the reaction product obtained in step ②, adjust the pH to neutral; Continue stirring to neutralize any remaining catalyst; filter using filter paper; ④ The filtrate is purified to obtain colorless and transparent vinyl-terminated fluorinated polysiloxane.

9. The application of the fluorosilicone-modified polyacrylate emulsion prepared by any one of claims 1 to 8, characterized in that: It is mixed with liquid disperse dyes and other materials to prepare printing pastes for waterless printing on fabrics.

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