PET screen cloth roughing-free treating agent for shoe making industry and preparation method of PET screen cloth roughing-free treating agent

Abstract

The invention discloses a PET screen cloth roughing-free treating agent for the shoe making industry and a preparation method thereof, and belongs to the technical field of treating agents. The high-temperature-resistant and corrosion-resistant coating is prepared from the following components in parts by weight: 20 to 25 parts of hydroxyl-terminated polyester resin, 8 to 12 parts of silane modified TPU, 5 to 8 parts of PDMS-g-acrylate, 3 to 5 parts of monoethyl fumarate, 0.05 to 0.16 part of an antioxidant DHOP / 168, 0.2 to 0.5 part of ZrO2-CeO2, 0.04 to 0.06 part of a metal ion passivator, 30 to 40 parts of ethyl acetate / dimethyl carbonate and 0.15 to 0.3 part of TCCA. The treatment agent prepared by the preparation method disclosed by the invention has high peel strength, low yellowing and excellent hydrolysis resistance while realizing no roughing of the PET screen cloth, solves the problem that adhesion and weather resistance of a traditional treatment agent are difficult to consider at the same time, and remarkably improves the efficiency of a shoemaking process and the durability of a product.

Description

Technical Field

[0001] The invention belongs to the technical field of treatment agents, and particularly relates to a roughening-free treatment agent for PET mesh used in the shoemaking industry and a preparation method thereof. Background Art

[0002] In the footwear industry, polyethylene terephthalate (PET) mesh has become a mainstream material for athletic shoe uppers due to its lightweight, high strength, and cost advantages. However, its inert surface and low surface energy result in insufficient adhesion with traditional adhesives. To overcome this obstacle, traditional processes rely on two main pretreatment methods: Mechanical roughening: Physically grinding the mesh surface with sandpaper or a wire brush to create a micron-scale roughness, increasing the surface area and enhancing mechanical interlocking. While this method improves adhesion, it also reduces the tensile strength of the mesh. Chemical treatment agents: Early treatment agents were based on a chloroprene rubber / styrene solution combined with a chlorinating agent such as trichloroisocyanuric acid. However, these treatments can cause PET molecular chain scission, leading to an increase in the yellowing index of the mesh and a loss of whiteness.

[0003] Patent application publication number CN 111647324 A discloses a process for producing a shoe treatment agent for roughening-free rubber surface treatment. The agent is synthesized through high-temperature grafting of polyolefin resins, various high-molecular-weight polyester materials, and methacrylic monomers. The resulting liquid has excellent affinity for rubber substrates, requiring only half the B powder (TCCA) of conventional treatment agents to achieve excellent adhesion. However, the soaking time is too long, and the shoemaking industry typically requires seconds to complete PET mesh treatment (usually ≤5 minutes), making it unsuitable for high-speed production lines. Therefore, developing a new treatment agent that requires no roughening, exhibits low yellowing, and exhibits high adhesion has become a key concern for the shoemaking industry. Summary of the Invention

[0004] The object of the present invention is to provide a roughening-free treatment agent for PET mesh for the shoemaking industry and a preparation method thereof. The prepared treatment agent aims to improve the adhesion between PET mesh and other materials, realize a roughening-free process and reduce yellowing, thereby solving the core pain point problem of PET mesh processing in the shoemaking industry; the preparation method is used to prepare the above-mentioned roughening-free treatment agent for PET mesh for the shoemaking industry.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A roughening-free treating agent for PET mesh used in the shoemaking industry comprises, by weight, 20-25 parts of hydroxyl-terminated polyester resin, 8-12 parts of silane-modified TPU, 5-8 parts of PDMS-g-acrylate (polydimethylsiloxane grafted acrylate), 3-5 parts of monoethyl fumarate, 0.05-0.16 parts of antioxidant DHOP / 168, 0.2-0.5 parts of ZrO2-CeO2, 0.04-0.06 parts of a metal ion passivator, 30-40 parts of ethyl acetate / dimethyl carbonate, and 0.15-0.3 parts of TCCA (chlorinating agent).

[0006] Furthermore, the ZrO2-CeO2 is prepared by the following steps: S1. Dissolve ZrOCl2·8H2O in deionized water and add PVP; adjust the pH to 9.0±0.2, and allow to stand for aging; centrifuge, wash, dry, calcine, and cool naturally to obtain ZrO2; S2. Disperse ZrO2 in deionized water and preheat to obtain a ZrO2 suspension; dissolve Ce(NO3)3·6H2O in deionized water, slowly add it dropwise to the ZrO2 suspension, and continue stirring at 68-72°C for 1.5-2.5h; centrifuge, wash, and dry; calcine, and naturally cool to obtain ZrO2-CeO2.

[0007] Furthermore, the weight ratio of the ZrOCl2·8H2O, deionized water and PVP is (8-12):(80-120):1.

[0008] Furthermore, the calcination is carried out by heating the temperature to 480-520° C. at a heating rate of 4-6° C. / min and keeping the temperature for 1.5-3.5 hours.

[0009] Furthermore, the usage ratio of ZrO2 and Ce(NO3)3·6H2O is (95-105):(13-17).

[0010] Furthermore, the silane-modified TPU is prepared by the following steps: VTMS is mixed with anhydrous ethanol, DBTL catalyst is added, and ultrasonic dispersion is performed to obtain a VTMS / ethanol solution; TPU particles are mixed with the above solution, stirred, extruded into granules, and dried to obtain silane-modified TPU.

[0011] Furthermore, the weight ratio of the TPU particles, VTMS, anhydrous ethanol and DBTL catalyst is (95-105): (1.3-1.7): (15-20): (0.04-0.06).

[0012] Furthermore, the mixing and stirring is carried out at 35-40°C for 30-40 minutes; the temperature of each zone of the extrusion granulation twin-screw is set as zone 1: 75-80°C, zone 2: 85-90°C, zone 3: 95-100°C, zone 4: 105-110°C, and zones 5-8: 110-105°C.

[0013] Furthermore, the acrylate grafting rate in the PDMS-g-acrylate is 15%-20%.

[0014] A method for preparing a roughening-free treatment agent for PET mesh used in the shoemaking industry comprises the following steps: S1. Add hydroxyl-terminated polyester resin and silane-modified TPU to a reactor, add ethyl acetate and dimethyl carbonate, raise the temperature to 55-60°C, and stir to dissolve; add monoethyl fumarate, and react at 75-80°C with ultrasound assistance for 30-40 minutes; slowly add PDMS-g-acrylate dropwise, and simultaneously add initiator benzoyl peroxide, raise the temperature to 85-90°C, and react at ultrasound assistance for 50-60 minutes; S2. After the reaction system is cooled to 50-55° C., a premix of phosphite DHOP and antioxidant 168, ZrO2-CeO2, and N,N'-di(ethylhexyl)imidazoline are added in sequence. The temperature is controlled at 45-55° C. and stirred for 25-35 minutes to obtain a mixed solution. S3. Mix TCCA with acrylic resin and prepare microcapsules with a particle size of 10-15 μm by spray condensation method; add the mixed solution under low-speed stirring at 40-45° C., stir for 30-40 minutes, and filter to obtain a roughening-free treatment agent for PET mesh for the shoemaking industry.

[0015] Furthermore, the power of the ultrasonic assistance is 800-1400W.

[0016] Furthermore, the pore size of the filter screen is 180-240 mesh.

[0017] Furthermore, the low-speed stirring rate is 60-120 rpm.

[0018] Beneficial effects of the present invention: (1) The acrylate grafted chains in the PDMS-g-acrylate used in the present invention have higher reactivity with the hydroxyl groups of the hydroxyl-terminated polyester resin and the double bonds of monoethyl fumarate, which can form a denser cross-linked network. At the same time, there is an intermolecular force between the PDMS segments and the siloxane structure in the silane-modified TPU, which significantly improves the interfacial bonding strength of the two phases, improves the tensile strength and elongation at break of the coating, and effectively solves the coating embrittlement problem caused by the poor compatibility between the fluorine segments and the matrix in traditional fluorine-containing systems, and enhances the interfacial compatibility and integrity of the coating system. The reflectivity of the PDMS segments to ultraviolet light (about 35%-40%) is higher than that of the fluorocarbon chains, and forms a synergistic relationship with the high reflectivity of ZrO2 to reduce the amount of ultraviolet photons absorbed by the PET mesh. At the same time, the interfacial affinity of siloxane and CeO2 is strong, which can stabilize the coating. The existence of redox pairs reduces the yellowing index of the coating.

[0019] (2) The ZrO2-CeO2 composite material used in the present invention, The redox couple quenches free radicals, blocking the PET photodegradation chain reaction. ZrO2's high reflectivity reduces photon flux, lowering CeO2's photocatalytic activity and preventing self-oxidation. Combined with the antioxidant DHOP / 168 and a metal ion passivator, DHOP scavenges free radicals, 168 decomposes peroxides, and the passivator complexes heavy metal ions, reducing the yellowing index and significantly extending the product's service life.

[0020] (3) The preparation method of the present invention reduces the amount of chlorinating agent used and precisely controls its release, thus inhibiting yellowing at the source. The microencapsulated TCCA only ruptures during hot pressing to release active chlorine, preventing chlorination byproducts from accelerating material aging. The ethyl acetate / dimethyl carbonate mixed solvent has lower VOC emissions than pure ethyl acetate and has moderate volatility, which facilitates uniform film formation. DETAILED DESCRIPTION

[0021] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0022] Example 1 This embodiment provides a roughening-free treatment agent for PET mesh for the shoemaking industry, which is prepared by the following steps: S1. Dissolve 10 parts of ZrOCl2·8H2O in 100 parts of deionized water, add 1 part of PVP (polyvinyl pyrrolidone); place in a constant temperature water bath at 30°C, and under stirring, add ammonia water dropwise to adjust the pH of the solution to 9.0. After the addition is completed, continue stirring for 1 hour and let it stand for 2 hours; centrifuge and collect the precipitate, wash the precipitate with deionized water and anhydrous ethanol alternately 3 times, and then dry it at 60°C for 12 hours to obtain a Zr(OH)4 precursor; place the Zr(OH)4 precursor in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at this temperature for 3 hours, and cool it naturally to obtain ZrO2; 10 parts of ZrO2 were dispersed in 1000 parts of deionized water, ultrasonically dispersed for 30 minutes, placed in a constant temperature water bath at 70°C, stirred and preheated for 10 minutes to obtain a ZrO2 suspension; 1.5 parts of Ce(NO3)3·6H2O were weighed, dissolved in 500 parts of deionized water, and slowly added dropwise to the ZrO2 suspension. After the addition was completed, stirring was continued at 70°C for 2 hours; after the reaction was completed, the mixture was cooled to room temperature, centrifuged and collected, and the precipitate was washed alternately with deionized water and anhydrous ethanol for 3 times, and dried at 60°C for 12 hours; the dried product was placed in a muffle furnace, heated to 450°C at a heating rate of 3°C / min, kept warm for 2 hours, and naturally cooled to obtain ZrO2-CeO2; S2. 1.5 parts of VTMS were mixed with 18 parts of anhydrous ethanol, 0.05 parts of DBTL catalyst were added, and ultrasonic dispersion was performed to obtain a VTMS / ethanol solution; 100 parts of TPU particles were mixed with the above solution and stirred at 35°C for 30 minutes, and extruded into pellets. The temperatures of each zone of the twin-screw extruder were set to: zone 1: 75°C, zone 2: 85°C, zone 3: 95°C, zone 4: 105°C, and zones 5-8: 110°C; and dried at 60°C to obtain silane-modified TPU; S3. Add 22 parts of hydroxyl-terminated polyester resin and 10 parts of silane-modified TPU into a reactor, add 20 parts of ethyl acetate and 10 parts of dimethyl carbonate, heat to 60°C and stir at 150 rpm to dissolve for 40 minutes; add 4 parts of monoethyl fumarate, ultrasonic power 1000W (frequency 25kHz), temperature 75°C to react for 30 minutes; slowly add 6 parts of PDMS-g-acrylate (acrylate grafting rate 15%) dropwise, simultaneously add 0.08 parts of initiator benzoyl peroxide, heat to 85°C, increase ultrasonic power to 1200W, and react for 50 minutes; S4. After the reaction system was cooled to 50° C., 0.07 parts of a premix of phosphite DHOP and 0.04 parts of antioxidant 168, 0.4 parts of ZrO2-CeO2, and 0.05 parts of N,N'-di(ethylhexyl)imidazoline were added in sequence. The temperature was controlled at 45-55° C. and stirred at 300 rpm for 25 minutes to obtain a mixed solution. S5. Mix 0.25 parts of TCCA with 2 parts of acrylic resin, and prepare microcapsules with a particle size of 10-15 μm by a spray condensation method; add the mixed solution under low-speed stirring (80 rpm) at 40°C, stir for 30 minutes, and filter through a 200-mesh filter to obtain a PET mesh roughening-free treatment agent for the shoemaking industry.

[0023] Example 2 Compared with Example 1, this embodiment differs in that the power of ultrasonic assistance is increased, and the specific implementation steps of S3 are: S3. Add 22 parts of hydroxyl-terminated polyester resin and 10 parts of silane-modified TPU into a reactor, add 20 parts of ethyl acetate and 10 parts of dimethyl carbonate, heat to 60°C and stir at 150 rpm to dissolve for 40 minutes; add 4 parts of monoethyl fumarate, ultrasonic power 1200W (frequency 25kHz), temperature 75°C to react for 30 minutes; slowly add 6 parts of PDMS-g-acrylate (acrylate grafting rate 20%) dropwise, simultaneously add 0.08 parts of initiator benzoyl peroxide, heat to 85°C, increase ultrasonic power to 1400W, and react for 50 minutes; The remaining raw materials and preparation process remain the same as in Example 1.

[0024] Example 3 Compared with Example 1, this embodiment differs in that the power of ultrasonic assistance is reduced. The specific implementation steps of S3 are: S3. Add 22 parts of hydroxyl-terminated polyester resin and 10 parts of silane-modified TPU into a reactor, add 20 parts of ethyl acetate and 10 parts of dimethyl carbonate, heat to 60°C and stir at 150 rpm to dissolve for 40 minutes; add 4 parts of monoethyl fumarate, ultrasonic power 800W (frequency 25kHz), temperature 75°C to react for 30 minutes; slowly add 6 parts of PDMS-g-acrylate (acrylate grafting rate 18%) dropwise, simultaneously add 0.08 parts of initiator benzoyl peroxide, heat to 85°C, increase ultrasonic power to 900W, and react for 50 minutes; The remaining raw materials and preparation process remain the same as in Example 1.

[0025] Example 4 Compared with Example 1, this embodiment differs in that the amount of VTMS is increased. The specific implementation steps of S2 are: S2. 1.7 parts of VTMS were mixed with 20 parts of anhydrous ethanol, 0.04 parts of DBTL catalyst were added, and ultrasonic dispersion was performed to obtain a VTMS / ethanol solution; 100 parts of TPU particles were mixed with the above solution and stirred at 35°C for 30 minutes, and extruded into pellets. The temperatures of each zone of the twin-screw extruder were set to: zone 1: 75°C, zone 2: 85°C, zone 3: 95°C, zone 4: 105°C, and zones 5-8: 110°C; and dried at 60°C to obtain silane-modified TPU; The remaining raw materials and preparation process remain the same as in Example 1.

[0026] Example 5 Compared with Example 1, this embodiment differs in that the amount of VTMS used is reduced. The specific implementation steps of S2 are: S2. 1.3 parts of VTMS were mixed with 15 parts of anhydrous ethanol, 0.06 parts of DBTL catalyst were added, and ultrasonic dispersion was performed to obtain a VTMS / ethanol solution; 100 parts of TPU particles were mixed with the above solution and stirred at 35°C for 30 minutes, and extruded into pellets. The temperatures of each zone of the twin-screw extruder were set to: zone 1: 75°C, zone 2: 85°C, zone 3: 95°C, zone 4: 105°C, and zones 5-8: 110°C; and dried at 60°C to obtain silane-modified TPU; The remaining raw materials and preparation process remain the same as in Example 1.

[0027] Example 6 Compared with Example 1, this embodiment differs in that the amount of Ce(NO3)3·6H2O is increased. The specific implementation steps of S1 are: S1. Dissolve 10 parts of ZrOCl2·8H2O in 100 parts of deionized water, add 1 part of PVP (polyvinyl pyrrolidone); place in a constant temperature water bath at 30°C, and under stirring, add ammonia water dropwise to adjust the pH of the solution to 9.0. After the addition is completed, continue stirring for 1 hour and let it stand for 2 hours; centrifuge and collect the precipitate, wash the precipitate with deionized water and anhydrous ethanol alternately 3 times, and then dry it at 60°C for 12 hours to obtain a Zr(OH)4 precursor; place the Zr(OH)4 precursor in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at this temperature for 3 hours, and cool it naturally to obtain ZrO2; 9.5 parts of ZrO2 were dispersed in 1000 parts of deionized water, ultrasonically dispersed for 30 minutes, placed in a constant temperature water bath at 70°C, stirred and preheated for 10 minutes to obtain a ZrO2 suspension; 1.7 parts of Ce(NO3)3·6H2O were weighed, dissolved in 500 parts of deionized water, and slowly added dropwise to the ZrO2 suspension. After the addition was completed, stirring was continued at 70°C for 2 hours; after the reaction was completed, the mixture was cooled to room temperature, centrifuged and collected, and the precipitate was washed alternately with deionized water and anhydrous ethanol for 3 times, and dried at 60°C for 12 hours; the dried product was placed in a muffle furnace, heated to 450°C at a heating rate of 3°C / min, kept warm for 2 hours, and naturally cooled to obtain ZrO2-CeO2; The remaining raw materials and preparation process remain the same as in Example 1.

[0028] Example 7 Compared with Example 1, this embodiment differs in that the amount of Ce(NO3)3·6H2O is reduced. The specific implementation steps of S1 are: S1. Dissolve 10 parts of ZrOCl2·8H2O in 100 parts of deionized water, add 1 part of PVP (polyvinyl pyrrolidone); place in a constant temperature water bath at 30°C, and under stirring, add ammonia water dropwise to adjust the pH of the solution to 9.0. After the addition is completed, continue stirring for 1 hour and let it stand for 2 hours; centrifuge and collect the precipitate, wash the precipitate with deionized water and anhydrous ethanol alternately 3 times, and then dry it at 60°C for 12 hours to obtain a Zr(OH)4 precursor; place the Zr(OH)4 precursor in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at this temperature for 3 hours, and cool it naturally to obtain ZrO2; 10.5 parts of ZrO2 were dispersed in 1000 parts of deionized water, ultrasonically dispersed for 30 minutes, placed in a constant temperature water bath at 70°C, stirred and preheated for 10 minutes to obtain a ZrO2 suspension; 1.3 parts of Ce(NO3)3·6H2O were weighed, dissolved in 500 parts of deionized water, and slowly added dropwise to the ZrO2 suspension. After the addition was completed, stirring was continued at 70°C for 2 hours; after the reaction was completed, the mixture was cooled to room temperature, centrifuged and collected, and the precipitate was washed alternately with deionized water and anhydrous ethanol for 3 times, and dried at 60°C for 12 hours; the dried product was placed in a muffle furnace, heated to 450°C at a heating rate of 3°C / min, kept warm for 2 hours, and naturally cooled to obtain ZrO2-CeO2; The remaining raw materials and preparation process remain the same as in Example 1.

[0029] Comparative Example 1 Compared with Example 1, this comparative example differs in that CeO2 is not added. The specific implementation steps are as follows: S1. Dissolve 10 parts of ZrOCl2·8H2O in 100 parts of deionized water, add 1 part of PVP (polyvinyl pyrrolidone); place in a constant temperature water bath at 30°C, and under stirring, add ammonia water dropwise to adjust the pH of the solution to 9.0. After the addition is completed, continue stirring for 1 hour and let it stand for 2 hours; centrifuge and collect the precipitate, wash the precipitate with deionized water and anhydrous ethanol alternately 3 times, and then dry it at 60°C for 12 hours to obtain a Zr(OH)4 precursor; place the Zr(OH)4 precursor in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at this temperature for 3 hours, and cool it naturally to obtain ZrO2; S2. 1.5 parts of VTMS were mixed with 18 parts of anhydrous ethanol, 0.05 parts of DBTL catalyst were added, and ultrasonic dispersion was performed to obtain a VTMS / ethanol solution; 100 parts of TPU particles were mixed with the above solution and stirred at 35°C for 30 minutes, and extruded into pellets. The temperatures of each zone of the twin-screw extruder were set to: zone 1: 75°C, zone 2: 85°C, zone 3: 95°C, zone 4: 105°C, and zones 5-8: 110°C; and dried at 60°C to obtain silane-modified TPU; S3. Add 22 parts of hydroxyl-terminated polyester resin and 10 parts of silane-modified TPU into a reactor, add 20 parts of ethyl acetate and 10 parts of dimethyl carbonate, heat to 60°C and stir at 150 rpm to dissolve for 40 minutes; add 4 parts of monoethyl fumarate, ultrasonic power 1000W (frequency 25kHz), temperature 75°C to react for 30 minutes; slowly add 6 parts of PDMS-g-acrylate (acrylate grafting rate 15%) dropwise, simultaneously add 0.08 parts of initiator benzoyl peroxide, heat to 85°C, increase ultrasonic power to 1200W, and react for 50 minutes; S4. After the reaction system was cooled to 50° C., a premix of 0.07 parts of phosphite DHOP and 0.04 parts of antioxidant 168, 0.4 parts of ZrO2, and 0.05 parts of N,N'-di(ethylhexyl)imidazoline were added in sequence. The temperature was controlled at 45-55° C. and stirred at 300 rpm for 25 minutes to obtain a mixed solution. S5. Mix 0.25 parts of TCCA with 2 parts of acrylic resin, and prepare microcapsules with a particle size of 10-15 μm by a spray condensation method; add the mixed solution under low-speed stirring (80 rpm) at 40°C, stir for 30 minutes, and filter through a 200-mesh filter to obtain a PET mesh roughening-free treatment agent for the shoemaking industry.

[0030] The remaining raw materials and preparation process remain the same as in Example 1.

[0031] Comparative Example 2 Compared with Example 1, this comparative example is different in that ZrO2 is not added. The specific implementation steps are as follows: S1. 1.5 parts of VTMS were mixed with 18 parts of anhydrous ethanol, 0.05 parts of DBTL catalyst were added, and ultrasonic dispersion was performed to obtain a VTMS / ethanol solution; 100 parts of TPU particles were mixed with the above solution and stirred at 35°C for 30 minutes, and extruded into pellets. The temperatures of each zone of the twin-screw extruder were set to: zone 1: 75°C, zone 2: 85°C, zone 3: 95°C, zone 4: 105°C, and zones 5-8: 110°C; and dried at 60°C to obtain silane-modified TPU; S2. Add 22 parts of hydroxyl-terminated polyester resin and 10 parts of silane-modified TPU into a reactor, add 20 parts of ethyl acetate and 10 parts of dimethyl carbonate, heat to 60°C and stir at 150 rpm to dissolve for 40 minutes; add 4 parts of monoethyl fumarate, ultrasonic power 1000W (frequency 25kHz), temperature 75°C to react for 30 minutes; slowly add 6 parts of PDMS-g-acrylate (acrylate grafting rate 15%) dropwise, simultaneously add 0.08 parts of initiator benzoyl peroxide, heat to 85°C, increase ultrasonic power to 1200W, and react for 50 minutes; S3. After the reaction system was cooled to 50° C., 0.07 parts of a premix of phosphite DHOP and 0.04 parts of antioxidant 168, 0.4 parts of CeO2, and 0.05 parts of N,N'-di(ethylhexyl)imidazoline were added in sequence. The temperature was controlled at 45-55° C. and stirred at 300 rpm for 25 minutes to obtain a mixed solution. S4. Mix 0.25 parts of TCCA with 2 parts of acrylic resin, and prepare microcapsules with a particle size of 10-15 μm by a spray condensation method; add the mixed solution under low-speed stirring (80 rpm) at 40°C, stir for 30 minutes, and filter through a 200-mesh filter to obtain a PET mesh roughening-free treatment agent for the shoemaking industry.

[0032] The remaining raw materials and preparation process remain the same as in Example 1.

[0033] Comparative Example 3 Compared with Example 1, this comparative example differs in that ZrO2-CeO2 is not added. The specific implementation steps are as follows: S1. 1.5 parts of VTMS were mixed with 18 parts of anhydrous ethanol, 0.05 parts of DBTL catalyst were added, and ultrasonic dispersion was performed to obtain a VTMS / ethanol solution; 100 parts of TPU particles were mixed with the above solution and stirred at 35°C for 30 minutes, and extruded into pellets. The temperatures of each zone of the twin-screw extruder were set to: zone 1: 75°C, zone 2: 85°C, zone 3: 95°C, zone 4: 105°C, and zones 5-8: 110°C; and dried at 60°C to obtain silane-modified TPU; S2. Add 22 parts of hydroxyl-terminated polyester resin and 10 parts of silane-modified TPU into a reactor, add 20 parts of ethyl acetate and 10 parts of dimethyl carbonate, heat to 60°C and stir at 150 rpm to dissolve for 40 minutes; add 4 parts of monoethyl fumarate, ultrasonic power 1000W (frequency 25kHz), temperature 75°C to react for 30 minutes; slowly add 6 parts of PDMS-g-acrylate (acrylate grafting rate 15%) dropwise, simultaneously add 0.08 parts of initiator benzoyl peroxide, heat to 85°C, increase ultrasonic power to 1200W, and react for 50 minutes; S3. After the reaction system was cooled to 50° C., 0.07 parts of a premix of phosphite DHOP and 0.04 parts of antioxidant 168 and 0.05 parts of N,N'-di(ethylhexyl)imidazoline were added in sequence. The temperature was controlled at 45-55° C. and stirred at 300 rpm for 25 minutes to obtain a mixed solution. S4. Mix 0.25 parts of TCCA with 2 parts of acrylic resin, and prepare microcapsules with a particle size of 10-15 μm by a spray condensation method; add the mixed solution under low-speed stirring (80 rpm) at 40°C, stir for 30 minutes, and filter through a 200-mesh filter to obtain a PET mesh roughening-free treatment agent for the shoemaking industry.

[0034] The remaining raw materials and preparation process remain the same as in Example 1.

[0035] Comparative Example 4 Compared with Example 1, this comparative example differs in that TPU is not silane-modified. The specific implementation steps are as follows: S1. Dissolve 10 parts of ZrOCl2·8H2O in 100 parts of deionized water, add 1 part of PVP (polyvinyl pyrrolidone); place in a constant temperature water bath at 30°C, and under stirring, add ammonia water dropwise to adjust the pH of the solution to 9.0. After the addition is completed, continue stirring for 1 hour and let it stand for 2 hours; centrifuge and collect the precipitate, wash the precipitate with deionized water and anhydrous ethanol alternately 3 times, and then dry it at 60°C for 12 hours to obtain a Zr(OH)4 precursor; place the Zr(OH)4 precursor in a muffle furnace, heat it to 500°C at a heating rate of 5°C / min, keep it at this temperature for 3 hours, and cool it naturally to obtain ZrO2; 10 parts of ZrO2 were dispersed in 1000 parts of deionized water, ultrasonically dispersed for 30 minutes, placed in a constant temperature water bath at 70°C, stirred and preheated for 10 minutes to obtain a ZrO2 suspension; 1.5 parts of Ce(NO3)3·6H2O were weighed, dissolved in 500 parts of deionized water, and slowly added dropwise to the ZrO2 suspension. After the addition was completed, stirring was continued at 70°C for 2 hours; after the reaction was completed, the mixture was cooled to room temperature, centrifuged and collected, and the precipitate was washed alternately with deionized water and anhydrous ethanol for 3 times, and dried at 60°C for 12 hours; the dried product was placed in a muffle furnace, heated to 450°C at a heating rate of 3°C / min, kept warm for 2 hours, and naturally cooled to obtain ZrO2-CeO2; S2. Add 22 parts of hydroxyl-terminated polyester resin and 10 parts of TPU into a reactor, add 20 parts of ethyl acetate and 10 parts of dimethyl carbonate, heat to 60°C and stir at 150 rpm to dissolve for 40 minutes; add 4 parts of monoethyl fumarate, ultrasonic power 1000W (frequency 25kHz), temperature 75°C to react for 30 minutes; slowly add 6 parts of PDMS-g-acrylate (acrylate grafting rate 15%) dropwise, simultaneously add 0.08 parts of initiator benzoyl peroxide, heat to 85°C, increase ultrasonic power to 1200W, and react for 50 minutes; S3. After the reaction system was cooled to 50° C., 0.07 parts of a premix of phosphite DHOP and 0.04 parts of antioxidant 168, 0.4 parts of ZrO2-CeO2, and 0.05 parts of N,N'-di(ethylhexyl)imidazoline were added in sequence. The temperature was controlled at 45-55° C. and stirred at 300 rpm for 25 minutes to obtain a mixed solution. S4, 0.25 parts of TCCA was mixed with 2 parts of acrylic resin, and microcapsules with a particle size of 10-15 μm were prepared by a spray condensation method; the mixed solution was added under low-speed stirring (80 rpm) at 40°C, stirred for 30 minutes, filtered through a 200-mesh screen, and a PET mesh cloth processing agent for the shoemaking industry without roughening treatment was obtained.

[0036] The remaining raw materials and preparation process were the same as in Example 1.

[0037] Comparative Example 5 This comparative example is different from Example 1 in that TCCA is directly added. The specific implementation steps of S5 are as follows: S5, 0.25 parts of TCCA was mixed with 2 parts of acrylic resin, and microcapsules with a particle size of 10-15 μm were prepared by a spray condensation method; the mixed solution was added under low-speed stirring (80 rpm) at 40°C, stirred for 30 minutes, filtered through a 200-mesh screen, and a PET mesh cloth processing agent for the shoemaking industry without roughening treatment was obtained.

[0038] The remaining raw materials and preparation process were the same as in Example 1.

[0039] Performance test The processing agent was coated by a double-roller transfer method: the upper roller was made of silicone (hardness Shore A 60), and the lower roller was made of stainless steel; the roller spacing was 0.15 mm, and the speed ratio was 1:1.2. The PET mesh cloth passed at a speed of 3 m / min, and the liquid amount was controlled at 25±3 g / m 2 After drying with hot air at 80°C for 2 minutes, it was directly combined with the EVA midsole at a pressure of 0.4 MPa for 8-10 seconds.

[0040] Peeling strength (N / cm): according to GB / T 2791-1995 "Adhesives T Peeling Strength Test Method Flexible Materials on Flexible Materials", the peeling strength of the roughening-free processing agent obtained in each example and comparative example of the present application was tested; Yellowing index Δb (500h UV): according to AATCC 16.3-2020 "Light Fastness: Xenon Arc Lamp", the yellowing index Δb of the roughening-free processing agent obtained in each example and comparative example of the present application was tested; Hydrolysis resistance (70°C / 95%RH): according to GB / T 1733-1993 "Paint Film Resistance to Water Determination Method", the hydrolysis resistance of the roughening-free processing agent obtained in each example and comparative example of the present application was tested; The results are shown in Table 1. Table 1 As shown in Table 1, the overall performance of Example 1 (peel strength 36.5 N / cm, Δb = 3.0, and 200h hydrolysis resistance) is far superior to that of the comparative example lacking any single component. The peel strength of Example 1 reaches 36.5 N / cm, while that of Comparative Example 4 (TPU without silane modification) is only 16.5 N / cm, a 121% improvement. This directly demonstrates the critical role of silane-modified TPU in interfacial bonding. The acrylate grafted chains of PDMS-g-acrylate form a dense crosslinked network with the hydroxyl-terminated polyester resin and monoethyl fumarate, while the siloxy groups of the silane-modified TPU form covalent bonds with the hydroxyl groups on the PET surface, synergistically enhancing interfacial bonding.

[0041] The peel strengths of Example 2 (increased ultrasonic power) and Example 3 (reduced power) (36.2 N / cm and 32.3 N / cm) were both lower than that of Example 1 (1000 W / 1200 W), indicating that moderate ultrasonic power can promote the penetration of PDMS-g-acrylate into the gaps between PET fibers, forming a three-dimensional interwoven interface layer with monoethyl fumarate, further improving the peel strength and verifying the role of ultrasonic assistance.

[0042] CeO2 The redox pair effectively quenches free radicals generated by photoaging in PET. However, when used alone (Comparative Example 2), the photocatalytic activity of CeO2 accelerates its own oxidation, resulting in a Δb of 4.2. ZrO2 itself has no free radical scavenging ability (Comparative Example 1, Δb = 4.8), but its high reflectivity (35%-40%) reduces UV damage to PET and simultaneously inhibits the photocatalytic activity of CeO2. When the two are combined (Example 1), Δb drops to 3.0, a 28.6%-37.5% reduction compared to either component alone. This demonstrates that the "physical shielding" of ZrO2 and the "chemical quenching" of CeO2 synergize to both scavenge free radicals and reduce the sources of their generation.

[0043] TCCA releases active chlorine during hot-pressing to activate the PET surface. However, free TCCA (Comparative Example 5) reacts prematurely with the resin to form chlorinated byproducts, accelerating aging (delamination failure after 72 hours). After microencapsulation (Example 1), the acrylic resin wall isolates the TCCA from the resin, allowing it to rupture and release only during hot pressing (0.4 MPa, 8-10 seconds). This ensures effective activation (peel strength of 36.5 N / cm, close to 32 N / cm in Comparative Example 5) while preventing premature degradation. This extends hydrolysis resistance from 72 hours to 200 hours (with 85% strength retention), demonstrating the synergistic effect of "controlled-release activation + resin protection."

[0044] In addition, the yellowing index Δb of Example 1 (containing PDMS-g-acrylate and ZrO2-CeO2) is 3.0, while the Δb of Comparative Example 1 (no CeO2, only containing ZrO2 and PDMS-g-acrylate) is 4.8, and the Δb of Comparative Example 2 (no ZrO2, only containing CeO2 and PDMS-g-acrylate) is 4.2, both significantly higher than Example 1. This indicates that the PDMS segments (reflecting 35%-40% of UV light) and the high reflectivity of ZrO2 form a synergistic effect, reducing the damage of UV photons to PET. At the same time, the strong interfacial affinity between siloxane and CeO2 stabilizes the The redox couple enables it to continuously and efficiently quench free radicals. Under the joint action of the two, the yellowing index is significantly reduced, which confirms the synergistic effect of PDMS segments and ZrO2-CeO2 in anti-ultraviolet yellowing.

[0045] The above disclosures are only a few specific embodiments of the present invention. However, the embodiments of the present invention are not limited thereto. Any changes that can be conceived by those skilled in the art should fall within the scope of protection of the present invention.

Claims

1. A roughening-free treatment agent for PET mesh used in the shoemaking industry, characterized in that: By weight, it includes 20-25 parts of hydroxyl-terminated polyester resin, 8-12 parts of silane-modified TPU, 5-8 parts of PDMS-g-acrylate, 3-5 parts of monoethyl fumarate, 0.05-0.16 parts of antioxidant DHOP / 168, 0.2-0.5 parts of ZrO2-CeO2, 0.04-0.06 parts of metal ion passivator, 30-40 parts of ethyl acetate / dimethyl carbonate and 0.15-0.3 parts of TCCA.

2. The PET mesh roughening-free treating agent for the shoemaking industry according to claim 1, characterized in that: The ZrO2-CeO2 is prepared by the following steps: S1. Dissolve ZrOCl2·8H2O in deionized water and add PVP; adjust the pH to 9.0±0.2, and allow to stand for aging; centrifuge, wash, dry, calcine, and cool naturally to obtain ZrO2; S2. Disperse ZrO2 in deionized water and preheat to obtain a ZrO2 suspension; dissolve Ce(NO3)3·6H2O in deionized water, slowly add it dropwise to the ZrO2 suspension, and continue stirring at 68-72°C for 1.5-2.5h; centrifuge, wash, and dry; calcine, and naturally cool to obtain ZrO2-CeO2.

3. The PET mesh roughening-free treating agent for the shoemaking industry according to claim 2, characterized in that: The weight ratio of the ZrOCl2·8H2O, deionized water and PVP is (8-12):(80-120):

1.

4. The PET mesh roughening-free treating agent for the shoemaking industry according to claim 2, characterized in that: The calcination is carried out by heating the temperature to 480-520° C. at a heating rate of 4-6° C. / min and keeping the temperature for 1.5-3.5 hours.

5. The roughening-free treating agent for PET mesh used in the shoemaking industry according to claim 2, characterized in that: The usage ratio of ZrO2 and Ce(NO3)3·6H2O is (95-105):(13-17).

6. The roughening-free treating agent for PET mesh used in the shoemaking industry according to claim 1, characterized in that: The silane-modified TPU is prepared by the following steps: VTMS is mixed with anhydrous ethanol, DBTL catalyst is added, and ultrasonic dispersion is performed to obtain a VTMS / ethanol solution; TPU particles are mixed with the above solution, stirred, extruded into granules, and dried to obtain silane-modified TPU.

7. The roughening-free treating agent for PET mesh used in the shoemaking industry according to claim 6, characterized in that: The weight ratio of the TPU particles, VTMS, anhydrous ethanol and DBTL catalyst is (95-105): (1.3-1.7): (15-20): (0.04-0.06).

8. The roughening-free treating agent for PET mesh used in the shoemaking industry according to claim 6, characterized in that: The mixing and stirring is carried out at 35-40°C for 30-40 minutes; the temperature of each zone of the extrusion granulation twin-screw is set as zone 1: 75-80°C, zone 2: 85-90°C, zone 3: 95-100°C, zone 4: 105-110°C, and zones 5-8: 110-105°C.

9. A method for preparing a roughening-free treatment agent for PET mesh used in the shoemaking industry, characterized in that: The method for preparing the roughening-free treatment agent according to any one of claims 1 to 8 comprises the following steps: S1. Add hydroxyl-terminated polyester resin and silane-modified TPU to a reactor, add ethyl acetate and dimethyl carbonate, raise the temperature to 55-60°C, and stir to dissolve; add monoethyl fumarate, and react at 75-80°C with ultrasound assistance for 30-40 minutes; slowly add PDMS-g-acrylate dropwise, and simultaneously add initiator benzoyl peroxide, raise the temperature to 85-90°C, and react at ultrasound assistance for 50-60 minutes; S2. After the reaction system is cooled to 50-55° C., a premix of phosphite DHOP and antioxidant 168, ZrO2-CeO2, and N,N'-di(ethylhexyl)imidazoline are added in sequence. The temperature is controlled at 45-55° C. and stirred for 25-35 minutes to obtain a mixed solution. S3. Mix TCCA with acrylic resin and prepare microcapsules with a particle size of 10-15 μm by spray condensation method; add the mixed solution under low-speed stirring at 40-45° C., stir for 30-40 minutes, and filter to obtain a roughening-free treatment agent for PET mesh for the shoemaking industry.

10. The method for preparing a roughening-free treatment agent for PET mesh used in the shoemaking industry according to claim 9, characterized in that: The acrylate grafting rate in the PDMS-g-acrylate is 15%-20%; the power of the ultrasonic assistance is 800-1400W; the pore size of the filter screen is 180-240 mesh; and the low-speed stirring rate is 60-120 rpm.

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