High-stripping-force oil-proofing agent emulsion as well as preparation method and application thereof

Abstract

The invention relates to the technical field of oil-proofing agent emulsion production, in particular to a high-stripping-force oil-proofing agent emulsion and a preparation method and application thereof. Comprising the following raw materials in parts by mass: 32-35 parts of epoxidized soybean oil acrylate; 12 to 15 parts of amino polyether modified polysiloxane; 4.5 to 5 parts of 1H, 1H, 2H, 2H-perfluorohexyltriethoxysilane; 6-8 parts of a hyperbranched reinforcing agent; 4 to 5 parts of a nano modifier; 13 to 15 parts of a diluent; 2.5 to 3 parts of a photoinitiator; 1 to 1.2 parts of a stabilizer; and 33.5 to 35 parts of ethyl lactate. Through surface functionalization of the short-chain fluorosilane, network enhancement of the hyperbranched polymer and multifunctional integration of the core-shell nanoparticles, a low-toxicity, high-strength and light-transmitting synergistic system is constructed, and an oil-proofing agent solution considering performance and safety is provided for the field of 3D printing.

Description

Technical Field

[0001] The invention relates to the technical field of oil-proofing agent emulsion production, in particular to a high-peeling-force oil-proofing agent emulsion and a preparation method and application thereof. Background Art

[0002] The core environmental flaw of existing oil-proofing emulsions lies in their reliance on long-chain fluorinated compounds (C8PFAS). These substances, known as persistent organic pollutants (POPs), are prone to bioaccumulation and can cause toxic effects (such as endocrine disruption and immunotoxicity). EU REACH regulations have restricted the use of perfluorooctane sulfonic acid (PFOS) and its derivatives to below 1000 ppm, yet C8PFAS levels in traditional processes often exceed this limit by 3-5 times. This restriction directly risks raw material supply disruptions in sectors such as electronics manufacturing, healthcare, and 3D printing, particularly in 3D printing.

[0003] While traditional silicone materials (such as polydimethylsiloxane) possess low surface energy, weak intermolecular forces make segmental slippage a common problem during repeated peeling during 3D printing, leading to coating thickness loss exceeding 30% (after 200 cycles). In SLA printing, the adhesion between the resin and the coating can fluctuate by up to ±25%, causing tearing at the edges of the model. While common SiO2 fillers can improve wear resistance through physical reinforcement, they scatter >15% of 405nm UV light, resulting in insufficient curing of the base resin during LCD printing and layer thickness deviations exceeding ±10μm. While reducing filler dosage can increase transmittance to over 85%, abrasion resistance plummets to >3mg / 1000 cycles, failing to meet industrial-grade recyclability requirements. Furthermore, the interfacial bonding strength between traditional soluble support materials (such as PVA) and oil-repellent coatings is less than 0.05N / cm, and the coating peels off >35% upon contact with water, significantly increasing the risk of clogging the 3D printing nozzle. Summary of the Invention

[0004] In view of the above deficiencies in the prior art, the purpose of the present invention is to provide a high-peeling force oil-proof agent emulsion. Through the surface functionalization of short-chain fluorosilanes, network enhancement of hyperbranched polymers, and multifunctional integration of core-shell nanoparticles, a "low toxicity-high strength-light transmittance" synergistic system is constructed. It not only breaks through the environmental restrictions of long-chain fluorine, but also solves the contradiction between light transmittance and wear resistance through precise design at the molecular level, providing an oil-proof agent solution for the 3D printing field that takes into account both performance and safety.

[0005] Another object of the present invention is to provide a method for preparing a high-peeling-force oil-proofing agent emulsion, which has strong process compatibility, high quality stability, and greatly improved raw material utilization.

[0006] A third object of the present invention is to provide an application of a high-peeling-force oil-proofing agent emulsion for use in release films for digital light processing (DLP) printers; soluble or peelable support structures for stereolithography (SLA) printing; and translucent molding platforms for liquid crystal display (LCD) light-curing printers.

[0007] The present invention is achieved by adopting the following technical solutions: The high-peeling-force oil-proofing agent emulsion comprises the following raw materials in parts by mass: 32-35 parts of epoxy soybean oil acrylate; 12-15 parts of amino polyether-modified polysiloxane; 4.5-5 parts of 1H,1H,2H,2H-perfluorohexyltriethoxysilane; 6-8 parts of hyperbranched reinforcing agent; 4-5 parts of nano-modifier; 13-15 parts of diluent; 2.5-3 parts of photoinitiator; 1-1.2 parts of stabilizer; and 33.5-35 parts of ethyl lactate. The photoinitiators are TPO-L and ITX.

[0008] The hyperbranched enhancer is a hyperbranched polyester amine; the nano-modifier is hydrophobic nano-TiO2@SiO2 core-shell particles; the diluent is trimethylolpropane triacrylate (TMPTA); the photoinitiator is TPO-L photoinitiator and ITX photoinitiator, wherein the mass ratio of TPO-L to ITX is 4:1; the stabilizer is polyether-modified polydimethylsiloxane, preferably BYK-331.

[0009] The preparation method of the hydrophobic nano-TiO2@SiO2 core-shell particles is as follows: nano-TiO2 is added to an ethanol / water mixture (the volume ratio of alcohol to water is 9:1), ultrasonically treated (500W, 40kHz) for 1 hour, then 0.1M hydrochloric acid is added dropwise to adjust the pH to 3, ultrasonication is continued for 30 minutes, and then the mixture is transferred to a three-necked flask, placed in a water bath at 40°C, TEOS is added dropwise at a rate of 1 g / min, and after the addition is completed, the mixture is mechanically stirred (300rpm) at a constant temperature of 40°C for 24 hours, and then KH-570 is added, maintained at 40°C and stirred for 6 hours, centrifuged (8000rpm×15min), precipitated with ethanol, vacuum dried at 60°C for 4 hours, and then ground and sieved (400 mesh) in an agate mortar to obtain hydrophobic nano-TiO2@SiO2 core-shell particles, wherein the mass ratio of nano-TiO2, TEOS and KH-570 is: 20:4:1.

[0010] The preparation method of the hyperbranched polyesteramine comprises: controlling the temperature of ethylenediamine at 42-45°C under nitrogen protection, adding methyl acrylate dropwise (dropping rate 1 g / min), then keeping the temperature for reaction for 12-14 hours, adding diethanolamine, raising the temperature to 100-110°C, and reflux reaction for 8-10 hours (closed system), starting a vacuum pump (-0.1 MPa) to remove methanol byproducts (the receiving bottle is placed in an ice bath), then dissolving the product in deionized water, placing it in a dialysis bag (MWCO 3000Da), dialyzing with flowing deionized water for 48 hours, and then freeze-drying to obtain the hyperbranched polyesteramine, wherein the molar ratio of methyl acrylate, ethylenediamine, and diethanolamine is 12:5:2.

[0011] The method for preparing the high-peeling-force oil-proofing agent emulsion comprises the following steps: (1) Add the nano-modifier to ethyl lactate and ultrasonicate for 30-40 min; then transfer to a high-pressure homogenizer and cycle 3 times at 150 MPa pressure with an outlet temperature of ≤40°C to obtain a nano-dispersion liquid; (2) Under nitrogen protection, the following ingredients were added to the reactor in sequence: pre-dehydrated epoxy soybean oil acrylate, amino polyether modified polysiloxane (APSi), hyperbranched enhancer, and diluent. The temperature was kept constant at 58-60°C and mechanically stirred for 30-40 minutes. (3) Add nanodispersion, raise the temperature to 75°C, and continue stirring for 1-1.5 hours; (4) Lower the temperature to 60-70°C, add the pretreated 1H,1H,2H,2H-perfluorohexyltriethoxysilane dropwise, and keep warm for 30-40 minutes; (5) Add polyether-modified polydimethylsiloxane, add ITX photoinitiator in a dark state, and stir for 20-25 minutes; (6) Cool down to 30-35°C, add TPO-L photoinitiator, and stir until completely dissolved; (7) Add the remaining ethyl lactate and filter through a 0.2 μm PTFE membrane to obtain a high-peeling-force oil-proof agent emulsion.

[0012] In the step (1), the nano-modifier is hydrophobic nano-TiO2@SiO2 core-shell particles, the mass ratio of the nano-modifier to ethyl lactate is 1:2, and the ultrasonic treatment is carried out at 40kHz and 500W for 30-40min; in the step (2), the stirring speed is 300rpm; in the step (4), the insulation temperature is controlled at 78-82°C; in the step (1), the mass ratio of the nano-modifier to ethyl lactate is 1:2.

[0013] The treatment method of the pre-dehydrated epoxidized soybean oil acrylate (ESOA) is as follows: adding the epoxidized soybean oil acrylate to a vacuum reactor, adding 200-300 ppm of p-hydroxyanisole, evacuating to -0.1 MPa, heating to 50-55° C., stirring and dehydrating for 2-2.5 hours, and cooling to 30° C. after the moisture content is ≤200 ppm; the hyperbranched enhancer is a hyperbranched polyesteramine solution, and the preparation method thereof is as follows: adding the hyperbranched polyesteramine to ethyl lactate and bubbling with N2 for 1-1.5 hours.

[0014] The pretreatment method of 1H,1H,2H,2H-perfluorohexyltriethoxysilane is as follows: 1H,1H,2H,2H-perfluorohexyltriethoxysilane is sealed and oscillated with 4Å molecular sieve for 22-24 hours, and filtered through a 0.45μm PTFE filter membrane to obtain a moisture content of ≤50ppm.

[0015] The treatment process of trimethylolpropane triacrylate (TMPTA) is as follows: TMPTA passes through an alkaline alumina column (column height: diameter = 5:1) at a flow rate of 1BV / h, and the collected liquid is tested for MEHQ ≤ 10ppm.

[0016] The high-peeling-force oil-proofing agent emulsion is used for release films of digital light processing (DLP) printers; soluble or peelable support structures of stereolithography (SLA) printing; and translucent molding platforms of liquid crystal display (LCD) light-curing printers.

[0017] Dynamic migration and directed assembly: During the initial UV curing phase, short-chain C6 fluorosilane (1H,1H,2H,2H-perfluorohexyltriethoxysilane) migrates to the coating surface due to molecular thermal motion. Its -CF3 groups form a gradient structure with the C18 alkyl chains of ESOA through van der Waals forces, ultimately forming a fluorine-rich layer approximately 50-80 nm thick on the coating surface. This fluorine-rich layer has a surface energy as low as 10.8 mN / m, 25% lower than traditional C8PFAS coatings. The interfacial tension difference with 3D printing resins (such as photosensitive acrylates) is greater than 20 mN / m, significantly reducing the adhesion work of the resin to the coating, reducing the peel force from 0.22 N / cm to 0.09 N / cm (a 60% reduction).

[0018] The branched structure of hyperbranched polyesteramine (HBP) contains a high density of amino groups (amine content 5.6 mmol / g), which immobilize fluorine through hydrogen bonding or condensation reactions, forming a "core-shell" cross-linked network. This network secures fluorine within the coating, slowing its migration and loss, significantly reducing the decay rate of fluorine content after 500 cycles.

[0019] The hydrophobic nano-TiO2@SiO2 core-shell particles are bonded to the HBP amino groups via a KH-570 silane coupling agent (KH-570 hydrolyzes and condenses with the SiO2 shell, and its methacryloyloxy groups react with the HBP amino groups), forming a "rigid node." The TiO2 core absorbs 300-400nm UV light, minimizing interference with resin curing (405nm transmittance >90%). The hydroxyl groups in the SiO2 shell form hydrogen bonds with the coating matrix, improving abrasion resistance to 0.8mg / 1000 strokes (compared to 3.2mg / 1000 strokes for conventional SiO2 fillers).

[0020] Dual-initiator spatiotemporal synergistic effects: Rapid surface curing: TPO-L (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) absorbs 385nm UV light (molar extinction coefficient ε≈250 L / mol·cm), cleaving to generate benzoyl radicals (·PhCO), which initiate rapid polymerization of the acrylate double bonds of ESOA. TPO-L, a Type I initiator (homolytic), achieves a surface cure rate >80mJ / cm², forming a high-crosslink density, wear-resistant layer (pencil hardness ≥3H). Deep, progressive crosslinking: ITX (2-isopropylthioxanthone), a Type II initiator, absorbs 405nm light (ε≈5000 L / mol·cm), generating excited ITX* states that abstract hydrogen atoms from the tertiary amino group (—N(CH3)H) of HBP, generating HBP· radicals (reduced state). HBP· attacks TMPTA: HBP· reacts with the triacrylate groups of TMPTA to form long-chain free radicals (TMPTA·), which gradually diffuse deep into the ESOA layer and initiate crosslinking. ITX absorbs 405nm light to generate excited ITX* states, which abstract hydrogen atoms from the tertiary amino groups of the hyperbranched polyesteramine (HBP) to form HBP· free radicals, which in turn initiate polymerization of the acrylate groups of TMPTA and ESOA, achieving deep crosslinking. TMPTA's trifunctional structure connects HBP (amino groups) with ESOA (acrylates), forming crosslinking points throughout the network (see below): HBP-NH•+CH2=CH-COO-TMPTA→HBP-NH-CH2-CH•-COO-TMPTA; TMPTA•+ESOA→TMPTA-ESOA•.

[0021] Compared with the prior art, the present invention has the following beneficial effects: (1) The oil-proofing agent emulsion prepared by the present invention has a peeling force as low as 0.08-0.12 N / cm, a cycle life of more than 430 times (due to the surface enrichment of short-chain C6 fluorosilane and the anchoring of fluorine elements in the HBP three-dimensional network, which delays migration and loss), a good balance between light transmittance and wear resistance (solving the contradiction of the traditional solution of "reducing fillers for increasing transmittance and increasing fillers for wear resistance"), and is environmentally friendly (cytotoxicity level 0, meeting medical-grade application requirements).

[0022] (2) The preparation method of the present invention has strong process compatibility. The solvent-based emulsion is suitable for spray coating / spin coating / gravure coating. The solid content of 52±1% ensures leveling. The quality stability is high. The gradient temperature control and dripping of fluorosilane inhibits self-polymerization. The free monomer content is less than 0.3%. The raw material utilization rate is greatly improved. The qualified rate of high-pressure homogenization dispersion of nanoparticles is 100%, and the loss rate is reduced by 40%.

[0023] (3) The oil-proofing agent emulsion prepared by the present invention can be used as a release film for a digital light processing (DLP) printer; a soluble or peelable support structure for stereolithography (SLA) printing; and a light-transmitting molding platform for a liquid crystal display (LCD) light-curing printer. DETAILED DESCRIPTION

[0024] In order to make the purpose and technical solution of the present invention more clear, the present invention is further described in detail below.

[0025] Manufacturer: Epoxidized soybean oil acrylate (ESOA): commercially available from Sartomer (Guangzhou) Chemical Co., Ltd. 1H,1H,2H,2H-Perfluorohexyltriethoxysilane (short-chain C6 fluorosilane): commercially available from Daikin Fluorochemicals (China) Co., Ltd. Trimethylolpropane triacrylate (TMPTA): allnex Resins (China) Co., Ltd.; Polyether modified polydimethylsiloxane (stabilizer BYK-331): BYK Chemical Co., Ltd., Germany; Bisphenol A epoxy acrylate CN9010NS: commercially available product from Sartomer (Guangzhou) Chemical Co., Ltd. Polyamide resin Versamid-125: Evonik Specialty Chemicals (Shanghai) Co., Ltd. Hydrophobic fumed silica AEROSIL-R812: Evonik Specialty Chemicals (Shanghai) Co., Ltd.

[0026] Test method: Peel force: tested using a universal material testing machine according to ASTM D3330, with a peel speed of 5 mm / s, unit: N / cm.

[0027] Contact angle: measured by contact angle meter with deionized water as the medium according to ASTM D7490.

[0028] UV transmittance (405nm): tested by UV spectrophotometer, refer to GB / T2410-2008 standard.

[0029] Abrasion Resistance: Taber abrasion tester, 500g load, results expressed in mg / 1000, in accordance with ASTM D4060-2019. Tested at a dry film thickness of 10μm.

[0030] Cytotoxicity: The MTT assay (L929 cells) was used to evaluate the cytotoxicity according to ISO 10993-5:2009. The results were expressed as toxicity levels.

[0031] Surface energy: calculated by Owens-Wendt equation according to GB / T24368-2009 standard.

[0032] Processing methods and preparation methods of some raw materials: The preparation method of hydrophobic nano-TiO2@SiO2 core-shell particles is as follows: nano-TiO2 is added to an ethanol / water mixture (the volume ratio of alcohol to water is 9:1), ultrasonically treated (500W, 40kHz) for 1h, then 0.1M hydrochloric acid is added dropwise to adjust the pH to 3, and ultrasonication is continued for 30min. Then, the mixture is transferred to a three-necked flask and placed in a water bath at 40°C. TEOS is added dropwise at a rate of 1g / min. After the addition is completed, the mixture is mechanically stirred (300rpm) at a constant temperature of 40°C for 24h, and then KH-570 is added. The mixture is stirred at 40°C for 6h, centrifuged (8000rpm×15min), the precipitate is washed with ethanol, and vacuum dried at 60°C for 4h. Then, the mixture is ground and sieved (400 mesh) in an agate mortar to obtain hydrophobic nano-TiO2@SiO2 core-shell particles, wherein the mass ratio of nano-TiO2, TEOS and KH-570 is: 20:4:1. Shell thickness: 8-10nm; contact angle: 152±3°; UV shielding rate: 405nm transmittance >92%.

[0033] The hyperbranched polyesteramine was prepared by the following method: Under nitrogen, ethylenediamine was maintained at 45°C, and methyl acrylate was added dropwise (at a rate of 1 g / min). The reaction was then incubated for 12 hours, followed by the addition of diethanolamine. The temperature was raised to 110°C and the reaction was refluxed for 10 hours. A vacuum pump (-0.1 MPa) was then used to remove the methanol byproduct (the receiving flask was kept in an ice bath). The product was then dissolved in deionized water, placed in a dialysis bag (MWCO 3000 Da), and dialyzed against flowing deionized water for 48 hours before freeze-drying to obtain the hyperbranched polyesteramine. The molar ratio of methyl acrylate, ethylenediamine, and diethanolamine was 12:5:2. The degree of branching was 0.82, the amine value was 5.6 mmol / g, and the molecular weight was Mn = 3200.

[0034] The treatment method for pre-dehydrated epoxy soybean oil acrylate is as follows: take epoxy soybean oil acrylate and add it into a vacuum reactor, add 250ppm of p-hydroxyanisole, evacuate to -0.1MPa, heat to 53°C, stir and dehydrate for 2.5h, and then cool to 30°C after the moisture content reaches 200ppm; the preparation method of hyperbranched polyesteramine solution is as follows: add hyperbranched polyesteramine to ethyl lactate and bubble N2 for 1h.

[0035] The pretreatment method of 1H,1H,2H,2H-perfluorohexyltriethoxysilane is as follows: take 1H,1H,2H,2H-perfluorohexyltriethoxysilane and 4Å molecular sieve, seal and oscillate for 24 hours, filter through 0.45μm PTFE filter membrane, and the moisture content is ≤50ppm.

[0036] The treatment process of trimethylolpropane triacrylate (TMPTA) is as follows: TMPTA passes through an alkaline alumina column (column height: diameter = 5:1) at a flow rate of 1BV / h, and the collected liquid is tested for MEHQ ≤ 10ppm.

[0037] Example 1 A high-peel strength oil-proofing emulsion comprises the following raw materials by weight: 35 parts epoxy soybean oil acrylate (ESOA); 15 parts amino polyether-modified polysiloxane (APSi); 5 parts 1H,1H,2H,2H-perfluorohexyltriethoxysilane; 8 parts hyperbranched polyesteramine; 5 parts hydrophobic nano-TiO2@SiO2 core-shell particles; 15 parts trimethylolpropane triacrylate; 2.5 parts photoinitiator; 1 part BYK-331; and 35 parts ethyl lactate. The photoinitiators are TPO-L and ITX, with a TPO-L to ITX weight ratio of 4:1.

[0038] The preparation method of the high-peeling-force oil-proof agent emulsion comprises the following steps: (1) Add hydrophobic nano-TiO2@SiO2 core-shell particles to ethyl lactate and ultrasonicate for 40 min; then transfer to a high-pressure homogenizer, cycle 3 times at 150 MPa pressure, and set the outlet temperature at 40°C to obtain a nano-dispersion liquid; (2) Under nitrogen protection, the following ingredients were added to the reactor in sequence: pre-dehydrated epoxy soybean oil acrylate, amino polyether modified polysiloxane, hyperbranched polyesteramine solution, and trimethylolpropane triacrylate. The temperature was kept constant at 60°C and mechanically stirred for 40 min. (3) Add nanodispersion, raise the temperature to 75°C, and continue stirring for 1.5 hours; (4) Lower the temperature to 60°C, add pretreated 1H,1H,2H,2H-perfluorohexyltriethoxysilane dropwise, and keep warm for 40 minutes; (5) Add polyether-modified polydimethylsiloxane, add ITX photoinitiator in a dark state, and stir for 25 minutes; (6) Cool down to 30°C, add TPO-L photoinitiator, and stir until completely dissolved; (7) Add the remaining ethyl lactate and filter through a 0.2 μm PTFE membrane to obtain a high-peeling-force oil-proof agent emulsion.

[0039] In step (1), the mass ratio of hydrophobic nano-TiO2@SiO2 core-shell particles to ethyl lactate is 1:2, and ultrasonic treatment is performed at 40 kHz and 500 W for 40 min; in step (2), the stirring speed is 300 rpm; in step (4), the insulation temperature is controlled at 82°C; in step (1), the mass ratio of nano-modifier to ethyl lactate is 1:2.

[0040] Example 2 A high-peel strength oil-proofing emulsion comprises the following raw materials in parts by weight: 35 parts epoxy soybean oil acrylate; 12 parts amino polyether-modified polysiloxane; 4.5 parts 1H,1H,2H,2H-perfluorohexyltriethoxysilane; 7 parts hyperbranched polyesteramine; 4 parts hydrophobic nano-TiO2@SiO2 core-shell particles; 14 parts trimethylolpropane triacrylate; 2.5 parts photoinitiator; 1.2 parts BYK-331; and 33.5 parts ethyl lactate. The photoinitiators are TPO-L and ITX, with a TPO-L to ITX weight ratio of 4:1.

[0041] The preparation method of the high-peeling-force oil-proof agent emulsion comprises the following steps: (1) Add hydrophobic nano-TiO2@SiO2 core-shell particles to ethyl lactate and ultrasonicate for 30 min; then transfer to a high-pressure homogenizer, cycle 3 times at 150 MPa pressure, and set the outlet temperature at 40°C to obtain a nano-dispersion liquid; (2) Under nitrogen protection, the following ingredients were added to the reactor in sequence: pre-dehydrated epoxy soybean oil acrylate, amino polyether modified polysiloxane, hyperbranched polyesteramine solution, and trimethylolpropane triacrylate. The temperature was kept constant at 58°C and mechanically stirred for 30 min. (3) Add nanodispersion, raise the temperature to 75°C, and continue stirring for 1 hour; (4) Lower the temperature to 70°C, add the pretreated 1H,1H,2H,2H-perfluorohexyltriethoxysilane dropwise, and keep warm for 30 minutes; (5) Add polyether-modified polydimethylsiloxane, add ITX photoinitiator in a dark state, and stir for 20 minutes; (6) Cool down to 32°C, add TPO-L photoinitiator, and stir until completely dissolved; (7) Add the remaining ethyl lactate and filter through a 0.2 μm PTFE membrane to obtain a high-peeling-force oil-proof agent emulsion.

[0042] In step (1), the mass ratio of hydrophobic nano-TiO2@SiO2 core-shell particles to ethyl lactate is 1:2, and ultrasonic treatment is performed at 40 kHz and 500 W for 30 min; in step (2), the stirring speed is 300 rpm; in step (4), the insulation temperature is controlled at 78°C; in step (1), the mass ratio of nano-modifier to ethyl lactate is 1:2.

[0043] Example 3 A high-peel strength oil-proofing emulsion comprises the following raw materials in parts by weight: 32 parts epoxy soybean oil acrylate (ESOA); 15 parts amino polyether-modified polysiloxane (APSi); 4.5 parts 1H,1H,2H,2H-perfluorohexyltriethoxysilane; 6 parts hyperbranched polyesteramine; 5 parts hydrophobic nano-TiO2@SiO2 core-shell particles; 13 parts trimethylolpropane triacrylate; 3 parts photoinitiator; 1 part BYK-331; and 35 parts ethyl lactate. The photoinitiators are TPO-L and ITX, with a TPO-L to ITX weight ratio of 4:1.

[0044] The preparation method of the high-peeling-force oil-proof agent emulsion comprises the following steps: (1) Add hydrophobic nano-TiO2@SiO2 core-shell particles to ethyl lactate and ultrasonicate for 35 min; then transfer to a high-pressure homogenizer, cycle 3 times at 150 MPa pressure, and set the outlet temperature at 40°C to obtain a nano-dispersion liquid; (2) Under nitrogen protection, the following ingredients were added to the reactor in sequence: pre-dehydrated epoxy soybean oil acrylate, amino polyether modified polysiloxane, hyperbranched polyesteramine solution, and trimethylolpropane triacrylate. The temperature was kept constant at 60°C and mechanically stirred for 40 min. (3) Add nanodispersion, raise the temperature to 75°C, and continue stirring for 1.5 hours; (4) Lower the temperature to 65°C, add pretreated 1H,1H,2H,2H-perfluorohexyltriethoxysilane dropwise, and keep warm for 35 minutes; (5) Add polyether-modified polydimethylsiloxane, add ITX photoinitiator in a dark state, and stir for 20 minutes; (6) Cool down to 35°C, add TPO-L photoinitiator, and stir until completely dissolved; (7) Add the remaining ethyl lactate and filter through a 0.2 μm PTFE membrane to obtain a high-peeling-force oil-proof agent emulsion.

[0045] In step (1), the mass ratio of hydrophobic nano-TiO2@SiO2 core-shell particles to ethyl lactate is 1:2, and ultrasonic treatment is performed at 40 kHz and 500 W for 30 min; in step (2), the stirring speed is 300 rpm; in step (4), the insulation temperature is controlled at 80°C; in step (1), the mass ratio of nano-modifier to ethyl lactate is 1:2.

[0046] Comparative Example 1 Compared with Example 1, the difference is that the epoxy soybean oil acrylate is replaced by an equal amount of bisphenol A epoxy acrylate CN9010NS.

[0047] Comparative Example 2 Compared with Example 1, the difference is that no short-chain fluorosilane is used, and the amount of amino polyether modified polysiloxane used is 20 parts.

[0048] Comparative Example 3 Compared with Example 1, the difference is that the hyperbranched polyester amine is replaced by an equal amount of polyamide resin Versamid-125.

[0049] Comparative Example 4 Compared with Example 1, the difference is that the hydrophobic nano-TiO2@SiO2 core-shell particles are replaced by an equal amount of hydrophobic fumed silica AEROSIL-R812.

[0050] Comparative Example 5 Compared with Example 1, the difference is that TPO-L+ITX is replaced by an equal amount of TPO-L.

[0051] The test data of Examples 1-3 and Comparative Examples 1-5 are shown in Table 1.

[0052] Table 1: Test data of Examples 1-3 and Comparative Examples 1-5

[0053] Table 1 shows that the peel forces of Examples 1-3 range from 0.08 to 0.12 N / cm, significantly lower than those of Comparative Examples 1-5 (0.13 to 0.21 N / cm). Comparative Example 1, in which ESOA is replaced with bisphenol A epoxy acrylate, exhibits increased peel force due to disordered alkyl chains. Comparative Example 2, lacking fluorosilane and possessing a high surface energy (22.3 mN / m), exhibits the highest peel force. The Examples exhibit contact angles >105° and surface energies <14.2 mN / m. Comparative Example 4 (replaced with hydrophobic SiO2) exhibits a contact angle of 107.8° but a transmittance of only 83.6%, demonstrating the core-shell structure's optimized light transmittance. The Examples exhibit cycle life >350 cycles and abrasion resistance <1.5 mg / 1000 cycles. Comparative Example 3 (replacing HBP with polyamide resin) exhibits a cycle life of 270 cycles and abrasion resistance of 4.7 mg / 1000 cycles, demonstrating the critical role of the hyperbranched structure in network stability. The cytotoxicity of all Examples is grade 0.

[0054] Application Example 1 The oil repellent emulsion obtained in Example 1 was used for a release film of a digital light processing (DLP) printer.

[0055] First, treat the substrate: corona treatment (8kW, 52-55 dynes) of 125μm PET film, then ultrasonic cleaning with ethanol and drying at 60℃.

[0056] Then apply the oil-proof agent emulsion using a micro-gravure roller (200 mesh) with a wet film thickness of 10 μm.

[0057] Pre-drying: 80℃ hot air drying for 1 min (conveyor belt speed 2m / min).

[0058] UV curing: 385nm LED light source (100mW / cm²), cumulative energy 800mJ / cm².

[0059] Post-curing: 60℃ hot air in nitrogen atmosphere for 30min.

[0060] Application Example 2 The oil repellent emulsion obtained in Example 1 is used for a soluble or peelable support structure printed by stereolithography (SLA).

[0061] First, the substrate was activated: BASFUltrafuse® PVA particles were vacuum dried at 60°C for 4 hours and then treated with oxygen plasma for 5 minutes (100W).

[0062] Spraying: air spraying (0.3mm nozzle, 0.2MPa), dry film thickness 4μm.

[0063] Curing: 395nm UV irradiation (600mJ / cm²), no heat drying.

[0064] Application Example 3 The oil-proofing agent emulsion obtained in Example 1 was used for a light-transmitting molding platform of a liquid crystal display (LCD) light-curing printer.

[0065] The substrate was cleaned first: tempered glass (5 mm) was first cleaned with argon plasma (300 W, 5 min) and then wiped with acetone.

[0066] Spin coating: 1500 rpm for 30 seconds, dry film thickness 2.5 μm.

[0067] Curing: 405nm LED (120mW / cm²), cumulative energy 1000mJ / cm².

[0068] Comparative Application Example 1 The difference from Application Example 1 is that the oil-proofing agent emulsion obtained in Example 1 is replaced by the oil-proofing agent emulsion obtained in Comparative Example 1.

[0069] Application Comparative Example 2 The difference from Application Example 1 is that the oil-proofing agent emulsion obtained in Example 1 is replaced by the oil-proofing agent emulsion obtained in Comparative Example 2.

[0070] Application Comparative Example 3 The difference from Application Example 1 is that the oil-proofing agent emulsion obtained in Example 1 is replaced by the oil-proofing agent emulsion obtained in Comparative Example 4.

[0071] Comparative Application Example 4 The difference from Application Example 2 is that the oil-proofing agent emulsion obtained in Example 1 is replaced by the oil-proofing agent emulsion obtained in Comparative Example 3.

[0072] Application Comparative Example 5 The difference from Application Example 2 is that the oil-proofing agent emulsion obtained in Example 1 is replaced by the oil-proofing agent emulsion obtained in Comparative Example 5.

[0073] Application Comparative Example 6 The difference from Application Example 3 is that the oil-proofing agent emulsion obtained in Example 1 is replaced by the oil-proofing agent emulsion obtained in Comparative Example 2.

[0074] Application Comparative Example 7 The difference from Application Example 3 is that the oil-proofing agent emulsion obtained in Example 1 is replaced by the oil-proofing agent emulsion obtained in Comparative Example 4.

[0075] The test data of Application Example 1 and Application Comparative Examples 1-3 are shown in Table 2.

[0076] Table 2: Test data of application example 1 and application comparative examples 1-3

[0077] As shown in Table 2, the peeling force of Comparative Example 1 increased by 89% due to disordered alkyl chains, and the residue exceeded the standard. The transmittance of Comparative Example 3 did not meet the standard due to severe light scattering, and the lifespan decreased by 52%.

[0078] The test data of Application Example 2 and Application Comparative Examples 4-5 are shown in Table 3.

[0079] Table 3: Test data of application example 2 and application comparative examples 4-5

[0080] As shown in Table 3, the coating shedding rate increased in Comparative Example 4 due to the lack of three-dimensional network anchoring, which caused the nanoparticles to fall off. The removal force in Comparative Example 5 still exceeded the standard due to insufficient deep curing.

[0081] The test data of Application Example 3 and Application Comparative Examples 6-7 are shown in Table 4.

[0082] Table 4: Test data of application example 3 and application comparative examples 6-7

[0083] As shown in Table 4, the application of comparative example 6 has a high surface energy (22.3 mN / m) and the resin impregnates the glass, resulting in a high first-layer peeling failure rate; the application of comparative example 7 has poor local curing due to the lack of uniform light transmission due to the scattering of ultraviolet rays by ordinary SiO2.

Claims

1. A high peeling force oil repellent emulsion, characterized in that: The invention comprises the following raw materials in parts by weight: 32-35 parts of epoxy soybean oil acrylate; 12-15 parts of amino polyether modified polysiloxane; 4.5-5 parts of 1H,1H,2H,2H-perfluorohexyltriethoxysilane; 6-8 parts of hyperbranched reinforcing agent; and 4-5 parts of nano-modifier. Diluent: 13-15 parts; Photoinitiator: 2.5-3 parts; Stabilizer: 1-1.2 parts; Ethyl lactate: 33.5-35 parts; Photoinitiators are TPO-L and ITX.

2. The high peeling force oil repellent emulsion according to claim 1, characterized in that: The hyperbranched enhancer is a hyperbranched polyester amine; the nano-modifier is a hydrophobic nano-TiO2@SiO2 core-shell particle; the diluent is trimethylolpropane triacrylate; the mass ratio of TPO-L to ITX is 4:1; and the stabilizer is polyether-modified polydimethylsiloxane.

3. The high peeling force oil repellent emulsion according to claim 2, characterized in that: The preparation method of the hydrophobic nano-TiO2@SiO2 core-shell particles is as follows: nano-TiO2 is added to an ethanol / water mixture, subjected to ultrasonic treatment, and then hydrochloric acid is added dropwise to adjust the pH to 3. The mixture is then placed in a water bath at 40°C and TEOS is added dropwise. After the addition is complete, the mixture is stirred, and then KH-570 is added and continued to be stirred. After centrifugal separation, washing and precipitation, and vacuum drying, the hydrophobic nano-TiO2@SiO2 core-shell particles are obtained, wherein the mass ratio of nano-TiO2, TEOS, and KH-570 is 20:4:

1.

4. The high peeling force oil repellent emulsion according to claim 2, characterized in that: The preparation method of the hyperbranched polyesteramine comprises the following steps: under nitrogen protection, controlling the temperature of ethylenediamine at 42-45° C., adding methyl acrylate dropwise, then keeping the temperature for reaction for 12-14 hours, adding diethanolamine, raising the temperature to 100-110° C., reflux reaction for 8-10 hours, starting a vacuum pump to remove methanol byproducts, dissolving the product in deionized water, dialyzing, and then freeze-drying to obtain the hyperbranched polyesteramine, wherein the molar ratio of methyl acrylate, ethylenediamine, and diethanolamine is 12:5:

2.

5. A method for preparing the high-peeling-force oil-proofing agent emulsion according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) Add the nano-modifier to ethyl lactate and ultrasonicate for 30-40 min; then transfer to a high-pressure homogenizer and cycle 3 times at 150 MPa pressure with an outlet temperature of ≤40°C to obtain a nano-dispersion liquid; (2) Under nitrogen protection, the following ingredients were added to the reactor in sequence: pre-dehydrated epoxy soybean oil acrylate, amino polyether modified polysiloxane, hyperbranched enhancer, and diluent. The mixture was kept at a constant temperature of 58-60°C and mechanically stirred for 30-40 minutes. (3) Add nanodispersion, raise the temperature to 75°C, and continue stirring for 1-1.5 hours; (4) Lower the temperature to 60-70°C, add the pretreated 1H,1H,2H,2H-perfluorohexyltriethoxysilane dropwise, and keep warm for 30-40 minutes; (5) Add polyether-modified polydimethylsiloxane, add ITX photoinitiator in a dark state, and stir for 20-25 minutes; (6) Cool down to 30-35°C, add TPO-L photoinitiator, and stir until completely dissolved; (7) Add the remaining ethyl lactate and filter through a 0.2 μm PTFE membrane to obtain a high-peeling-force oil-proof agent emulsion.

6. The method for preparing the high-peeling-force oil-proofing agent emulsion according to claim 5, characterized in that: In the step (1), the nano-modifier is hydrophobic nano-TiO2@SiO2 core-shell particles, the mass ratio of the nano-modifier to ethyl lactate is 1:2, and the ultrasonic treatment is carried out at 40kHz and 500W for 30-40min; in the step (2), the stirring speed is 300rpm; in the step (4), the insulation temperature is controlled at 78-82°C; in the step (1), the mass ratio of the nano-modifier to ethyl lactate is 1:

2.

7. The method for preparing the high-peeling-force oil-proofing agent emulsion according to claim 5, characterized in that: The treatment method of the pre-dehydrated epoxy soybean oil acrylate is as follows: adding the epoxy soybean oil acrylate to a vacuum reactor, evacuating to -0.1 MPa, heating to 60-62°C, stirring and dehydrating for 2-2.5 hours, cooling to 40°C after the moisture content is ≤200 ppm; the hyperbranched enhancer is a hyperbranched polyesteramine solution, and its preparation method is as follows: adding the hyperbranched polyesteramine to ethyl lactate and bubbling with N2 for 1-1.5 hours.

8. The method for preparing the high-peeling-force oil-proofing agent emulsion according to claim 5, characterized in that: The pretreatment method of 1H,1H,2H,2H-perfluorohexyltriethoxysilane is as follows: 1H,1H,2H,2H-perfluorohexyltriethoxysilane is sealed and oscillated with 4Å molecular sieve for 22-24 hours, and filtered through a 0.45μm PTFE filter membrane to obtain a moisture content of ≤50ppm.

9. An application of the high peeling force oil repellent emulsion according to any one of claims 1 to 4, characterized in that: Release films for digital light processing printers; soluble or peelable support structures for stereolithography printing; and translucent molding platforms for LCD stereolithography printers.

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