High release force oil repellent emulsion, method of making and use thereof

Abstract

The application relates to the technical field of oil-proof agent emulsion production, in particular to high-peeling-force oil-proof agent emulsion and a preparation method and application thereof. The oil-proof agent emulsion comprises the following raw materials in mass fractions: 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-perfluorohexyl triethoxysilane; 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 application constructs a synergistic system of low toxicity, high strength and light transmission through surface functionalization of short-chain fluorosilane, network enhancement of hyperbranched polymer and multifunctional integration of core-shell nanoparticles, and provides an oil-proof agent solution scheme with performance and safety for the field of 3D printing.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil repellent emulsion production, in particular to a high-peeling-force oil repellent emulsion, a preparation method and application thereof. BACKGROUND

[0002] The core environmental protection defect of the existing oil repellent emulsion lies in the dependence on long-chain fluorinated compounds (C8PFAS), which are persistent organic pollutants (POPs) and are easy to accumulate in organisms and cause toxicity (such as endocrine disruption, immunotoxicity). The use of perfluorooctane sulfonic acid (PFOS) and its derivatives is limited to below 1000 ppm by the EU REACH regulation, while the content of C8PFAS in the traditional process often exceeds 3-5 times. This limitation directly leads to the risk of raw material supply in the fields of electronic manufacturing, medical treatment, 3D printing, etc., especially in 3D printing.

[0003] Although the traditional organic silicon material (such as polydimethylsiloxane) has the characteristics of low surface energy, the intermolecular chain force is weak, and the chain segment is easy to slip in the repeated peeling process of 3D printing, resulting in a coating thickness decay of >30% (after 200 cycles). In the SLA printing scene, the adhesion of the resin and the coating fluctuates by ±25%, causing the model edge to tear. Although the ordinary SiO2 filler can improve the wear resistance through physical enhancement, the scattering rate of 405 nm ultraviolet light is >15%, which causes the bottom resin to be not fully cured during LCD printing, and the layer thickness deviation is >±10 μm. Reducing the amount of filler can increase the light transmittance to more than 85%, but the wear resistance decreases to more than 3 mg / 1000 times, which cannot meet the industrial-level recycling requirements. In addition, the interfacial bonding force between the traditional soluble support material (such as PVA) and the oil repellent coating is <0.05 N / cm, and the coating shedding rate is >35% after encountering water, which significantly increases the risk of clogging the 3D printing nozzle. SUMMARY

[0004] In view of the above deficiencies in the prior art, the purpose of the present application is to provide a high-peeling-force oil repellent emulsion, which builds a synergistic system of "low toxicity-high strength-transparency" through surface functionalization of short-chain fluorosilane, network enhancement of hyperbranched polymer, and multifunctional integration of core-shell nanoparticles, not only breaking through the environmental protection limit of long-chain fluorine, but also solving the contradiction between light transmittance and wear resistance through precise design at the molecular level, and providing an oil repellent solution for the 3D printing field that takes into account performance and safety.

[0005] Another purpose of the present application is to provide a preparation method of a high-peeling-force oil repellent emulsion, which has strong process compatibility, high quality stability, and greatly improved raw material utilization rate.

[0006] A third object of the present application is to provide an application of a high-peeling-force oil-proof agent emulsion for a release film of a digital light processing (DLP) printer; a soluble or peelable support structure of stereolithography (SLA) printing; a light-transmitting molding platform of a liquid crystal display (LCD) light-curing printer.

[0007] The present application is implemented by using the following technical solutions:

[0008] The high-peeling-force oil-proof agent emulsion comprises the following raw materials in mass fractions: epoxy soybean oil acrylate: 32-35 parts; amino-polyether-modified polysiloxane: 12-15 parts; 1H, 1H, 2H, 2H-perfluorohexyl triethoxysilane: 4.5-5 parts; hyperbranched reinforcing agent: 6-8 parts; nano-modifier: 4-5 parts; diluent: 13-15 parts; photoinitiator: 2.5-3 parts; stabilizer: 1-1.2 parts; ethyl lactate: 33.5-35 parts; and the photoinitiator is TPO-L and ITX.

[0009] The hyperbranched reinforcing agent is a hyperbranched polyester amine; the nano-modifier is a hydrophobic nano TiO2@SiO2core-shell particle; 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; and the stabilizer is a polyether-modified polydimethylsiloxane, preferably BYK-331.

[0010] The preparation method of the hydrophobic nano TiO2@SiO2core-shell particle is as follows: nano TiO2 is added into an ethanol / water mixture (alcohol and water in a volume ratio of 9:1), ultrasonic treatment (500 W, 40 kHz) is performed for 1 h, then 0.1M hydrochloric acid is added dropwise to adjust pH=3, ultrasonic treatment is continued for 30 min, then it is transferred to a three-necked flask, water bath treatment is performed at 40℃, TEOS is added dropwise at a speed of 1 g / min, after the dropwise addition is completed, constant-temperature 40℃ mechanical stirring (300 rpm) is performed for 24 h, then KH-570 is added, stirring is maintained at 40℃ for 6 h, after centrifugal separation (8000 rpm x 15 min), ethanol cleaning of the precipitate, and 60℃ vacuum drying for 4 h, the hydrophobic nano TiO2@SiO2core-shell particle is obtained by grinding in a garnet mortar and sieving (400 mesh), wherein the mass ratio of nano TiO2, TEOS and KH-570 is 20:4:1.

[0011] The preparation method of the hyperbranched polyester amine is as follows: under nitrogen protection, ethylenediamine is controlled at a temperature of 42-45 DEG C, and methyl acrylate is added dropwise (drop rate 1 g / min), then the reaction is maintained for 12-14 h, diethanolamine is added, the temperature is raised to 100-110 DEG C, and the reaction is refluxed for 8-10 h (in a closed system), a vacuum pump is opened (-0.1 MPa) to remove the by-product methanol (the receiving bottle is ice-bathed), then the product is dissolved in deionized water, is loaded into a dialysis bag (MWCO 3000 Da), is dialyzed against flowing deionized water for 48 h, and is freeze-dried to obtain the hyperbranched polyester amine, wherein the molar ratio of methyl acrylate, ethylenediamine and diethanolamine is 12:5:2.

[0012] The preparation method of the high-peeling-force oil repellent emulsion comprises the following steps:

[0013] (1) The nano modifier is added to ethyl lactate, and is ultrasonically treated for 30-40 min; then it is transferred into a high-pressure homogenizer, is circulated for 3 times at a pressure of 150 MPa, and the outlet temperature is ≤40 DEG C to obtain a nano dispersion liquid;

[0014] (2) Under nitrogen protection, the following are sequentially added into a reaction kettle: pre-dehydrated epoxy soybean oil acrylate, amino-polyether-modified polysiloxane (APSi), hyperbranched reinforcing agent and diluent, and the temperature is kept at 58-60 DEG C, and mechanical stirring is carried out for 30-40 min;

[0015] (3) The nano dispersion liquid is added, the temperature is raised to 75 DEG C, and stirring is continued for 1-1.5 h;

[0016] (4) The temperature is lowered to 60-70 DEG C, the pretreated 1H, 1H, 2H, 2H-perfluorohexyl triethoxysilane is added dropwise, and the temperature is kept for 30-40 min;

[0017] (5) Polyether-modified polydimethylsiloxane is added, and ITX photoinitiator is added under light shielding, and stirring is carried out for 20-25 min;

[0018] (6) The temperature is lowered to 30-35 DEG C, TPO-L photoinitiator is added, and stirring is carried out until complete dissolution;

[0019] (7) The remaining ethyl lactate is added, and is filtered through a 0.2 mu m PTFE filter membrane to obtain the high-peeling-force oil repellent emulsion.

[0020] In the step (1), the nano modifier is hydrophobic nano TiO2@SiO2core-shell particles, and the mass ratio of the nano modifier to ethyl lactate is 1:2, and ultrasonic treatment is carried out for 30-40 min at 40 kHz and 500 W; in the step (2), the stirring speed is 300 rpm; in the step (4), the temperature is controlled at 78-82 DEG C; and in the step (1), the mass ratio of the nano modifier to ethyl lactate is 1:2.

[0021] The treatment method of the pre-dehydrated epoxy soybean oil acrylate (ESOA) is: take epoxy soybean oil acrylate and add 200-300 ppm of p-hydroxyanisole into a vacuum reaction kettle, vacuumize to -0.1 MPa, heat to 50-55°C, stir and dehydrate for 2-2.5 h, and then cool to 30°C after the moisture content is ≤200 ppm; the hyperbranched reinforcing agent is a hyperbranched polyester amine solution, and the preparation method thereof is: add hyperbranched polyester amine into ethyl lactate, and bubble with N2 for 1-1.5 h.

[0022] The pretreatment method of the 1H,1H,2H,2H-perfluorohexyltriethoxysilane is: take 1H,1H,2H,2H-perfluorohexyltriethoxysilane and 4 Å molecular sieves, seal and oscillate for 22-24 h, filter through a 0.45 μm PTFE filter membrane, and the moisture content is ≤50 ppm.

[0023] The treatment process of trimethylolpropane triacrylate (TMPTA) is: TMPTA passes through an alkaline alumina column (column height:diameter=5:1) at a flow rate of 1 BV / h, and the collection liquid is detected for MEHQ ≤10 ppm.

[0024] The application of the high-peel-release oil repellent emulsion is used for a release film of a digital light processing (DLP) printer, a soluble or peelable support structure of a stereolithography (SLA) printing, and a light-transmitting forming platform of a liquid crystal display (LCD) light-curing printer.

[0025] The dynamic migration-orientation assembly process: short-chain C6 fluorosilane (1H,1H,2H,2H-perfluorohexyltriethoxysilane) migrates to the coating surface due to molecular thermal motion at the initial stage of UV curing, and the -CF3 group forms a gradient arrangement structure with the C18 alkyl chain of ESOA through van der Waals force, and finally forms a fluorine-rich layer with a thickness of about 50-80 nm on the coating surface. The surface energy of the fluorine-rich layer is as low as 10.8 mN / m, which is reduced by 25% compared with the traditional C8 PFAS coating, and the interfacial tension difference with the 3D printing resin (such as photosensitive acrylate) is >20 mN / m, thereby significantly reducing the adhesion work of the resin to the coating, and reducing the peel force from 0.22 N / cm to 0.09 N / cm (a decrease of 60%).

[0026] The branched structure of the hyperbranched polyester amine (HBP) contains a high density of amino groups (amine value 5.6 mmol / g), which can fix fluorine elements through hydrogen bonding or condensation reaction, forming a “core-shell” cross-linked network. This network fixes fluorine elements inside the coating, delays their migration and loss, and greatly reduces the fluorine content decay rate after 500 cycles.

[0027] The hydrophobic nano TiO2@SiO2 core-shell particles are bonded with HBP amino through KH-570 silane coupling agent (KH-570 is condensed with the SiO2 shell layer after hydrolysis, and the methacryloyloxy thereof is reacted with the amino of HBP to form a "rigid node"). The TiO2 inner core absorbs 300-400 nm ultraviolet light, reduces the interference on the curing of the resin (the 405 nm light transmittance is greater than 90%), the hydroxyl groups of the SiO2 shell layer form hydrogen bonds with the coating matrix, and the wear resistance is improved to 0.8 mg / 1000 times (the traditional SiO2 filler is 3.2 mg / 1000 times).

[0028] Dual initiator space-time synergistic effect: surface rapid curing: TPO-L (2,4,6-trimethylbenzoyl-diphenyl phosphine oxide) absorbs 385 nm ultraviolet light (molar extinction coefficient ε≈250 L / mol·cm), and generates benzoyl free radicals (·PhCO) by cracking to initiate the rapid polymerization of the acrylate double bond of ESOA. TPO-L is a type I initiator (homolysis), and the surface curing rate is greater than 80 mJ / cm², forming a high cross-linking density wear-resistant layer (pencil hardness ≥ 3H). Progressive cross-linking in deep layer: ITX (2-isopropyl thioxanthone) as a type II initiator, absorbs 405 nm light (ε≈5000 L / mol·cm) to generate excited state ITX*, which abstracts hydrogen atoms from the tertiary amino group (—N(CH3)H) of HBP to generate HBP· free radicals (reduced state). HBP· attacks TMPTA: HBP· reacts with the triacrylate group of TMPTA to form a long-chain free radical (TMPTA·), which gradually diffuses to the deep layer to initiate the cross-linking of ESOA. ITX absorbs 405 nm light to generate excited state ITX*, which abstracts hydrogen atoms from the tertiary amino group of hyperbranched polyesteramine (HBP) to form HBP· free radicals, which further initiate the polymerization of the acrylate groups of TMPTA and ESOA, realizing deep layer cross-linking. The three functional groups of TMPTA connect HBP (amino) and ESOA (acrylate) to form cross-linking points throughout the network (as follows):

[0029] HBP-NH•+CH2=CH-COO-TMPTA→HBP-NH-CH2-CH•-COO-TMPTA;

[0030] TMPTA•+ESOA→TMPTA-ESOA•。

[0031] Compared with the prior art, the present application has the following advantages:

[0032] (1) The oil repellent emulsion prepared by the present application has a release force as low as 0.08-0.12 N / cm, a cycle life > 430 times (benefiting from short-chain C6 fluorosilane surface enrichment and HBP three-dimensional network anchoring fluorine element, delaying migration loss), light transmission-wear resistance balance (solving the contradiction of traditional solutions “increasing light transmission requires reducing fillers, and wear resistance requires increasing fillers”), and environmental friendliness (cell toxicity 0 level, meeting the requirements of medical grade applications).

[0033] (2) The preparation method of the present application has strong process compatibility, and the solvent type emulsion is suitable for spraying, spin coating and gravure coating, the solid content is 52±1% to ensure the leveling property; the mass stability is high, the gradient controlled temperature dropping fluorosilane inhibits self-polymerization, and the free monomer content is <0.3%; the raw material utilization rate is greatly improved, the nanoparticle high-pressure homogenization dispersion qualified rate is 100%, and the loss rate is reduced by 40%.

[0034] (3) The oil repellent emulsion prepared by the present application can be used for the release film of a digital light processing (DLP) printer, a soluble or peelable support structure for stereolithography (SLA) printing, and a light transmission forming platform for liquid crystal display (LCD) light curing printers. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical scheme of the present application clearer, the present application will be further described in detail below.

[0036] Manufacturer:

[0037] Epoxy soybean oil acrylate (ESOA): commercially available product of Shadoma (Guangzhou) Chemical Co., Ltd.;

[0038] 1H, 1H, 2H, 2H-perfluorohexyltriethoxysilane (short-chain C6 fluorosilane): commercially available product of Daikin Fluorochemicals (China) Co., Ltd.;

[0039] Trimethylolpropane triacrylate (TMPTA): Zannan Resin (China) Co., Ltd.;

[0040] Polyether-modified polydimethylsiloxane (stabilizer BYK-331): Germany BYK-Chemie Co., Ltd.;

[0041] Bisphenol A epoxy acrylate CN9010NS: commercially available product of Shadoma (Guangzhou) Chemical Co., Ltd.;

[0042] Polyamide resin Versamid-125: Evonik Special Chemicals (Shanghai) Co., Ltd.;

[0043] Hydrophobic fumed silica AEROSIL-R812: Evonik Special Chemicals (Shanghai) Co., Ltd.

[0044] Test method:

[0045] Peeling force: measured by universal material testing machine, according to the standard of ASTM D3330, peeling speed 5mm / s, unit N / cm.

[0046] Contact angle: measured by contact angle measuring instrument, with deionized water as medium, according to the standard of ASTM D7490.

[0047] UV transmittance (405nm): detected by ultraviolet spectrophotometer, according to the standard of GB / T2410-2008.

[0048] Wear resistance: tested by Taber abrasion tester, load 500g, result expressed in mg / 1000 times, in accordance with the standard of ASTM D4060-2019. Dry film thickness 10μm.

[0049] Cytotoxicity: evaluated by MTT method (L929 cells), according to the standard of ISO10993-5:2009, result expressed in toxicity grade.

[0050] Surface energy: calculated by Owens-Wendt equation, according to the standard of GB / T24368-2009.

[0051] Processing method and preparation method of part of raw materials:

[0052] The preparation method of hydrophobic nano TiO2@SiO2core-shell particles is as follows: nano TiO2 is added into ethanol / water mixed solution (alcohol, water volume ratio is 9:1), ultrasonic treatment (500W, 40kHz) for 1h, then 0.1M hydrochloric acid is added dropwise to adjust pH=3, continue to ultrasonic for 30min, then transfer to a three-necked flask, water bath at 40℃, drop TEOS at a speed of 1g / min, after drop completion, constant temperature 40℃ mechanical stirring (300rpm) for 24h, then add KH-570, maintain 40℃ stirring for 6h, centrifugal separation (8000rpm×15min), ethanol washing of precipitate, 60℃ vacuum drying for 4h, then grind with agate mortar and sieve (400 mesh), get hydrophobic nano TiO2@SiO2core-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°; ultraviolet shielding rate: 405nm transmittance >92%.

[0053] The preparation method of the hyperbranched polyester amine is as follows: under nitrogen protection, ethylenediamine is controlled at 45 ℃, and methyl acrylate is added dropwise (drop rate 1 g / min), then the reaction is kept for 12 h, diethanolamine is added, the temperature is raised to 110 ℃, and the reaction is kept for 10 h under reflux, then a vacuum pump (-0.1 MPa) is opened to remove the by-product methanol (the receiving bottle is ice-bathed), then the product is dissolved in deionized water, loaded into a dialysis bag (MWCO 3000 Da), dialyzed in flowing deionized water for 48 h, and then freeze-dried to obtain the hyperbranched polyester amine, wherein the molar ratio of methyl acrylate, ethylenediamine and diethanolamine is 12:5:2. The degree of branching is 0.82; the amine value is 5.6 mmol / g; and the molecular weight is Mn=3200.

[0054] The treatment method of the pre-dehydrated epoxy soybean oil acrylate is as follows: epoxy soybean oil acrylate is taken into a vacuum reaction kettle, 250 ppm of p-hydroxyanisole is added, vacuum is drawn to -0.1 MPa, the temperature is raised to 53 ℃, and the stirring dehydration is kept for 2.5 h, and then the temperature is lowered to 30 ℃ after the water content is 200 ppm; the preparation method of the hyperbranched polyester amine solution is as follows: the hyperbranched polyester amine is added into ethyl lactate, and N2 bubbling is kept for 1 h.

[0055] The pretreatment method of 1H,1H,2H,2H-perfluorohexyltriethoxysilane is as follows: 1H,1H,2H,2H-perfluorohexyltriethoxysilane is sealed and oscillated with 4 Å molecular sieves for 24 h, filtered through a 0.45 μm PTFE filter membrane, and the water content is ≤50 ppm.

[0056] The treatment process of trimethylolpropane triacrylate (TMPTA) is as follows: TMPTA is passed through an alkaline alumina column (column height:diameter=5:1) at a flow rate of 1 BV / h, and the collected liquid is detected for MEHQ ≤10 ppm.

[0057] Example 1

[0058] The high-peeling-force oil repellent emulsion comprises the following raw materials in mass fractions: epoxy soybean oil acrylate (ESOA): 35 parts; amino polyether modified polysiloxane (APSi): 15 parts; 1H,1H,2H,2H-perfluorohexyltriethoxysilane: 5 parts; hyperbranched polyester amine: 8 parts; hydrophobic nano TiO2@SiO2core-shell particles: 5 parts; trimethylolpropane triacrylate: 15 parts; photoinitiator: 2.5 parts; BYK-331: 1 part; and ethyl lactate: 35 parts. The photoinitiator is TPO-L and ITX, and the mass ratio of TPO-L to ITX is 4:1.

[0059] The preparation method of the high-peeling-force oil repellent emulsion comprises the following steps:

[0060] (1) Hydrophobic nano TiO2@SiO2core-shell particles were added to ethyl lactate, and ultrasonic treatment was performed for 40 min. Then, the mixture was transferred to a high-pressure homogenizer, and was subjected to 3 cycles of 150 MPa pressure, with an outlet temperature of 40℃, to obtain a nano dispersion liquid;

[0061] (2) Under nitrogen protection, a reaction kettle was sequentially added with pre-dehydrated epoxy soybean oil acrylate, amino-polyether-modified polysiloxane, hyperbranched polyester amine solution, and trimethylolpropane triacrylate, and was subjected to constant temperature at 60℃ for 40 min under mechanical stirring;

[0062] (3) The nano dispersion liquid was added, and the temperature was raised to 75℃, and stirring was continued for 1.5 h;

[0063] (4) The temperature was lowered to 60℃, and pretreated 1H,1H,2H,2H-perfluorohexyl triethoxysilane was added dropwise, and was kept at the temperature for 40 min;

[0064] (5) Polyether-modified polydimethylsiloxane was added, and ITX photoinitiator was added in the dark, and stirring was performed for 25 min;

[0065] (6) The temperature was lowered to 30℃, TPO-L photoinitiator was added, and stirring was performed until complete dissolution;

[0066] (7) The remaining ethyl lactate was added, and was filtered through a 0.2 μm PTFE filter membrane, to obtain a high-peeling power oil repellent emulsion.

[0067] In step (1), the mass ratio of hydrophobic nano TiO2@SiO2core-shell particles to ethyl lactate was 1:2, and ultrasonic treatment was performed for 40 min at 40 kHz and 500 W; in step (2), the stirring speed was 300 rpm; in step (4), the temperature was controlled at 82℃; and in step (1), the mass ratio of nano modifier to ethyl lactate was 1:2.

[0068] Example 2

[0069] The high-peeling power oil repellent emulsion included the following raw materials in mass fractions: epoxy soybean oil acrylate: 35 parts; amino-polyether-modified polysiloxane: 12 parts; 1H,1H,2H,2H-perfluorohexyl triethoxysilane: 4.5 parts; hyperbranched polyester amine: 7 parts; hydrophobic nano TiO2@SiO2core-shell particles: 4 parts; trimethylolpropane triacrylate: 14 parts; photoinitiator: 2.5 parts; BYK-331: 1.2 parts; and ethyl lactate: 33.5 parts. The photoinitiator was TPO-L and ITX, and the mass ratio of TPO-L to ITX was 4:1.

[0070] The preparation method of the high-peeling power oil repellent emulsion included the following steps:

[0071] (1) Hydrophobic nano TiO2@SiO2core-shell particles were added to ethyl lactate and ultrasonically treated for 30 min; then transferred into a high-pressure homogenizer, and subjected to 3 cycles of 150 MPa pressure, with an outlet temperature of 40°C, to obtain a nano dispersion liquid;

[0072] (2) Under nitrogen protection, a reaction kettle was sequentially added with pre-dehydrated epoxy soybean oil acrylate, amino-polyether-modified polysiloxane, hyperbranched polyester amine solution, and trimethylolpropane triacrylate, and subjected to constant temperature at 58°C and mechanical stirring for 30 min;

[0073] (3) The nano dispersion liquid was added, and the temperature was raised to 75°C, and stirring was continued for 1 h;

[0074] (4) The temperature was lowered to 70°C, and pretreated 1H, 1H, 2H, 2H-perfluorohexyl triethoxysilane was added, and incubated for 30 min;

[0075] (5) Polyether-modified polydimethylsiloxane was added, and ITX photoinitiator was added in the dark, and stirred for 20 min;

[0076] (6) The temperature was lowered to 32°C, TPO-L photoinitiator was added, and stirring was continued until complete dissolution;

[0077] (7) The remaining ethyl lactate was added, and filtered through a 0.2 μm PTFE filter membrane to obtain a high-peeling power oil repellent emulsion.

[0078] In step (1), the mass ratio of hydrophobic nano TiO2@SiO2core-shell particles to ethyl lactate was 1:2, and ultrasonic treatment was performed at 40 kHz and 500 W for 30 min; in step (2), the stirring speed was 300 rpm; in step (4), the incubation temperature was controlled at 78°C; and in step (1), the mass ratio of nano modifier to ethyl lactate was 1:2.

[0079] Example 3

[0080] The high-peeling power oil repellent emulsion included the following raw materials in mass fractions: epoxy soybean oil acrylate (ESOA): 32 parts; amino-polyether-modified polysiloxane (APSi): 15 parts; 1H, 1H, 2H, 2H-perfluorohexyl triethoxysilane: 4.5 parts; hyperbranched polyester amine: 6 parts; hydrophobic nano TiO2@SiO2core-shell particles: 5 parts; trimethylolpropane triacrylate: 13 parts; photoinitiator: 3 parts; BYK-331: 1 part; and ethyl lactate: 35 parts. The photoinitiator was TPO-L and ITX, and the mass ratio of TPO-L to ITX was 4:1.

[0081] The preparation method of the high-peeling power oil repellent emulsion included the following steps:

[0082] (1) Hydrophobic nano TiO2@SiO2core-shell particles were added to ethyl lactate, and ultrasonic treatment was performed for 35 min. Then, the mixture was transferred to a high-pressure homogenizer, and was subjected to 3 cycles of 150 MPa pressure, with an outlet temperature of 40°C, to obtain a nano dispersion liquid;

[0083] (2) Under nitrogen protection, a reaction kettle was sequentially added with pre-dehydrated epoxy soybean oil acrylate, amino-polyether-modified polysiloxane, hyperbranched polyester amine solution, and trimethylolpropane triacrylate, and was subjected to constant temperature at 60°C and mechanical stirring for 40 min;

[0084] (3) The nano dispersion liquid was added, and the temperature was increased to 75°C, and stirring was continued for 1.5 h;

[0085] (4) The temperature was decreased to 65°C, and pretreated 1H,1H,2H,2H-perfluorohexyl triethoxysilane was added dropwise, and was kept at the temperature for 35 min;

[0086] (5) Polyether-modified polydimethylsiloxane was added, and ITX photoinitiator was added in the dark, and stirring was performed for 20 min;

[0087] (6) The temperature was decreased to 35°C, TPO-L photoinitiator was added, and stirring was performed until complete dissolution;

[0088] (7) The remaining ethyl lactate was added, and was filtered through a 0.2 μm PTFE filter membrane, to obtain a high-peeling-force oil-repellent agent emulsion.

[0089] In step (1), the mass ratio of hydrophobic nano TiO2@SiO2core-shell particles to ethyl lactate was 1:2, ultrasonic treatment was performed for 30 min at 40 kHz and 500 W; in step (2), the stirring speed was 300 rpm; in step (4), the temperature was controlled at 80°C; and in step (1), the mass ratio of nano modifier to ethyl lactate was 1:2.

[0090] Comparative Example 1

[0091] Compared with Example 1, the difference lies in that the epoxy soybean oil acrylate is replaced with an equal amount of bisphenol A epoxy acrylate CN9010NS.

[0092] Comparative Example 2

[0093] Compared with Example 1, the difference lies in that the short-chain fluorosilane is not used, and the amount of amino-polyether-modified polysiloxane is 20 parts.

[0094] Comparative Example 3

[0095] Compared with Example 1, the difference lies in that the hyperbranched polyester amine is replaced with an equal amount of polyamide resin Versamid-125.

[0096] Comparative Example 4

[0097] The difference compared with Example 1 is that the hydrophobic nano TiO2@SiO2core-shell particles are replaced with equal amount of hydrophobic fumed silica AEROSIL-R812.

[0098] Comparative Example 5

[0099] The difference compared with Example 1 is that TPO-L+ITX is replaced with equal amount of TPO-L.

[0100] The test data of Examples 1-3 and Comparative Examples 1-5 are shown in Table 1.

[0101] Table 1: Test data of Examples 1-3 and Comparative Examples 1-5

[0102]

[0103] From Table 1, it can be seen that the peel force of Examples 1-3 is 0.08-0.12 N / cm, which is significantly lower than that of Comparative Examples 1-5 (0.13-0.21 N / cm). In Comparative Example 1, ESOA is replaced with bisphenol A epoxy acrylate, and the peel force increases due to the disorder of alkyl chains. In Comparative Example 2, there is no fluorosilane, and the surface energy is high (22.3 mN / m), resulting in the highest peel force. In Examples, the contact angle is >105°, and the surface energy is <14.2 mN / m. In Comparative Example 4 (hydrophobic SiO2is replaced), the contact angle is 107.8°, but the light transmittance is only 83.6%, which shows the optimization effect of core-shell structure on light transmittance. In Examples, the cycle life is >350 times, and the wear resistance is <1.5 mg / 1000 times. In Comparative Example 3 (polyamide resin is replaced by HBP), the cycle life is 270 times, and the wear resistance is 4.7 mg / 1000 times, which shows the key role of hyperbranched structure in network stability. The cytotoxicity of Examples is all 0 level.

[0104] Application Example 1

[0105] The oil repellent emulsion obtained in Example 1 is used for the release film of a digital light processing (DLP) printer.

[0106] First, the substrate is treated: 125 μm PET film is subjected to corona treatment (8 kW, 52-55 dynes), and then cleaned by ultrasonic ethanol and dried at 60°C.

[0107] Then, coating is performed: the oil repellent emulsion is coated by a micro-gravure roll (200 mesh) with a wet film thickness of 10 μm.

[0108] Pre-drying: hot air drying at 80°C for 1 min (conveyer speed 2 m / min).

[0109] UV curing: 385 nm LED light source (100 mW / cm2), cumulative energy 800 mJ / cm2.

[0110] Post-curing: hot air at 60°C in nitrogen atmosphere for 30 min.

[0111] Application Example 2

[0112] The oil repellent emulsion obtained from Example 1 was used for soluble or peelable support structures for stereolithography (SLA) printing.

[0113] First, the substrate was activated: BASF Ultrafuse® PVA particles were vacuum dried at 60 °C for 4 h, followed by oxygen plasma treatment for 5 min (100 W).

[0114] Spraying: Air spraying (0.3 mm nozzle, 0.2 MPa), dry film thickness 4 pm.

[0115] Curing: 395 nm UV irradiation (600 mJ / cm2), no thermal baking.

[0116] Application Example 3

[0117] The oil repellent emulsion obtained from Example 1 was used for light transmissive molding platform for liquid crystal display (LCD) light curing printers.

[0118] First, the substrate was cleaned: the tempered glass (5 mm) was first cleaned by argon plasma (300 W, 5 min), followed by wiping with acetone.

[0119] Spin coating: spin coating at 1500 rpm for 30 seconds, dry film thickness 2.5 pm.

[0120] Curing: 405 nm LED (120 mW / cm2), cumulative energy 1000 mJ / cm2.

[0121] Application Comparative Example 1

[0122] The difference from Application Example 1 is that the oil repellent emulsion obtained from Example 1 is replaced by the oil repellent emulsion obtained from Comparative Example 1.

[0123] Application Comparative Example 2

[0124] The difference from Application Example 1 is that the oil repellent emulsion obtained from Example 1 is replaced by the oil repellent emulsion obtained from Comparative Example 2.

[0125] Application Comparative Example 3

[0126] The difference from Application Example 1 is that the oil repellent emulsion obtained from Example 1 is replaced by the oil repellent emulsion obtained from Comparative Example 4.

[0127] Application Comparative Example 4

[0128] The difference from Application Example 2 is that the oil repellent emulsion obtained from Example 1 is replaced by the oil repellent emulsion obtained from Comparative Example 3.

[0129] Application Comparative Example 5

[0130] The difference from application example 2 is that the oil repellent emulsion obtained in example 1 is replaced by the oil repellent emulsion obtained in application comparative example 5.

[0131] Application Comparative Example 6

[0132] The difference from application example 3 is that the oil repellent emulsion obtained in example 1 is replaced by the oil repellent emulsion obtained in application comparative example 2.

[0133] Application Comparative Example 7

[0134] The difference from application example 3 is that the oil repellent emulsion obtained in example 1 is replaced by the oil repellent emulsion obtained in application comparative example 4.

[0135] The test data of application example 1 and application comparative examples 1-3 are shown in Table 2.

[0136] Table 2: Test data of application example 1 and application comparative examples 1-3

[0137]

[0138] As can be seen from Table 2, the peeling force of application comparative example 1 rises by 89% due to the disorder of alkyl chains, and the residue exceeds the standard; the light transmittance of application comparative example 3 does not meet the standard due to serious light scattering, and the service life decreases by 52%.

[0139] The test data of application example 2 and application comparative examples 4-5 are shown in Table 3.

[0140] Table 3: Test data of application example 2 and application comparative examples 4-5

[0141]

[0142] As can be seen from Table 3, the coating peeling rate of application comparative example 4 increases due to the falling of nanoparticles caused by the lack of three-dimensional network anchoring; the removal force of application comparative example 5 still exceeds the standard due to insufficient deep curing.

[0143] The test data of application example 3 and application comparative examples 6-7 are shown in Table 4.

[0144] Table 4: Test data of application example 3 and application comparative examples 6-7

[0145]

[0146] As can be seen from Table 4, the first layer peeling failure rate of application comparative example 6 is high due to the high surface energy (22.3 mN / m) of the resin, which causes the glass to be infiltrated; the local curing of application comparative example 7 is poor due to the scattering of ultraviolet light by ordinary SiO2, which causes insufficient uniformity of light transmission.

Claims

1. A high-peel-strength anti-oil emulsion, characterized in that, The raw materials include the following parts by weight: epoxidized soybean oil acrylate: 32-35 parts; amino polyether modified polysiloxane: 12-15 parts; 1H,1H,2H,2H-perfluorohexyltriethoxysilane: 4.5-5 parts; hyperbranched reinforcing agent: 6-8 parts; nano-modifier: 4-5 parts; 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; The hyperbranched reinforcing agent is hyperbranched polyesteramine; the nano-modifier is hydrophobic nano-TiO2@SiO2 core-shell particles; The preparation method of the hydrophobic nano-TiO2@SiO2 core-shell particles is as follows: nano-TiO2 is added to an ethanol / water mixture and subjected to ultrasonic treatment. Then, hydrochloric acid is added dropwise to adjust the pH to 3. After that, the mixture is placed in a water bath at 40°C and TEOS is added dropwise. After the addition is completed, the mixture is stirred. Then, KH-570 is added and stirring is continued. After centrifugation, washing of the precipitate and vacuum drying, hydrophobic nano-TiO2@SiO2 core-shell particles are obtained. The mass ratio of nano-TiO2, TEOS and KH-570 is 20:4:

1. The preparation method of the hyperbranched polyesteramine is as follows: under nitrogen protection, ethylenediamine is heated to 42-45℃, methyl acrylate is added dropwise, and the reaction is maintained at this temperature for 12-14 hours. Diethanolamine is then added, the temperature is raised to 100-110℃, and the reaction is refluxed for 8-10 hours. A vacuum pump is turned on to remove methanol byproducts. The product is then dissolved in deionized water, dialyzed, and freeze-dried to obtain hyperbranched polyesteramine. The molar ratio of methyl acrylate, ethylenediamine, and diethanolamine is 12:5:

2.

2. The high peel strength anti-oil emulsion according to claim 1, characterized in that, The diluent is trimethylolpropane triacrylate; the mass ratio of TPO-L to ITX is 4:1; the stabilizer is polyether-modified polydimethylsiloxane.

3. A method for preparing a high-peel-strength anti-oil emulsion as described in claim 1 or 2, characterized in that, Includes the following steps: (1) Add the nano-modifier to ethyl lactate and sonicate for 30-40 min; then transfer it to a high-pressure homogenizer and cycle it 3 times at 150 MPa pressure, with an outlet temperature ≤40℃ to obtain a nano-dispersion. (2) Under nitrogen protection, the following are added to the reactor in sequence: pre-dehydrated epoxidized soybean oil acrylate, amino polyether modified polysiloxane, hyperbranched reinforcing agent and diluent. The reactor is kept at a constant temperature of 58-60℃ and mechanically stirred for 30-40 minutes. (3) Add the nano-dispersion, heat to 75℃, and continue stirring for 1-1.5h; (4) Lower the temperature to 60-70℃, add the pretreated 1H,1H,2H,2H-perfluorohexyltriethoxysilane dropwise, and keep warm for 30-40 min; (5) Add polyether-modified polydimethylsiloxane, add ITX photoinitiator under light-protected conditions, and stir for 20-25 min; (6) Cool down to 30-35℃, 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 peel strength oil repellent emulsion.

4. The method for preparing the high peel strength anti-oil emulsion according to claim 3, characterized in that, In step (1), the nano-modifier is a hydrophobic nano-TiO2@SiO2 core-shell particle, and its mass ratio with ethyl lactate is 1:

2. It is ultrasonically treated at 40kHz and 500W for 30-40min. In step (2), the stirring speed is 300rpm. In step (4), the heat preservation temperature is controlled at 78-82℃. In step (1), the mass ratio of nano-modifier to ethyl lactate is 1:

2.

5. The method for preparing the high peel strength anti-oil emulsion according to claim 3, characterized in that, The treatment method for the pre-dehydrated epoxidized soybean oil acrylate is as follows: epoxidized soybean oil acrylate is added to a vacuum reactor, vacuumed to -0.1 MPa, heated to 60-62℃, stirred and dehydrated for 2-2.5 hours, and after the moisture content is ≤200 ppm, the temperature is lowered to 40℃; the hyperbranching reinforcing agent is a hyperbranched polyesteramine solution, which is prepared by adding hyperbranched polyesteramine to ethyl lactate and bubbling with N2 for 1-1.5 hours.

6. The method for preparing the high peel strength anti-oil emulsion according to claim 3, characterized in that, The pretreatment method for 1H,1H,2H,2H-perfluorohexyltriethoxysilane is as follows: take 1H,1H,2H,2H-perfluorohexyltriethoxysilane and 4Å molecular sieve, seal and shake for 22-24 hours, filter through a 0.45μm PTFE filter membrane, and the moisture content should be ≤50ppm.

7. The application of a high peel strength anti-oil emulsion as described in claim 1 or 2, characterized in that, Release films for digital light processing printers; soluble or peelable support structures for stereolithography printing; light-transmitting molding platforms for liquid crystal display photopolymerization printers.

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