A self-cleaning film material composition and its preparation method and application

Abstract

The present invention relates to a super-slippery resin, a self-cleaning film material composition and a self-cleaning film comprising the super-slippery resin, and the application of the self-cleaning film material composition or the self-cleaning film in rail transit vehicles. Taking the total mass of the super-slippery resin as 100%, the super-slippery resin includes the following components in mass percentage: 23% to 28% of a first monomer, 1% to 4% of a second monomer, 10% to 16% of a third monomer, 3% to 6% of a polymerization-active silane coupling agent, 6% to 10% of a trifluoro non-isocyanate polyurethane acrylate, 1% to 2% of an initiator, 0.1% to 0.5% of a chain transfer agent, and the remainder of a first solvent; wherein the first monomer is selected from one or more of methacrylic acid and methacrylate in any proportion; the second monomer is selected from a fluorine-containing acrylate monomer; and the third monomer is selected from a hydroxyl-containing active cross-linking monomer. The self-cleaning film of the present invention can significantly improve the corrosion resistance, stain resistance, animal protein resistance and mildew resistance of the original paint film of the vehicle.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a self-cleaning film material composition and a preparation method and application thereof. Background Art

[0002] The cleanliness of the exterior surface of rail transit vehicles (including but not limited to high-speed trains, high-speed EMUs, ordinary railway passenger cars and urban rail transit vehicles) is an important indicator of the vehicle's beautiful image and an important factor affecting passengers' riding experience. In high-speed operation, particulate matter in the air, dust particles and insects along the track, and protein residues from bird strikes will contaminate the exterior surface of the vehicle body. This is particularly prominent on the bodies of high-speed trains and high-speed EMUs that operate at high frequencies. For external surface pollution, cleaning agents are generally used, and cleaning is carried out manually or mechanically. Among them, manual cleaning is more thorough and clean, but the cost is relatively high. Taking a high-speed EMU with 8 sections as an example, according to statistics from the railway bureau, an average of 4 external cleanings per EMU during the day cost 120 yuan each time, and 300 yuan for one cleaning in the depot, totaling 286,160 yuan for the whole year. A railway bureau has no less than 150 EMUs, and the cleaning fee alone is as high as more than 50 million yuan a year, not to mention the costs of other vehicles, water, electricity, and cleaning agents. At the same time, manual cleaning can easily damage the paint on the car body. Aging, yellowing and partial peeling of the paint have become common problems, reducing the service life of the paint. Mechanical and automated cleaning cannot clean many dead corners, resulting in incomplete cleaning; in addition, long-term accumulation of pollutants will also damage the paint.

[0003] In daily life fields such as automotive glass, building glass exterior walls, and high-end fields such as optical devices and optoelectronic devices, it has been reported that the surface self-cleaning effect can be achieved by coating a super-hydrophobic film. The so-called super-hydrophobicity requires that the stable contact angle of the material surface is greater than 150°, the rolling contact angle is less than 10°, and the water droplets on the surface are spherical. Under the action of their own gravity or external force, the water droplets can roll off the surface. For example, the invention patent application with publication number CN107513176A discloses a method for preparing a transparent super-hydrophobic polymer film, comprising subjecting a formed transparent thermoplastic polymer film to supercritical CO 2Foaming forms a special structure of nano-papillae and grooves on the surface of the polymer film, achieving super-hydrophobicity and low reflection while maintaining transparency. However, this method requires special process conditions, is difficult to prepare, and is difficult to promote. The invention patent application with publication number CN106835043A discloses a transparent super-hydrophobic film including a zinc oxide film and a fluorinated carbon film loaded on the surface of the zinc oxide film. Among them, the preparation of the zinc oxide film includes first preparing a zinc film using a radio frequency magnetron sputtering system, and then annealing the zinc film; the prepared zinc oxide film is then subjected to fluorination treatment, such as using a gas containing carbon and fluorine elements as a working gas in an etching system to fluorinate the zinc oxide film. To complete the above-mentioned preparation process, special and expensive equipment is required. There is also a patent application with publication number CN101492544A that discloses that a mixed solution of ethyl orthosilicate, ethanol, ammonia water and water is placed in an alkyl and fluorine-containing silane coupling agent solution and self-assembled into a super-hydrophobic self-cleaning film. The inventors have found that although the mechanical strength of the film prepared by this method is high, the weather resistance is poor.

[0004] Applying super-hydrophobic film to the outer surface of rail transit vehicles may be an effective way to solve vehicle surface pollution and improve the appearance of cleanliness. However, the film must at least meet the relevant standards, such as the relevant technical indicators of Q / CR546.1-2016 "Paints and coatings for EMUs Part 1: Paints and coating systems for vehicle body exterior surfaces" shown in Table 1.

[0005] Table 1 Technical conditions for surface varnish of high-speed trains in my country

[0006]

[0007] Secondly, the film also needs to have specific properties and characteristics suitable for rail transit, such as low cost, simple and easy preparation method, excellent adhesion, weather resistance, etc. Obviously, there is no self-cleaning super-hydrophobic film in the prior art that can be applied to the anti-fouling of the outer surface of rail transit vehicles, especially high-speed rail vehicles. Summary of the invention

[0008] In order to overcome the shortcomings of the prior art, the present invention provides a self-cleaning film material composition and a preparation method thereof. The composition of the present invention is coated on the surface of a rail vehicle body and, after a simple curing treatment, a firm and uniform self-cleaning film with a thickness of 30 to 50 μm can be formed on the surface of the vehicle body.

[0009] In order to achieve the above technical effects, the present invention adopts the following technical solutions:

[0010] A super-slippery resin, comprising the following components in percentage by mass, with the total mass of the super-slippery resin being 100%:

[0011] 23% to 28% of the first monomer, 1% to 4% of the second monomer, 10% to 16% of the third monomer, 3% to 6% of the polymerization-active silane coupling agent, 6% to 10% of trifluoro non-isocyanate polyurethane acrylate (FNIPUA), 1% to 2% of the initiator, 0.1% to 0.5% of the chain transfer agent, and the remainder of the first solvent; wherein,

[0012] The first monomer is selected from one or more of methacrylic acid and methacrylate in any proportion;

[0013] The second monomer is selected from fluorine-containing acrylate monomers;

[0014] The third monomer is selected from hydroxyl-containing active cross-linking monomers.

[0015] Preferably, the methacrylate is selected from one of methyl methacrylate, butyl methacrylate, lauryl methacrylate, isobornyl methacrylate and octadecyl methacrylate.

[0016] Preferably, the fluorine-containing acrylic ester monomer is at least one selected from trifluoroethyl acrylate, tetrafluoropropyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate and hexafluoroisopropyl methacrylate.

[0017] Further preferably, the fluorine-containing alkyl acrylate monomer is at least one selected from hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate and hexafluoroisopropyl methacrylate.

[0018] Preferably, the hydroxyl-containing active cross-linking monomer is selected from at least two of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate and hydroxyethyl caprolactone acrylate.

[0019] Further preferably, the hydroxyl-containing active cross-linking monomer is selected from at least one of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.

[0020] Preferably, the polymerization active silane coupling agent is selected from at least one of γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacrylic acid oxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acetoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltriisopropoxysilane.

[0021] Further preferably, the polymerization active silane coupling agent is selected from at least one of γ-methacrylic acid oxypropylmethyldimethoxysilane and γ-methacryloxypropylmethyldiethoxysilane.

[0022] Preferably, the initiator is selected from at least one of 2,2'-azobis(2-methylpropionitrile) and 2,2'-disazo-(2,4-dimethylvaleronitrile).

[0023] Preferably, the chain transfer agent is selected from at least one of n-dodecyl mercaptan, secondary dodecyl mercaptan, tert-dodecyl mercaptan, cyclohexyl mercaptan, isooctyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, n-octyl mercaptan, mercaptoethanol and thioglycolic acid.

[0024] Further preferably, the chain transfer agent is selected from at least one of n-dodecyl mercaptan, isooctyl 3-mercaptopropionate and n-butyl 3-mercaptopropionate.

[0025] Preferably, the trifluoro non-isocyanate polyurethane acrylate (FNIPUA) has the following structure:

[0026]

[0027] Wherein R is selected from -H or -CH 3 .

[0028] Preferably, the first solvent is selected from at least one of a benzene solvent, an ester solvent and a ketone solvent.

[0029] Further preferably, the first solvent is selected from at least one of xylene, butyl acetate and methyl isobutyl ketone.

[0030] The present invention also provides a method for preparing the super-slip resin, comprising the following steps:

[0031] I. Prepare each component according to the mass ratio;

[0032] II. The first solvent and the initiator are each divided into three parts, based on the total mass of each, each independently accounting for 8% to 12% of the first part, 78% to 82% of the second part, and 10% of the third part;

[0033] III. Mix the first part of the first solvent and the first part of the initiator, heat to 75°C to 85°C, dropwise add the second part of the first solvent, the second part of the initiator, the first monomer, the second monomer, the third monomer, the polymerization active silane coupling agent and the mixture of trifluoro non-isocyanate polyurethane acrylate, and keep warm for 2h to 4h after the dropwise addition; then add the third part of the first solvent and the third part of the initiator mixture, keep warm for 1h to 3h; finally add the chain transfer agent, cool to 20°C to 30°C, and obtain.

[0034] Preferably, the method for preparing the super-slippery resin comprises the following steps:

[0035] I. Prepare each component according to the mass ratio;

[0036] II. The first solvent and the initiator are each divided into three parts, based on the total mass of each, each independently accounting for 8% to 12% of the first part, 78% to 82% of the second part, and 10% of the third part;

[0037] III. Mix the first part of the first solvent and the first part of the initiator, heat to 75°C to 85°C, dropwise add the second part of the first solvent, the second part of the initiator, the first monomer, the second monomer, the third monomer, the polymerization active silane coupling agent and the mixture of trifluoro non-isocyanate polyurethane acrylate, and keep warm for 2.5h to 3.5h; then add the third part of the first solvent and the third part of the initiator mixture, keep warm for 1.5h to 2.5h; finally, add the chain transfer agent, cool to 20°C to 30°C, and obtain.

[0038] Preferably, the mixture of the solvent, the initiator, the first monomer, the second monomer, the third monomer, the polymerization active silane coupling agent and the trifluoro non-isocyanate polyurethane acrylate is added dropwise for 1.5 h to 2.5 h.

[0039] The present invention also provides application of the super-slip resin in preparing a self-cleaning film material.

[0040] Therefore, the present invention also provides a self-cleaning film material composition comprising the above-mentioned super-slip resin; the self-cleaning film material composition is composed of component A and component B, and the mass ratio of component A to component B is 1.5 to 2.5:1; wherein,

[0041] Component A comprises: 20 to 70 parts by weight of the above-mentioned super-slip resin, 2 to 15 parts by weight of organic silicone resin, 3 to 20 parts by weight of silane-modified nano-alumina, 0.01 to 0.1 parts by weight of catalyst, 0.2 to 2 parts by weight of surface additive and 5 to 20 parts by weight of second solvent;

[0042] Component B includes: 5 to 25 parts by weight of an isocyanate curing agent and 15 to 30 parts by weight of a third solvent.

[0043] Preferably, the mass ratio of component A to component B is 2:1.

[0044] Preferably, the component A comprises: 30-60 parts by weight of the above-mentioned super-smooth resin, 2-10 parts by weight of silicone resin, 3-15 parts by weight of silane-modified nano-alumina, 0.01-0.1 parts by weight of catalyst, 0.2-2 parts by weight of surface additive and 5-20 parts by weight of second solvent.

[0045] Further preferably, the component A comprises: 40 to 50 parts by weight of the above-mentioned super-smooth resin, 3 to 5 parts by weight of silicone resin, 6 to 10 parts by weight of silane-modified nano-alumina, 0.02 to 0.05 parts by weight of catalyst, 0.5 to 1 parts by weight of surface additive and 10 to 15 parts by weight of a second solvent.

[0046] Preferably, the B component comprises: 5 to 20 parts by weight of an isocyanate curing agent and 15 to 30 parts by weight of a third solvent.

[0047] More preferably, the B component includes: 10-15 parts by weight of an isocyanate curing agent and 2025 parts by weight of a third solvent.

[0048] Preferably, the organic silicone resin is selected from one or both of MQ silicone resin and polyhedral oligomeric silsesquioxane (POSS).

[0049] Preferably, the M / Q molar ratio of the MQ silicone resin is 0.5 to 2.0:1.

[0050] More preferably, the M / Q molar ratio of the MQ silicone resin is 0.6 to 1.0:1.

[0051] Also preferably, the weight average molecular weight of the MQ silicone resin is 5,000-30,000.

[0052] More preferably, the weight average molecular weight of the MQ silicone resin is 6000-15000.

[0053] Preferably, the polyhedral oligomeric silsesquioxane is Q8M8H from Aldrich.

[0054] Preferably, the silane-modified nano-alumina is C 12 -C 18 The surface of the nano-alumina is modified by long-chain alkyltriethoxysilane, and the average particle size is 5 to 20 nm.

[0055] Also preferably, the silane-modified nano-alumina is prepared by the following method:

[0056] Nano-alumina, C 12 -C 18 The long-chain alkyl triethoxysilane, isopropanol and ion exchange resin catalyst are mixed, the reaction mass is heated to 70-80°C, refluxed for 4-6 hours, cooled to room temperature and filtered, and the filter cake is dried at 100-110°C for 1-3 hours to obtain; wherein the mass percentage of each component is as follows based on the total mass of the reaction mass:

[0057] Nano-alumina 25-35%, C 12 -C 184-6% of long-chain alkyltriethoxysilane, 1.5-2.5% of ion exchange resin catalyst and the balance of isopropanol.

[0058] Preferably, the ion exchange resin catalyst is the ion exchange resin catalyst K16 produced by the Chemical Research Institute of Guangdong Academy of Sciences.

[0059] Preferably, the catalyst is selected from at least one of an organic tin catalyst and an organic bismuth catalyst.

[0060] Preferably, the organotin catalyst is selected from dibutyltin dilaurate, di-n-octyltin dilaurate, dimethyltin dilaurate, dibutyltin diacetate, dimethyltin diacetate, stannous octoate, monobutyltin oxide or dibutyltin maleate.

[0061] Preferably, the organic bismuth catalyst is selected from bismuth neodecanoate, bismuth laurate, bismuth isooctanoate or bismuth cyclohexaneate.

[0062] Preferably, the surface additive is a wetting agent or a leveling agent.

[0063] More preferably, the surface additive is selected from at least one of Gemini wetting agent SE-5100 and silicone leveling agent BOW-307 containing polyester modified hydroxyl functional groups. Both of the above surface additives are produced by Guangdong Jinbo Chemical Co., Ltd.

[0064] Preferably, the second solvent and the third solvent are each independently selected from at least one of a benzene solvent, an ester solvent and a ketone solvent.

[0065] More preferably, the second solvent and the third solvent are each independently selected from at least one of toluene, xylene, butyl acetate, ethyl acetate, amyl acetate, isooctyl acetate, butanone, methyl isobutyl ketone, ethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate and dimethyl phthalate.

[0066] Preferably, the A component is prepared by the following steps:

[0067] All the components in the A component are stirred and mixed according to the proportions to obtain the product.

[0068] Preferably, the B component is prepared by the following steps:

[0069] All the components in the B component are stirred and mixed according to the proportions to obtain the product.

[0070] Preferably, during the preparation of the component A and the component B, the rotation speed of the independent stirring and mixing is 50 r / min to 400 r / min, more preferably 100 r / min to 300 r / min.

[0071] Preferably, during the preparation of the component A and the component B, the stirring and mixing temperature is independently 5°C to 60°C, more preferably 10°C to 40°C, and further preferably 20 to 25°C.

[0072] Preferably, during the preparation of the component A and the component B, the stirring and mixing time is independently 5 to 40 minutes, more preferably 10 to 20 minutes.

[0073] Another object of the present invention is to provide a self-cleaning film material, which is formed by curing the self-cleaning film material composition as a raw material.

[0074] The present invention also provides a method for preparing the self-cleaning membrane material, comprising the following steps:

[0075] The component A and the component B are uniformly mixed according to the mass ratio, formed into a film on a carrier, and cured at 30 to 80° C. for 2 to 48 hours to obtain the product.

[0076] Preferably, the curing temperature is 40 to 70°C, more preferably 55 to 65°C.

[0077] Preferably, the curing time is 12 to 24 hours.

[0078] In addition, another object of the present invention is to provide an application of the self-cleaning film material composition in rail transit vehicles, the specific operation is as follows:

[0079] Clean the outer surface of the rail transit vehicle paint; mix the A component and the B component evenly according to the mass ratio, spray them on the outer surface of the rail transit vehicle paint, and cure them at 30 to 80° C. for 2 to 48 hours to form a self-cleaning film with a thickness of 30 to 50 μm.

[0080] Preferably, the rail transit vehicles include ordinary high-speed trains, high-speed EMU trains and subway trains.

[0081] The super-slip resin provided by the present invention utilizes the synergistic effect of two isooctyl groups in the fluorinated acrylate monomer and the trifluoro non-isocyanate polyurethane acrylate (FNIPUA) structural unit to reduce the surface energy of the self-cleaning film material, thereby giving the self-cleaning film excellent hydrophobic and weather-resistant properties.

[0082] The super-slippery resin provided by the present invention is mainly composed of trifluoro non-isocyanate polyurethane acrylate (FNIPUA) monomer as a film-forming component. Because FNIPUA contains both the amide bond and the ester bond of polyurethane, it has the advantages of both polyurethane and polyacrylate, so that the self-cleaning film of the present invention has good compatibility and adhesion with the acrylic-polyurethane paint on the outer surface of the rail vehicle body. In addition, the polymerization active silane coupling agent contained in the super-slippery resin can greatly improve the system compatibility of the super-slippery resin with the silicone resin and modified nano-alumina of the self-cleaning film material, improve the adhesion of the self-cleaning film to the acrylic-polyurethane paint on the outer surface of the rail vehicle body, and also solve the problem that the body paint film (including the paint itself and the self-cleaning film) is easily damaged and peeled off during high-speed operation of rail transit vehicles (especially EMUs).

[0083] The self-cleaning membrane provided by the present invention uses organic silicon resin and modified nano-alumina as the reinforcing materials of the membrane material. The organic silicon resin is dissolved in the solvent system, and in the process of curing the membrane, the organic silicon resin fills into the gaps between the modified nano-alumina particles, thereby improving the density and strength of the membrane, and ensuring the impact resistance of the membrane during the high-speed operation of the EMU. At the same time, after the surface of the nano-alumina is modified by a long-chain alkyl, the dynamic friction coefficient of the membrane material can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] The present invention will be further described below in conjunction with the accompanying drawings.

[0085] Figure 1 This is the infrared spectrum of the super-smooth resin prepared in Example 1 of the present invention.

[0086] Figure 2 The water contact angle of the self-cleaning membrane material prepared in Example 4 of the present invention is shown.

[0087] Figure 3 The water contact angle of the self-cleaning membrane material prepared in Example 5 of the present invention is shown. DETAILED DESCRIPTION

[0088] The present invention is described below with reference to specific examples. It will be appreciated by those skilled in the art that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention in any way.

[0089] The experimental methods in the following examples are conventional methods unless otherwise specified. The raw materials, reagents and materials used in the following examples are commercially available products unless otherwise specified. The purchase of some reagents and raw materials is as follows:

[0090] Trifluoro non-isocyanate polyurethane acrylate (FNIPUA), Gemini wetting agent SE-5100, silicone leveling agent BOW-307: purchased from Guangdong Jinbo Chemical Co., Ltd.;

[0091] Polyhedral oligomeric silsesquioxane (POSS) Q8M8H: Aldrich Corporation.

[0092] The silane-modified nano-alumina used in the following examples and comparative examples was prepared by the following method:

[0093] Nano-alumina, C 12 -C 18 The long-chain alkyl triethoxysilane, isopropanol and ion exchange resin catalyst K16 are mixed, the reaction mass is heated to 70-80°C, refluxed for 4-6 hours, cooled to room temperature and filtered, and the filter cake is dried at 100-110°C for 1-3 hours to obtain; wherein the mass percentage of each component is as follows based on the total mass of the reaction mass:

[0094] Nano-alumina 25-35%, C 12 -C 18 4-6% of long-chain alkyltriethoxysilane, 1.5-2.5% of ion exchange resin catalyst and the balance of isopropanol.

[0095] The ion exchange resin catalyst can be selected from the ion exchange resin catalyst K16 produced by the Chemical Research Institute of Guangdong Academy of Sciences.

[0096] Example 1 A super-slip resin

[0097] The raw material formula of the super-slippery resin of this embodiment is shown in Table 2; it is prepared by the following method:

[0098] Mix 42.2g of xylene and 1.5g of 2,2'-azobis(2-methylpropionitrile), heat to 80°C, add dropwise a mixture of 337.6g of xylene, 12g of 2,2'-azobis(2-methylpropionitrile), 210g of methyl methacrylate, 10g of methacrylic acid, 50g of methyl methacrylate, 20g of hexafluorobutyl methacrylate, 60g of γ-methacrylic acid oxypropylmethyldimethoxysilane, 80g of trifluoro non-isocyanate polyurethane acrylate (FNIPUA), and 130g of 2-hydroxyethyl methacrylate, and add dropwise for 2h; keep the temperature at 85°C to react for 3h, then add a mixture of 42.2g of xylene and 1.5g of 2,2'-azobis(2-methylpropionitrile), keep the temperature at 85°C to react for 1.5h to 2.5h, add 3g of n-dodecyl mercaptan, cool to 25°C, and obtain a super-smooth resin.

[0099] The infrared spectrum of the super-slippery resin prepared in this embodiment is shown in FIG. Figure 1 . Figure 1 Shown: 3485cm -1The broad and strong peak at 2955cm is the -OH stretching vibration absorption peak, which indicates that the modified acrylic resin chain segment is grafted with a hydroxyl-containing structural unit (methacrylic acid, 2-hydroxyethyl methacrylate); -1 and 2856cm -1 The corresponding is -CH 3 and -CH 2 -Stretching vibration absorption peak; 1732cm -1 It is the asymmetric stretching vibration absorption peak of the C=O bond on the ester group, which comes from the C=O absorption peak of acrylic resin; 1151cm -1 The asymmetric stretching peak of COC is at 1263cm -1 The corresponding one is -CF 3 and -CF 2 - characteristic absorption peak, 1020cm -1 and 1093cm -1 The absorption peak of Si-OC indicates that both organic fluorine (hexafluorobutyl methacrylate and FNIPUA) and organic silane coupling agent monomers participated in the polymerization reaction, and the peak at 1680 cm-1 did not appear in the spectrum. -1 、1620cm -1 The C=C stretching vibration peak indicates that the monomer polymerization is basically completed, confirming that the desired super-smooth resin structure is obtained.

[0100] Example 2 A super-slip resin

[0101] The raw material formula of the super-slippery resin in this embodiment is shown in Table 2; it is prepared by the following method:

[0102] Mix 49.5g of butyl acetate and 1g of 2,2'-azobis(2-methylpropionitrile), heat to 85°C, add dropwise a mixture of 396g of butyl acetate, 8g of 2,2'-azobis(2-methylpropionitrile), 130g of methyl methacrylate, 20g of methacrylic acid, 110g of butyl methacrylate, 40g of hexafluorobutyl methacrylate, 30g of γ-methacryloxypropylmethyldiethoxysilane, 60g of trifluoro non-isocyanate polyurethane acrylate (FNIPUA), and 100g of 2-hydroxyethyl acrylate, and add dropwise for 1.5h; keep the temperature at 85°C to react for 2.5h, then add a mixture of 49.5g of butyl acetate and 1g of 2,2'-azobis(2-methylpropionitrile), keep the temperature at 85°C to react for 2.5h, add 5g of 3-isooctyl mercaptopropionate, cool to 20°C, and obtain a super-smooth resin.

[0103] The infrared spectrum of the super-slippery resin of this embodiment (spectrum omitted) is similar to the infrared spectrum characteristics of the super-slippery resin of Example 1.

[0104] Example 3 A super-slip resin

[0105] The raw material formula of the super-slippery resin in this embodiment is shown in Table 2; it is prepared by the following method:

[0106] 20g of butyl acetate, 19.9g of methyl isobutyl ketone and 2g of 2,2'-bisazo-(2,4-dimethylvaleronitrile) were mixed and heated to 75°C, and 160g of butyl acetate, 159.2g of methyl isobutyl ketone, 16g of 2,2'-bisazo-(2,4-dimethylvaleronitrile), 180g of methyl methacrylate, 30g of isobornyl methacrylate, 10g of methacrylic acid, 60g of octadecyl methacrylate, 10g of hexafluoroisopropyl methacrylate, 30g of γ-methacrylic acid oxide propylene glycol were added dropwise. A mixture of 1,2-dimethoxymethylsilane, 100g trifluoro non-isocyanate polyurethane acrylate (FNIPUA), and 160g 2-hydroxyethyl methacrylate was added dropwise for 2.5h; the temperature was kept at 75°C for reaction for 3.5h, and then 20g butyl acetate, 19.9g methyl isobutyl ketone and 2g 2,2'-disazo-(2,4-dimethylvaleronitrile) were added, and the temperature was kept at 75°C for reaction for 1.5h, 1 part of 3-mercaptopropionic acid n-butyl ester was added, and the temperature was lowered to 30°C to obtain a super-smooth resin.

[0107] The infrared spectrum of the super-slippery resin of this embodiment (spectrum omitted) is similar to the infrared spectrum characteristics of the super-slippery resin of Example 1.

[0108] Table 2 Raw material formula of super-slip resin of Examples 1 to 3

[0109]

[0110] Example 4 A self-cleaning film material composition and prepared self-cleaning film

[0111] The self-cleaning film material composition of this embodiment is formed by mixing component A and component B in a mass ratio of 2:1, wherein the raw material composition of component A is (10 g = 1 part by weight):

[0112] 450 g of the super-slip resin of Example 1;

[0113] MQ silicone resin (M / Q=0.8 (mol / mol), weight average molecular weight 10000) 30 g;

[0114] 80 g of dodecyltriethoxysilane-modified nano-alumina (average particle size 10 nm);

[0115] Dibutyltin dilaurate 0.3g;

[0116] Gemini wetting agent SE-5100 8g;

[0117] Propylene glycol methyl ether acetate 120g;

[0118] The raw material composition of component B is (10 g = 1 part by weight):

[0119] 1,6-hexamethylene diisocyanate 130 g;

[0120] Methyl isobutyl ketone 160g;

[0121] Dimethyl glutarate 50g.

[0122] The self-cleaning film material composition of this embodiment is prepared by the following steps:

[0123] (1) All raw materials of component A were stirred at room temperature at a speed of 200 r / min for 15 minutes to obtain component A;

[0124] (2) stirring all the raw materials of component B at room temperature at a speed of 100 r / min for 10 minutes to obtain component B;

[0125] (3) stirring the component A obtained in step (1) and the component B obtained in step (2) at a mass ratio of 2:1 at room temperature and a speed of 100 r / min for 10 minutes to obtain a self-cleaning membrane material composition;

[0126] The self-cleaning film material composition was sprayed on the white outer paint surface of a rail transit EMU and cured at 60° C. for 24 hours to obtain a self-cleaning film with a film thickness of 45 μm attached to the outer paint surface.

[0127] Example 5 A self-cleaning film material composition and prepared self-cleaning film

[0128] The self-cleaning membrane material of this embodiment is formed by mixing component A and component B in a mass ratio of 2:1, wherein the raw material composition of component A is (10 g = 1 part by weight):

[0129] 500 g of the super-slip resin of Example 2;

[0130] MQ silicone resin (M / Q=0.6 (mol / mol), weight average molecular weight 15000) 30 g;

[0131] Hexadecyltriethoxysilane modified nano-alumina (average particle size 5 nm) 60 g;

[0132] Stannous octoate 0.2g;

[0133] Gemini wetting agent SE-5100 10g;

[0134] Xylene 100g;

[0135] The raw material composition of component B is (10 g = 1 part by weight):

[0136] 1,6-hexamethylene diisocyanate 100g;

[0137] Methyl isobutyl ketone 200g;

[0138] Dimethyl adipate 50g.

[0139] The self-cleaning film material composition of this embodiment is prepared by the following steps:

[0140] (1) All raw materials of component A were stirred at room temperature at a speed of 100 r / min for 20 minutes to obtain component A;

[0141] (2) stirring all the raw materials of component B at room temperature at a speed of 100 r / min for 10 minutes to obtain component B;

[0142] (3) Component A obtained in step (1) and component B obtained in step (2) were stirred at a mass ratio of 2:1 at a speed of 100 r / min at room temperature for 10 minutes to obtain the self-cleaning film material composition of this embodiment.

[0143] The self-cleaning film material composition was sprayed on the white outer paint surface of a rail transit EMU, and cured at 60° C. for 12 h to obtain a self-cleaning film with a film thickness of 30 μm attached to the outer paint surface.

[0144] Example 6 A self-cleaning film material composition and prepared self-cleaning film

[0145] The self-cleaning membrane material of this embodiment is formed by mixing component A and component B in a mass ratio of 2:1, wherein the raw material composition of component A is (10 g = 1 part by weight):

[0146] Example 3: Super-slip resin 400g;

[0147] MQ silicone resin (M / Q=1.0 (mol / mol), weight average molecular weight 6000) 50 g;

[0148] Octadecyltriethoxysilane modified nano-alumina (average particle size 20 nm) 80 g;

[0149] Dioctyltin dilaurate 0.5g;

[0150] Polyester modified hydroxyl functional group silicone leveling agent BOW-307 5g;

[0151] Xylene 150g;

[0152] The raw material composition of component B is (10 g = 1 part by weight):

[0153] 150 g of bis(4-isocyanatecyclohexyl)methane;

[0154] Xylene 140 g;

[0155] Propylene glycol ethyl ether acetate 50g.

[0156] The self-cleaning film material composition of this embodiment is prepared by the following steps:

[0157] (1) All raw materials of component A were stirred at room temperature at a speed of 300 r / min for 10 minutes to obtain component A;

[0158] (2) stirring all the raw materials of component B at room temperature at a speed of 100 r / min for 10 minutes to obtain component B;

[0159] (3) Component A obtained in step (1) and component B obtained in step (2) were stirred at a mass ratio of 2:1 at a speed of 100 r / min at room temperature for 10 minutes to obtain the self-cleaning film material composition of this embodiment.

[0160] The self-cleaning film material composition was sprayed on the white outer paint surface of a rail transit EMU, and cured at 60° C. for 18 h to obtain a self-cleaning film with a film thickness of 50 μm attached to the outer paint surface.

[0161] Example 7 A self-cleaning film material composition and prepared self-cleaning film

[0162] The self-cleaning membrane material liquid of this embodiment is formed by mixing component A and component B in a mass ratio of 2:1, wherein the raw material composition of component A is (10 g = 1 part by weight):

[0163] 450 g of the super-slip resin of Example 1;

[0164] 30 g of silicone resin (M / Q=0.8, weight average molecular weight 10000);

[0165] Octadecyltriethoxysilane modified nano-alumina (average particle size 15 nm) 100 g;

[0166] 0.5 g of organic bismuth catalyst;

[0167] Gemini wetting agent SE-5100 8g;

[0168] Propylene glycol methyl ether acetate 120g;

[0169] The raw material composition of component B is (10 g = 1 part by weight):

[0170] 1,6-hexamethylene diisocyanate 130 g;

[0171] Methyl isobutyl ketone 160g;

[0172] Dimethyl glutarate 50g.

[0173] The self-cleaning film material composition of this embodiment is prepared by the following steps:

[0174] (1) All raw materials of component A were stirred at room temperature at a speed of 200 r / min for 15 minutes to obtain component A;

[0175] (2) stirring all the raw materials of component B at room temperature at a speed of 100 r / min for 10 minutes to obtain component B;

[0176] (3) Component A obtained in step (1) and component B obtained in step (2) were stirred at a mass ratio of 2:1 at a speed of 100 r / min at room temperature for 10 minutes to obtain the self-cleaning film material composition of this embodiment.

[0177] The self-cleaning film material composition was sprayed on the white outer paint surface of a rail transit EMU, and cured at 60° C. for 24 hours to obtain a self-cleaning film with a film thickness of 45 μm attached to the outer paint surface.

[0178] Example 8 A self-cleaning film material composition and prepared self-cleaning film

[0179] The self-cleaning film material composition of this embodiment is formed by mixing component A and component B in a mass ratio of 2:1, wherein the raw material composition of component A is (10 g = 1 part by weight):

[0180] 500 g of the super-slip resin of Example 2;

[0181] MQ silicone resin (M / Q=1.0 (mol / mol), weight average molecular weight 15000) 30 g;

[0182] Hexadecyltriethoxysilane modified nano-alumina (average particle size 5 nm) 100 g;

[0183] Dibutyltin diacetate 0.2 g;

[0184] Gemini wetting agent SE-5100 10g;

[0185] Xylene 100g;

[0186] The raw material composition of component B is (10 g = 1 part by weight):

[0187] 1,6-hexamethylene diisocyanate 100g;

[0188] Methyl isobutyl ketone 200g;

[0189] Dimethyl adipate 50g.

[0190] The self-cleaning film material composition of this embodiment is prepared by the following steps:

[0191] (1) All raw materials of component A were stirred at room temperature at a speed of 100 r / min for 20 minutes to obtain component A;

[0192] (2) stirring all the raw materials of component B at room temperature at a speed of 100 r / min for 10 minutes to obtain component B;

[0193] (3) Component A obtained in step (1) and component B obtained in step (2) were stirred at a mass ratio of 2:1 at a speed of 100 r / min at room temperature for 10 minutes to obtain the self-cleaning film material composition of this embodiment.

[0194] The self-cleaning film material composition was sprayed on the white outer paint surface of a rail transit EMU and cured at 60° C. for 12 h to obtain a self-cleaning film with a film thickness of 30 μm attached to the outer paint surface.

[0195] Comparative Example 1: A modified hydroxypropyl resin

[0196] A modified hydroxypropyl resin is prepared by the following preparation method: 45.2g of xylene and 1.5g of 2,2'-azobis(2-methylpropionitrile) are mixed, heated to 80°C, 361.6g of xylene, 12g of 2,2'-azobis(2-methylpropionitrile), 210g of methyl methacrylate, 10g of methacrylic acid, 130g of lauryl methacrylate, 20g of hexafluorobutyl methacrylate, 20g of γ-methacrylic acid oxypropylmethyldimethoxysilane and 130g of 2-hydroxyethyl methacrylate are added dropwise for 2h; the mixture is kept at 85°C for reaction for 3h, then 45.2g of xylene and 1.5g of 2,2'-azobis(2-methylpropionitrile) are added, the mixture is kept at 85°C for reaction for 1.5h to 2.5h, 3g of n-dodecyl mercaptan is added, and the temperature is lowered to 25°C to obtain a super-smooth resin.

[0197] Comparative Example 2 A self-cleaning film material composition and a self-cleaning film prepared therefrom

[0198] The self-cleaning film material composition of this comparative example is prepared by mixing component A and component B in a mass ratio of 2:1, wherein the raw material composition of component A is (10 g = 1 part by weight):

[0199] 450 g of the modified hydroxypropyl resin of Comparative Example 1;

[0200] MQ silicone resin (M / Q=0.8 (mol / mol), weight average molecular weight 10000) 30 g;

[0201] 80 g of dodecyltriethoxysilane-modified nano-alumina (average particle size 10 nm);

[0202] Dibutyltin dilaurate 0.3g;

[0203] Gemini wetting agent SE-5100 8g;

[0204] Propylene glycol methyl ether acetate 120g;

[0205] The raw material composition of component B is (10 g = 1 part by weight):

[0206] 1,6-hexamethylene diisocyanate 130 g;

[0207] Methyl isobutyl ketone 160g;

[0208] Dimethyl glutarate 50g.

[0209] The self-cleaning film material composition of this comparative example is prepared by the following steps:

[0210] (1) All raw materials of component A were stirred at room temperature at a speed of 200 r / min for 15 minutes to obtain component A;

[0211] (2) stirring all the raw materials of component B at room temperature at a speed of 100 r / min for 10 minutes to obtain component B;

[0212] (3) Component A obtained in step (1) and component B obtained in step (2) were stirred at a mass ratio of 2:1 at a speed of 100 r / min at room temperature for 10 minutes to obtain a self-cleaning membrane material composition of a comparative example.

[0213] The self-cleaning film material composition was sprayed on the white exterior paint surface of a rail transit EMU and cured at 60° C. for 24 hours to obtain a film material with a film thickness of 45 μm attached to the exterior paint surface.

[0214] Comparative Example 3: A transparent self-cleaning film

[0215] According to the method of Example 8 in Chinese invention patent CN200810056918 "A transparent self-cleaning film and its preparation method and application", a transparent self-cleaning film attached to the outer surface of the car paint was prepared. Test Example Self-cleaning Film Performance Determination of Examples 4-6 and Comparative Examples 2-3

[0216] The self-cleaning membranes prepared in Examples 4 to 6 of the present invention and Comparative Examples 2 and 3 were tested for performance, wherein the test method for animal protein resistance was:

[0217] Chicken blood and chicken breast were put into a meat grinder in a mass ratio of 1:1 and crushed repeatedly for 3 times as animal protein simulants. Then 2g of animal protein simulants were coated on the surface of the prepared membrane material according to an area of ​​5cm×5cm, placed in a 60℃ oven for 2h, and the animal protein simulants were directly rinsed with tap water for 1min. The degree of removal of animal protein simulants was used as the standard of animal protein resistance of the membrane material, divided into 0-5 levels, 0 level = animal protein simulants were completely removed, 1 level = animal protein simulants were removed between (100% and 80%], 2 level = animal protein simulants were removed between (80% and 60%], 3 level = animal protein simulants were removed between (60% and 40%], 4 level = animal protein simulants were removed between (40% and 20%], and 5 level = animal protein simulants were removed <20%.

[0218] The test results are shown in Table 3.

[0219] Table 3 Performance test results of self-cleaning membranes of examples and comparative examples

[0220]

[0221]

[0222] As can be seen from Table 3, the original white paint film of the EMU basically has no corrosion resistance, stain resistance, animal protein resistance and mildew resistance. After the self-cleaning film material composition of the present invention is sprayed and cured on its surface, the above-mentioned properties are significantly improved. Specifically, the self-cleaning films prepared in Examples 4 to 8 have a paint film surface energy of <25mN / m, which is a low-energy surface, has a high water contact angle and good anti-fouling performance, and has an extremely low dynamic friction coefficient. It is a super-slip film material with anti-fouling and self-cleaning capabilities. The water contact angle measurement results of the self-cleaning films of Example 4 and Example 5 are shown respectively. Figure 2 and Figure 3 shown.

[0223] In addition, the self-cleaning films of Examples 4 to 8 have high mechanical properties, high gloss, high adhesion, high weather resistance, water and mildew resistance, chemical solvent resistance and other properties, and all the properties are significantly better than those of Comparative Example 2, Comparative Example 3 and the original white paint film of the EMU, among which:

[0224] (1) Compared with Examples 4 to 8 of the present invention, Comparative Example 2 does not use trifluoro non-isocyanate polyurethane acrylate (FNIPUA) as the super-slip resin component, has a higher surface energy, and does not belong to the low surface energy film material. Its weather resistance, stain resistance, animal protein resistance, deicing strength and other properties are far inferior to the film materials of Examples 4 to 8 of the present invention. The dynamic friction coefficient U of Examples 4 to 8 of the present invention is dIt is about 0.05, which belongs to a super-lubricant film material, which is one order of magnitude lower than that of Comparative Example 2, Comparative Example 3 and the original white paint film of the EMU. The reason may be that the two large isooctyl groups at the tail end of the trifluoro non-isocyanate polyurethane acrylate (FNIPUA) molecule can greatly increase the free volume of the film, reduce the cohesion of the film material, provide a super-lubricant effect, reduce the physical adhesion of stains such as dust and animal protein on the film surface, and achieve a self-cleaning effect.

[0225] (2) Although the contact angle of water of Comparative Example 3 is greater than 150°, achieving a super-hydrophobic effect, its mechanical properties such as adhesion and flexibility, as well as its acid and alkali resistance and weather resistance are very poor, and it is not suitable for use in rail transit vehicles, especially high-speed trains.

[0226] Based on the present invention, combined with the technical requirements of Q / CR546.1-2016, technical requirements for anti-pollution self-cleaning membrane materials for high-speed EMUs are proposed, as shown in Table 4.

[0227] Table 4 Technical requirements for self-cleaning materials for paint surfaces of high-speed EMUs

[0228]

[0229] In summary, the present invention can prepare a self-cleaning film on the outer body of a rail transit vehicle (such as an EMU vehicle) through a simple and quick construction method, thereby effectively improving the self-cleaning ability of the vehicle surface against dust and animal protein, reducing the deicing intensity of the EMU, improving the weather resistance of the paint film, extending the service life of the vehicle's outer paint, and reducing the cost of vehicle cleaning and maintenance.

Claims

1. A self-cleaning film material composition, consisting of component A and component B, wherein the mass ratio of component A to component B is 1.5 to 2.5:1; in, Component A includes: 20-70 parts by weight of super-slip resin, 2-15 parts by weight of silicone resin, 3-20 parts by weight of silane-modified nano-alumina, 0.01-0.1 parts by weight of catalyst, 0.2-2 parts by weight of surface additive and 5-20 parts by weight of second solvent; Component B includes: 5 to 25 parts by weight of an isocyanate curing agent and 15 to 30 parts by weight of a third solvent; Wherein, taking the total mass of the super-slippery resin as 100%, the super-slippery resin includes the following components in mass percentage: 23% to 28% of the first monomer, 1% to 4% of the second monomer, 10% to 16% of the third monomer, 3% to 6% of the polymerization-active silane coupling agent, 6% to 10% of the trifluoro non-isocyanate polyurethane acrylate, 1% to 2% of the initiator, 0.1% to 0.5% of the chain transfer agent, and the balance of the first solvent; wherein, The first monomer is selected from one or more of methacrylic acid and methacrylate in any proportion; The second monomer is selected from fluorine-containing acrylate monomers; The third monomer is selected from a hydroxyl-containing active cross-linking monomer; The trifluoro non-isocyanate polyurethane acrylate has the following structure: Wherein R is selected from -H or -CH 3 .

2. The self-cleaning film material composition according to claim 1, It is characterized in that The component A comprises: 30 to 60 parts by weight of the super-smooth resin, 2 to 10 parts by weight of an organic silicone resin, 3 to 15 parts by weight of silane-modified nano-alumina, 0.01 to 0.1 parts by weight of a catalyst, 0.2 to 2 parts by weight of a surface additive, and 5 to 20 parts by weight of a second solvent.

3. The self-cleaning film material composition according to claim 2, It is characterized in that The component A comprises: 40 to 50 parts by weight of the super-slip resin, 3 to 5 parts by weight of the organosilicon resin, 6 to 10 parts by weight of silane-modified nano-alumina, 0.02 to 0.05 parts by weight of a catalyst, 0.5 to 1 parts by weight of a surface additive, and 10 to 15 parts by weight of a second solvent.

4. The self-cleaning film material composition according to claim 1, It is characterized in that The B component includes: 5 to 20 parts by weight of an isocyanate curing agent and 15 to 30 parts by weight of a third solvent.

5. The self-cleaning film material composition according to claim 4, It is characterized in that The B component includes: 10 to 15 parts by weight of an isocyanate curing agent and 20 to 25 parts by weight of a third solvent.

6. The self-cleaning film material composition according to any one of claims 1 to 5, It is characterized in that The mass ratio of the A component to the B component is 2:

1.

7. The self-cleaning film material composition according to claim 1, 2 or 3, It is characterized in that The organic silicone resin is selected from one or both of MQ silicone resin and polyhedral oligomeric silsesquioxane.

8. The self-cleaning film material composition according to claim 7, It is characterized in that The M / Q molar ratio of the MQ silicone resin is 0.5-2.0:

1.

9. The self-cleaning film material composition according to claim 8, It is characterized in that The M / Q molar ratio of the MQ silicone resin is 0.6 to 1.0:

1.

10. The self-cleaning film material composition according to claim 7, It is characterized in that The weight average molecular weight of the MQ silicone resin is 5,000 to 30,000.

11. The self-cleaning film material composition according to claim 10, It is characterized in that The weight average molecular weight of the MQ silicone resin is 6,000 to 15,000.

12. The self-cleaning film material composition according to claim 7, It is characterized in that The polyhedral oligomeric silsesquioxane is Q8M8H from Aldrich.

13. The self-cleaning film material composition according to claim 1, 2 or 3, It is characterized in that The silane-modified nano-alumina is 12 -C 18 The surface of the nano-alumina is modified by long-chain alkyltriethoxysilane, and the average particle size is 5 to 20 nm.

14. The self-cleaning film material composition according to claim 13, It is characterized in that The silane-modified nano-alumina is prepared by the following method: nano-alumina, C 12 -C 18 The long-chain alkyl triethoxysilane, isopropanol and ion exchange resin catalyst are mixed, the reaction mass is heated to 70-80°C, refluxed for 4-6 hours, cooled to room temperature and filtered, and the filter cake is dried at 100-110°C for 1-3 hours to obtain; wherein the mass percentage of each component is as follows based on the total mass of the reaction mass: Nano-alumina 25-35%, C 12 -C 18 4-6% of long-chain alkyltriethoxysilane, 1.5-2.5% of ion exchange resin catalyst and the balance of isopropanol.

15. The self-cleaning film material composition according to claim 14, It is characterized in that The ion exchange resin catalyst is the ion exchange resin catalyst K16 produced by the Chemical Research Institute of Guangdong Academy of Sciences.

16. The self-cleaning film material composition according to claim 1, 2 or 3, It is characterized in that The catalyst is selected from at least one of an organic tin catalyst and an organic bismuth catalyst.

17. The self-cleaning film material composition according to claim 16, It is characterized in that The organotin catalyst is selected from dibutyltin dilaurate, di-n-octyltin dilaurate, dimethyltin dilaurate, dibutyltin diacetate, dimethyltin diacetate, stannous octoate, monobutyltin oxide or dibutyltin maleate.

18. The self-cleaning film material composition according to claim 16, It is characterized in that The organic bismuth catalyst is selected from bismuth neodecanoate, bismuth laurate, bismuth isooctanoate or bismuth cyclohexaneate.

19. The self-cleaning film material composition according to claim 1, 2 or 3, It is characterized in that The surface additive is a wetting agent or a leveling agent.

20. The self-cleaning film material composition according to claim 19, It is characterized in that The surface additive is selected from at least one of a Gemini wetting agent SE-5100 and an organosilicon leveling agent BOW-307 containing a polyester-modified hydroxyl functional group.

21. The self-cleaning film material composition according to claim 1, 2 or 3, It is characterized in that The second solvent is selected from at least one of a benzene solvent, an ester solvent and a ketone solvent.

22. The self-cleaning film material composition according to claim 21, It is characterized in that The second solvent is selected from at least one of toluene, xylene, butyl acetate, ethyl acetate, amyl acetate, isooctyl acetate, butanone, methyl isobutyl ketone, ethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate and dimethyl phthalate.

23. The self-cleaning film material composition according to claim 1, 4 or 5, It is characterized in that The third solvent is selected from at least one of a benzene solvent, an ester solvent and a ketone solvent.

24. The self-cleaning film material composition according to claim 23, It is characterized in that The third solvent is selected from at least one of toluene, xylene, butyl acetate, ethyl acetate, amyl acetate, isooctyl acetate, butanone, methyl isobutyl ketone, ethylene glycol butyl ether acetate, ethylene glycol diacetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate and dimethyl phthalate.

25. The self-cleaning film material composition according to claim 1, 2 or 3, It is characterized in that The A component is prepared by the following steps: All the components in the A component are stirred and mixed according to the proportions to obtain the product.

26. The self-cleaning film material composition according to claim 25, It is characterized in that During the preparation of component A, the stirring and mixing speed is 50 r / min to 400 r / min, the stirring and mixing temperature is 5° C. to 60° C., and the stirring and mixing time is 5 to 40 min.

27. The self-cleaning film material composition according to claim 26, It is characterized in that The speed of stirring and mixing is 100r / min~300r / min.

28. The self-cleaning film material composition according to claim 26, It is characterized in that The temperature for stirring and mixing is 10°C to 40°C.

29. The self-cleaning film material composition according to claim 28, It is characterized in that The stirring and mixing temperature is 20 to 25°C.

30. The self-cleaning film material composition according to claim 26, It is characterized in that The stirring and mixing time is 10 to 20 minutes.

31. The self-cleaning film material composition according to claim 1, 4 or 5, It is characterized in that The B component is prepared by the following steps: All the components in the B component are stirred and mixed according to the proportions to obtain the product.

32. The self-cleaning film material composition according to claim 31, It is characterized in that During the preparation of the B component, the stirring and mixing speed is 50 r / min to 400 r / min, the stirring and mixing temperature is 5° C. to 60° C., and the stirring and mixing time is 5 to 40 min.

33. The self-cleaning film material composition according to claim 32, It is characterized in that The speed of stirring and mixing is 100r / min~300r / min.

34. The self-cleaning film material composition according to claim 32, It is characterized in that The temperature for stirring and mixing is 10°C to 40°C.

35. The self-cleaning film material composition according to claim 34, It is characterized in that The stirring and mixing temperature is 20 to 25°C.

36. The self-cleaning film material composition according to claim 32, It is characterized in that The stirring and mixing time is 10 to 20 minutes.

37. A self-cleaning film, formed by curing the self-cleaning film material composition according to any one of claims 1 to 36 as a raw material.

38. The method for preparing the self-cleaning membrane according to claim 37, comprising the following operations: The component A and the component B are uniformly mixed according to the mass ratio, formed into a film on a carrier, and cured at 30 to 80° C. for 2 to 48 hours to obtain the product.

39. The preparation method according to claim 38, It is characterized in that The curing temperature is 40-70°C.

40. The preparation method according to claim 39, It is characterized in that The curing temperature is 55-65°C.

41. The preparation method according to claim 38, It is characterized in that The curing time is 12 to 24 hours.

42. Use of the self-cleaning film material composition according to any one of claims 1 to 36 or the self-cleaning film according to claim 37 in rail transit vehicles.

43. The use according to claim 42, It is characterized in that The specific operations of the application are: Clean the outer surface of the rail transit vehicle paint; mix the A component and the B component evenly according to the mass ratio, spray them on the outer surface of the rail transit vehicle paint, and cure them at 30 to 80° C. for 2 to 48 hours to form a self-cleaning film with a thickness of 30 to 50 μm.

44. Use according to claim 42 or 43, It is characterized in that The rail transit vehicles include ordinary high-speed trains, high-speed EMU trains and subway trains.

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