CN116004137B

CN116004137B - Double-dummy composite car sticker and production process thereof

Info

Publication number: CN116004137B
Application number: CN202310037537.4A
Authority: CN
Inventors: 贾文光
Original assignee: Zhejiang Xinminglong Technology Co ltd
Current assignee: Zhejiang Xinminglong Technology Co ltd
Priority date: 2023-01-09
Filing date: 2023-01-09
Publication date: 2023-12-22
Anticipated expiration: 2043-01-09
Also published as: CN116004137A

Abstract

The application relates to the technical field of automobile film preparation, in particular to a double-dummy composite automobile film and a production process thereof. A double-dummy composite car adhesive film and a production process thereof comprise a TPU (thermoplastic polyurethane) protective outer film with wear-resistant and anti-fouling functions, wherein the TPU protective outer film is in hot-press lamination with a TPU high-efficiency heat-insulating film; the TPU high-efficiency heat-insulating film is formed with a nanoparticle layer through magnetron sputtering; the TPU high-efficiency heat-insulating film is compounded with a TPU modified PVC matrix film; the surface of the TPU modified PVC matrix film, which is back to the TPU high-efficiency heat insulation film, is compounded with a connection adhesive film; a release film is compounded on the surface of the connecting adhesive film; the thickness ratio of the TPU protective outer film to the TPU high-efficiency heat-insulating film to the TPU modified PVC matrix film is controlled to be (0.8-1.0): (0.8-1.0): (2.5-4.0). The anti-ultraviolet anti-aging plastic has the advantages of excellent anti-ultraviolet aging, anti-yellowing, weather resistance and wear resistance, difficult degumming and bubble removal under long-time sun exposure, and better service life.

Description

Double-dummy composite car sticker and production process thereof

Technical Field

The application relates to the technical field of automobile film preparation, in particular to a double-dummy composite automobile film and a production process thereof.

Background

With the improvement of the economic level, the automobile enters the home of common people and becomes a main transportation means for riding instead of walking. Currently, some automobile owners do not meet the appearance of automotive base paint, and are expected to pursue personalized automotive film appearance so as to meet the personalized pursuit of individuals, which promotes the rapid development of the automobile beauty industry.

The automobile coating film not only improves the overall appearance of the automobile, but also plays a role in protecting paint on the surface layer of the automobile, namely, the quality of the automobile coating film influences the use comfort and the service life of the automobile. At present, most of used car cover films mainly comprise PVC films, pressure-sensitive adhesive layers compounded on the PVC films and release films compounded on the pressure-sensitive adhesive layers.

PVC film in the related art, such as a yellowing-resistant ultraviolet-resistant car cover film disclosed in application publication No. CN110467785A, comprises the following components in parts by weight: the raw materials of the car cover film comprise the following components: 100 parts of PVC powder, 30-50 parts of DOP plasticizer, 1-5 parts of barium-zinc stabilizer, 1-5 parts of impact resistant ACR, 0.1-3 parts of ultraviolet absorber, 0.1-3 parts of light stabilizer, 0.1-3 parts of antioxidant and 0-10 parts of titanium pigment. However, the PVC film of the related art has a high plasticizer content, and is likely to cause precipitation of the plasticizer, which affects the service performance and the service life.

In addition, the service life of the integral vehicle-mounted film is influenced by the use environment, especially under the strong sunlight irradiation environment in summer, the PVC film and the bonding layer thereof are damaged by ultraviolet rays and thermal oxygen degradation, and the service performance and the service life are influenced. The molecular chain segments of the pressure-sensitive adhesive layer in the whole automobile adhesive film are easily damaged by ultraviolet damage and thermal oxygen degradation, so that the automobile outer paint film surface is affected by waxing, the automobile coating film in a strong sunlight irradiation environment is easy to deglue and bubble for a long time, and the service performance and the service life are affected.

Disclosure of Invention

In order to solve the problem that the automobile coating film in the related art is relatively poor in service performance and service life, the application provides a double-dummy composite automobile coating film with excellent ultraviolet aging resistance, yellowing resistance, weather resistance and wear resistance and a production process thereof.

The application provides a two dumb compound car pad pasting, it is realized through following technical scheme:

the double-dummy composite car adhesive film comprises a TPU (thermoplastic polyurethane) protective outer film with wear-resistant and anti-fouling functions, wherein the TPU protective outer film is in hot-press lamination with a TPU high-efficiency heat-insulating film with ultraviolet and/or infrared ray reflection and/or absorption functions; the TPU high-efficiency heat-insulating film is formed with a nanoparticle layer which reflects and/or absorbs ultraviolet rays and infrared rays through magnetron sputtering; the nanoparticle layer is positioned between the TPU protective outer film and the TPU high-efficiency heat-insulating film; the TPU high-efficiency heat-insulating film is compounded with a TPU modified PVC matrix film; the surface of the TPU modified PVC matrix film, which is opposite to the TPU high-efficiency heat insulation film, is compounded with a connecting adhesive film used for bonding with an automobile outer paint film; the surface of the connecting adhesive film, which is opposite to the TPU modified PVC matrix film, is compounded with a release film; the thickness ratio of the TPU protective outer film to the TPU high-efficiency heat-insulating film to the TPU modified PVC matrix film is controlled to be (0.8-1.0): (0.8-1.0): (2.5-4.0).

The TPU protective outer film in the application endows the whole good wear-resistant, anti-fouling, anti-yellowing and flexible performances, and the polyol in the TPU is compounded by adopting the polycarbonate diol, the fluorine modified polyester polyol and the double-end diol type reactive silicone, so that on one hand, the whole flexibility, the hydrolysis resistance, the oil resistance and the corrosion resistance are ensured, and on the other hand, the problem of weaker solidifying adhesive force of the water-based ink is solved, the water-based polyurethane ink is adopted to be homogeneous with the TPU protective outer film, and the formed pattern-shaped ink is convenient to be stably adhered to the TPU protective outer film.

The utility model provides a but set up the nanoparticle layer of reflection and/or absorption ultraviolet ray, infrared ray in the TPU high-efficient thermal-insulated membrane in this application, can effectively eliminate ultraviolet ray, infrared ray and near infrared ray under the effect of TPU high-efficient thermal-insulated membrane, avoid the harmful ray of process to wear to establish TPU high-efficient thermal-insulated membrane and destroy TPU modified PVC matrix membrane, connect the glued membrane, and then can guarantee ageing resistance, stability in use, the life of this application, be difficult for degumping under the long-time sun insolateing, quality problems such as bubble play good sun-proof thermal-insulated effect.

The bonding stability of the TPU protective outer film and the TPU high-efficiency heat-insulating film is influenced by the surface bonding stability after the TPU protective outer film is subjected to fluorine modification treatment, and the surface of the TPU protective outer film is subjected to low-temperature plasma treatment during processing, so that the treatment temperature, the treatment time and the treatment gas are strictly controlled, and the bonding stability of the TPU protective outer film and the TPU high-efficiency heat-insulating film is improved on the premise that the physicochemical performance of the TPU protective outer film is not influenced, and the overall quality is further ensured.

The TPU modified PVC matrix film in the application is a TPU/PVC composite film material formed by taking soft PVC as a base material and taking TPU as a modified material, one surface of the TPU blended modification can improve the mechanical property, wear resistance, weather resistance, oil resistance, chemical resistance, low-temperature property and composite bonding stability of the whole film material, and on the other hand, the developed TPU can be used as a plasticizer of PVC, so that the dosage of the plasticizer DINP is reduced, the environmental problems caused by easy migration and volatilization of the plasticizer existing in soft PVC are eliminated, and the whole production and preparation cost is reduced. The TPU modified PVC matrix film prepared in the application also has good weather resistance, yellowing resistance, flame retardance and corrosion resistance, and ensures the quality of the whole composite film material. In conclusion, the double-dummy composite car sticker provided by the application has the advantages of excellent ultraviolet aging resistance, yellowing resistance, weather resistance and wear resistance, difficult degumming and bubble formation under long-time sun exposure, and good service life, and the undeniable overall cost is slightly higher than that of common like products, so that the double-dummy composite car sticker is suitable for the middle-high-end car clothing market.

Preferably, the TPU modified PVC matrix film is prepared by a three-layer coextrusion technology and comprises a first mucosa-increasing layer, a TPU modified PVC main body film and a second mucosa-increasing layer, wherein the TPU modified PVC main body film is integrally formed between the first mucosa-increasing layer and the second mucosa-increasing layer; the surface of the first mucosa increasing layer, which is opposite to the TPU modified PVC main body film, is compounded on the surface of the TPU efficient heat insulation film, which is opposite to the nanoparticle layer; the surface of the second mucosa increasing layer, which is opposite to the TPU modified PVC main body film, is compounded on the surface of the connecting adhesive film, which is opposite to the release film; the thickness of the first and second mucosa-increasing layers is controlled to be 15-20 nm; the thickness of the TPU modified PVC main body film is controlled to be 45-60 um.

In the research and development test process, the TPU modified PVC matrix film taking the TPU modified PVC matrix film as a whole is found that the bonding stability of the TPU modified PVC matrix film and the TPU high-efficiency heat-insulating film is not ideal, and the main reason is that a nanoparticle layer is formed on the surface of the TPU high-efficiency heat-insulating film; the adhesion stability of the TPU modified PVC matrix film to the tie film is also not very desirable, and providing an improved dosage of TPU and compatibilizer would effectively solve the above problems, but at a corresponding cost increase. Therefore, the TPU modified PVC matrix film is designed into a three-layer co-extrusion structure, the formula of the first and second mucosa layers is optimally designed, the bonding stability of the first mucosa layer and the TPU high-efficiency heat insulation film and the bonding stability of the second mucosa layer and the connection adhesive film are improved, and the overall material cost can be reduced by about 30%. Different from the conventional hot-pressing composite technology, the three-layer coextrusion technology is adopted, so that the production cost and the production effect are better, the quality of the TPU modified PVC matrix film is better, the performance of the whole film is more stable, the quality stability of the same batch of products is good, the approval of the market is easier to obtain, and the market development potential is stronger.

Preferably, the TPU modified PVC main film is mainly prepared from the following raw materials in parts by weight: 80-90 parts of film-grade PVC resin, 10-20 parts of modified TPU resin A, 8-14 parts of plasticizer DINP, 2-4 parts of compatilizer, 1-3 parts of barium-zinc stabilizer, 8-12 parts of inorganic functional mixed filler and 1-2 parts of liquid rare earth flame retardant; the total parts of the film-grade PVC resin and the modified TPU resin A are 100 parts; the compatilizer is EVA-MAH or CPE; the inorganic functional mixed filler is composed of the following raw materials in percentage by mass: 5-20% of nano titanium nitride with the average particle size of 10-100nm, 10-25% of rutile crystal type nano titanium dioxide with the average particle size of 30-200nm, 5-10% of molybdenum disilicide with the average particle size of 0.10-1um, and the balance of nano silicon dioxide or nano calcium carbonate with the average particle size of 50-200 nm.

According to the formula, the formula of the TPU modified PVC main body film is optimally designed, the dosage of the plasticizer DINP is reduced under the condition that the TPU is preferably used as the quantity, the environmental problem caused by easy migration and volatilization of the plasticizer in soft PVC is reduced or even eliminated, the production formula with better comprehensive performance is obtained, and the TPU modified PVC main body film produced by adopting the formula is relatively good in mechanical property, weather resistance and yellowing resistance. In addition, in order to adapt to the new energy vehicle market and aim at the problem of thermal runaway protection of the new energy vehicle, a flame-retardant system of molybdenum disilicide, liquid rare earth flame retardant and nano silicon dioxide or nano calcium carbonate is adopted in the formula, so that halogen is not introduced, the environment friendliness is strong, the three wastes of production enterprises are avoided, and the manufacturing cost is reduced; and the molybdenum disilicide forms a compact passivation layer at a high temperature in fire, so that the burning-through and cracking period of the whole automobile outer shell can be delayed, the gold escape time is strived for, and the whole safety performance of the automobile is facilitated.

Preferably, the first and second mucosa-increasing layers are prepared from the following raw materials in parts by weight: 72-76 parts of film-grade PVC resin, 24-28 parts of modified TPU resin B, 6-12 parts of plasticizer DINP, 4-6 parts of compatilizer, 1-3 parts of barium-zinc stabilizer, 8-12 parts of inorganic functional mixed filler and 1-2 parts of liquid rare earth flame retardant; the total part of the film-grade PVC resin and the modified TPU resin B is 100 parts; the compatilizer is EVA-MAH or CPE; the inorganic functional mixed filler is composed of the following raw materials in percentage by mass: 5-20% of nano titanium nitride with the average particle size of 10-100nm, 10-25% of rutile crystal type nano titanium dioxide with the average particle size of 30-200nm, 5-10% of molybdenum disilicide with the average particle size of 0.10-1um, and the balance of nano silicon dioxide or nano calcium carbonate with the average particle size of 50-200 nm.

The formula optimizes the dosage of the PVC resin, the modified TPU resin B and the compatilizer and the physicochemical property of the modified TPU resin B, ensures that the bonding stability of the first mucosa-increasing layer and the TPU high-efficiency heat-insulating film and the bonding stability of the second mucosa-increasing layer and the connecting adhesive film are improved, reduces the cost of the whole material, simultaneously relatively optimizes the flexibility of the first mucosa-increasing layer and the second mucosa-increasing layer, and ensures that the interlayer bonding stability of the TPU modified PVC matrix film is better and the use stability of the whole film is better under the influence of external force and internal stress of the three-layer coextrusion material.

Preferably, the modified TPU resin A in the TPU modified PVC main film is mainly prepared from the following substances: diisocyanate, chain extender, polyol, catalyst and antioxidant auxiliary agent; the catalyst is organic bismuth, and the mass of the organic bismuth accounts for 0.001-0.1% of the total mass of diisocyanate, chain extender and polyol; the weight of the antioxidant auxiliary agent accounts for 0.2-0.8% of the total weight of diisocyanate, chain extender and polyol; the antioxidant auxiliary agent consists of an antioxidant 1010, an antioxidant 168, nano titanium nitride with the average particle size of 10-100nm and nano silicon nitride with the average particle size of 10-50 nm; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average grain diameter of 10-100nm to the nano silicon nitride with the average grain diameter of 10-50nm is controlled at 8:2 (0.2-0.5): 1; the diisocyanate is MDI and HDI, and the MDI accounts for 80-84% of the total molar amount of the diisocyanate; the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 75-85% of the total molar weight of the chain extender; the chain extender is polycarbonate diol with the molecular weight of 2000-3000 and polytetrahydrofuran diol with the molecular weight of 2000-3000, wherein the polycarbonate diol accounts for 65-75% of the total molar weight of the chain extender; the sum of the molar quantity of-NCO-in the diisocyanate and the molar quantity of hydroxyl in the chain extender and the polyol has an R value of (0.988-0.996) 1, and the hard segment content in the TPU resin is controlled to be 42-48wt%;

The preparation method of the modified TPU resin A comprises the following steps:

firstly, putting a chain extender with accurate measurement into a first material groove of a double-screw extruder; meanwhile, accurately-metered polyol is put into a second material groove of the double-screw extruder; uniformly stirring diisocyanate, a catalyst and an antioxidant auxiliary agent, and then putting the mixture into a third material groove of a double-screw extruder;

extruding and granulating, wherein the temperature interval of a metering section in the double-screw extruder is 180-200 ℃, the temperature interval of a compression section is 170-190 ℃, the temperature interval of a feeding section is 170-185 ℃, the temperature of a die head is 185-195 ℃, the rotating speed of a screw is 25-40rpm, discharging the material from the double-screw extruder by using a gear pump, and performing water cooling and granulating to obtain semi-finished TPU granules;

and thirdly, placing the prepared semi-finished TPU granules at 80-90 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at 75-80 ℃ for heat treatment for 20-24 hours to obtain the finished modified TPU resin granules A.

The hardness of the modified TPU resin A prepared according to the application is similar to that of the PCV base material, the compatibility of the modified TPU resin A and the PCV base material is good, and the prepared TPU modified PVC main body film has excellent comprehensive performance. The preparation method of the modified TPU resin A provided by the application is relatively simple, the adopted production equipment is relatively common, the whole production cost is relatively economic, and the industrialized production is convenient to realize. The formula and the preparation method thereof can be provided for entrusting manufacturers of TPU with stronger professionals to replace workers, and the sales cost of the whole membrane material can be further reduced.

Preferably, the modified TPU resin B in the first and second mucosa layers is mainly prepared from the following materials: diisocyanate, chain extender, polyol, catalyst and antioxidant auxiliary agent; the catalyst is organic bismuth, and the mass of the organic bismuth accounts for 0.001-0.1% of the total mass of diisocyanate, chain extender and polyol; the weight of the antioxidant auxiliary agent accounts for 0.2-0.8% of the total weight of diisocyanate, chain extender and polyol; the antioxidant auxiliary agent consists of an antioxidant 1010, an antioxidant 168, nano titanium nitride with the average particle size of 10-100nm and nano silicon nitride with the average particle size of 10-50 nm; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average grain diameter of 10-100nm to the nano silicon nitride with the average grain diameter of 10-50nm is controlled at 8:2 (0.4-0.8): 1; the diisocyanate is MDI and HDI, and the MDI accounts for 76-80% of the total molar amount of the diisocyanate; the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 60-80% of the total molar weight of the chain extender; the polyol is composed of polycarbonate diol with a molecular weight of 2000-4000, polytetrahydrofuran diol with a molecular weight of 2000-4000 and FM-4425 double-end diol type reactive silicone with a molecular weight of 10000, wherein the polycarbonate diol accounts for 60-70% of the total mole of the chain extender, and the FM-4425 double-end diol type reactive silicone accounts for 5-10% of the total mole of the chain extender; the R value of the sum of the molar quantity of-NCO-in the diisocyanate and the molar quantity of hydroxyl in the chain extender and the polyol is (0.988-0.996) 1, and the hard segment content in the TPU resin is controlled to be 42-45wt% and is smaller than the hard segment content in the modified TPU resin in the TPU modified PVC main film;

The preparation method of the modified TPU resin B comprises the following steps:

and thirdly, placing the prepared semi-finished TPU granules at 80-90 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at 75-80 ℃ for heat treatment for 20-24 hours to obtain finished modified TPU resin granules B.

The hardness of the modified TPU resin B prepared according to the application is similar to that of the PCV base material, the compatibility of the modified TPU resin B and the PCV base material is good, and the prepared TPU modified PVC main body film has excellent comprehensive performance. Compared with the modified TPU resin A, the modified TPU resin B introduces double-end glycol type reactive silicone, mainly adjusts and optimizes the quality and hard segment content of polycarbonate glycol, polytetrahydrofuran glycol and double-end glycol type reactive silicone, improves the flexibility and mechanical property of the obtained modified TPU resin B material, further improves the bonding stability with TPU high-efficiency heat insulation films and connection adhesive films, and ensures the quality stability of the whole film material.

The preparation method of the modified TPU resin B provided by the application is relatively simple, the adopted production equipment is relatively common, the whole production cost is relatively economic, and the industrialized production is convenient to realize. The formula and the preparation method thereof can be provided for entrusting manufacturers of TPU with stronger professionals to replace workers, and the sales cost of the whole membrane material can be further reduced.

Preferably, the preparation method of the TPU modified PVC matrix film comprises the following steps: the method comprises the following steps:

step one, preparing modified TPU resin A and modified TPU resin B respectively for later use;

step two, preparing a mixture A for preparing the TPU modified PVC main body film: weighing film-grade PVC resin, a plasticizer DINP, a compatilizer, a barium zinc stabilizer, an inorganic function mixed filler and a liquid rare earth flame retardant according to a proportion, uniformly stirring, discharging the mixture into a ten-thousand horsepower machine, wherein the refining current of the ten-thousand horsepower machine reaches 240-250A, judging to be ripe, discharging the mixture into a binding machine, filtering the mixture by a filter after uniform plasticization, and obtaining a finished product mixture A;

simultaneously preparing a mixture B for preparing a first mucosa-increasing layer and a second mucosa-increasing layer: weighing film-grade PVC resin, the modified TPU resin B in the first step, the plasticizer DINP, the compatilizer, the barium zinc stabilizer, the inorganic function mixed filler and the liquid rare earth flame retardant according to the proportion, uniformly stirring, discharging the mixture into a ten-thousand horsepower machine, wherein the refining current of the ten-thousand horsepower machine reaches 240-250A, judging to be ripe, discharging the mixture into a binding machine, filtering the mixture by a filter after uniform plasticization, and obtaining a finished product mixture B;

Putting the finished product mixture A prepared in the step two into a single-screw extruder A, putting the finished product mixture B into the single-screw extruder B, controlling the temperature of a casting film roller to be 160-170 ℃ in unit time, adjusting the clearance of the die lip and the speed of the casting film roller, and enabling the casting film thickness D=180-250 um to be obtained;

step four, the film material obtained in the step three is sent into a synchronous stretching system to be subjected to biaxial stretching treatment, and the stretching multiplying power is increased: the transverse stretching multiplying power is 2.25-2.5, the longitudinal stretching multiplying power is 2.25-2.5, and the transverse stretching multiplying power is equal to the longitudinal stretching multiplying power, so that the three-layer co-extrusion TPU modified PVC matrix film with 88-120um is obtained;

fifth, traction embossing, natural cooling and rolling are carried out, and the finished TPU modified PVC matrix film is obtained.

The whole production process of the TPU modified PVC matrix film is relatively simple, the adopted equipment is relatively popular, the whole production cost is relatively economical, the realization of industrial production is facilitated, and the market sales promotion and application are easy.

Preferably, the TPU outer protective film is prepared from the following materials: diisocyanate, chain extender, polyol, catalyst and functional auxiliary agent; the catalyst is organic bismuth, and the mass of the organic bismuth accounts for 0.001-0.1% of the total mass of diisocyanate, chain extender and polyol; the mass of the functional auxiliary agent accounts for 2.0-3.2% of the total mass of diisocyanate, chain extender and polyol, the functional auxiliary agent comprises an antioxidant auxiliary agent and a functional filler, and the mass ratio of the antioxidant auxiliary agent to the functional filler is (2-3) (7-8); the functional filler mainly comprises nano molybdenum silicide and nano titanium oxynitride, wherein the mass ratio of the nano molybdenum silicide to the nano titanium oxynitride is 1 (0.2-0.5); the antioxidant auxiliary agent consists of an antioxidant 1010, an antioxidant 168, nano titanium nitride with the average particle size of 10-100nm and nano silicon nitride with the average particle size of 10-50 nm; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average grain diameter of 10-100nm to the nano silicon nitride with the average grain diameter of 10-50nm is controlled at 8:2 (2-4) to 2-4; the diisocyanate is MDI and HDI, and the MDI accounts for 80-90% of the total molar weight of the diisocyanate; the chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 8-12.5% of the total molar amount of the chain extender; the polyol is prepared from polycarbonate diol with a molecular weight of 3000, fluorine modified polyester polyol with a molecular weight of 3000 and FM-4425 double-end diol type reactive silicone with a molecular weight of 10000, wherein the polycarbonate diol accounts for 75-80% of the total molar weight of the chain extender, and the FM-4425 double-end diol type reactive silicone accounts for 5-10% of the total molar weight of the chain extender; the sum of the molar quantity of-NCO-in the diisocyanate and the molar quantity of hydroxyl in the chain extender and the polyol has an R value of (0.988-0.996) 1, and the hard segment content in the TPU resin is controlled to be 48-52wt%; the fluorine modified polyester polyol is prepared from adipic acid, 1, 4-bis (2-hydroxyhexafluoroisopropyl) benzene and 3-methyl-1, 5-pentanediol;

The preparation method of the TPU protective outer film comprises the following steps:

step one, preparing fluorine modified polyester polyol: adipic acid, 1, 4-bis (2-hydroxyhexafluoroisopropyl) benzene, 3-methyl-1, 5-pentanediol in a molar ratio of 2:0.5-1.0:2, adding tetraisopropyl titanate, and uniformly mixing, wherein the dosage of the tetraisopropyl titanate is 60ppm of the total mass of adipic acid, 1, 4-bis (2-hydroxyhexafluoroisopropyl) benzene and 3-methyl-1, 5-pentanediol; heating to 132-135 ℃, regulating the temperature to 226-228 ℃ after the reaction is carried out until the effluent is discharged, carrying out transesterification for 2.0h, detecting an acid value, continuing the transesterification for 5min if the acid value is higher than 25mgKOH/g, sampling again, detecting the acid value, and repeating the operation until the detected acid value is lower than 25mgKOH/g; when the acid value is lower than 25mgKOH/g, starting a vacuumizing device, vacuumizing from 0.020MPa to 0.099MPa, continuously vacuumizing for 15min, and detecting the hydroxyl value content of the material, wherein when the hydroxyl value content is controlled to be 37.4+/-0.1, the fluorine modified polyester polyol with the molecular weight of 3000;

step two, adding a chain extender with accurate measurement into a first material groove of a double-screw extruder; meanwhile, accurately-metered polyol is put into a second material groove of the double-screw extruder; uniformly stirring diisocyanate, a catalyst and a functional auxiliary agent, and then putting the stirred diisocyanate, the catalyst and the functional auxiliary agent into a third material groove of a double-screw extruder;

Extruding and granulating, wherein the temperature interval of a metering section in the double-screw extruder is 180-200 ℃, the temperature interval of a compression section is 175-195 ℃, the temperature interval of a feeding section is 175-190 ℃, the temperature of a die head is 190-195 ℃, the rotating speed of a screw is 30-50rpm, discharging the material from the double-screw extruder by using a gear pump, and performing water cooling and granulating to obtain semi-finished TPU granules;

and fourthly, placing the prepared semi-finished TPU granules at 80-90 ℃, drying until the moisture content is lower than 0.02%, placing the semi-finished TPU granules at 75-80 ℃ for 20-24 hours, obtaining finished modified TPU resin granules, and preparing the TPU protective outer film by adopting the finished modified TPU resin granules.

The TPU outer protective film prepared by the obtained formula has good wear resistance, ageing resistance, yellowing resistance and dirt resistance and flexibility. In the method, 2, 3-tetrafluoro-1, 4-butanediol with a proper proportion is introduced into hard segment micromolecule alcohol, a proper amount of fluorine modified polyester polyol is adopted in soft segment polyol, the defect of poor hydrolysis resistance of the polyester polyol is overcome, partial advantages of the polyester polyol are reserved, the problem of weaker solidifying adhesive force of water-based ink is solved, the water-based polyurethane ink is homogeneous with a TPU protective outer film, and the formed pattern-shaped ink is convenient to stably adhere to the TPU protective outer film. The fluorine modified polyester polyol molecular chain is introduced with 1, 4-bis (2-hydroxy hexafluoroisopropyl) benzene, so that the overall rigidity and wear resistance can be improved, the flexibility of the overall film material is adjusted through double-end glycol type reactive silicone compounding, meanwhile, the application has good flexibility, hydrolysis resistance, oil resistance, stain resistance and corrosion resistance, and antibacterial hygienic property, the fluorine modified polyester polyol can be used as a plain car cover film, and individual patterns can be formed by spraying ink and other designs, so that the demands of individual users are ensured. In addition, the TPU protective outer film production process is relatively simple, the adopted equipment is relatively popular, the whole production cost is relatively economic, the industrial production is convenient to realize, and the TPU efficient heat insulation film is easy to market, popularize and apply and is preferred, the TPU efficient heat insulation film comprises two layers of TPU matrix films, and only one surface of each TPU matrix film is provided with a nanoparticle layer for reflecting and/or absorbing ultraviolet rays and infrared rays; the interface of the TPU matrix film compounded with the TPU protective outer film does not form a nanoparticle layer A; the interface of the TPU matrix film compounded with the TPU modified PVC matrix film does not form a nanoparticle layer B; the nanoparticle layer A is a silicon nitride film layer with the thickness of 45-50nm, the nanoparticle layer B is a silicon nitride film with the thickness of 140-180nm, the nanoparticle layer A is positioned at the upper part of the nanoparticle layer B, and the composite position of the nanoparticle layer A is close to the TPU protective outer film; the TPU matrix film is mainly prepared from 80-85A TPU resin and modified nano inorganic filler; the TPU resin is Elastollan TPU 1190A10 and Elastollan TPU 1185A10 of Basoff; the dosage of the modified nano inorganic filler is 4.0-6.0% of the total mass of the TPU matrix film; the modified nano inorganic filler is nano titanium nitride and surface modified porous nano silicon dioxide, and the mass ratio of the nano titanium nitride to the surface modified porous nano silicon dioxide is (1-3): (7-9);

The preparation method of the modified nano inorganic filler comprises the following steps:

step one, preparing surface modified porous nano silicon dioxide: to 100g of porous nanosilica, 10ml of aniline solution, 1.0ml of concentrated hydrochloric acid, 2.5g (NH 4) were added ₂ S ₂ O ₈ Reacting for 3 hours at 50-52 ℃, centrifugally separating, washing with distilled water and ethanol for at least 3 times respectively, drying, heating to 100 ℃ at 5-6 ℃/min, preserving heat for 60-65min, heating to 400-420 ℃ at 5-6 ℃/min, preserving heat for 2 hours, naturally cooling to obtain modified porous nano silicon dioxide, uniformly mixing the obtained modified porous nano silicon dioxide with aqueous polyurethane emulsion, and drying by a spraying method, wherein polyurethane glue is formed on the surface of the modified porous nano silicon dioxide;

uniformly mixing the accurately measured nano titanium nitride, placing the mixture into 4.0-6.0g/L KH550 water solution, performing ultrasonic dispersion for 20-40min, leaching and drying to obtain the finished product nano titanium nitride;

and thirdly, uniformly mixing the finished product nano titanium nitride and the surface modified porous nano silicon dioxide.

The TPU high-efficient thermal-insulated membrane in this application can effectively eliminate ultraviolet ray, infrared ray and near infrared ray, avoids the harmful ray of process to wear to establish TPU high-efficient thermal-insulated membrane and destroys TPU modified PVC matrix membrane, connection glued membrane, and then can guarantee anti yellowing ageing resistance, stability in use, the life of this application, quality problems such as difficult degumping, bubble under long-time sun insolation play good sun-proof heat-proof effect. The prepared modified nano inorganic filler has good compatibility with a base material, the mechanical property and weather resistance of the whole TPU high-efficiency heat-insulating film are good, and heat conducting particles are formed on the surface of the surface modified porous nano silicon dioxide, so that the whole heat dissipation and heat conduction of the TPU high-efficiency heat-insulating film are facilitated, the heat generated by ultraviolet or infrared light can be absorbed by the nano particle layer to be released to the outside relatively quickly, and the service life of the TPU high-efficiency heat-insulating film is prolonged. The production method of the two-layer TPU matrix film is relatively simple, external processing can be commissioned, the magnetron sputtering process of the obtained TPU matrix film is relatively simple, external processing can be commissioned, the positive overall production cost of the TPU high-efficiency heat-insulating film is compressible, the lower production cost can be embodied in the competitive advantage of a sales end, and the market potential is good.

In a second aspect, the present application provides a production process of a double-dummy composite vehicle film, which is implemented by the following technical scheme:

a production process of a double-dummy composite car sticker comprises the following steps:

step one, preparing a TPU protective outer film, a TPU high-efficiency heat-insulating film and a TPU modified PVC matrix film respectively for later use;

secondly, carrying out low-temperature plasma treatment on one surface of the TPU protective outer film, sticking a release film on the other surface, wherein the treatment temperature is 0-8 ℃, the treatment gas is compressed air, the treatment time is 800-860s, after the low-temperature plasma treatment is finished, removing the release film on the other surface, and then carrying out matte embossing treatment to obtain the single-sided tackifying modified TPU protective outer film;

step three, the surface of the single-sided tackifying modified TPU outer protective film subjected to low-temperature plasma treatment is compounded with the surface of the TPU high-efficiency heat-insulating film, which is not plated with the nanoparticle layer, in a hot-pressing manner, so as to obtain a composite film A; the TPU modified PVC matrix film is compounded with the surface of the TPU high-efficiency heat-insulating film coated with the nanoparticle layer in the composite film A by hot pressing, namely the TPU high-efficiency heat-insulating film is compounded between the TPU outer protective film and the TPU modified PVC matrix film by hot pressing, so as to obtain a composite film B;

step four, inputting the composite film B into the environment of 75-80 ℃ for thermal adjustment for 60-90min, and naturally cooling;

And fifthly, coating connection glue on the surface of the TPU modified PVC matrix film in the composite film B obtained in the step four, curing to form a connection glue film, compositing a release film on the surface of the connection glue film to form a release film, cutting, and rolling to obtain the finished double-dummy composite car sticker.

The preparation method provided by the double-dummy composite car film is relatively simple, the adopted equipment is relatively common, the equipment investment is relatively low, the whole production cost is relatively economic, the industrial production is convenient to realize, and the double-dummy composite car film is easy to market, popularize and apply.

The automobile coating film product in the comprehensive cost relatively low-end market has no obvious competitive advantage, but the economic capability of the consumer groups in the middle-high-end automobile coating market is superior and the consumer functions are advanced according to market research, the automobile coating film product is easy to accept novel technical products, and the double-dummy composite automobile coating film prepared by the application has the advantages of technology and quality in the environment of entering the high-end automobile coating market under the condition that the quality of the competition in the middle-high-end automobile coating market is uneven and the price is also in a virtual high-grade environment at present. And the industrial technology threshold of the application is relatively low, the film material part in the double-dummy composite car film can be subjected to external operation, the overall input cost is relatively low, the core production line is mainly a preparation production line of the double-dummy composite car film, the quality of the obtained double-dummy composite car film is ensured, the production cost is effectively reduced at the same time, and the production of small and medium enterprises is facilitated. After future technology and funds are more mature, industrial chain layout is carried out, and the entrusted labor part is subjected to self-assembly production line production, so that the quality of the formed film material can be further ensured, the cost of the formed film material is reduced, and the competitive advantage of enterprises can be effectively improved.

In summary, the present application has the following advantages:

1. the anti-ultraviolet anti-aging anti-yellowing weather-resistant wear-resistant fabric has excellent anti-ultraviolet anti-aging, anti-yellowing, weather-resistant and wear-resistant performances, is not easy to degum and bubble under long-time sun exposure, has a better service life, and is suitable for the middle-high-end automobile and vehicle clothing market.

2. The preparation method provided by the application is relatively simple, the adopted equipment is relatively popular, the whole production cost is relatively economical, the industrial production is convenient to realize, and the market sales promotion and application are easy to carry out.

Drawings

Fig. 1 is a schematic view of the overall structure in embodiment 1 in the present application.

In the figure, 1, TPU outer protective film; 2. TPU high-efficiency heat insulation film; 20. a nanoparticle layer; 201. a nanoparticle layer A; 202. a nanoparticle layer B; 21. a TPU matrix film; 3. TPU modified PVC matrix film; 31. a first enhancement layer; 32. TPU modified PVC main body film; 33. a second enhancement layer; 4. connecting an adhesive film; 5. and (3) a release film.

Detailed Description

The present application is described in further detail below with reference to the drawings, comparative examples and examples.

Preparation example

Preparation example 1

The modified TPU resin A is mainly prepared from the following substances: diisocyanate, chain extender, polyol, catalyst, antioxidant assistant and release agent polyethylene wax.

The catalyst is organic bismuth, specifically bismuth octodecanoate, and the mass of the bismuth octodecanoate accounts for 0.001-0.01% of the total mass of diisocyanate, chain extender and polyalcohol. In the preparation example, the mass of bismuth octodecanoate accounts for 0.06 percent of the total mass of diisocyanate, chain extender and polyol.

The weight of the antioxidant auxiliary agent accounts for 0.2-0.8% of the total weight of the diisocyanate, the chain extender and the polyol. The weight of the antioxidant auxiliary agent in the preparation example accounts for 0.5 percent of the total weight of diisocyanate, chain extender and polyol.

The antioxidant auxiliary agent is prepared from antioxidant 1010, antioxidant 168, and nanometer titanium nitride (cubic crystal form, specific surface area 60.2 m) with average particle diameter of 20nm ² /g), nano silicon nitride with average particle diameter of 20nm (amorphous state, specific surface area 59.6m2/g). Wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride to the nano silicon nitride is controlled at 8:2:0.4:1.

The diisocyanate was MDI and HDI, and MDI accounted for 84% of the total molar amount of diisocyanate.

The chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 80 percent of the total mole of the chain extender.

The chain extender is a polycarbonate diol with a molecular weight of 2000 and a polytetrahydrofuran diol (basf) with a molecular weight of 2000, wherein the polycarbonate diol accounts for 75% of the total molar weight of the chain extender, the polycarbonate diol is a caprolactone type polycarbonate diol, and the caprolactone type polycarbonate diol is prepared by taking PCL as an initiator and is selected from Japanese cellophane Co.

The R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender and the polyol is 0.995:1, and the hard segment content in the TPU resin is controlled to 45.0wt%.

The specific formulation of the modified TPU resin A is as follows: 2091.67g of MDI, 267.76g of HDI, 881.72g of 3-methyl-1, 5-pentanediol, 220.43g of 1, 6-hexanediol, 1010.3g of polycarbonate diol with a molecular weight of 2000, 336.77g of polytetrahydrofuran diol with a molecular weight of 2000, 2.89g of bismuth octodecanoate as a catalyst, 16.88g of antioxidant 1010, 4.22g of antioxidant 168, 0.85g of nano titanium nitride, 2.11g of nano silicon nitride and 9.62g of polyethylene wax as a mold release agent.

step one, 881.72g of 3-methyl-1, 5-pentanediol and 220.43g of 1, 6-hexanediol with accurate metering are put into a first trough of a double-screw extruder; simultaneously, 1010.3g of polycarbonate diol with molecular weight of 2000 and 336.77g of polytetrahydrofuran diol with molecular weight of 2000 which are accurately metered are put into a second trough of a double-screw extruder; 2091.67g of MDI, 267.76g of HDI, 2.89g of bismuth octodecanoate serving as a catalyst, 16.88g of antioxidant 1010, 4.22g of antioxidant 168, 0.85g of nano titanium nitride, 2.11g of nano silicon nitride and 9.62g of polyethylene wax serving as a mold release agent are stirred uniformly and then put into a third trough of a double-screw extruder;

Extruding and granulating, wherein the temperature interval of a metering section in the double-screw extruder is 186-187 ℃, the temperature interval of a compression section is 176-177 ℃, the temperature interval of a feeding section is 182-183 ℃, the temperature of a die head is 192.4 ℃, the rotating speed of a screw is 32rpm, discharging the material from the double-screw extruder by using a gear pump, and performing water cooling and granulating to obtain semi-finished TPU granules;

and thirdly, placing the prepared semi-finished TPU granules at the temperature of 85.0 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at the temperature of 80.0 ℃ for heat treatment for 24.0 hours to obtain finished modified TPU resin granules A.

Preparation example 2

Preparation 2 differs from preparation 1 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender and the polyol is 0.995:1, and the hard segment content in the TPU resin is controlled to be 42.0wt%.

Preparation example 3

Preparation 3 differs from preparation 1 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender and the polyol is 0.995:1, and the hard segment content in the TPU resin is controlled to 48.0wt%.

Preparation example 4

Preparation example 4 differs from preparation example 1 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender and the polyol is 0.995:1, and the hard segment content in the TPU resin is controlled to be 40.0wt%.

Preparation example 5

Preparation 5 differs from preparation 1 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender and the polyol is 0.995:1, and the hard segment content in the TPU resin is controlled to be 50.0wt%.

Preparation example 6

Preparation example 6 differs from preparation example 1 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 75 percent of the total mole of the chain extender

Preparation example 7

Preparation 7 differs from preparation 1 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 85 percent of the total mole of the chain extender

Preparation example 8

Preparation 8 differs from preparation 1 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 70 percent of the total mole of the chain extender.

Preparation example 9

Preparation 9 differs from preparation 1 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 90 percent of the total mole of the chain extender.

Preparation example 10

Preparation 9 differs from preparation 1 in that: the chain extender is 3-methyl-1, 5-pentanediol.

PREPARATION EXAMPLE 11

Preparation 11 differs from preparation 1 in that: the chain extender is polycarbonate diol with molecular weight of 2000 and polytetrahydrofuran diol with molecular weight of 2000, wherein the polycarbonate diol accounts for 65 percent of the total mole of the chain extender.

Preparation example 12

Preparation 12 differs from preparation 1 in that: the chain extender is polycarbonate diol with molecular weight of 2000 and polytetrahydrofuran diol with molecular weight of 2000, wherein the polycarbonate diol accounts for 70 percent of the total mole of the chain extender.

Preparation example 13

Preparation 13 differs from preparation 1 in that: the chain extender is polycarbonate diol with molecular weight of 2000 and polytetrahydrofuran diol with molecular weight of 2000, wherein the polycarbonate diol accounts for 60 percent of the total mole of the chain extender.

PREPARATION EXAMPLE 14

Preparation 14 differs from preparation 1 in that: the chain extender is polycarbonate diol with molecular weight of 2000 and polytetrahydrofuran diol with molecular weight of 2000, wherein the polycarbonate diol accounts for 80 percent of the total mole of the chain extender.

Preparation example 15

Preparation 15 differs from preparation 1 in that: the chain extender is a polycarbonate diol with a molecular weight of 2000.

PREPARATION EXAMPLE 16

Preparation example 16 differs from preparation example 1 in that: the antioxidant auxiliary agent consists of antioxidant 1010, antioxidant 168 and nano titanium nitride with average particle size of 20 nm. The mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average particle diameter of 20nm is controlled to be 8:2:0.4.

Preparation example 17

Preparation 17 differs from preparation 1 in that: the antioxidant auxiliary agent consists of antioxidant 1010, antioxidant 168 and nano silicon nitride with average particle size of 20 nm. The mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano silicon nitride with the average particle diameter of 20nm is controlled to be 8:2:1.

PREPARATION EXAMPLE 18

Preparation 18 differs from preparation 1 in that: the antioxidant auxiliary agent consists of an antioxidant 1010 and an antioxidant 168. The mass ratio of the antioxidant 1010 to the antioxidant 168 is controlled to be 8:2.

Preparation example 19

The modified TPU resin B is mainly prepared from the following substances: diisocyanate, chain extender, polyol, catalyst, antioxidizing assistant and polyethene wax. Wherein the catalyst is organic bismuth, specifically bismuth octodecanoate, and the mass of the organic bismuth accounts for 0.06 percent of the total mass of diisocyanate, chain extender and polyol.

The weight of the antioxidant auxiliary agent accounts for 0.2-0.8% of the total weight of the diisocyanate, the chain extender and the polyol. In the preparation example, the mass of the antioxidant auxiliary agent accounts for 0.5 percent of the total mass of diisocyanate, chain extender and polyol. The antioxidant auxiliary agent consists of antioxidant 1010, antioxidant 168, nanometer titanium nitride with average grain size of 20nm and nanometer silicon nitride with average grain size of 20 nm. The mass ratio of antioxidant 1010, antioxidant 168, nano titanium nitride with average particle diameter of 20nm and nano silicon nitride with average particle diameter of 20nm is controlled at 8:2:0.6:1.

The diisocyanate was MDI and HDI, and MDI accounted for 78% of the total molar amount of diisocyanate.

The chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 72 percent of the total mole of the chain extender.

The polyol is composed of polycarbonate diol with molecular weight of 2000, polytetrahydrofuran diol with molecular weight of 2000 and FM-4425 double-end glycol type reactive silicone with molecular weight of 10000, wherein the polycarbonate diol accounts for 65 percent of the total mole of the chain extender, and the FM-4425 double-end glycol type reactive silicone accounts for 7.0 percent of the total mole of the chain extender.

The R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender and the polyol is 0.995:1, and the hard segment content in the TPU resin is controlled to 44 weight percent and is smaller than that in the modified TPU resin A in the TPU modified PVC main body film.

The formulation of the specific modified TPU resin B is as follows: 1942.27g of MDI, 368.17g of HDI, 791.34g of 3-methyl-1, 5-pentanediol, 307.74g of 1, 6-hexanediol, 909.25g of polycarbonate diol with a molecular weight of 2000, 391.67g of polytetrahydrofuran diol with a molecular weight of 2000, 489.6g of FM-4425 double-terminal diol reactive silicone with a molecular weight of 10000, 3.12g of bismuth octodecanoate as a catalyst, 18.25g of antioxidant 1010, 4.56g of antioxidant 168, 0.91g of nano titanium nitride, 2.28g of nano silicon nitride and 10.4g of a mold release polyethylene wax.

step one, 791.34g of 3-methyl-1, 5-pentanediol and 307.74g of 1, 6-hexanediol with accurate metering are put into a first trough of a double-screw extruder; simultaneously, 909.25g of polycarbonate diol with molecular weight of 2000, 391.67g of polytetrahydrofuran diol with molecular weight of 2000 and 489.6g of FM-4425 double-end diol type reactive silicone with molecular weight of 10000, which are accurately metered, are put into a second trough of a double-screw extruder; 1942.27g of MDI, 368.17g of HDI, 3.12g of catalyst-bismuth octodecanoate, 18.25g of antioxidant 1010, 4.56g of antioxidant 168, 0.91g of nano titanium nitride, 2.28g of nano silicon nitride and 10.4g of release agent polyethylene wax are stirred uniformly and then put into a third trough of a double-screw extruder;

extruding and granulating, wherein the temperature interval of a metering section in the double-screw extruder is 188-190 ℃, the temperature interval of a compression section is 181-182 ℃, the temperature interval of a feeding section is 178-180 ℃, the temperature of a die head is 194.6 ℃, the rotating speed of a screw is 30rpm, discharging the material from the double-screw extruder by using a gear pump, and performing water cooling and granulating to obtain semi-finished TPU granules;

and thirdly, placing the prepared semi-finished TPU granules at 85 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at 80 ℃ for heat treatment for 24.0h to obtain finished modified TPU resin granules B.

Preparation example 20

Preparation 20 differs from preparation 19 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender, polyol was 0.995:1, and the hard segment content in the TPU resin was controlled to 42% by weight.

Preparation example 21

Preparation 21 differs from preparation 19 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender, polyol was 0.995:1, and the hard segment content in the TPU resin was controlled to 45wt%.

PREPARATION EXAMPLE 22

Preparation 22 differs from preparation 19 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender, polyol was 0.995:1, and the hard segment content in the TPU resin was controlled to 40% by weight.

Preparation example 23

Preparation 23 differs from preparation 19 in that: the R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender, polyol was 0.995:1, and the hard segment content in the TPU resin was controlled to 48wt%.

PREPARATION EXAMPLE 24

Preparation 24 differs from preparation 19 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 60 percent of the total mole of the chain extender.

Preparation example 25

Preparation 25 differs from preparation 19 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 80 percent of the total mole of the chain extender.

PREPARATION EXAMPLE 26

Preparation 26 differs from preparation 19 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 55 percent of the total mole of the chain extender.

Preparation example 27

Preparation 27 differs from preparation 19 in that: the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 85 percent of the total mole of the chain extender.

PREPARATION EXAMPLE 28

Preparation 29 differs from preparation 19 in that: the polycarbonate diol represents 60% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 5.0% of the total molar amount of the chain extender.

Preparation example 29

Preparation 29 differs from preparation 19 in that: the polycarbonate diol represents 70% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 10% of the total molar amount of the chain extender.

Preparation example 30

Preparation 30 differs from preparation 19 in that: the polyol is composed of polycarbonate diol with molecular weight of 2000 and polytetrahydrofuran diol with molecular weight of 2000, wherein the polycarbonate diol accounts for 65 percent of the total mole of the chain extender.

Preparation example 31

Preparation 31 differs from preparation 19 in that: the polycarbonate diol represents 60% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 3.0% of the total molar amount of the chain extender.

PREPARATION EXAMPLE 32

Preparation 32 differs from preparation 19 in that: the polycarbonate diol represents 60% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 12.0% of the total molar amount of the chain extender.

PREPARATION EXAMPLE 33

The TPU protective outer film is mainly prepared from the following substances: the catalyst is organic bismuth, specifically bismuth octodecanoate, and the mass of the organic bismuth accounts for 0.06% of the total mass of the diisocyanate, the chain extender and the polyol.

The mass of the functional auxiliary agent accounts for 3.0% of the total mass of the diisocyanate, the chain extender and the polyol.

The functional auxiliary agent comprises an antioxidant auxiliary agent and a functional filler, and the mass ratio of the antioxidant auxiliary agent to the functional filler is 2:8. The functional filler mainly comprises nano molybdenum silicide with the average grain diameter of 100nm and nano titanium oxynitride with the average grain diameter of 100nm, wherein the mass ratio of the nano molybdenum silicide to the nano titanium oxynitride is 1:0.4.

The antioxidant auxiliary agent consists of antioxidant 1010, antioxidant 168, nanometer titanium nitride with average grain size of 20nm and nanometer silicon nitride with average grain size of 20 nm. Wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average particle size of 20nm to the nano silicon nitride with the average particle size of 20nm is controlled to be 8:2:2:2.

The diisocyanate was MDI and HDI, MDI accounting for 85% of the total molar amount of diisocyanate.

The chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 8% of the total mole of the chain extender.

The polyol is composed of a polycarbonate diol (UBE PH300, U.S.A.) having a molecular weight of 3000, a fluorine-modified polyester polyol having a molecular weight of 3000, and an FM-4425 double-terminal diol-type reactive silicone having a molecular weight of 10000, wherein the polycarbonate diol accounts for 80% of the total molar amount of the chain extender, and the FM-4425 double-terminal diol-type reactive silicone accounts for 5% of the total molar amount of the chain extender.

The R value of the sum of the molar amount of-NCO-in the diisocyanate and the molar amount of hydroxyl groups in the chain extender and the polyol is 0.995:1, and the hard segment content in the TPU resin is controlled to be 50 weight percent.

The fluorine modified polyester polyol is prepared from adipic acid, 1, 4-bis (2-hydroxy hexafluoroisopropyl) benzene and 3-methyl-1, 5-pentanediol.

The specific formulation of the TPU protective outer film is as follows: 2116.57g of MDI, 251.02g of HDI, 1049.09g of 1, 6-hexanediol, 125.12g of 2, 3-tetrafluoro-1, 4-butanediol, 841.25g of polycarbonate diol with a molecular weight of 3000, 157.73g of fluorine-modified polyester polyol with a molecular weight of 3000, 175.26g of FM-4425 double-terminal diol-type reactive silicone with a molecular weight of 10000, 2.76g of bismuth octodecanoate, 1.58g of antioxidant 1010, 0.39g of antioxidant 168, 0.39g of nano titanium nitride with an average particle size of 20nm, 0.39g of nano silicon nitride with an average particle size of 20nm, 7.89g of nano molybdenum silicide, 3.16g of nano titanium oxynitride, 9.43g of polyethylene wax.

step one, preparing fluorine modified polyester polyol: adipic acid, 1, 4-bis (2-hydroxyhexafluoroisopropyl) benzene, 3-methyl-1, 5-pentanediol in a molar ratio of 2:0.6:2, adding tetraisopropyl titanate, and uniformly mixing, wherein the dosage of the tetraisopropyl titanate is 60ppm of the total mass of adipic acid, 1, 4-bis (2-hydroxyhexafluoroisopropyl) benzene and 3-methyl-1, 5-pentanediol; heating to 132-135 ℃, regulating the temperature to 226-228 ℃ after the reaction is carried out until the effluent is discharged, carrying out transesterification for 2.0h, detecting an acid value, continuing the transesterification for 5min if the acid value is higher than 25mgKOH/g, sampling again, detecting the acid value, and repeating the operation until the detected acid value is lower than 25mgKOH/g; when the acid value is lower than 25mgKOH/g, starting a vacuumizing device, vacuumizing from 0.020MPa to 0.099MPa, continuously vacuumizing for 15min, and detecting the hydroxyl value content of the material, wherein when the hydroxyl value content is controlled to be 37.4+/-0.1, the fluorine modified polyester polyol with the molecular weight of 3000;

step two, adding 1049.09g of 1, 6-hexanediol and 125.12g of 2, 3-tetrafluoro-1, 4-butanediol with accurate metering into a first material groove of a double-screw extruder; simultaneously, 841.25g of polycarbonate diol with a molecular weight of 3000, 157.73g of fluorine modified polyester polyol with a molecular weight of 3000 and 175.26g of FM-4425 double-end diol type reactive silicone with a molecular weight of 10000, which are accurately metered, are put into a second material groove of a double-screw extruder; 2116.57g of MDI, 251.02g of HDI, 2.76g of bismuth octodecanoate, 1.58g of antioxidant 1010, 0.39g of antioxidant 168, 0.39g of nano titanium nitride with the average particle size of 50nm, 0.39g of nano silicon nitride with the average particle size of 50nm, 7.89g of nano molybdenum silicide, 3.16g of nano titanium oxynitride and 9.43g of polyethylene wax are stirred uniformly and then put into a third trough of a double-screw extruder;

Extruding and granulating, wherein the temperature interval of a metering section in the double-screw extruder is 188-189 ℃, the temperature interval of a compression section is 182-183 ℃, the temperature interval of a feeding section is 178-180 ℃, the temperature of a die head is 194.8 ℃, the rotating speed of a screw is 32rpm, discharging the material from the double-screw extruder by using a gear pump, and performing water cooling and granulating to obtain semi-finished TPU granules;

step four, placing the prepared semi-finished TPU granules at 85 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at 80 ℃ for 24 hours for heat treatment to obtain finished modified TPU resin granules;

and step four, adopting finished product modified TPU resin granules as raw materials of TPU protective outer films, placing the raw materials in a double-screw extruder, extruding a melt, casting, and cooling to obtain the finished product TPU protective outer films with the thickness of 40+/-1.0 um.

PREPARATION EXAMPLE 34

Preparation 34 differs from preparation 33 in that: the chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 10% of the total mole of the chain extender.

Preparation example 35

Preparation 35 differs from preparation 33 in that: the chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 12.5% of the total mole of the chain extender.

Preparation example 36

Preparation 36 differs from preparation 33 in that: the chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 5% of the total mole of the chain extender.

Preparation example 37

Preparation 37 differs from preparation 33 in that: the chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 15% of the total mole of the chain extender.

Preparation example 38

Preparation 38 differs from preparation 33 in that: the polycarbonate diol represents 77% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 8% of the total molar amount of the chain extender.

Preparation example 39

Preparation 39 differs from preparation 33 in that: the polycarbonate diol represents 75% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 10% of the total molar amount of the chain extender.

Preparation example 40

Preparation 40 differs from preparation 33 in that: the polycarbonate diol represents 83% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 2% of the total molar amount of the chain extender.

PREPARATION EXAMPLE 41

Preparation 41 differs from preparation 33 in that: the polycarbonate diol represents 73% of the total molar amount of the chain extender and the FM-4425 double-terminal diol-type reactive silicone represents 12% of the total molar amount of the chain extender.

PREPARATION EXAMPLE 42

Preparation 42 differs from preparation 33 in that: the chain extender is 1, 6-hexanediol.

Preparation example 43

Preparation 43 differs from preparation 33 in that: the polyol is prepared from polycarbonate diol with a molecular weight of 3000 and fluorine modified polyester polyol with a molecular weight of 3000, wherein the polycarbonate diol accounts for 80 percent of the total molar weight of the chain extender.

PREPARATION EXAMPLE 44

The PU matrix film is mainly prepared from 90A TPU resin and modified nano inorganic filler. The TPU resin is Elastollan TPU 1190A10 of Basoff. The dosage of the modified nano inorganic filler is 5% of the total mass of the TPU matrix film, the modified nano inorganic filler is nano titanium nitride and surface modified porous nano silicon dioxide, and the mass ratio of the nano titanium nitride to the surface modified porous nano silicon dioxide is 2:8.

step one, preparing surface modified porous nano silicon dioxide: to 100g of porous nanosilica, 10ml of aniline solution, 1.0ml of concentrated hydrochloric acid, 2.5g (NH 4) were added ₂ S ₂ O ₈ Reacting for 3.0h at 50-52 ℃, centrifugally separating, washing with distilled water and ethanol for 3 times respectively, drying, heating to 100 ℃ at 6 ℃/min, preserving heat for 60min, heating to 420 ℃ at 5 ℃/min, preserving heat for 2.0h, naturally cooling to obtain modified porous nano silicon dioxide, uniformly mixing the obtained modified porous nano silicon dioxide with aqueous polyurethane emulsion, drying by a spray method, and forming polyurethane gel on the surface of the modified porous nano silicon dioxide;

Uniformly mixing the accurately measured nano titanium nitride, placing the mixture into 5.0g/L KH550 aqueous solution, performing ultrasonic dispersion for 30min, leaching and drying to obtain a finished product of nano titanium nitride;

and thirdly, uniformly mixing the finished product nano titanium nitride and the surface modified porous nano silicon dioxide to obtain the finished product modified nano inorganic filler.

The preparation method of the PU matrix film comprises the steps of uniformly mixing a finished product modified nano inorganic filler and a dried Elastollan TPU1190A10 resin, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out cooling granulation to obtain casting master batches; and (3) drying the obtained casting master batch, placing the dried casting master batch in a double-screw extruder, extruding a melt, casting, and cooling to obtain a finished PU matrix film with the thickness of 15+/-0.5 mu m.

PREPARATION EXAMPLE 45

Preparation 45 differs from preparation 44 in that: the PU matrix film is mainly prepared from 90A TPU resin and nano inorganic filler. The TPU resin is Elastollan TPU1190A10 of Basoff. The dosage of the modified nano inorganic filler is 5% of the total mass of the TPU matrix film, the nano inorganic filler is nano titanium nitride and nano silicon dioxide, and the mass ratio of the nano titanium nitride to the nano silicon dioxide is 2:8.

examples

Example 1

Referring to fig. 1, for the double-dummy composite vehicle film disclosed in the application, the double-dummy composite vehicle film comprises a TPU protection outer film 1, wherein the TPU protection outer film 1 is in hot-press compounding with a TPU high-efficiency heat insulation film 2 which is capable of reflecting and/or absorbing ultraviolet rays, the TPU high-efficiency heat insulation film 2 is compounded with a TPU modified PVC matrix film 3, the surface of the TPU modified PVC matrix film 3, which is back to the TPU high-efficiency heat insulation film 2, is compounded with a connection adhesive film 4 which is used for bonding with an automobile outer paint film, and the surface of the connection adhesive film 4, which is back to the TPU modified PVC matrix film 3, is compounded with a release film 5. The thickness ratio of the TPU protective outer film 1, the TPU high-efficiency heat-insulating film 2 and the TPU modified PVC matrix film 3 is controlled to be (0.8-1.0): (0.8-1.0): (2.5-4.0).

Referring to fig. 1, the TPU modified PVC matrix film 3 is prepared by a three-layer co-extrusion technology, and includes a first adhesion promoting layer 31, a TPU modified PVC body film 32, and a second adhesion promoting layer 33, where the TPU modified PVC body film 32 is integrally formed between the first adhesion promoting layer 31 and the second adhesion promoting layer 33 by the three-layer co-extrusion technology. The surface of the first mucosa layer 31 facing away from the TPU modified PVC main body film 32 is compounded on the surface of the TPU efficient heat insulation film 2 facing away from the nanoparticle layer 20, and the surface of the second mucosa layer 33 facing away from the TPU modified PVC main body film 32 is compounded on the surface of the connection adhesive film 4 facing away from the release film 5. The thickness of the first and second mucosa layers 31 and 33 is controlled to be 15-20nm, and the thickness of the TPU-modified PVC main film 32 is controlled to be 45-60 um. In this embodiment, the thickness of the first and second adhesion promoting layers 31 and 33 is controlled to be 15±0.5um, and the thickness of the TPU modified PVC body film 32 is controlled to be 60±0.5um, i.e. the total thickness of the TPU modified PVC body film 3 is 80±0.5um.

Referring to fig. 1, the TPU high efficiency heat insulation film 2 includes two TPU matrix films 21, and only one surface of a single TPU matrix film 21 is formed with a nanoparticle layer 20 that reflects and/or absorbs ultraviolet and infrared rays. The interface of the TPU substrate film 21 compounded with the TPU protective outer film 1 is not provided with a nanoparticle layer A201, and the nanoparticle layer A201 is a silicon nitride film layer with the thickness of 45-50 nm. The interface of the TPU substrate film 21 compounded with the TPU modified PVC substrate film 3 is not provided with a nanoparticle layer B202, the nanoparticle layer B202 is a silicon nitride film 202 with the thickness of 140-180nm, the compounded position of the nanoparticle layer A201 is positioned at the upper part of the nanoparticle layer B202, and the compounded position of the nanoparticle layer A201 is close to the TPU protective outer film 1.

The TPU modified PVC main body film 32 is prepared from the following raw materials in parts by weight: 85 parts of film-grade PVC resin (DuPont 1125 AC) and 15 parts of modified TPU resin A in preparation example 1, 10 parts of plasticizer DINP, 3.2 parts of compatilizer EVA-MAH, 2 parts of barium zinc stabilizer, 10 parts of inorganic functional mixed filler and 1.5 parts of liquid rare earth flame retardant.

The inorganic functional mixed filler is composed of the following raw materials in percentage by mass: 16% of nano titanium nitride with an average particle size of 200nm, 24% of rutile crystal type nano titanium dioxide with an average particle size of 200nm, 10% of molybdenum disilicide with an average particle size of 500nm, and the balance of nano silicon dioxide with an average particle size of 100 nm.

The first and second mucosa-increasing layers 31 and 33 are prepared from the following raw materials in parts by weight: 75 parts of film-grade PVC resin (DuPont 1125 AC) in U.S. A, 25 parts of modified TPU resin B in preparation example 19, 8 parts of plasticizer DINP, 5.6 parts of compatilizer EVA-MAH, 1.8 parts of barium zinc stabilizer, 12 parts of inorganic functional mixed filler and 2 parts of liquid rare earth flame retardant.

The inorganic functional mixed filler is composed of the following raw materials in percentage by mass: 20% of nano titanium nitride with the average particle size of 10-100nm, 20% of rutile crystal type nano titanium dioxide with the average particle size of 30-200nm, 8% of molybdenum disilicide with the average particle size of 0.10-1um and the balance of nano silicon dioxide with the average particle size of 100 nm.

The preparation method of the TPU modified PVC matrix film 3 in the embodiment comprises the following steps: the method comprises the following steps:

the preparation of the modified TPU resin A is described in preparation example 1;

preparation of modified TPU resin B see preparation example 19,

step two, preparation of a mixture A for preparing the TPU-modified PVC main film 32: weighing film-grade PVC resin, a plasticizer DINP, a compatilizer, a barium zinc stabilizer, an inorganic function mixed filler and a liquid rare earth flame retardant according to a proportion, uniformly stirring, discharging the mixture into a ten-thousand horsepower machine, wherein the refining current of the ten-thousand horsepower machine reaches 250A, judging that the mixture is well-done, discharging the mixture into a binding machine, filtering the mixture by a filter after uniform plasticization, and obtaining a finished product mixture A;

the preparation of the mixture B for preparing the first and second mucosae 31, 33 is performed simultaneously: weighing film-grade PVC resin, the modified TPU resin B in the first step, a plasticizer DINP, a compatilizer, a barium zinc stabilizer, an inorganic function mixed filler and a liquid rare earth flame retardant according to a proportion, uniformly stirring, discharging the mixture into a ten-thousand horsepower machine, wherein the refining current of the ten-thousand horsepower machine reaches 250A, judging that the mixture is well-done, and then discharging the mixture into a binding machine, filtering the mixture by a filter after uniform plasticization to obtain a finished product mixture B;

Putting the finished product mixture A prepared in the step two into a single-screw extruder A, putting the finished product mixture B into the single-screw extruder B, wherein the melt quantity of the extruded finished product mixture A is 2.85 times of that of the finished product mixture B in unit time, the melt of the finished product mixture B of the extruder B is evenly divided into an upper runner and a lower runner of a die head distributor after passing through a connecting pipe to the die head distributor, the melt extruded by the finished product mixture A in the single-screw extruder A is a core layer, the melt of the finished product mixture B flowing out of the upper runner and the lower runner and the core layer are co-extruded into a die lip, casting is carried out on a casting sheet roller section, the temperature of the casting sheet roller is controlled to 165 ℃, and the speed of the die lip gap and the casting sheet roller is regulated, so that the thickness D=250um of the casting film material is obtained;

step four, the film material obtained in the step three is sent into a synchronous stretching system to be subjected to biaxial stretching treatment, and the stretching multiplying power is increased: the transverse stretching multiplying power is 2.5, the longitudinal stretching multiplying power is 2.5 times, and the transverse stretching multiplying power is equal to the longitudinal stretching multiplying power, so that a 100um three-layer co-extrusion TPU modified PVC matrix film is obtained;

The TPU outer protective film 1 is the finished TPU outer protective film in preparation example 33 and has a thickness of 40+ -1.0 um.

TPU matrix film 21 is the final TPU matrix film of preparation example 44 having a thickness of 15.+ -. 0.5. Mu.m. Wherein a 45nm silicon nitride film layer is formed on the surface of one TPU matrix film 21 through magnetron sputtering to form a nanoparticle layer A201; the other TPU substrate film 21 is formed with a 150nm silicon nitride film layer on the surface by magnetron sputtering to form a nanoparticle layer B202. The adhesive film 4 in this embodiment is a conventional pressure-sensitive adhesive with a thickness of 10-12um, and the release film 5 is also a conventional release film with a thickness of 15-25um.

step one, preparation of TPU outer protective film 1 see preparation example 33;

referring to preparation example 44, the preparation of the TPU substrate films 21 in the TPU high-efficiency heat-insulating film 2 is that two TPU substrate films 21 are hot-pressed and compounded to form the TPU high-efficiency heat-insulating film 2, and a nanoparticle layer A201 is arranged between the adjacent TPU substrate films 21;

preparation of TPU modified PVC matrix film 3 see the preparation method of TPU modified PVC matrix film 3 in this example;

firstly, cleaning surfaces of a TPU protective outer film 1, a TPU high-efficiency heat-insulating film 2 and a TPU modified PVC matrix film 3 respectively, and removing impurities such as surface floating hair, dust, organic matters and the like for later use;

step two, performing low-temperature plasma treatment on one surface of the TPU protective outer film 1, and attaching a release film on the other surface for protection, wherein the low-temperature plasma treatment process parameters are as follows: the treatment temperature is 4 ℃, the treatment gas is compressed air, the treatment time is 820s, and after the low-temperature plasma treatment is completed, the release film on the TPU outer protective film 1 is removed, so that the single-sided tackifying modified TPU outer protective film is obtained;

Step three, the surface of the single-sided tackifying modified TPU outer protective film subjected to low-temperature plasma treatment is subjected to hot-pressing compounding with the surface of the TPU high-efficiency heat-insulating film 2, to which the nanoparticle layer 20 is not plated, so as to obtain a composite film A; the TPU modified PVC matrix film 3 is compounded with the surface of the TPU high-efficiency heat-insulating film 2 coated with the nanoparticle layer 20 in the composite film A by hot-pressing, and the composite film is hot-pressed by five hot-pressing roller groups, wherein the temperature of the first hot-pressing roller group is 80 ℃, and the hot-pressing pressure is 50N; the temperature of the second hot pressing roller set is 105 ℃, and the hot pressing pressure is 60N; the temperature of the third hot pressing roller set is 120 ℃, and the hot pressing pressure is 80N; the temperature of the fourth hot pressing roller set is 118 ℃, and the hot pressing pressure is 60N; the temperature of the fifth hot-pressing roller set is 88 ℃, the hot-pressing pressure is 50N, and natural cooling is carried out after hot pressing is finished, namely, the TPU high-efficiency heat-insulating film 2 is hot-pressed and compounded between the TPU protective outer film 1 and the TPU modified PVC matrix film 3, so as to obtain a compound film B;

step four, inputting the composite film B into a baking oven, wherein the initial temperature is normal temperature, heating to 80 ℃ for 30min at 4 ℃/min, cooling to 40 ℃ at 1.0 ℃/min, and naturally cooling to room temperature to finish film material heat adjustment;

and fifthly, coating commercially available acrylic acid pressure-sensitive glue on the surface of the TPU modified PVC matrix film 3 in the composite film B subjected to film material thermal adjustment, curing to form a connection adhesive film 4 with the thickness of 10-12 mu m, compositing a release film on the surface of the connection adhesive film 4 to form a release film 5, cutting, and rolling to obtain the finished double-dummy composite car adhesive film.

Example 2

Example 2 differs from example 1 in that: the TPU modified PVC main body film 32 is prepared from the following raw materials in parts by weight: 80 parts of film-grade PVC resin, 20 parts of modified TPU resin A in preparation example 1, 8 parts of plasticizer DINP, 3.2 parts of compatilizer EVA-MAH, 2 parts of barium-zinc stabilizer, 10 parts of inorganic functional mixed filler and 1.5 parts of liquid rare earth flame retardant.

Example 3

Example 3 differs from example 1 in that: the TPU modified PVC main body film 32 is prepared from the following raw materials in parts by weight: 90 parts of film-grade PVC resin, 10 parts of modified TPU resin A in preparation example 1, 14 parts of plasticizer DINP, 3.2 parts of compatilizer EVA-MAH, 2 parts of barium-zinc stabilizer, 10 parts of inorganic functional mixed filler and 1.5 parts of liquid rare earth flame retardant.

Example 4

Example 4 differs from example 1 in that: the first and second mucosa-increasing layers 31 and 33 are prepared from the following raw materials in parts by weight: 72 parts of film-grade PVC resin, 28 parts of modified TPU resin B in preparation example 19, 6 parts of plasticizer DINP, 5.6 parts of compatilizer EVA-MAH, 1.8 parts of barium-zinc stabilizer, 12 parts of inorganic functional mixed filler and 2 parts of liquid rare earth flame retardant.

Example 5

Example 5 differs from example 1 in that: the first and second mucosa-increasing layers 31 and 33 are prepared from the following raw materials in parts by weight: 76 parts of film-grade PVC resin, 24 parts of modified TPU resin B in preparation example 19, 9 parts of plasticizer DINP, 5.6 parts of compatilizer EVA-MAH, 1.8 parts of barium-zinc stabilizer, 12 parts of inorganic functional mixed filler and 2 parts of liquid rare earth flame retardant.

Example 6

Example 6 differs from example 1 in that:

the TPU modified PVC main body film 32 is prepared from the following raw materials in parts by weight: 82 parts of film-grade PVC resin, 18 parts of modified TPU resin A in preparation example 3, 9 parts of plasticizer DINP, 3.5 parts of compatilizer EVA-MAH, 1.2 parts of barium-zinc stabilizer, 10 parts of inorganic functional mixed filler and 2 parts of liquid rare earth flame retardant.

The first and second mucosa-increasing layers 31 and 33 are prepared from the following raw materials in parts by weight: 74 parts of film-grade PVC resin, 26 parts of modified TPU resin B in preparation example 23, 7 parts of plasticizer DINP, 5.4 parts of compatilizer EVA-MAH, 1.2 parts of barium-zinc stabilizer, 12 parts of inorganic functional mixed filler and 2 parts of liquid rare earth flame retardant.

Comparative example

Comparative example 1 differs from example 1 in that: the TPU modified PVC main body film 32 is prepared from the following raw materials in parts by weight: 95 parts of film-grade PVC resin, 5 parts of modified TPU resin A in preparation example 1, 18 parts of plasticizer DINP, 3.2 parts of compatilizer EVA-MAH, 2 parts of barium-zinc stabilizer, 10 parts of inorganic functional mixed filler and 1.5 parts of liquid rare earth flame retardant.

Comparative example 2 differs from example 1 in that: the TPU modified PVC main body film 32 is prepared from the following raw materials in parts by weight: 75 parts of film-grade PVC resin, 25 parts of modified TPU resin A in preparation example 1, 8 parts of plasticizer DINP, 3.2 parts of compatilizer EVA-MAH, 2 parts of barium-zinc stabilizer, 10 parts of inorganic functional mixed filler and 1.5 parts of liquid rare earth flame retardant.

Comparative example 3 differs from example 1 in that: the first and second mucosa-increasing layers 31 and 33 are prepared from the following raw materials in parts by weight: 80 parts of film-grade PVC resin, 20 parts of modified TPU resin B in preparation example 19, 10 parts of plasticizer DINP, 5.6 parts of compatilizer EVA-MAH, 1.8 parts of barium-zinc stabilizer, 12 parts of inorganic functional mixed filler and 2 parts of liquid rare earth flame retardant.

Comparative example 4 differs from example 1 in that: the first and second mucosa-increasing layers 31 and 33 are prepared from the following raw materials in parts by weight: 70 parts of film-grade PVC resin, 30 parts of modified TPU resin B in preparation example 19, 6 parts of plasticizer DINP, 5.6 parts of compatilizer EVA-MAH, 1.8 parts of barium-zinc stabilizer, 12 parts of inorganic functional mixed filler and 2 parts of liquid rare earth flame retardant.

Comparative example 5 differs from example 1 in that: the inorganic functional mixed filler in the TPU modified PVC main body film 32 is nano titanium nitride with the average grain diameter of 200nm, rutile crystal type nano titanium dioxide with the average grain diameter of 200nm and nano silicon dioxide with the average grain diameter of 100nm, and the mass ratio is 1:1:1. The inorganic functional mixed filler in the first and second mucosa layers 31 and 33 is nano titanium nitride with an average particle size of 200nm, rutile crystal form nano titanium dioxide with an average particle size of 200nm, and nano silicon dioxide with an average particle size of 100nm, and the mass ratio is 1:1:1.

Comparative example 6 differs from example 1 in that: the inorganic functional mixed filler in the TPU modified PVC main body film 32 is nano titanium nitride with the average particle size of 200nm and nano silicon dioxide with the average particle size of 100nm, and the mass ratio is 1:1. The inorganic functional mixed filler in the first and second mucosa layers 31 and 33 is nano titanium nitride with an average particle size of 200nm and nano silicon dioxide with an average particle size of 100nm, and the mass ratio is 1:1.

Performance test

Detection method/test method

1. Mechanical strength test: tensile strength test the tensile test was carried out according to the GB1040-79 plastic tensile test method. Tensile failure test the tensile test was carried out according to the GB1040-79 plastic tensile test method. Mechanical strength test object: films prepared from the modified TPU resin A in preparation examples 1-18; films prepared from modified TPU resin A in preparation examples 19-32; TPU outer protective films in preparations 33-43; the PU matrix films in preparation examples 44-45.

2. Abrasion resistance test: abrasion resistance the abrasion resistance of the TPU protective outer films in preparation examples 33-43 was tested according to GB/T9867-2008.

3. Stain resistance test: TPU outer protective films in preparations 33-43 were tested according to GMW 3402.

4. weather-light-Jungle Test: after being placed in an environment with 80 ℃ and 75% humidity for 400 hours, the steel plate is bent for 10 ten thousand times at 25 ℃ to observe whether cracking occurs; and bending for 2 ten thousand times at the temperature of minus 20 ℃ to observe whether cracking occurs. Test object: films prepared from the modified TPU resin A in preparation examples 1-18; films prepared from modified TPU resin A in preparation examples 19-32; TPU outer protective films in preparations 33-43; the PU matrix films in preparation examples 44-45.

5. Light fastness test: xenon lamp testing was performed in accordance with ISO 105-B06. Test object: films prepared from the modified TPU resin A in preparation examples 1-18; films prepared from modified TPU resin A in preparation examples 19-32; TPU outer protective films in preparations 33-43; the PU matrix films in preparation examples 44-45.

6. Peel strength test: flexible materials were tested according to GB/T2791-1995 adhesive T peel strength test method flexible materials.

The peel strength of the TPU protective outer film 1 and the TPU high efficiency heat insulation film 2 was tested.

Test object: the TPU protective outer film 1 and the TPU high performance heat insulation film 2 in example 1 were peeled off to give test examples 1 to 4. Test example 1 the peel strength of the TPU protective outer film 1 and the TPU high performance heat insulation film 2 of preparation example 34 was tested. Test example 2 the peel strength of the TPU protective outer film 1 and the TPU high performance heat insulation film 2 of preparation example 35 was tested. Test example 3 the peel strength of the TPU protective outer film 1 and the TPU high performance heat insulation film 2 of preparation example 36 was tested. Test example 4 the peel strength of the TPU protective outer film 1 and the TPU high performance heat insulation film 2 of preparation example 34 was tested.

And (5) testing the peel strength of the TPU high-efficiency heat insulation film 2 and the TPU modified PVC matrix film 3.

Test object: peel strength of the first tie film and TPU high performance heat insulation film in example 1, examples 4 to 6, and comparative examples 3 to 6.

7. DH2000 aging test: test temperature: 85 ℃, test humidity: 85%, test time 2000h. Mechanical strength is tested after the aging test, and the test object: films prepared from the modified TPU resin A in preparation examples 1-18; films prepared from modified TPU resin A in preparation examples 19-32; TPU outer protective films in preparations 33-43; the PU matrix films in preparation examples 44-45.

Data analysis

Table 1 shows the parameters of the film produced from TPU resin A in preparation examples 1 to 18

As can be seen from the combination of preparation examples 1 to 18 and Table 1, the hard segment content in TPU resin A is preferably controlled to be 42 to 48wt% in comparison with preparation examples 4 to 5, and preferably the hard segment content in TPU resin A is controlled to be 45%, and the obtained film has relatively good mechanical properties and excellent aging resistance, flexibility and light resistance.

As can be seen from the combination of preparation examples 1 to 18 and Table 1, preparation examples 1,6 to 7 and preparation examples 8 to 10 show that the chain extender is composed of 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, the 3-methyl-1, 5-pentanediol accounts for 75 to 85 percent of the total mole of the chain extender, and the 3-methyl-1, 5-pentanediol accounts for 80 percent of the total mole of the chain extender, so that the obtained film has relatively good mechanical properties and better ageing resistance, flexibility and light resistance.

As can be seen from the comparison of preparation examples 1 to 18 and Table 1, preparation examples 1 and 11 to 12 and preparation examples 13 to 15, the polyhydric alcohol is a polycarbonate diol having a molecular weight of 2000 to 3000 and a polytetrahydrofuran diol having a molecular weight of 2000 to 3000, wherein the polycarbonate diol accounts for 65 to 75% of the total molar amount of the chain extender, preferably the polycarbonate diol accounts for 70% of the total molar amount of the chain extender, and the obtained film has relatively good mechanical properties and superior aging resistance, flexibility and light resistance.

As can be seen from the combination of preparation examples 1 to 18 and the combination of Table 1, the nano titanium nitride is effective in improving yellowing resistance and aging resistance as compared with preparation example 16. As can be seen from the comparison of preparation example 1 and preparation examples 16-18, the combined use of nano titanium nitride and nano silicon nitride can improve the overall anti-aging and anti-yellowing properties. Therefore, the mass of the antioxidant auxiliary agent accounts for 0.5 percent of the total mass of diisocyanate, the chain extender and the polyol, the antioxidant auxiliary agent consists of antioxidant 1010, antioxidant 168, nano titanium nitride with the average particle size of 10-100nm and nano silicon nitride with the average particle size of 10-50nm, the mass ratio of the antioxidant 1010, the antioxidant 168, the nano titanium nitride with the average particle size of 10-100nm and the nano silicon nitride with the average particle size of 10-50nm is controlled at 8:2:0.4:1, and the obtained film material has relatively good mechanical properties and better ageing resistance, flexibility and light resistance.

In summary, the modified TPU resin A in the preparation example 1 is adopted to prepare the TPU modified PVC main film in a modifying way by combining the formula design requirement of the TPU modified PVC main film.

Table 2 shows the parameters of the film produced from TPU resin B in preparation examples 19 to 32

As can be seen from the combination of preparation examples 19 to 32 and Table 2, the hard segment content of TPU resin B is controlled to be 42 to 45wt% in comparison with preparation examples 19 to 21 and preparation examples 22 to 23, and the obtained film has relatively good mechanical properties and excellent ageing resistance, flexibility and light resistance.

As can be seen from the combination of preparation examples 19-32 and Table 2, preparation examples 19, 24-25 and preparation examples 26-27 show that the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, the 3-methyl-1, 5-pentanediol accounts for 60-80% of the total mole of the chain extender, and the 3-methyl-1, 5-pentanediol accounts for 70% of the total mole of the chain extender, so that the obtained film has relatively good mechanical properties and excellent ageing resistance, flexibility and light resistance.

As can be seen from the comparison of preparation examples 19 to 32 and Table 2, preparation examples 19 and 28 to 29 with preparation examples 30 to 32, the polyol is composed of a polycarbonate diol having a molecular weight of 2000, a polytetrahydrofuran diol having a molecular weight of 2000 and an FM-4425 double-terminal diol type reactive silicone having a molecular weight of 10000, wherein the polycarbonate diol accounts for 60 to 70% of the total molar amount of the polyol, and the FM-4425 double-terminal diol type reactive silicone accounts for 5 to 10% of the total molar amount of the chain extender, and the obtained film has relatively good mechanical properties and superior aging resistance, flexibility and light resistance. Preferably, the polycarbonate diol comprises 65% of the total molar amount of polyol and the FM-4425 double terminal diol type reactive silicone comprises 7% of the total molar amount of chain extender.

In view of the above, it is preferable to modify the modified TPU resin B in preparation example 19 or 21 to prepare the first or second mucosa-increasing agent in combination with the formulation requirements of the first and second mucosa-increasing agents.

Table 3 shows the parameters of the TPU outer protective film of preparations 33 to 43

Table 4 shows the parameters of the TPU outer protective film of preparations 33 to 43

	Light fastness grade	Soil resistance grade	Abrasion resistance test
				PREPARATION EXAMPLE 33	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
PREPARATION EXAMPLE 34	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
				Preparation example 35	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
Preparation example 36	Grade 5	Grade 7 or more	CS-10 1KG 800 times without damage
				Preparation example 37	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
Preparation example 38	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
				Preparation example 39	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
Preparation example 40	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
				PREPARATION EXAMPLE 41	Grade 5	Grade 8 or more	CS-10 1KG 800 times without damage
PREPARATION EXAMPLE 42	Grade 5	Grade 7 or more	CS-10 1KG 800 times without damage
				Preparation example 43	Grade 5	Grade 7 or more	CS-10 1KG 800 times without damage

As can be seen by combining preparation examples 33-43 and combining tables 3-4, preparation examples 33-35 compare preparation examples 36-37, and the chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 8-12.5% of the total mole of the chain extender, and the resulting TPU protective outer film has relatively good mechanical properties and relatively good ageing resistance, flexibility, light resistance, stain resistance and wear resistance.

As can be seen by combining preparation examples 33-43 and tables 3-4, preparation examples 33, 38-39 compare with preparation examples 40-43, and the chain extender is composed of polycarbonate diol with a molecular weight of 3000, fluorine modified polyester polyol with a molecular weight of 3000, FM-4425 double-end diol type reactive silicone with a molecular weight of 10000, wherein the polycarbonate diol accounts for 75-80% of the total mole of the chain extender, the FM-4425 double-end diol type reactive silicone accounts for 5-10% of the total mole of the chain extender, and the obtained TPU protective outer film has relatively good mechanical properties and relatively good ageing resistance, flexibility, light resistance, stain resistance and abrasion resistance.

Table 5 shows the parameters for the detection of PU matrix films in preparation examples 44-45

As can be seen from the combination of preparation examples 44 to 45 and the combination of table 5, the amount of the modified nano inorganic filler is 5% of the total mass of the TPU matrix film, the modified nano inorganic filler is nano titanium nitride and surface modified porous nano silica, and the mass ratio of the nano titanium nitride to the surface modified porous nano silica is 2:8, the prepared PU matrix film has relatively good mechanical properties and relatively good ageing resistance, flexibility and light resistance.

As can be seen from the combination of preparation examples 1 to 45 and the combination of tables 1 to 5, the TPU modified PVC body film of the TPU modified PVC body film in the double dummy composite car sticker film of the present application is preferably prepared by using the modified TPU resin of preparation example 1; the modified TPU resin B in the preparation example 19 or the preparation example 21 is preferably used for preparing the first mucosa-increasing film or the second mucosa-increasing film; the PU matrix film is preferably the PU matrix film in preparation example 44; the TPU outer protective films of preparation example 33 and preparation example 34 are preferably used. The TPU modified PVC matrix film is prepared by a three-layer coextrusion technology, and the mechanical properties and weather resistance of the first mucosa-increasing layer, the TPU modified PVC main body film and the second mucosa-increasing layer are required to be optimally designed so as to ensure the physical and chemical properties of the whole TPU modified PVC matrix film.

The mechanical strength test and the mechanical properties test after DH2000 aging were performed on the TPU-modified PVC bulk film 31 and the tie film 32 in the TPU-modified PVC matrix films of examples 1 to 6 and comparative examples 1 to 6.

Table 6 shows the parameters of the TPU-modified PVC matrix films of examples 1 to 6 and comparative examples 1 to 6

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Table 7 shows the test parameters of the peel strength of the TPU outer protective film and the TPU high efficiency insulating film in example 1 and test examples 1 to 4

The TPU outer film of preparation example 33 and the TPU high-efficiency heat insulation film of example 1 are better in peel strength and better in aging resistance as can be seen from the combination of example 1 and test examples 1-4 and the combination of Table 7.

Table 8 shows the peel strength test parameters of the first tie films and TPU highly effective heat insulating films in example 1, examples 4 to 6, and comparative examples 3 to 6

As can be seen from the combination of examples 1, examples 4 to 6 and comparative examples 3 to 6 and Table 8, the first tie films and TPU high-efficiency heat-insulating films in examples 1 and examples 4 to 6 have relatively good peel strength and excellent aging resistance. Namely 72-76 parts of PVC resin, 24-28 parts of modified TPU resin and 6-12 parts of plasticizer DINP in the formula of the first grafting film, and the obtained first grafting film has excellent mechanical strength, weather resistance and ageing resistance.

In conclusion, the coating has excellent ultraviolet aging resistance, yellowing resistance, weather resistance and wear resistance, the long-time sun exposure is not easy to degum and bubble, and the service life is better.

The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims

1. The utility model provides a two dumb compound car pad pasting which characterized in that: the heat-resistant and anti-fouling TPU film comprises a TPU protective outer film (1) with a wear-resistant and anti-fouling function, wherein the TPU protective outer film (1) is compounded with a TPU high-efficiency heat-insulating film (2) with ultraviolet and/or infrared ray reflection and/or absorption functions in a hot-pressing manner; the TPU high-efficiency heat insulation film (2) is formed with a nanoparticle layer (20) which reflects and/or absorbs ultraviolet rays and infrared rays through magnetron sputtering; the nanoparticle layer (20) is positioned between the TPU protective outer film (1) and the TPU high-efficiency heat-insulating film (2); the TPU high-efficiency heat insulation film (2) is compounded with a TPU modified PVC matrix film (3); the surface of the TPU modified PVC matrix film (3) facing away from the TPU high-efficiency heat insulation film (2) is compounded with a connecting adhesive film (4) used for bonding with an automobile outer paint film; the surface of the connecting adhesive film (4) facing away from the TPU modified PVC matrix film (3) is compounded with a release film (5); the thickness ratio of the TPU protective outer film (1), the TPU high-efficiency heat insulation film (2) and the TPU modified PVC matrix film (3) is controlled to be (0.8-1.0): (0.8-1.0): (2.5-4.0);

The TPU modified PVC matrix film (3) is prepared by a three-layer coextrusion technology and comprises a first mucosa-increasing layer (31), a TPU modified PVC main body film (32) and a second mucosa-increasing layer (33), wherein the TPU modified PVC main body film (32) is integrally formed between the first mucosa-increasing layer (31) and the second mucosa-increasing layer (33); the surface of the first mucosa increasing layer (31) facing away from the TPU modified PVC main body film (32) is compounded on the surface of the TPU high-efficiency heat insulation film (2) facing away from the nanoparticle layer (20); the surface of the second mucosa increasing layer (33) facing away from the TPU modified PVC main body film (32) is compounded on the surface of the connecting adhesive film (4) facing away from the release film (5); the thickness of the first mucosa-increasing layer (31) and the second mucosa-increasing layer (33) is controlled to be 15-20 mu m; the thickness of the TPU modified PVC main body film (32) is controlled to be 45-60 mu m;

the TPU modified PVC main film (32) is mainly prepared from the following raw materials in parts by weight: 80-90 parts of film-grade PVC resin, 10-20 parts of modified TPU resin A, 8-14 parts of plasticizer DINP, 2-4 parts of compatilizer, 1-3 parts of barium-zinc stabilizer, 8-12 parts of inorganic functional mixed filler and 1-2 parts of liquid rare earth flame retardant; the total parts of the film-grade PVC resin and the modified TPU resin A are 100 parts; the compatilizer is EVA-MAH or CPE; the inorganic functional mixed filler is composed of the following raw materials in percentage by mass: 5-20% of nano titanium nitride with the average particle size of 10-100nm, 10-25% of rutile crystal type nano titanium dioxide with the average particle size of 30-200nm, 5-10% of molybdenum disilicide with the average particle size of 0.10-1 mu m, and the balance of nano silicon dioxide or nano calcium carbonate with the average particle size of 50-200 nm;

The first and second mucosa-increasing layers (31, 33) are prepared from the following raw materials in parts by weight: 72-76 parts of film-grade PVC resin, 24-28 parts of modified TPU resin B, 6-12 parts of plasticizer DINP, 4-6 parts of compatilizer, 1-3 parts of barium-zinc stabilizer, 8-12 parts of inorganic functional mixed filler and 1-2 parts of liquid rare earth flame retardant;

the total part of the film-grade PVC resin and the modified TPU resin B is 100 parts; the compatilizer is EVA-MAH or CPE; the inorganic functional mixed filler is composed of the following raw materials in percentage by mass: 5-20% of nano titanium nitride with the average particle size of 10-100nm, 10-25% of rutile crystal type nano titanium dioxide with the average particle size of 30-200nm, 5-10% of molybdenum disilicide with the average particle size of 0.10-1 mu m, and the balance of nano silicon dioxide or nano calcium carbonate with the average particle size of 50-200 nm;

the modified TPU resin A in the TPU modified PVC main film (32) is mainly prepared from the following substances: diisocyanate, chain extender, polyol, catalyst and antioxidant auxiliary agent; the catalyst is organic bismuth, and the mass of the organic bismuth accounts for 0.001-0.1% of the total mass of diisocyanate, chain extender and polyol; the weight of the antioxidant auxiliary agent accounts for 0.2-0.8% of the total weight of diisocyanate, chain extender and polyol; the antioxidant auxiliary agent consists of an antioxidant 1010, an antioxidant 168, nano titanium nitride with the average particle size of 10-100nm and nano silicon nitride with the average particle size of 10-50 nm; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average grain diameter of 10-100nm to the nano silicon nitride with the average grain diameter of 10-50nm is controlled at 8:2 (0.2-0.5): 1; the diisocyanate is MDI and HDI, and the MDI accounts for 80-84% of the total molar amount of the diisocyanate; the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 75-85% of the total molar weight of the chain extender; the polyalcohol is polycarbonate diol with a molecular weight of 2000-3000 and polytetrahydrofuran diol with a molecular weight of 2000-3000, wherein the polycarbonate diol accounts for 65-75% of the total molar weight of the chain extender; the sum of the molar quantity of-NCO-in the diisocyanate and the molar quantity of hydroxyl in the chain extender and the polyol has an R value of (0.988-0.996) 1, and the hard segment content in the TPU resin is controlled to be 42-48wt%;

step three, placing the prepared semi-finished TPU granules at 80-90 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at 75-80 ℃ for heat treatment for 20-24 hours to obtain finished modified TPU resin granules A;

the modified TPU resin B in the first and second mucosa layers (31, 33) is mainly prepared from the following substances: diisocyanate, chain extender, polyol, catalyst and antioxidant auxiliary agent; the catalyst is organic bismuth, and the mass of the organic bismuth accounts for 0.001-0.1% of the total mass of diisocyanate, chain extender and polyol; the weight of the antioxidant auxiliary agent accounts for 0.2-0.8% of the total weight of diisocyanate, chain extender and polyol; the antioxidant auxiliary agent consists of an antioxidant 1010, an antioxidant 168, nano titanium nitride with the average particle size of 10-100nm and nano silicon nitride with the average particle size of 10-50 nm; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average grain diameter of 10-100nm to the nano silicon nitride with the average grain diameter of 10-50nm is controlled at 8:2 (0.4-0.8): 1; the diisocyanate is MDI and HDI, and the MDI accounts for 76-80% of the total molar amount of the diisocyanate; the chain extender is 3-methyl-1, 5-pentanediol and 1, 6-hexanediol, and the 3-methyl-1, 5-pentanediol accounts for 60-80% of the total molar weight of the chain extender; the polyol is composed of polycarbonate diol with a molecular weight of 2000-4000, polytetrahydrofuran diol with a molecular weight of 2000-4000 and FM-4425 double-end diol type reactive silicone with a molecular weight of 10000, wherein the polycarbonate diol accounts for 60-70% of the total mole of the chain extender, and the FM-4425 double-end diol type reactive silicone accounts for 5-10% of the total mole of the chain extender; the sum of the molar quantity of-NCO-in the diisocyanate and the molar quantity of hydroxyl in the chain extender and the polyol has an R value of (0.988-0.996) 1, and the hard segment content in the TPU resin is controlled to be 42-45wt% and is smaller than the hard segment content in the modified TPU resin in the TPU modified PVC main film (32);

step three, placing the prepared semi-finished TPU granules at 80-90 ℃, drying until the moisture content is lower than 0.02%, and then placing the semi-finished TPU granules at 75-80 ℃ for heat treatment for 20-24 hours to obtain finished modified TPU resin granules B;

the TPU protective outer film (1) is mainly prepared from the following substances: diisocyanate, chain extender, polyol, catalyst and functional auxiliary agent; the catalyst is organic bismuth, and the mass of the organic bismuth accounts for 0.001-0.1% of the total mass of diisocyanate, chain extender and polyol; the mass of the functional auxiliary agent accounts for 2.0-3.2% of the total mass of diisocyanate, chain extender and polyol; the functional auxiliary agent comprises an antioxidant auxiliary agent and a functional filler, wherein the mass ratio of the antioxidant auxiliary agent to the functional filler is (2-3) (7-8); the functional filler mainly comprises nano molybdenum silicide and nano titanium oxynitride; the mass ratio of the nano molybdenum silicide to the nano titanium oxynitride is 1 (0.2-0.5); the antioxidant auxiliary agent consists of an antioxidant 1010, an antioxidant 168, nano titanium nitride with the average particle size of 10-100nm and nano silicon nitride with the average particle size of 10-50 nm; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the nano titanium nitride with the average grain diameter of 10-100nm to the nano silicon nitride with the average grain diameter of 10-50nm is controlled at 8:2 (2-4) to 2-4; the diisocyanate is MDI and HDI, and the MDI accounts for 80-90% of the total molar weight of the diisocyanate; the chain extender is 1, 6-hexanediol and 2, 3-tetrafluoro-1, 4-butanediol, and the 2, 3-tetrafluoro-1, 4-butanediol accounts for 8-12.5% of the total molar amount of the chain extender; the polyol is prepared from polycarbonate diol with a molecular weight of 3000, fluorine modified polyester polyol with a molecular weight of 3000 and FM-4425 double-end diol type reactive silicone with a molecular weight of 10000, wherein the polycarbonate diol accounts for 75-80% of the total molar weight of the chain extender, and the FM-4425 double-end diol type reactive silicone accounts for 5-10% of the total molar weight of the chain extender; the sum of the molar quantity of-NCO-in the diisocyanate and the molar quantity of hydroxyl in the chain extender and the polyol has an R value of (0.988-0.996) 1, and the hard segment content in the TPU resin is controlled to be 48-52wt%; the fluorine modified polyester polyol is prepared from adipic acid, 1, 4-bis (2-hydroxyhexafluoroisopropyl) benzene and 3-methyl-1, 5-pentanediol;

The preparation method of the TPU protective outer film (1) comprises the following steps:

step four, placing the prepared semi-finished TPU granules at 80-90 ℃, drying until the moisture content is lower than 0.02%, then placing the semi-finished TPU granules at 75-80 ℃ for heat treatment for 20-24 hours to obtain finished modified TPU resin granules, and preparing a TPU protective outer film by adopting the finished modified TPU resin granules;

the TPU efficient heat insulation film (2) comprises two TPU matrix films (21), wherein only one surface of each TPU matrix film (21) is provided with a nanoparticle layer (20) for reflecting and/or absorbing ultraviolet rays and infrared rays; the interface of the TPU matrix film (21) compounded with the TPU protective outer film (1) is not provided with a nanoparticle layer A (201); forming a nanoparticle layer B (202) at the interface of the TPU matrix film (21) compounded with the TPU modified PVC matrix film (3); the nanometer particle layer A (201) is a silicon nitride film layer with the thickness of 45-50nm, the nanometer particle layer B (202) is a silicon nitride film (202) with the thickness of 140-180nm, the nanometer particle layer A (201) is positioned at the upper part of the nanometer particle layer B (202), and the composite position of the nanometer particle layer A (201) is close to the TPU protective outer film (1); the TPU matrix film (21) is mainly prepared from 80-85A TPU resin and modified nano inorganic filler; the TPU resin is Elastollan TPU 1190A10 and Elastollan TPU 1185A10 of Basoff; the dosage of the modified nano inorganic filler is 4.0-6.0% of the total mass of the TPU matrix film (21); the modified nano inorganic filler is nano titanium nitride and surface modified porous nano silicon dioxide, and the mass ratio of the nano titanium nitride to the surface modified porous nano silicon dioxide is (1-3): (7-9); the preparation method of the modified nano inorganic filler comprises the following steps:

2. The double-dummy composite vehicle sticker according to claim 1, wherein: the preparation method of the TPU modified PVC matrix film (3) comprises the following steps: the method comprises the following steps:

Step two, preparing a mixture A for preparing the TPU modified PVC main body film (32): weighing film-grade PVC resin, a plasticizer DINP, a compatilizer, a barium zinc stabilizer, an inorganic function mixed filler and a liquid rare earth flame retardant according to a proportion, uniformly stirring, discharging the mixture into a ten-thousand horsepower machine, wherein the refining current of the ten-thousand horsepower machine reaches 240-250A, judging to be ripe, discharging the mixture into a binding machine, filtering the mixture by a filter after uniform plasticization, and obtaining a finished product mixture A;

simultaneously preparing a mixture B for preparing the first mucosa-increasing layer (31) and the second mucosa-increasing layer (33): weighing film-grade PVC resin, the modified TPU resin B in the first step, the plasticizer DINP, the compatilizer, the barium zinc stabilizer, the inorganic function mixed filler and the liquid rare earth flame retardant according to the proportion, uniformly stirring, discharging the mixture into a ten-thousand horsepower machine, wherein the refining current of the ten-thousand horsepower machine reaches 240-250A, judging to be ripe, discharging the mixture into a binding machine, filtering the mixture by a filter after uniform plasticization, and obtaining a finished product mixture B;

putting the finished product mixture A prepared in the step two into a single-screw extruder A, putting the finished product mixture B into the single-screw extruder B, controlling the temperature of a casting film roller to be 160-170 ℃ in unit time, adjusting the clearance of the die lip and the speed of the casting film roller, and enabling the casting film thickness D=180-250 mu m to be obtained;

Step four, the film material obtained in the step three is sent into a synchronous stretching system to be subjected to biaxial stretching treatment, and the stretching multiplying power is increased: the transverse stretching multiplying power is 2.25-2.5, the longitudinal stretching multiplying power is 2.25-2.5, and the transverse stretching multiplying power is equal to the longitudinal stretching multiplying power, so that the three-layer co-extrusion TPU modified PVC matrix film with the thickness of 88-120 mu m is obtained;

3. A process for producing a double-dummy composite car sticker according to any one of claims 1-2, characterized in that: the method comprises the following steps:

step one, preparing a TPU protective outer film (1), a TPU high-efficiency heat-insulating film (2) and a TPU modified PVC matrix film (3) respectively for later use;

secondly, carrying out low-temperature plasma treatment on one surface of the TPU protective outer film (1), sticking a release film on the other surface, wherein the treatment temperature is 0-8 ℃, the treatment gas is compressed air, the treatment time is 800-860s, after the low-temperature plasma treatment is finished, removing the release film on the other surface, and then carrying out matte embossing treatment to obtain the single-sided tackifying modified TPU protective outer film;

step three, the surface of the single-sided tackifying modified TPU outer protective film subjected to low-temperature plasma treatment is compounded with the surface of the TPU high-efficiency heat-insulating film (2) which is not plated with the nanoparticle layer (20) in a hot-pressing manner, so that a composite film A is obtained; the TPU modified PVC matrix film (3) is compounded with the surface of the TPU high-efficiency heat-insulating film (2) coated with the nanoparticle layer (20) in the composite film A by hot pressing, namely the TPU high-efficiency heat-insulating film (2) is compounded between the TPU outer protective film (1) and the TPU modified PVC matrix film (3) by hot pressing, so as to obtain a composite film B;

and fifthly, coating connection glue on the surface of the TPU modified PVC matrix film (3) in the composite film B obtained in the step four, curing to form a connection adhesive film (4), compositing a release film on the surface of the connection adhesive film (4) to form a release film (5), cutting, and rolling to obtain the finished double-dummy composite car adhesive film.