CN115819956B - Car cover protective film based on microprism structure and preparation method thereof - Google Patents
Car cover protective film based on microprism structure and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of car cover protective films, in particular to a car cover protective film based on a microprism structure and a preparation method thereof, and the car cover protective film comprises the following processes: and (3) taking a base film or a base film material, and placing the base film or the base film material in a microprism mould for hot pressing to form a microprism structure, thereby obtaining the car cover protective film. The invention uses the microprism structure as a structural unit of the retroreflection, and the prepared transparent or color-changing car cover protective film can realize the light adjusting function, embody more color layers, lead the car cover protective film to have a monochromatic or colorful effect, achieve the rainbow effect or colorful effect, have rich color layers, improve the beauty and the infection force of the car cover protective film, reduce the use of pigment, reduce carbon emission and be more beneficial to environmental protection.
Description
Technical Field
The invention relates to the technical field of car cover protective films, in particular to a car cover protective film based on a microprism structure and a preparation method thereof.
Background
As a novel high-performance environment-friendly film, the car cover protective film is widely applied to the car beauty maintenance industry and has good comprehensive performance. The existing automobile paint protective film is usually made of TPU, and is generally a colorless transparent film with higher light transmittance, low mechanical strength and poor high temperature resistance. The color modifying film is one that develops its color by reflecting the same color in the light rays from the body, typically using PVC as the substrate, and a small portion of TPU as the substrate. In order to enrich the color texture of the car cover protective film and improve the aesthetic property of the car cover protective film, we propose a car cover protective film based on a microprism structure and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a car cover protective film based on a microprism structure and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the car cover protective film based on the microprism structure comprises the following processes:
and (3) taking a base film or a base film material, and placing the base film or the base film material in a microprism mould for hot pressing to form a microprism structure, thereby obtaining the car cover protective film.
Further, the microprism structure is a regular triangular pyramid, and the angle of the vertex angle of the regular triangular pyramid is 55-65 degrees along the positive section of the edge.
Further, the base film is a TPU film, a PC film or a TPU/PC multilayer film.
Further, the thickness of the base film is 150-200 um.
In the above technical solution, the microprism structure may be formed in a hot-pressing process on the TPU film or the PVC film; the TPU film can also be formed in the casting process, the calendering of PVC or the casting process engineering; the micro-prism structure can be formed on the PC surface or the PVC surface of the PVC/PC multilayer film in the coextrusion casting process of the PVC/PC multilayer film. The microprism structure is used as a structural unit of the retroreflection, and the manufactured transparent or color-changing car cover protective film can realize the light adjusting function, embody more color layers, enable the car cover protective film to have a single color or colorful effect, achieve the rainbow effect or colorful effect, have rich color layers, improve the attractiveness and the infection force of the car cover protective film, reduce the use of pigment, reduce carbon emission and be more beneficial to environmental protection.
Further, the TPU film is specifically prepared by the following process:
(1) Mixing polyamine and N-methyl pyrrolidone, and stirring under the protection of nitrogen atmosphere until the polyamine and N-methyl pyrrolidone are completely dissolved; dianhydride is added and stirred to react for 6 to 12 hours at a low temperature of 5 to 20 ℃ to obtain polyamic acid solution;
adding organic base isoquinoline and N-methyl pyrrolidone, and stirring for 2h at 15-25 ℃; adding dehydrating agent acetic anhydride and catalyst pyridine, heating to 60-80 ℃ and stirring for reacting for 4-6 h; spin steaming and drying to obtain polyimide;
(2) Mixing hydroxyl-terminated polybutadiene, isophorone diisocyanate and dibutyltin dilaurate, and reacting for 2-3 hours at 50-70 ℃; adding polyether glycol to continue the reaction for 2-3 h, adding anhydride when the NCO content is 10-18%, and heating to 70-80 ℃ to react for 60-150 min to obtain polyurethane;
(3) Mixing polyurethane, polyimide and acetone, adding deionized water and an emulsifying agent, stirring for emulsification, and removing acetone by rotary evaporation; adding glass beads and a photoinitiator, and carrying out ultraviolet curing; and (5) casting, heat treatment and drying to obtain the TPU film.
Further, the polyamine in the step (1) comprises two or more of 4, 4-diaminodiphenyl ether, siloxane diamine, fluorine-containing triamine, 3-dimethyl-4, 4-diaminodiphenyl methane and 1, 4-bis (4 '-amino-2' -trifluoromethylphenoxy) biphenyl.
Further, the dianhydride in the step (1) comprises one or more of pyromellitic dianhydride, 3, 4' -tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride and 3,3',4' -biphenyl tetracarboxylic dianhydride.
Further, the solid content of the polyamic acid solution in the step (1) is 15 to 20%.
Further, the molar ratio of the polyamine to the dianhydride in the step (1) is 1 (1.02 to 1.05).
In the step (1), the molar ratio of polyamine, organic base isoquinoline, dehydrating agent acetic anhydride and catalyst pyridine is 1 (0.8-1.0): 1.0-1.1.
Further, the siloxane diamine is prepared by the following process:
mixing 3-mercaptopropyl methyl dimethoxy silane, decamethyl cyclopentasiloxane and 3-aminopropyl dimethyl methoxy silane, slowly adding trifluoromethane sulfonic acid and deionized water, and reacting at 75-80 ℃; cooling to room temperature, adding ethanol water mixed solution of saturated sodium carbonate, washing, taking organic phase, and distilling for 2h under vacuum degree-0.1 MPa and temperature 120 ℃ to obtain siloxane diamine.
Further, the molar ratio of the 3-mercaptopropyl methyl dimethoxy silane, the decamethyl cyclopentasiloxane and the 3-aminopropyl dimethyl methoxy silane is (22-70): (70-88): 1;
further, the addition amount of the trifluoromethanesulfonic acid is 0.5-2.0% of the mass of the reactant;
the addition amount of deionized water is 2.2-5.2% of the mass of the reactant.
Further, the fluorine-containing triamine is prepared by the following process:
mixing perfluoro diphenyl, aminophenol, cesium carbonate and N, N-dimethylformamide, and reacting at 120-130 ℃ for 10-15 h; cooling to room temperature, diluting with methyl butyl ether, washing with sodium bicarbonate water solution and sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, filtering, vacuum concentrating, passing through column chromatography, and eluting with petroleum ether and ethyl acetate mixture at volume ratio of 3:1.
Further, the aminophenol is a mixture of para-aminophenol and 4-amino-3-fluorophenol in a molar ratio of 1:1.
Further, the molar ratio of the perfluoro diphenyl, the aminophenol and the cesium carbonate is 1 (2.1-2.2) to 1.5-1.6.
The ratio of the perfluoro biphenyl to the N, N-dimethylformamide is (15-18) g/100mL.
Further, the polyurethane in the step (2) comprises the following components in mass percent: 60 to 64 parts of hydroxyl-terminated polybutadiene, 5.0 to 8.0 parts of polyether glycol, 2.1 to 2.5 parts of anhydride, 8.8 to 9.0 parts of isophorone diisocyanate and 0.3 to 0.6 part of dibutyltin dilaurate.
Further, the anhydride in the step (2) is one or more of maleic anhydride, N-decenyl succinic anhydride, allyl succinic anhydride and citraconic anhydride.
Further, the TPU film in the step (3) is prepared from the following components in parts by mass: 80 to 92 parts of polyurethane, 8 to 20 parts of polyimide, 80 to 160 parts of acetone, 40 to 80 parts of deionized water, 0.5 to 2.0 parts of emulsifier, 5 to 10 parts of glass beads and 1.6 to 4.5 parts of photoinitiator.
Further, the photoinitiator is photoinitiator 184;
the emulsifier is one of Tween-20, tween-60, OP-5, OP-10, EL, SE-10 and AEO;
glass beads: b250 is from Chengwei reflective material Co., ltd;
hydroxyl-terminated polybutadiene: HTPB has a hydroxyl value of 0.54-0.64mmol/g and is available from Ten-Yuan aviation materials (Yingkou) technology Co., ltd;
polyether glycol: PPG-1000 is derived from the sea-Ann petrochemical plant in Jiangsu province.
Further, the ultraviolet curing process comprises the following steps: and irradiating for 12-20 s by an ultraviolet lamp.
Further, the heat treatment process comprises the following steps: heating to 60-80 ℃ at a heating rate of 2 ℃/min for 1-3 h.
Further, the drying process comprises the following steps: drying at 50-60 deg.c for 12-24 hr.
In the technical scheme, the resin part in the TPU film is a polyurethane elastomer modified by polyimide, and polyimide is introduced into a polyurethane aqueous system, so that the mechanical strength and the high temperature resistance of the TPU film can be effectively improved; the inorganic component is glass beads, the high refraction performance of the glass beads, the reflection effect of the prepared car cover protective film during use and the light retroreflection formed by the microprism structure on the surface of the car cover protective film are utilized, and the mechanical performance, the water resistance, the high temperature resistance, the ultraviolet resistance and the like of the prepared TPU film can be improved, so that the TPU film and the car cover protective film with excellent comprehensive performance are obtained.
The polyimide is obtained by reacting polyamine with dianhydride, wherein the polyamine reacts with the dianhydride to obtain polyamic acid, then organic base isoquinoline is added to form polyamic acid salt, finally dehydrating agent acetic anhydride and catalyst pyridine are added, and dehydration cyclization is carried out to carry out reaction imidization, so that the organic matter polyamic acid salt-polyimide (namely polyimide in the process) is obtained. The introduction of the polyamic acid salt can effectively enhance the plasticity of the prepared polyimide and is beneficial to the improvement of the processability, flexibility and mechanical strength of the prepared TPU film.
In the preparation system of polyamide acid, there are side reactions such as hydrolysis of dianhydride, complexation of dianhydride and solvent, etc., and when the molecular terminal of the produced polymer polyamide acid is carboxyl, the polymer polyamide acid has higher molecular stability, and the consumption in the reaction needs to be compensated by increasing the amount of dianhydride. The formation reaction of the polyamide acid is exothermic reaction, has a larger reaction equilibrium constant at low temperature, and has higher reaction degree; with the progress of the reaction, the intrinsic viscosity of the system is increased, and after a period of reaction, the change of the intrinsic viscosity tends to be gentle, and the reaction is ended at the moment, so that the reverse reaction tendency of degradation is relieved. Therefore, under the process conditions of the amount, temperature, time and the like of the substances, the generated polyamide acid has higher molecular weight and molecular stability.
The polyamine used in the polyimide is two or more of siloxane diamine, fluorine-containing triamine, 4-diaminodiphenyl ether, 3-dimethyl-4, 4-diaminodiphenyl methane and 1, 4-bis (4 '-amino-2' -trifluoromethylphenoxy) biphenyl. The siloxane chain segment is introduced into a polyimide main chain structure, and the Si-O bond has higher bond energy, and meanwhile, the rigidity is reduced due to higher rotational freedom of the bond, so that the flexibility and the film forming property of the obtained polyimide and TPU film are improved. Meanwhile, the introduction of the silicon-containing group can improve the mechanical strength, chemical corrosion resistance and high temperature resistance of polyimide and TPU films and reduce the hygroscopicity of the polyimide and TPU films. The fluorine element is introduced, so that the electron polarization degree is small, the electronegativity and the bond energy of C-F are high, the molecular chain distance is increased to a certain extent, the free volume of molecules is increased, the interaction force among the molecules is reduced, the movement capability of the molecular chains is increased, the solubility of polyimide is improved, the dispersity between polyimide and polyurethane is improved, and the heat oxidation resistance and the hydrophobic property of polyimide can be improved; the higher electronegativity damages the conjugation of electron cloud in the polyimide molecular structure, reduces the transmission capacity of electrons in a system, ensures that the absorption of polyimide to visible light tends to develop in the short wave direction, and enhances the transparency of the TPU film; the hydrophobicity of the fluorine element also allows the water absorption of the TPU film to be further reduced.
The double bond is introduced into the polyurethane system through the component hydroxyl-terminated polybutadiene and anhydride; sulfydryl is introduced into the polyimide system through the siloxane diamine component; under the action of a photoinitiator, the two are subjected to click reaction of sulfhydryl-alkene, polyimide and polyurethane molecular chains are crosslinked, the crosslinking density of the TPU film is improved, a three-dimensional network structure is formed, and the wear resistance, impact resistance and medium resistance of the TPU film are also improved. The double bond in polyurethane and polyimide mercapto are subjected to photocatalysis reaction, so that the ultraviolet resistance and weather resistance of the TPU film prepared under natural conditions are improved. And after double bond reaction, the reduction of the number of carbon-carbon double bonds can effectively improve the ageing resistance of the TPU film, and the TPU film has more excellent toughness and mechanical properties in the ageing process.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the car cover protective film based on the microprism structure and the preparation method thereof, the microprism structure is used as a structural unit for retroreflection, and the prepared transparent or color-changing car cover protective film can realize a light adjusting function, embody more color layers, have a monochromatic or colorful effect, achieve a rainbow effect or colorful effect, have rich color layers, improve the attractiveness and the infectivity of the car cover protective film, reduce the use of pigment, reduce carbon emission and be more beneficial to environmental protection through arrangement and adjustment of the retroreflection structure.
2. According to the car cover protective film based on the microprism structure and the preparation method thereof, the polyimide modified polyurethane elastomer is used as a resin part in the TPU film, and polyimide is introduced into a polyurethane aqueous system, so that the mechanical strength and the high temperature resistance of the TPU film can be effectively improved; the inorganic component of the TPU film is glass beads, and the high refraction performance, the reflection effect when the prepared car cover protective film is used and the light retroreflection formed by the microprism structure on the surface of the car cover protective film are utilized, so that the mechanical performance, the water resistance, the high temperature resistance, the ultraviolet resistance and the like of the prepared TPU film can be improved, and the TPU film and the car cover protective film with excellent comprehensive performance are obtained.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic view of the structure of the microprism of the present invention at a 55℃angle along the positive cross-section apex angle of the edge;
FIG. 2 is a schematic view of the structure of the microprism of the present invention with a positive cross-sectional apex angle of 65 along the edge;
FIG. 3 is a schematic front cross-sectional view of the microprism structure of the present invention at a 60℃angle along the front cross-sectional apex angle of the edge;
FIG. 4 is a schematic front cross-sectional view of the microprism structure of the present invention at a 55℃angle along the front cross-sectional apex angle of the edge;
FIG. 5 is a schematic front cross-sectional view of the microprism structure of the present invention at a front cross-sectional apex angle of 65 along the edge;
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The photoinitiator is photoinitiator 184;
the emulsifier is Tween-20;
glass beads: b250 is from Chengwei reflective material Co., ltd;
hydroxyl-terminated polybutadiene: HTPB has a hydroxyl value of 0.54-0.64mmol/g and is available from Ten-Yuan aviation materials (Yingkou) technology Co., ltd;
polyether glycol: PPG-1000, which is derived from Jiangsu province sea-An petrochemical plant;
amino-terminated polydimethylsiloxane: aminopropyl-terminated polydimethylsiloxane having a molecular weight of 1000 and originating from new materials technology limited of the glauca of hubei;
the height of the microprism structure was 50 μm.
Example 1
(1) Preparing a TPU film:
1.1. preparation of siloxane diamine:
39.6g of 3-mercaptopropyl methyl dimethoxy silane, 260g of decamethyl cyclopentasiloxane and 1.5g of 3-aminopropyl dimethyl methoxy silane are taken and mixed, 1.5g of trifluoromethane sulfonic acid and 6.6g of deionized water are slowly added for reaction at 75 ℃; cooling to room temperature, adding ethanol water mixed solution of saturated sodium carbonate, washing, taking organic phase, and distilling for 2h under vacuum degree-0.1 MPa and temperature 120 ℃ to obtain siloxane diamine.
1.2. Preparation of fluorine-containing triamine:
33.4g of perfluorobiphenyl, 11.4g of para-aminophenol, 13.3g of 4-amino-3-fluorophenol, 48.9g of cesium carbonate and 200mLN, N-dimethylformamide are taken and mixed and reacted for 10 hours at 120 ℃; cooling to room temperature, diluting with methyl butyl ether, washing with sodium bicarbonate water solution and sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, filtering, vacuum concentrating, passing through column chromatography, and eluting with petroleum ether and ethyl acetate mixture at volume ratio of 3:1.
Preparation of TPU film:
40g of 4, 4-diaminodiphenyl ether, 3.0g of siloxane diamine, 5.8g of fluorine-containing triamine, 22.6g of 3, 3-dimethyl-4, 4-diaminodiphenyl methane and 1200 mLN-methylpyrrolidone are taken and mixed, and stirred under the protection of nitrogen atmosphere until the mixture is completely dissolved; 55.6g of pyromellitic dianhydride and 75.0g of 3, 4' -tetracarboxylic dianhydride are added and stirred at a low temperature of 5 ℃ for reaction for 12 hours to obtain a polyamic acid solution;
51.6g of isoquinoline as an organic base and 1000 mLN-methylpyrrolidone are added and stirred for 2 hours at 15 ℃; 51.5g of dehydrating agent acetic anhydride and 39.5g of catalyst pyridine are added, the temperature is raised to 60 ℃ and the mixture is stirred for reaction for 4 hours; spin steaming and drying to obtain polyimide;
2. 600g of hydroxyl-terminated polybutadiene, 88g of isophorone diisocyanate and 3g of dibutyltin dilaurate are taken and mixed and reacted for 2 hours at 50 ℃; adding 50g of polyether glycol for continuous reaction for 2 hours, when the NCO content is 10%, adding 21g of anhydride N-decenyl succinic anhydride, heating to 70 ℃ for reaction for 60 minutes to obtain polyurethane, and neutralizing the pH of the system to 7.0 by using triethylamine at the temperature of 35 ℃;
3. mixing 800g of polyurethane, 80g of polyimide and 800g of acetone, adding 400g of deionized water and 5g of emulsifying agent, stirring for emulsification, and removing the acetone by rotary evaporation; 5g of glass beads and 160g of photoinitiator are added, casting and ultraviolet curing are carried out, and the process is as follows: irradiating for 12s by an ultraviolet lamp; the heat treatment comprises the following steps: heating to 60 ℃ at a heating rate of 2 ℃/min for 3 hours; drying, wherein the process comprises the following steps: drying at 50 ℃ for 24 hours to obtain the TPU film.
(2) Preparation of a car cover protective film:
placing a base film in a microprism mould, and hot-pressing for 10min at 145 ℃ and 3MPa to form a microprism structure, wherein the microprism structure is a regular triangular pyramid, and the angle of the vertex angle of the regular triangular pyramid is 55 degrees along the regular cross section of an edge to obtain a car cover protective film; the thickness of the base film was 180um.
Example 2
(1) Preparing a TPU film:
1.1. preparation of siloxane diamine:
82.8g of 3-mercaptopropyl methyl dimethoxy silane, 293g of decamethyl cyclopentasiloxane and 1.5g of 3-aminopropyl dimethyl methoxy silane are taken and mixed, 4.5g of trifluoromethane sulfonic acid and 14g of deionized water are slowly added for reaction at 78 ℃; cooling to room temperature, adding ethanol water mixed solution of saturated sodium carbonate, washing, taking organic phase, and distilling for 2h under vacuum degree-0.1 MPa and temperature 120 ℃ to obtain siloxane diamine.
1.2. Preparation of fluorine-containing triamine:
33.4g of perfluorobiphenyl, 11.8g of para-aminophenol, 13.7g of 4-amino-3-fluorophenol, 50.5g of cesium carbonate and 200mLN, N-dimethylformamide are taken and mixed and reacted for 12 hours at the temperature of 125 ℃; cooling to room temperature, diluting with methyl butyl ether, washing with sodium bicarbonate water solution and sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, filtering, vacuum concentrating, passing through column chromatography, and eluting with petroleum ether and ethyl acetate mixture at volume ratio of 3:1.
Preparation of TPU film:
40g of 4, 4-diaminodiphenyl ether, 3.0g of siloxane diamine, 5.8g of fluorine-containing triamine, 22.6g of 3, 3-dimethyl-4, 4-diaminodiphenyl methane and 1200 mLN-methylpyrrolidone are taken and mixed, and stirred under the protection of nitrogen atmosphere until the mixture is completely dissolved; 56.1g of pyromellitic dianhydride and 75.7g of 2, 3',4' -biphenyl tetracarboxylic dianhydride are added and stirred at 12 ℃ for reaction for 8 hours to obtain polyamic acid solution;
58.0g of isoquinoline as an organic base and 1000 mLN-methylpyrrolidone are added and stirred for 2 hours at 20 ℃; 54.0g of dehydrating agent acetic anhydride and 41.5g of catalyst pyridine are added, the temperature is raised to 70 ℃ and the mixture is stirred for reaction for 5 hours; spin steaming and drying to obtain polyimide;
2. 620g of hydroxyl-terminated polybutadiene, 89g of isophorone diisocyanate and 4.5g of dibutyltin dilaurate are taken and mixed, and reacted for 2.5 hours at the temperature of 60 ℃; adding 65g of polyether glycol for continuous reaction for 2.5h, adding 23g of anhydride allyl succinic anhydride when the NCO content is 15%, heating to 75 ℃ for reaction for 100min to obtain polyurethane, and neutralizing the pH of the system to 7.0 by using triethylamine at the temperature of 35 ℃;
3. mixing 860g of polyurethane, 140g of polyimide and 1200g of acetone, adding 600g of deionized water and 12g of emulsifying agent, stirring for emulsification, and removing the acetone by rotary evaporation; 70g of glass beads and 30g of photoinitiator are added, casting and ultraviolet curing are carried out, and the process is as follows: irradiating for 15s by an ultraviolet lamp; the heat treatment comprises the following steps: heating to 70 ℃ at a heating rate of 2 ℃/min for 2h; drying, wherein the process comprises the following steps: drying at 55 ℃ for 18 hours to obtain the TPU film.
(2) Preparation of a car cover protective film:
placing a base film in a microprism mould, and hot-pressing for 5min at 150 ℃ under 4MPa to form a microprism structure, wherein the microprism structure is a regular triangular pyramid, and the angle of the vertex angle of the regular triangular pyramid is 60 degrees along the regular cross section of an edge to obtain a car cover protective film; the thickness of the base film was 180um.
Example 3
(1) Preparing a TPU film:
1.1. preparation of siloxane diamine:
126g of 3-mercaptopropyl methyl dimethoxy silane, 326.5g of decamethyl cyclopentasiloxane and 1.5g of 3-aminopropyl dimethyl methoxy silane are taken and mixed, 9g of trifluoromethane sulfonic acid and 23g of deionized water are slowly added for reaction at 80 ℃; cooling to room temperature, adding ethanol water mixed solution of saturated sodium carbonate, washing, taking organic phase, and distilling for 2h under vacuum degree-0.1 MPa and temperature 120 ℃ to obtain siloxane diamine.
1.2. Preparation of fluorine-containing triamine:
33.4g of perfluorobiphenyl, 11.9g of para-aminophenol, 13.9g of 4-amino-3-fluorophenol, 52.1g of cesium carbonate and 200mLN, N-dimethylformamide are taken and mixed and reacted for 15 hours at 130 ℃; cooling to room temperature, diluting with methyl butyl ether, washing with sodium bicarbonate water solution and sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, filtering, vacuum concentrating, passing through column chromatography, and eluting with petroleum ether and ethyl acetate mixture at volume ratio of 3:1.
Preparation of TPU film:
40g of 4, 4-diaminodiphenyl ether, 3.0g of siloxane diamine, 5.8g of fluorine-containing triamine, 22.6g of 3, 3-dimethyl-4, 4-diaminodiphenyl methane and 1200 mLN-methylpyrrolidone are taken and mixed, and stirred under the protection of nitrogen atmosphere until the mixture is completely dissolved; 57.2g of pyromellitic dianhydride and 77.2g of 3, 4' -tetracarboxylic dianhydride are added and stirred at 20 ℃ for reaction for 6 hours to obtain a polyamic acid solution;
64.5g of isoquinoline as an organic base and 1000 mLN-methylpyrrolidone are added and stirred for 2 hours at 25 ℃; 56.6g of dehydrating agent acetic anhydride and 43.4g of catalyst pyridine are added, the temperature is raised to 80 ℃ and the mixture is stirred for reaction for 6 hours; spin steaming and drying to obtain polyimide;
2. mixing 640g of hydroxyl-terminated polybutadiene, 90g of isophorone diisocyanate and 6g of dibutyltin dilaurate, and reacting for 3 hours at 70 ℃; adding 80g of polyether glycol for continuous reaction for 3 hours, when the NCO content is 18%, adding 25g of anhydride citraconic anhydride, heating to 80 ℃ for reaction for 150 minutes to obtain polyurethane, and neutralizing the pH of the system to 7.0 by using triethylamine at the temperature of 35 ℃;
3. mixing 920g of polyurethane, 200g of polyimide and 1600g of acetone, adding 800g of deionized water and 20g of emulsifying agent, stirring for emulsification, and removing the acetone by rotary evaporation; 100g of glass beads and 45g of photoinitiator are added, casting and ultraviolet curing are carried out, and the process is as follows: irradiating for 20s by an ultraviolet lamp; the heat treatment comprises the following steps: heating to 80 ℃ at a heating rate of 2 ℃/min for 1 hour; drying, wherein the process comprises the following steps: drying at 60 ℃ for 12 hours to obtain the TPU film.
(2) Preparation of a car cover protective film:
placing a base film in a microprism mould, and hot-pressing for 3min at 160 ℃ and 5MPa to form a microprism structure, wherein the microprism structure is a regular triangular pyramid, and the angle of the vertex angle of the regular triangular pyramid is 65 degrees along the regular cross section of an edge to obtain a car cover protective film; the thickness of the base film was 180um.
Comparative example 1
(1) Preparing a TPU film:
1.1. preparation of fluorine-containing diamine:
33.4g of perfluorobiphenyl, 22.8g of para-aminophenol, 13.3g of 4-amino-3-fluorophenol, 48.9g of cesium carbonate and 200mLN, N-dimethylformamide are taken and mixed and reacted for 10 hours at 120 ℃; cooling to room temperature, diluting with methyl butyl ether, washing with sodium bicarbonate water solution and sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, filtering, vacuum concentrating, passing through column chromatography, and eluting with petroleum ether and ethyl acetate mixture at volume ratio of 3:1.
Preparation of TPU film:
40g of 4, 4-diaminodiphenyl ether, 3.0g of amino-terminated polydimethylsiloxane, 5.8g of fluorine-containing diamine, 22.6g of 3, 3-dimethyl-4, 4-diaminodiphenylmethane and 1200 mLN-methylpyrrolidone are taken and mixed, and stirred under the protection of nitrogen atmosphere until the materials are completely dissolved; 55.6g of pyromellitic dianhydride and 75.0g of 3, 4' -tetracarboxylic dianhydride are added and stirred at a low temperature of 5 ℃ for reaction for 12 hours to obtain a polyamic acid solution;
51.6g of isoquinoline as an organic base and 1000 mLN-methylpyrrolidone are added and stirred for 2 hours at 15 ℃; 51.5g of dehydrating agent acetic anhydride and 39.5g of catalyst pyridine are added, the temperature is raised to 60 ℃ and the mixture is stirred for reaction for 4 hours; spin steaming and drying to obtain polyimide;
other steps were the same as in example 1 to obtain a protective film for a vehicle cover.
Comparative example 2
(1) Preparing a TPU film:
1. 40g of 4, 4-diaminodiphenyl ether, 3.0g of amino-terminated polydimethylsiloxane, 5.8g of 1, 4-bis (4 '-amino-2' -trifluoromethylphenoxy) biphenyl, 22.6g of 3, 3-dimethyl-4, 4-diaminodiphenylmethane and 1200 mLN-methylpyrrolidone are taken and mixed, and stirred under the protection of nitrogen atmosphere until the materials are completely dissolved; 55.6g of pyromellitic dianhydride and 75.0g of 3, 4' -tetracarboxylic dianhydride are added and stirred at a low temperature of 5 ℃ for reaction for 12 hours to obtain a polyamic acid solution;
51.6g of isoquinoline as an organic base and 1000 mLN-methylpyrrolidone are added and stirred for 2 hours at 15 ℃; 51.5g of dehydrating agent acetic anhydride and 39.5g of catalyst pyridine are added, the temperature is raised to 60 ℃ and the mixture is stirred for reaction for 4 hours; spin steaming and drying to obtain polyimide;
other steps were the same as in example 1 to obtain a protective film for a vehicle cover.
Comparative example 3
60g of 4, 4-diaminodiphenyl ether, 45.2g of 3, 3-dimethyl-4, 4-diaminodiphenyl methane and 1200 mLN-methylpyrrolidone are taken and mixed, and stirred under the protection of nitrogen atmosphere until the materials are completely dissolved; 55.6g of pyromellitic dianhydride and 75.0g of 3, 4' -tetracarboxylic dianhydride are added and stirred at a low temperature of 5 ℃ for reaction for 12 hours to obtain a polyamic acid solution;
51.6g of isoquinoline as an organic base and 1000 mLN-methylpyrrolidone are added and stirred for 2 hours at 15 ℃; 51.5g of dehydrating agent acetic anhydride and 39.5g of catalyst pyridine are added, the temperature is raised to 60 ℃ and the mixture is stirred for reaction for 4 hours; spin steaming and drying to obtain polyimide;
other steps were the same as in example 1 to obtain a protective film for a vehicle cover.
Comparative example 4
2. 600g of hydroxyl-terminated polybutadiene, 88g of isophorone diisocyanate and 3g of dibutyltin dilaurate are taken and mixed and reacted for 2 hours at 50 ℃; adding 50g of polyether glycol for continuous reaction for 2 hours, adding 21g of 1, 3-butanediol when the NCO content is 10%, heating to 70 ℃ for reaction for 60 minutes to obtain polyurethane, and neutralizing the pH of the system to 7.0 by using triethylamine at the temperature of 35 ℃;
3. mixing 800g of polyurethane, 80g of polyimide and 800g of acetone, adding 400g of deionized water and 5g of emulsifying agent, stirring for emulsification, and removing the acetone by rotary evaporation; 5g of glass beads and 160g of photoinitiator are added, casting and ultraviolet curing are carried out, and the process is as follows: irradiating for 12s by an ultraviolet lamp; the heat treatment comprises the following steps: heating to 60 ℃ at a heating rate of 2 ℃/min for 3 hours; drying, wherein the process comprises the following steps: drying at 50 ℃ for 24 hours to obtain the TPU film.
The other steps were the same as in comparative example 3, to obtain a car cover protective film.
Comparative example 5
3. Mixing 880g of polyurethane and 800g of acetone, adding 400g of deionized water and 5g of emulsifying agent, stirring for emulsification, and removing the acetone by rotary evaporation; 5g of glass beads and 160g of photoinitiator are added, casting and ultraviolet curing are carried out, and the process is as follows: irradiating for 12s by an ultraviolet lamp; the heat treatment comprises the following steps: heating to 60 ℃ at a heating rate of 2 ℃/min for 3 hours; drying, wherein the process comprises the following steps: drying at 50 ℃ for 24 hours to obtain the TPU film.
The other steps were the same as in comparative example 4, to obtain a car cover protective film.
Experiment
Taking the car cover protective films obtained in examples 1-3 and comparative examples 1-5, preparing test samples, respectively detecting the performances thereof and recording the detection results:
mechanical property test: using GB/T528 as a reference standard, and adopting a universal tensile machine to test the tensile property of the sample, wherein the tensile rate is 200mm/min;
water absorption test: placing a sample in deionized water, soaking for 48 hours at a test temperature of 25 ℃, taking out the wiped water, and calculating the weight change rate of the sample before and after water absorption;
retroreflective performance test: the method comprises the steps of (1) carrying out a retroreflection coefficient test on a sample by adopting a retroreflection coefficient detector, wherein alpha=0.2 degrees and beta=5 degrees;
ageing performance test: the test was conducted by irradiating with ultraviolet light (340 nm) at 0.63W/m2 at 60℃for 4 hours and exposing with moisture at 50℃for 4 hours, and the test was conducted in a cycle of 15 cycles, and the change in the properties of the test sample after the aging test was observed, with the retention of the retroreflectivity of the test sample before and after the aging as the test index.
From the data in the above table, the following conclusions can be clearly drawn:
the car cover protective films obtained in examples 1 to 3 were compared with the car cover protective films obtained in comparative examples 1 to 5, and the detection results revealed,
compared with the comparative examples, the car cover protective films obtained in examples 1-3 have higher data of tensile strength, retroreflectivity and retention rate of retroreflectivity after aging and lower data of water absorption, which fully demonstrates that the improvement of mechanical property, water resistance and ageing resistance of the car cover protective films is realized.
In comparison with example 1, the siloxane diamine in comparative example 1 was replaced with an equal mass of amino-terminated polydimethylsiloxane; the fluorine-containing triamine in comparative example 2 was replaced with 1, 4-bis (4 '-amino-2' -trifluoromethylphenoxy) biphenyl of equal mass; comparative example 3 was free of added siloxane diamine and fluorine-containing diamine; in comparison with comparative example 3, the anhydride in comparative example 4 was replaced with 1, 3-butanediol of equal mass; in contrast to comparative example 4, no polyimide was added to the TPU film component of comparative example 5; the data of the tensile strength, the retroreflection coefficient and the retention rate of the retroreflection coefficient after aging of the car cover protective films obtained in the comparative examples 1-5 are high, and the water absorption rate is high, so that the improvement of the mechanical property, the water resistance and the ageing resistance of the car cover protective film is promoted by setting the components and the process of the car cover protective film.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a car cover protective film based on a microprism structure is characterized by comprising the following steps: the method comprises the following steps:
taking a base film or a base film material, and placing the base film or the base film material in a microprism mould for hot pressing to form a microprism structure, thereby obtaining a car cover protective film;
the base film is a TPU film; the TPU film is specifically prepared by the following process:
(1) Mixing polyamine and N-methyl pyrrolidone, and stirring under the protection of nitrogen atmosphere until the polyamine and N-methyl pyrrolidone are completely dissolved; dianhydride is added and stirred at low temperature for reaction for 6 to 12 hours to obtain polyamic acid solution;
isoquinoline is added and stirred for 2 hours at the temperature of 15-25 ℃; adding a dehydrating agent and a catalyst, heating to 60-80 ℃ and stirring for reacting for 4-6 hours to obtain polyimide;
(2) Mixing hydroxyl-terminated polybutadiene, isophorone diisocyanate and dibutyltin dilaurate, and reacting for 2-3 hours at 50-70 ℃; adding polyether glycol to continue the reaction for 2-3 h, adding anhydride when the NCO content is 10-18%, and heating to 70-80 ℃ to react for 60-150 min to obtain polyurethane;
(3) Mixing polyurethane, polyimide and acetone, adding deionized water and an emulsifying agent, stirring for emulsification, and removing acetone by rotary evaporation;
adding glass beads and a photoinitiator, and carrying out ultraviolet curing; and (5) casting, heat treatment and drying to obtain the TPU film.
2. The method for preparing the car cover protective film based on the microprism structure according to claim 1, wherein the method comprises the following steps: the microprism structure is a regular triangular pyramid, and the angle of the vertex angle of the regular triangular pyramid is 55-65 degrees along the positive section of the edge.
3. The method for preparing the car cover protective film based on the microprism structure according to claim 1, wherein the method comprises the following steps: the polyamine in the step (1) comprises two or more of 4, 4-diaminodiphenyl ether, siloxane diamine, fluorine-containing triamine, 3-dimethyl-4, 4-diaminodiphenyl methane and 1, 4-bis (4 '-amino-2' -trifluoromethyl phenoxy) biphenyl.
4. The method for preparing the car cover protective film based on the microprism structure according to claim 1, wherein the method comprises the following steps: the dianhydride in the step (1) comprises one or more of pyromellitic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride and 3,3',4' -biphenyl tetracarboxylic dianhydride.
5. The method for preparing the car cover protective film based on the microprism structure according to claim 3, wherein the method comprises the following steps: the siloxane diamine is prepared by the following process:
mixing 3-mercaptopropyl methyl dimethoxy silane, decamethyl cyclopentasiloxane and 3-aminopropyl dimethyl methoxy silane, slowly adding trifluoromethane sulfonic acid and deionized water, and reacting at 75-80 ℃; cooling to room temperature, adding ethanol water mixed solution of saturated sodium carbonate, washing, taking organic phase, and distilling for 2h under vacuum degree-0.1 MPa and temperature 120 ℃ to obtain siloxane diamine.
6. The method for preparing the car cover protective film based on the microprism structure according to claim 5, wherein the method comprises the following steps: the fluorine-containing triamine is prepared by the following process:
mixing perfluoro diphenyl, aminophenol, cesium carbonate and N, N-dimethylformamide, and reacting at 120-130 ℃ for 10-15 h; cooling to room temperature, diluting with methyl butyl ether, washing with sodium bicarbonate water solution and sodium chloride solution, drying the organic phase with anhydrous sodium sulfate, filtering, vacuum concentrating, passing through column chromatography, and eluting with petroleum ether and ethyl acetate mixture at volume ratio of 3:1.
7. The method for preparing the car cover protective film based on the microprism structure according to claim 1, wherein the method comprises the following steps: the TPU film in the step (3) is prepared from the following components in parts by mass: 80 to 92 parts of polyurethane, 8 to 20 parts of polyimide, 80 to 160 parts of acetone, 40 to 80 parts of deionized water, 0.5 to 2.0 parts of emulsifier, 5 to 10 parts of glass beads and 1.6 to 4.5 parts of photoinitiator.
8. A car cover protective film based on a microprism structure produced by the production method according to any one of claims 1 to 7.
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| CN103935056B (en) * | 2014-04-28 | 2016-08-24 | 田武学 | A kind of extrusion molding produces equipment and the method for micro-prism light reflecting film |
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