Anti-fog head-up display film for automobile and preparation method of anti-fog head-up display film

Abstract

The invention discloses an anti-fog head-up display film for an automobile and a preparation method of the anti-fog head-up display film, and belongs to the technical field of anti-fog films. The preparation method comprises the following steps: weighing the raw materials in parts by weight, putting 100-110 parts of thermoplastic polyurethane resin, 20-30 parts of acrylate rubber, 15-25 parts of a modified filler, 1-3 parts of an antioxidant, 5-10 parts of an auxiliary agent and 0.01-0.05 part of a cross-linking agent into an internal mixer, carrying out internal mixing and mixing, adding the mixed material into a double-screw extruder, carrying out extrusion granulation, and finally preparing the film by adopting a casting or blow molding process. And rolling to obtain the anti-fog head-up display film for the automobile. The auxiliary agent contains rich hydroxyl hydrophilic groups and also contains a high-density quaternary ammonium salt structure, and chemical action exists between the auxiliary agent and the modified filler, so that the auxiliary agent can be highly dispersed and stably exist in the display film and jointly act with other raw materials, and the head-up display film for the automobile has an excellent and stable anti-fog effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-fog films, and in particular, relates to an anti-fog head-up display film for automobiles and a preparation method thereof. Background Art

[0002] In daily life, various substrates such as glasses, car glass, bathroom mirrors, building interior and exterior window glass, agricultural greenhouses, etc., often fog up in places with high temperature or humidity differences, affecting their use in daily life and production, and even causing a large amount of manpower and material losses. Car glass will produce window fog in damp, cold or rainy seasons, affecting drivers' driving and easily leading to traffic accidents.

[0003] Although the current head-up display film for automobiles has a certain anti-fog effect, the interaction between the materials of the anti-fog film is weak, which leads to a short anti-fog time or even failure. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide an anti-fog head-up display film for automobiles and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: An anti-fog head-up display film for automobiles comprises the following raw materials in parts by weight: 100-110 parts of thermoplastic polyurethane resin, 20-30 parts of acrylate rubber, 15-25 parts of modified filler, 1-3 parts of antioxidant, 5-10 parts of auxiliary agent and 0.01-0.05 parts of cross-linking agent.

[0006] Furthermore, the modified filler is prepared by the following steps: The inorganic filler and deionized water were mixed evenly in a three-necked flask, and then glacial acetic acid was slowly added to adjust the pH to 4. Subsequently, a mixed solution of coupling agent and anhydrous ethanol was slowly added while stirring. After the addition was completed, the temperature was raised to 65°C and the reaction was kept warm for 1 hour. After the reaction was completed, it was cooled to room temperature and centrifuged. After centrifugation, the lower layer of precipitate was taken and ultrasonically dispersed in anhydrous ethanol for 30 minutes, and finally dried at 80°C for 12 hours to obtain a modified filler. The amount ratio of inorganic filler to coupling agent was 30g:2g.

[0007] Furthermore, the inorganic filler is a mixture of nano-silicon dioxide and diatomaceous earth in a mass ratio of 1:(3-5).

[0008] Furthermore, the coupling agent is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, and 3-(methacryloyloxy)propyltrimethoxysilane.

[0009] Furthermore, the antioxidant is one or more of antioxidant 1010, antioxidant 2246, antioxidant 1076, and antioxidant 168.

[0010] Furthermore, the auxiliary agent is prepared by the following steps: S1. Add N,N'-dimethyl-1,3-propanediamine, pyridine and ethanol to a three-necked flask under nitrogen protection, stir and heat to 70°C, then slowly add 3-chloro-1,2-propanediol, and keep warm for 3 hours after the addition is complete. After the reaction is completed, cool to room temperature first, and then distill under reduced pressure to obtain intermediate 1; the dosage ratio of N,N'-dimethyl-1,3-propanediamine, 3-chloro-1,2-propanediol, pyridine and ethanol is 12.5mL:18mL:17.8mL:200mL; The molar ratio of 3-chloro-1,2-propanediol to N,N'-dimethyl-1,3-propanediamine is controlled to be 2.1-2.2:1, and then 3-chloro-1,2-propanediol and N,N'-dimethyl-1,3-propanediamine undergo a di-substitution reaction with pyridine as an acid-binding agent. The reaction process is as follows:

[0011] S2. Add intermediate 1, triethylamine and dimethyl sulfoxide to a dry three-necked flask under nitrogen protection, stir and dissolve, heat to 70°C, then slowly add 4-chloro-1-butene, keep warm at 70°C for 3h after the addition is complete, cool to room temperature after the reaction is completed, and distill under reduced pressure to obtain intermediate 2; the amount ratio of intermediate 1, 4-chloro-1-butene, triethylamine and dimethyl sulfoxide is 21.3g:9.3mL:14.2mL:240mL; Triethylamine is used as an acid binding agent, and the molar ratio of intermediate 1 and 4-chloro-1-butene is controlled to be 1:1.05-1.1, then the tertiary amine of intermediate 1 and -Cl of 4-chloro-1-butene undergo nucleophilic substitution reaction, and the reaction process is as follows:

[0012] S3. Under nitrogen protection, add intermediate 2, triethylamine and dimethyl sulfoxide to a dry three-necked flask, stir and dissolve, then heat to 75°C, then slowly add chlorododecane, and keep at 75°C for 3 hours after the addition. After the reaction is completed, cool to room temperature and distill under reduced pressure to obtain an auxiliary agent; the amount ratio of intermediate 2, chlorododecane, triethylamine and dimethyl sulfoxide is 14g:10.3mL:6.7mL:240mL.

[0013] Triethylamine is used as an acid binding agent, and the molar ratio of intermediate 2 to chlorododecane is controlled to be 1:1.05-1.1, so that the tertiary amine of intermediate 2 and -Cl of chlorododecane undergo nucleophilic substitution reaction, and the reaction process is as follows:

[0014] The additive contains a quaternary ammonium salt structure. As a type of cationic surfactant, the quaternary ammonium salt structure can effectively absorb moisture in the air due to its special chemical structure and properties, so that water molecules exist in the form of a water film on the glass surface instead of gathering into droplets, thereby showing an excellent anti-fog effect. The abundant hydroxyl groups in the additive further improve the water absorption of the display film, thereby improving the anti-fog effect. In addition, the quaternary ammonium salt structure has antibacterial effects in five aspects: destroying the cell membrane structure, denaturing proteins, interfering with the enzyme system, changing the cell membrane permeability, and interfering with nucleic acid and protein synthesis, thereby showing that the display film has an excellent antibacterial effect.

[0015] The double bonds in the additive can react chemically with the carbon-carbon double bonds on the surface of the modified filler under the action of the cross-linking agent, so that the additive can stably exist in the display film and exert an anti-fog effect for a long time.

[0016] Furthermore, the cross-linking agent is one or more of benzoyl peroxide, triallyl isocyanurate, dicumyl peroxide, and azobisisobutyronitrile.

[0017] An anti-fog head-up display film for automobile and a preparation method thereof, comprising the following steps: Weigh each raw material by weight, then place all the raw materials in an internal mixer for internal mixing, then add the mixed materials into a twin-screw extruder for extrusion granulation, finally adopt a casting or blow molding process to prepare a film, and roll it up to obtain an anti-fog head-up display film for automobiles.

[0018] Beneficial effects of the present invention: the auxiliary agent of the present invention contains abundant hydroxyl hydrophilic groups and high-density quaternary ammonium salt structures, and there is a chemical reaction between the auxiliary agent and the modified filler, so the auxiliary agent can be highly dispersed and stably present in the display film, and work together with other raw materials to give the automotive head-up display film of the present invention an excellent and stable anti-fogging effect. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] Example 1, preparing the modified filler, the specific steps are as follows: 5g of nano-silicon dioxide, 25g of diatomaceous earth and 250mL of deionized water were mixed evenly in a 500mL three-necked flask, and glacial acetic acid was slowly added to adjust the pH to 4. Subsequently, a mixed solution of 2g of vinyltriethoxysilane and 10mL of anhydrous ethanol was slowly added while stirring. After the addition was completed, the temperature was raised to 65°C and the reaction was kept warm for 1h. After the reaction was completed, it was cooled to room temperature and centrifuged. After centrifugation, the lower layer of precipitate was taken and ultrasonically dispersed in anhydrous ethanol for 30min, and finally dried at 80°C for 12h to obtain a modified filler.

[0021] Example 2, preparing the modified filler, the specific steps are as follows: 6 g of nano-silicon dioxide, 24 g of diatomaceous earth and 250 mL of deionized water were mixed evenly in a 500 mL three-necked flask, and glacial acetic acid was slowly added to adjust the pH to 4. Subsequently, a mixed solution of 1 g of vinyltrimethoxysilane, 1 g of vinyltriethoxysilane and 10 mL of anhydrous ethanol was slowly added while stirring. After the addition was completed, the temperature was raised to 65°C and the reaction was kept warm for 1 hour. After the reaction was completed, it was cooled to room temperature and centrifuged. After centrifugation, the lower layer of precipitate was taken out and ultrasonically dispersed in anhydrous ethanol for 30 minutes, and finally dried at 80°C for 12 hours to obtain a modified filler.

[0022] Example 3, preparing the modified filler, the specific steps are as follows: 7.5 g of nano-silicon dioxide, 22.5 g of diatomaceous earth and 250 mL of deionized water were mixed evenly in a 500 mL three-necked flask, and glacial acetic acid was slowly added to adjust the pH to 4. Subsequently, a mixed solution of 2 g of 3-(methacryloyloxy)propyltrimethoxysilane and 10 mL of anhydrous ethanol was slowly added while stirring. After the addition was completed, the temperature was raised to 65°C and the reaction was kept warm for 1 hour. After the reaction was completed, it was cooled to room temperature and centrifuged. After centrifugation, the lower layer of precipitate was taken out and ultrasonically dispersed in anhydrous ethanol for 30 minutes, and finally dried at 80°C for 12 hours to obtain a modified filler.

[0023] Example 4, preparation of auxiliary agent, the specific steps are as follows: S1. Under nitrogen protection, add 12.5 mL of N,N'-dimethyl-1,3-propylenediamine, 17.8 mL of pyridine and 200 mL of ethanol to a 500 mL three-necked flask, stir and heat to 70°C, then slowly add 18 mL of 3-chloro-1,2-propylene glycol, and keep warm for 3 h after the addition is complete. After the reaction is completed, cool to room temperature first, and then distill under reduced pressure to obtain intermediate 1; S2. Under nitrogen protection, add 21.3 g of intermediate 1, 14.2 mL of triethylamine and 240 mL of dimethyl sulfoxide to a 500 mL dry three-necked flask, stir to dissolve and heat to 70°C, then slowly add 9.3 mL of 4-chloro-1-butene, keep warm at 70°C for 3 h after the addition is complete, cool to room temperature after the reaction is completed, and distill under reduced pressure to obtain intermediate 2; S3. Under nitrogen protection, add 14 g of intermediate 2, 6.7 mL of triethylamine and 240 mL of dimethyl sulfoxide into a 500 mL dry three-necked flask, stir to dissolve and then heat to 75°C, then slowly add 10.3 mL of chlorododecane, keep warm at 75°C for 3 h after the addition is complete, cool to room temperature after the reaction is completed, and distill under reduced pressure to obtain an auxiliary agent.

[0024] Example 5, preparing an anti-fog head-up display film for automobiles, the specific steps are as follows: Each raw material is weighed by weight, and then 100 parts of thermoplastic polyurethane resin, 20 parts of acrylic rubber, 15 parts of modified filler prepared in Example 3, 1 part of antioxidant 1010, 5 parts of auxiliary agent prepared in Example 4, and 0.01 part of benzoyl peroxide are placed in an internal mixer for internal mixing. The mixed material is then added to a twin-screw extruder for extrusion granulation. Finally, a film is prepared by a casting or blow molding process, and the film is rolled up to obtain an anti-fog head-up display film for automobiles.

[0025] Example 6: Preparation of an anti-fog head-up display film for automobiles, the specific steps are as follows: Each raw material is weighed by weight, and then 108 parts of thermoplastic polyurethane resin, 27 parts of acrylic rubber, 23 parts of modified filler prepared in Example 2, 2 parts of antioxidant 2246, 8 parts of auxiliary agent prepared in Example 4, and 0.03 parts of triallyl isocyanurate are placed in an internal mixer for internal mixing, and then the mixed material is added to a twin-screw extruder for extrusion granulation, and finally a film is prepared by a casting or blow molding process, and then rolled up to obtain an anti-fog head-up display film for automobiles.

[0026] Example 7, preparing an anti-fog head-up display film for automobiles, the specific steps are as follows: Each raw material is weighed by weight, and then 110 parts of thermoplastic polyurethane resin, 30 parts of acrylic rubber, 25 parts of modified filler prepared in Example 1, 2 parts of antioxidant 1076, 1 part of antioxidant 168, 10 parts of auxiliary agent prepared in Example 4, and 0.05 part of diisopropylbenzene peroxide are placed in an internal mixer for internal mixing. The mixed material is then added to a twin-screw extruder for extrusion and granulation. Finally, a film is prepared by a casting or blow molding process, and the film is rolled up to obtain an anti-fog head-up display film for automobiles.

[0027] Comparative Example 1: A head-up display film for an automobile is prepared in the following specific steps: The remaining steps remained unchanged, except that the modified filler in Example 5 was replaced with 3.75 parts of nano-silicon dioxide and 11.25 parts of diatomaceous earth without any treatment, thereby preparing a head-up display film for automobiles.

[0028] Comparative Example 2: A head-up display film for an automobile is prepared, and the specific steps are as follows: The remaining steps remained unchanged, except that the auxiliary agent in Example 5 was removed and replaced with 5 parts of didodecyl dimethyl ammonium chloride, thereby preparing a head-up display film for automobiles.

[0029] Performance Testing The display films prepared in Examples 5-7 and Comparative Examples 1-2 were subjected to an anti-fog test (anti-fog test: a 500 mL beaker was filled with water to 1 cm from the cup mouth, and placed in a constant temperature water bath at 60°C. After reaching the constant temperature, a piece of anti-fog film sample larger than the diameter of the cup mouth was placed on the cup mouth, with the anti-fog film facing downward. After 15 minutes, the area percentage of the opaque part was read by visual inspection and recorded as the fog area rate; the head-up display film was then used in a car, and the fog area rate was tested again after one month of use). The test results are shown in Table 1 below: Table 1

[0030] From the above data, it can be seen that the automotive head-up display film prepared by the present invention has a low fog area rate, good anti-fog performance, and a long anti-fog time, and has broad application prospects.

[0031] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0032] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An anti-fog head-up display film for automobiles, characterized in that: The invention comprises the following raw materials in parts by weight: 100-110 parts of thermoplastic polyurethane resin, 20-30 parts of acrylic rubber, 15-25 parts of modified filler, 1-3 parts of antioxidant, 5-10 parts of auxiliary agent and 0.01-0.05 parts of cross-linking agent; Wherein, the modified filler is prepared by the following steps: The inorganic filler and deionized water were mixed in a flask, the pH was adjusted to 4, a coupling agent and anhydrous ethanol were added, the temperature was raised to 65°C, the reaction was performed for 1 hour, the mixture was cooled, and the mixture was centrifuged. After centrifugation, the lower precipitate was taken out and ultrasonically dispersed in anhydrous ethanol, and dried to obtain a modified filler. The auxiliary agent is prepared by the following steps: S1. Add N,N'-dimethyl-1,3-propanediamine, pyridine and ethanol into a flask under nitrogen protection, stir and heat to 70°C, add 3-chloro-1,2-propanediol, react for 3h, cool, and distill under reduced pressure to obtain intermediate 1; S2. Add intermediate 1, triethylamine and dimethyl sulfoxide to a flask under nitrogen protection, heat to 70°C with stirring, add 4-chloro-1-butene, react for 3 hours, cool, and distill under reduced pressure to obtain intermediate 2; S3. Under nitrogen protection, add intermediate 2, triethylamine and dimethyl sulfoxide into the flask, stir and heat to 75°C, add chlorododecane, react for 3 hours, cool, and distill under reduced pressure to obtain an auxiliary agent.

2. The anti-fog head-up display film for automobile according to claim 1, characterized in that: The dosage ratio of N,N'-dimethyl-1,3-propylenediamine, 3-chloro-1,2-propylene glycol, pyridine and ethanol in step S1 is 12.5 mL: 18 mL: 17.8 mL: 200 mL.

3. The anti-fog head-up display film for automobile according to claim 1, characterized in that: The usage ratio of the intermediate 1, 4-chloro-1-butene, triethylamine and dimethyl sulfoxide in step S2 is 21.3 g: 9.3 mL: 14.2 mL: 240 mL.

4. The anti-fog head-up display film for automobile according to claim 1, characterized in that: The usage ratio of the intermediate 2, chlorododecane, triethylamine and dimethyl sulfoxide in step S3 is 14 g: 10.3 mL: 6.7 mL: 240 mL.

5. The anti-fog head-up display film for automobile according to claim 1, characterized in that: The usage ratio of the inorganic filler to the coupling agent is 30g:2g.

6. The anti-fog head-up display film for automobile according to claim 5, characterized in that: The inorganic filler is a mixture of nano silicon dioxide and diatomaceous earth in a mass ratio of 1:(3-5).

7. The anti-fog head-up display film for automobile according to claim 5, characterized in that: The coupling agent is one or more of vinyl trimethoxy silane, vinyl triethoxy silane and 3-(methacryloyloxy)propyl trimethoxy silane.

8. The anti-fog head-up display film for automobile according to claim 1, characterized in that: The antioxidant is one or more of antioxidant 1010, antioxidant 2246, antioxidant 1076, and antioxidant 168.

9. The anti-fog head-up display film for automobile according to claim 1, characterized in that: The cross-linking agent is one or more of benzoyl peroxide, triallyl isocyanurate, dicumyl peroxide, and azobisisobutyronitrile.

10. The anti-fog head-up display film for automobile and the preparation method thereof according to claim 1, characterized in that: The steps include: Weigh each raw material by weight, then place all the raw materials in an internal mixer for internal mixing, then add the mixed materials into a twin-screw extruder for extrusion granulation, finally adopt a casting or blow molding process to prepare a film, and roll it up to obtain an anti-fog head-up display film for automobiles.

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