A method for manufacturing a variable-angle HUD visual enhancement type PVB interlayer film

Abstract

The present invention discloses a method for manufacturing a variable-angle HUD visual enhancement PVB interlayer film, and belongs to the technical field of PVB interlayer processing. The present invention is used to solve the technical problems in the prior art that the PVB interlayer film has a single angle on the main HUD area, poor molding accuracy, and the light transmittance and radiation resistance of the PVB interlayer need to be further improved. The present invention not only effectively improves the light transmittance, tensile strength, radiation resistance and high and low temperature resistance of the PVB interlayer film by modifying the PVB material and compounding it with the prepared polysiloxane additive, but also improves the fluidity of the melt, thereby improving the thickness uniformity and gradient difference control accuracy of the PVB interlayer film. It is compounded with the temperature and opening angle of the molding mold to expand the variable angle of the HUD interlayer film, avoid seeing double images during driving, and improve driving safety.

Description

Technical Field

[0001] The invention relates to the technical field of PVB interlayer processing, and in particular to a method for manufacturing a variable-angle HUD vision-enhancing PVB interlayer. Background Art

[0002] PVB interlayer is widely used in the automotive, construction and photovoltaic industries. Among them, the PVB interlayer in the automotive industry has higher technical barriers, such as sound insulation, heat insulation, sunshade and HUD wedge mold. With the combined development of the automotive industry and the artificial intelligence industry, the application of HUD technology in automotive front windshields is gradually increasing.

[0003] Head-up display is abbreviated as HUD, also known as head-up display system, which refers to a multi-functional instrument panel centered on the vehicle driver, which can be operated blindly. The vehicle head-up display system (HUD) is a system that uses the principles of optical reflection and refraction to project the driving information on the instrument panel onto the front windshield. Its function is to project important driving information such as speed and navigation onto the windshield in front of the driver, so that the driver can see important driving information such as speed and navigation without lowering or turning his head.

[0004] There are two main types of front-mounted HUDs, W-HUD and C-HUD. C-HUD is a small piece of independent optical plate placed in front of the driving console. W-HUD uses an optical projector and PVB wedge mold. It has higher costs in optical design and structure, and is basically used in luxury models. At present, the more advanced technology in the automotive industry is to combine the HUD system with AR technology, ADAS system, and entertainment system to obtain a better driving experience, produce more combined applications, and further enhance driving safety and experience. ARHUD, an advanced technology with a full sense of science and technology, is the development trend of the automotive industry in the future. Due to the inconsistent loading positions of the HUD projection and ADAS system, a variable-angle HUD wedge film is required to make up for multiple combined applications.

[0005] Traditional HUD interlayer uses PVB as the main material, and the molding process adopts a simple extrusion molding method. Affected by the fluidity of the PVB material, the uniformity of the thickness and the thickness gradient difference of the PVB interlayer are difficult to be accurately controlled. The angle on the main HUD area is single, and drivers of different body heights will see certain double images when driving on bumpy roads or adjusting their sitting postures. Looking at double images for a long time can easily cause eye fatigue and affect safe driving. In addition, the light transmittance and radiation resistance of the existing PVB interlayer need to be further improved.

[0006] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention

[0007] The purpose of the present invention is to provide a method for manufacturing a variable-angle HUD vision-enhancing PVB interlayer, which is used to solve the technical problems that the angle of the PVB interlayer in the main HUD area in the prior art is single, and drivers of different body heights will see certain double images when driving on bumpy roads or adjusting their sitting postures, which affects safe driving, and the light transmittance and radiation resistance of the existing PVB interlayer need to be further improved.

[0008] The purpose of the present invention can be achieved by the following technical solutions:

[0009] A method for manufacturing a variable-angle HUD visual enhancement PVB interlayer film comprises the following steps:

[0010] S1, adding polyvinyl butyral, dihydrofurandione monopolybutenyl derivative, and N,N-dimethylformamide into a three-necked flask and stirring until the system is dissolved, adding a catalyst into the three-necked flask, raising the temperature of the three-necked flask to 60-70° C., keeping the temperature for reaction for 5-6 hours, and post-treating to obtain intermediate I;

[0011] The synthetic reaction principle of intermediate I is:

[0012]

[0013]

[0014] S2, adding intermediate I, modification aid, and N,N-dimethylformamide into a three-necked flask and stirring until the system is dissolved, adding a catalyst into the three-necked flask, raising the temperature of the three-necked flask to 80-90°C, and keeping the temperature for reaction for 6-8h, lowering the temperature of the three-necked flask to 40-50°C, slowly dropping isocyanatepropyltriethoxysilane into the three-necked flask, and after the dropping is complete, keeping the temperature for reaction for 60-90min, and post-treating to obtain modified PVB;

[0015] The synthetic reaction principle of modified PVB is:

[0016]

[0017]

[0018] S3, adding modified PVB and 92wt% methanol aqueous solution into a three-necked flask, heating and stirring until the system is dissolved, adding polysiloxane additive into the three-necked flask, raising the temperature of the three-necked flask to reflux the system, keeping the temperature for reaction for 6-8h, and post-treating to obtain composite PVB;

[0019] S4. Add the composite PVB, plasticizer and antistatic agent into the extruder for plasticization and mixing, and melt extrude into the molding die. According to the distance between the main HUD and ADAS areas, calculate the relative position of the mold bolt control and the temperature control, adjust the temperature of the mold and the angle of the mold opening, keep the temperature for 180-240s, cool down and mold, and obtain the PVB intermediate film.

[0020] Further, in step S1, the amount ratio of polyvinyl butyral, dihydrofurandione monopolybutenyl derivative, N,N-dimethylformamide and catalyst is 10g:1.5g:35mL:0.25g, the catalyst is p-toluenesulfonic acid, and the post-treatment operation includes: after the reaction is completed, the temperature of the three-necked flask is lowered to room temperature, a beaker is taken, and a 40vt% ethanol aqueous solution is added to the beaker, and the reaction system in the three-necked flask is slowly added to the beaker under stirring, a large amount of solid is precipitated, and the filter cake is washed three times with purified water and then dried, and the filter cake is transferred to a temperature of 65-7 5°C drying oven, drying to constant weight to obtain intermediate I; in step S2, the amount ratio of intermediate I, modification aid, N,N-dimethylformamide, catalyst and isocyanatepropyltriethoxysilane is 10g:1g:30mL:0.1g:2g, the catalyst is chloroplatinic acid, and the post-treatment operation includes: after the reaction is completed, the temperature of the three-necked flask is reduced to room temperature, anhydrous ethanol is added to the three-necked flask, a large amount of solid is precipitated, and suction filtration is performed, the filter cake is washed three times with purified water and then dried, and the filter cake is transferred to a drying oven at a temperature of 65-75°C, and dried to constant weight to obtain modified PVB.

[0021] Furthermore, the processing method of the polysiloxane additive is: add the auxiliary additive, hydrogenated silicone oil and isopropanol into a three-necked flask and stir, add a catalyst into the three-necked flask, increase the temperature of the three-necked flask to 75-80°C, keep the temperature for reaction for 6-8h, and post-treat to obtain the polysiloxane additive.

[0022] Furthermore, the weight ratio of the auxiliary additive, hydrogen-containing silicone oil, isopropanol and catalyst is 1:15:50:0.1, the hydrogen content of the hydrogen-containing silicone oil is 1.5-1.6%, and the post-treatment operation includes: after the reaction is completed, the temperature of the three-necked flask is kept at 75-80° C., and the solvent is evaporated under reduced pressure to obtain a polysiloxane additive.

[0023] Further, the auxiliary additive is processed by the following steps:

[0024] A1. Add vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane and methanol into a beaker and mix well to obtain a mixed solution for later use;

[0025] A2. Add zinc acetate, methanol and purified water into a three-necked flask and stir until the system is dissolved. Add the activator into the three-necked flask and stir for 10-15 min. Add 20 wt % potassium hydroxide aqueous solution into the three-necked flask and adjust the pH of the system to 9-10. Stir the reaction at room temperature for 20-30 min. Heat the temperature of the three-necked flask to 55-65° C. at a rate of 3-5° C. / min, keep warm and stir for 2-3 h. Add the mixed solution into the three-necked flask and keep warm for 8-10 h after the addition is complete. Post-treat to obtain the auxiliary additive.

[0026] Furthermore, in step A1, the dosage ratio of vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane and methanol is 1 mol: 1 mol: 400 mL; in step A2, the weight ratio of zinc acetate, methanol, purified water, active agent and mixed solution is 5 g: 10 mL: 8 mL: 1 g: 6 g, and the active agent is composed of sodium dodecylbenzenesulfonate and isooctyl polyoxyethylene ether phosphate in a weight ratio of 2: 1. The post-treatment operation includes: after the reaction is completed, centrifuging and washing to obtain a solid, transferring the solid to a drying oven at a temperature of 60-70° C., and air drying for 40-48 hours to obtain an auxiliary additive.

[0027] Furthermore, the preparation method of the modified auxiliary agent is: add 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and toluene into a three-necked flask, stir and dissolve, increase the temperature of the three-necked flask to 55-65°C, add 2-chloroethyl isocyanate dropwise into the three-necked flask, keep warm for reaction for 2-3h, and post-treat to obtain the modified auxiliary agent.

[0028] The synthetic reaction principle of the modified additive is:

[0029]

[0030] Furthermore, the amount ratio of the 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 2-chloroethyl isocyanate is 1 mol:1 mol, the amount ratio of the 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and toluene is 1 g:3 mL, and the post-treatment operation includes: after the reaction is completed, the temperature of the three-necked flask is increased to 70-80° C., and the solvent is evaporated under reduced pressure to obtain a modified auxiliary agent.

[0031] Furthermore, in step S3, the usage ratio of the modified PVB, the 92 wt % methanol aqueous solution and the polysiloxane additive is 10 g:50 mL:1 g, and the post-treatment operation includes: after the reaction is completed, distilling off the solvent under reduced pressure to obtain the composite PVB.

[0032] Furthermore, in step S5, the weight ratio of the composite PVB, the plasticizer, and the antistatic agent is 100:30:1, the plasticizer is dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di(2-ethyl)hexyl phthalate, and diisononyl phthalate, and one or more of the antistatic agent is dodecyl polyoxyethylene ether; the molding mold is a T-shaped mold, and the film-forming mold is composed of two-lobed molds. The total length of the mold is 2m, and each lobe mold has 10 heating zones, and the temperature settings are 180-230°C from low to high, and each zone rises in a step-by-step manner. The adjustment range of the mold opening is 0.05-0.50mm.

[0033] The present invention has the following beneficial effects:

[0034] 1. The present invention uses polyvinyl butyral as a basic raw material, and prepares a composite PVB material reinforced with a long straight-chain polysiloxane by modifying it and then compounding and mixing it with a polysiloxane additive. Transparent polysiloxane usually has a lower refractive index, which helps to reduce the scattering and absorption of the material, thereby improving the overall light transmittance; transparent polysiloxane may provide additional strength and high and low temperature resistance, and has a positive effect on the tensile strength of the PVB material and maintaining stable size under different temperature conditions; the long straight-chain structure of the polysiloxane molecule forms a weaker interaction between molecules, reduces the viscosity of the overall mixture, improves the fluidity of the composite PVB material, and helps the material to fill the mold or extrude more smoothly during the processing process. The PVB interlayer is mixed with composite PVB, plasticizer and dodecyl polyoxyethylene ether, plasticized and mixed, and melt-extruded. Then, the relative positions of mold bolt control and temperature control are calculated through the distance between HUD projection and ADAS system loading position, and the temperature of the mold and the angle of the mold opening are adjusted. This cooperates with the melt with high fluidity to improve the control accuracy of the thickness uniformity and thickness gradient difference of the PVB interlayer, reduce the extreme difference of the high and low body position ghosting angle, and effectively form two or more wedge angles on the same gradient, expand the variable angle of the HUD interlayer, avoid seeing ghosting virtual images during driving, and improve driving safety.

[0035] 2. When preparing the modified PVB of the present invention, a dihydrofurandione monopolybutenyl derivative is subjected to an esterification polymerization reaction with polyvinyl butyral under the action of a catalyst to obtain an intermediate I in which an olefin double bond and a carboxyl group are grafted and modified on the molecular chain of polyvinyl butyral; the alcohol hydroxyl group on 3,5-di-tert-butyl-4-hydroxybenzyl alcohol is subjected to a condensation reaction with the isocyanate group on 2-chloroethyl isocyanate to prepare a modified auxiliary agent of halogen-modified 2,6-di-tert-butylphenol; the halogen on the modified auxiliary agent is subjected to a substitution addition reaction with the olefin double bond modified on the molecular chain of the intermediate I; and isocyanatepropyltriethoxysilane is reacted with the intermediate I to obtain a modified auxiliary agent. The active groups on the molecular chain of polysiloxane I react to generate modified PVB with triethoxysilane and 2,6-di-tert-butylphenol modified polyvinyl butyral; 2,6-di-tert-butylphenol has the ability to inhibit the generation and propagation of free radicals, reduce the oxidation and degradation reaction of PVB materials by ultraviolet radiation, and the polysiloxane additive can form a uniform protective layer in the PVB material, improve the barrier properties of the material, and prevent the penetration of oxygen and other oxidizing substances. The combination of the polysiloxane additive and the antioxidant property of 2,6-di-tert-butylphenol can comprehensively improve the radiation resistance of the material in outdoor exposure environments.

[0036] 3. When preparing the polysiloxane additive of the present invention, zinc acetate is used as a raw material, and an acid-base neutralization reaction is carried out with potassium hydroxide in an emulsion composed of methanol, water and an activator to prepare a zinc hydroxide precipitate with a nano-particle structure. Vinyl trimethoxysilane and 3-aminopropyl trimethoxysilane are subjected to hydrolysis and self-assembly reaction in an alkaline environment. In the alkaline environment, the amine group can chemically adsorb with the surface of zinc hydroxide, thereby improving the adhesion of the silane molecule on the surface and facilitating the formation of a siloxane coating on the surface of nano zinc hydroxide. The zinc hydroxide is oxidized into zinc oxide by thermal oxidation treatment to obtain an auxiliary additive with olefin and amino-coated modified nano zinc oxide. During the reaction, the activator composed of sodium dodecylbenzene sulfonate and isooctyl alcohol polyoxyethylene ether phosphate disperses the zinc hydroxide particles during the reaction to form a thin film on the reaction interface to regulate the reaction between the reactants and the reactants. The interface between the media prevents excessive growth during the reaction, thereby maintaining the required nanosize and improving the dispersion of zinc hydroxide particles, making them more easily suspended in the solution without precipitation. The polysiloxane coated on the surface of zinc oxide and the modified olefin double bonds and amino groups can improve the dispersibility of zinc oxide particles and ensure that the zinc oxide particles are more evenly dispersed in the hydrogen-containing silicone oil. Under the action of the catalyst, the olefin double bonds modified on the surface of the auxiliary additive can undergo substitution and addition reactions with the hydrogen on the hydrogen-containing silicone oil to form stable chemical crosslinks. Zinc oxide itself is an antioxidant, and its absorption and scattering of ultraviolet rays can improve the ultraviolet resistance of PVB materials. The amino groups modified on the outside of zinc oxide can also serve as active functional groups to crosslink with the silanol groups formed after hydrolysis of siloxane, thereby improving the crosslinking degree of the composite PVB material, thereby improving the strength and high and low temperature resistance of the composite PVB material. DETAILED DESCRIPTION

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than 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.

[0038] Example 1

[0039] This embodiment provides a method for preparing a composite PVB material for a PVB interlayer, comprising the following steps:

[0040] S1. Preparation of modified PVB

[0041] Weigh: 100 g of polyvinyl butyral, 15 g of a monopolybutenyl derivative of dihydrofurandione, and 350 mL of N,N-dimethylformamide, add them to a three-necked flask and stir until the system is dissolved, add 2.5 g of p-toluenesulfonic acid to the three-necked flask, raise the temperature of the three-necked flask to 60° C., keep the reaction warm for 5 hours, lower the temperature of the three-necked flask to room temperature, take a beaker, add 800 mL of a 40vt% ethanol aqueous solution to the beaker, slowly add the reaction system in the three-necked flask to the beaker under stirring, a large amount of solid precipitates, filter, wash the filter cake three times with purified water and then drain, transfer the filter cake to a drying oven at a temperature of 65° C., and dry to constant weight to obtain an intermediate I; wherein the ratio of vinyl butyral, ethylene glycol and vinyl acetate in the polyvinyl butyral is 76:22:2.

[0042] Weigh: 23.6 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 70.8 mL of toluene are added into a three-necked flask and stirred to dissolve. The temperature of the three-necked flask is raised to 55°C. 10.6 g of 2-chloroethyl isocyanate is added dropwise into the three-necked flask. After the addition is complete, the reaction is kept warm for 2 hours. The temperature of the three-necked flask is raised to 70°C. The solvent is evaporated under reduced pressure to obtain a modified auxiliary agent.

[0043] Weigh: 100 g of intermediate I, 10 g of modification aid, and 300 mL of N,N-dimethylformamide are added to a three-necked flask and stirred until the system is dissolved. 1 g of chloroplatinic acid is added to the three-necked flask, the temperature of the three-necked flask is increased to 80°C, and the reaction is kept warm for 6 hours. The temperature of the three-necked flask is reduced to 40°C, and 20 g of isocyanatepropyltriethoxysilane is slowly added dropwise to the three-necked flask. After the addition is completed, the reaction is kept warm for 60 minutes. The temperature of the three-necked flask is reduced to room temperature, and 1200 mL of anhydrous ethanol is added to the three-necked flask. A large amount of solid is precipitated, and it is filtered. The filter cake is washed three times with purified water and then dried. The filter cake is transferred to a drying oven at a temperature of 65°C and dried to constant weight to obtain modified PVB.

[0044] S2. Preparation of auxiliary additives

[0045] Weigh: 14.8 g of vinyltrimethoxysilane, 17.9 g of 3-aminopropyltrimethoxysilane and 40 mL of methanol, add into a beaker and mix well to obtain a mixed solution for later use;

[0046] Weigh: 20g of zinc acetate, 40mL of methanol, and 32mL of purified water are added to a three-necked flask and stirred until the system is dissolved, 4g of an active agent is added to the three-necked flask, stirred for 10min, 20wt% potassium hydroxide aqueous solution is added dropwise to the three-necked flask, the pH of the system is adjusted to 9, the reaction is stirred for 20min at room temperature, the temperature of the three-necked flask is raised to 55°C at a rate of 3°C / min, and the mixture is stirred for 2h, 24g of the mixed solution is added dropwise to the three-necked flask, the addition is completed, the reaction is kept warm for 8h, the temperature of the three-necked flask is lowered to room temperature, centrifuged, washed to obtain a solid, the solid is transferred to a drying oven at a temperature of 60°C, and air dried for 40h to obtain an auxiliary additive, wherein the active agent is composed of sodium dodecylbenzenesulfonate and isooctyl alcohol polyoxyethylene ether phosphate in a weight ratio of 2:1.

[0047] S3. Preparation of polysiloxane additives

[0048] Weigh: 10 g of auxiliary additive, 150 g of hydrogen-containing silicone oil, and 500 g of isopropanol, add into a three-necked flask and stir, add 1 g of chloroplatinic acid into the three-necked flask, raise the temperature of the three-necked flask to 75° C., keep the temperature for 6 hours, keep the temperature of the three-necked flask at 75° C., and evaporate the solvent under reduced pressure to obtain a polysiloxane additive, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.5-1.6%.

[0049] S4. Preparation of composite PVB

[0050] Weigh: 200g of modified PVB and 1000mL of 92wt% methanol aqueous solution into a three-necked flask, heat and stir until the system is dissolved, add 20g of polysiloxane additive into the three-necked flask, increase the temperature of the three-necked flask to reflux, keep the reaction warm for 6h, and evaporate the solvent under reduced pressure to obtain composite PVB.

[0051] Example 2

[0052] This embodiment provides a method for preparing a composite PVB material for a PVB interlayer, comprising the following steps:

[0053] S1. Preparation of modified PVB

[0054] Weigh: 100 g of polyvinyl butyral, 15 g of a monopolybutenyl derivative of dihydrofurandione, and 350 mL of N,N-dimethylformamide, add them to a three-necked flask and stir until the system is dissolved, add 2.5 g of p-toluenesulfonic acid to the three-necked flask, raise the temperature of the three-necked flask to 65° C., keep the reaction warm for 5.5 hours, lower the temperature of the three-necked flask to room temperature, take a beaker, add 800 mL of a 40vt% ethanol aqueous solution to the beaker, slowly add the reaction system in the three-necked flask to the beaker under stirring, a large amount of solid precipitates, filter, wash the filter cake three times with purified water and then drain, transfer the filter cake to a drying oven at a temperature of 70° C., and dry to constant weight to obtain an intermediate I; wherein the ratio of vinyl butyral, ethylene glycol and vinyl acetate in the polyvinyl butyral is 76:22:2.

[0055] Weigh: 23.6 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 70.8 mL of toluene are added into a three-necked flask and stirred to dissolve. The temperature of the three-necked flask is raised to 60°C. 10.6 g of 2-chloroethyl isocyanate is added dropwise into the three-necked flask. After the addition is complete, the reaction is kept warm for 2.5 hours. The temperature of the three-necked flask is raised to 75°C. The solvent is evaporated under reduced pressure to obtain a modified auxiliary agent.

[0056] Weigh: 100g of intermediate I, 10g of modification aid, and 300mL of N,N-dimethylformamide are added to a three-necked flask and stirred until the system is dissolved. 1g of chloroplatinic acid is added to the three-necked flask, the temperature of the three-necked flask is increased to 85°C, and the reaction is kept warm for 7h. The temperature of the three-necked flask is reduced to 45°C, and 20g of isocyanatepropyltriethoxysilane is slowly added dropwise to the three-necked flask. After the addition is completed, the reaction is kept warm for 75min. The temperature of the three-necked flask is reduced to room temperature, and 1200mL of anhydrous ethanol is added to the three-necked flask. A large amount of solid is precipitated, which is filtered, and the filter cake is washed three times with purified water and then dried. The filter cake is transferred to a drying oven at a temperature of 70°C and dried to constant weight to obtain modified PVB.

[0057] S2. Preparation of auxiliary additives

[0058] Weigh: 14.8 g of vinyltrimethoxysilane, 17.9 g of 3-aminopropyltrimethoxysilane and 40 mL of methanol, add into a beaker and mix well to obtain a mixed solution for later use;

[0059] Weigh: 20g of zinc acetate, 40mL of methanol, and 32mL of purified water are added to a three-necked flask and stirred until the system is dissolved, 4g of an active agent is added to the three-necked flask, stirred for 13min, 20wt% potassium hydroxide aqueous solution is added dropwise to the three-necked flask, the pH of the system is adjusted to 9.5, and the reaction is stirred for 25min at room temperature, the three-necked flask is heated to 60°C at a rate of 4°C / min, and the mixture is stirred for 2.5h, 24g of the mixed solution is added dropwise to the three-necked flask, the addition is completed, and the reaction is kept warm for 9h, the temperature of the three-necked flask is lowered to room temperature, centrifuged, washed to obtain a solid, and the solid is transferred to a drying oven at a temperature of 65°C, and air dried for 44h to obtain an auxiliary additive, wherein the active agent is composed of sodium dodecylbenzene sulfonate and isooctyl alcohol polyoxyethylene ether phosphate in a weight ratio of 2:1.

[0060] S3. Preparation of polysiloxane additives

[0061] Weigh: 10 g of auxiliary additive, 150 g of hydrogen-containing silicone oil, and 500 g of isopropanol, add into a three-necked flask and stir, add 1 g of chloroplatinic acid into the three-necked flask, raise the temperature of the three-necked flask to 78° C., keep the temperature for 7 hours, keep the temperature of the three-necked flask at 78° C., and evaporate the solvent under reduced pressure to obtain a polysiloxane additive, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.5-1.6%.

[0062] S4. Preparation of composite PVB

[0063] Weigh: 200g of modified PVB and 1000mL of 92wt% methanol aqueous solution into a three-necked flask, heat and stir until the system is dissolved, add 20g of polysiloxane additive into the three-necked flask, increase the temperature of the three-necked flask to reflux, keep the reaction warm for 7h, and evaporate the solvent under reduced pressure to obtain composite PVB.

[0064] Example 3

[0065] This embodiment provides a method for preparing a composite PVB material for a PVB interlayer, comprising the following steps:

[0066] S1. Preparation of modified PVB

[0067] Weigh: 100 g of polyvinyl butyral, 15 g of a monopolybutenyl derivative of dihydrofurandione, and 350 mL of N,N-dimethylformamide, add them to a three-necked flask and stir until the system is dissolved, add 2.5 g of p-toluenesulfonic acid to the three-necked flask, raise the temperature of the three-necked flask to 70° C., keep the reaction warm for 6 hours, lower the temperature of the three-necked flask to room temperature, take a beaker, add 800 mL of a 40vt% ethanol aqueous solution to the beaker, slowly add the reaction system in the three-necked flask to the beaker under stirring, a large amount of solid precipitates, filter, wash the filter cake three times with purified water and then drain, transfer the filter cake to a drying oven at a temperature of 75° C., and dry to constant weight to obtain an intermediate I; wherein the ratio of vinyl butyral, ethylene glycol and vinyl acetate in the polyvinyl butyral is 76:22:2.

[0068] Weigh: 23.6 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 70.8 mL of toluene are added into a three-necked flask and stirred to dissolve. The temperature of the three-necked flask is raised to 65°C. 10.6 g of 2-chloroethyl isocyanate is added dropwise into the three-necked flask. After the addition is complete, the reaction is kept warm for 3 hours. The temperature of the three-necked flask is raised to 80°C. The solvent is evaporated under reduced pressure to obtain a modified auxiliary agent.

[0069] Weigh: 100 g of intermediate I, 10 g of modification aid, and 300 mL of N,N-dimethylformamide are added to a three-necked flask and stirred until the system is dissolved. 1 g of chloroplatinic acid is added to the three-necked flask, the temperature of the three-necked flask is increased to 90°C, and the reaction is kept warm for 8 hours. The temperature of the three-necked flask is reduced to 50°C, and 20 g of isocyanatepropyltriethoxysilane is slowly added dropwise to the three-necked flask. After the addition is completed, the reaction is kept warm for 90 minutes. The temperature of the three-necked flask is reduced to room temperature, and 1200 mL of anhydrous ethanol is added to the three-necked flask. A large amount of solid is precipitated, and it is filtered. The filter cake is washed three times with purified water and then dried. The filter cake is transferred to a drying oven at a temperature of 75°C and dried to constant weight to obtain modified PVB.

[0070] S2. Preparation of auxiliary additives

[0071] Weigh: 14.8 g of vinyltrimethoxysilane, 17.9 g of 3-aminopropyltrimethoxysilane and 40 mL of methanol, add into a beaker and mix well to obtain a mixed solution for later use;

[0072] Weigh: 20g of zinc acetate, 40mL of methanol, and 32mL of purified water are added to a three-necked flask and stirred until the system is dissolved, 4g of an active agent is added to the three-necked flask, stirred for 15min, 20wt% potassium hydroxide aqueous solution is added dropwise to the three-necked flask, the pH of the system is adjusted to 10, and the reaction is stirred for 30min at room temperature, the three-necked flask is heated to 65°C at a rate of 5°C / min, and the mixture is stirred for 3h, 24g of the mixed solution is added dropwise to the three-necked flask, the addition is completed, the reaction is kept warm for 10h, the temperature of the three-necked flask is lowered to room temperature, centrifuged and washed to obtain a solid, the solid is transferred to a drying oven at a temperature of 70°C, and air dried for 48h to obtain an auxiliary additive, wherein the active agent is composed of sodium dodecylbenzene sulfonate and isooctyl alcohol polyoxyethylene ether phosphate in a weight ratio of 2:1.

[0073] S3. Preparation of polysiloxane additives

[0074] Weigh: 10 g of auxiliary additive, 150 g of hydrogen-containing silicone oil, and 500 g of isopropanol, add into a three-necked flask and stir, add 1 g of chloroplatinic acid into the three-necked flask, raise the temperature of the three-necked flask to 80° C., keep the temperature for 8 hours, keep the temperature of the three-necked flask at 80° C., and evaporate the solvent under reduced pressure to obtain a polysiloxane additive, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.5-1.6%.

[0075] S4. Preparation of composite PVB

[0076] Weigh: 200g of modified PVB and 1000mL of 92wt% methanol aqueous solution into a three-necked flask, heat and stir until the system is dissolved, add 20g of polysiloxane additive into the three-necked flask, increase the temperature of the three-necked flask to reflux, keep the reaction warm for 8h, and evaporate the solvent under reduced pressure to obtain composite PVB.

[0077] Example 4

[0078] This embodiment provides a method for manufacturing a variable-angle HUD visual enhancement PVB interlayer, comprising the following steps:

[0079] Step 1: Add the composite PVB, dimethyl phthalate and dodecyl polyoxyethylene ether prepared in Example 1 into an extruder in a weight ratio of 100:30:1, plasticize and mix, and melt-extrude into a molding mold. The extruder has a total of 10 heating zones, and the heating temperatures are 100°C, 145°C, 165°C, 165°C, 160°C, 155°C, 152°C, 150°C, 150°C, and 150°C, respectively.

[0080] Step 2: The molding mold is a T-shaped mold. The film-forming mold is composed of two halves of the mold. The total length of the mold is 2m. Each halves of the mold has 10 heating zones. The temperature settings are 180-230°C from low to high. Each zone rises in a step-by-step manner. The adjustment range of the mold opening is 0.05-0.50mm. According to the distance between the main HUD and ADAS areas, the relative positions of the mold bolt control and the temperature control are calculated, and the temperature of the mold and the angle of the mold opening are adjusted. The mold is kept warm for 180s, cooled and formed to obtain the PVB intermediate film.

[0081] Example 5

[0082] This embodiment provides a method for manufacturing a variable-angle HUD visual enhancement PVB interlayer, comprising the following steps:

[0083] Step 1: Add the composite PVB, diethyl phthalate and dodecyl polyoxyethylene ether prepared in Example 2 into an extruder in a weight ratio of 100:30:1, plasticize and mix, and melt-extrude into a molding mold. The extruder has a total of 10 heating zones, and the heating temperatures are 100°C, 145°C, 165°C, 165°C, 160°C, 155°C, 152°C, 150°C, 150°C, and 150°C, respectively.

[0084] Step 2: The molding mold is a T-shaped mold. The film-forming mold is composed of two halves of the mold. The total length of the mold is 2m. Each halves of the mold has 10 heating zones. The temperature settings are 180-230°C from low to high. Each zone rises in a step-by-step manner. The adjustment range of the mold opening is 0.05-0.50mm. According to the distance between the main HUD and ADAS areas, the relative positions of the mold bolt control and the temperature control are calculated, and the temperature of the mold and the angle of the mold opening are adjusted. The mold is kept warm for 210s, cooled and formed to obtain the PVB intermediate film.

[0085] Example 6

[0086] This embodiment provides a method for manufacturing a variable-angle HUD visual enhancement PVB interlayer, comprising the following steps:

[0087] Step 1: Add the composite PVB, butyl benzyl phthalate and dodecyl polyoxyethylene ether prepared in Example 3 into an extruder in a weight ratio of 100:30:1, plasticize and mix, and melt-extrude into a molding mold. The extruder has a total of 10 heating zones, and the heating temperatures are 100°C, 145°C, 165°C, 165°C, 160°C, 155°C, 152°C, 150°C, 150°C, and 150°C, respectively.

[0088] Step 2: The molding mold is a T-shaped mold. The film-forming mold is composed of two halves of the mold. The total length of the mold is 2m. Each halves of the mold has 10 heating zones. The temperature settings are 180-230°C from low to high. Each zone rises in a step-by-step manner. The adjustment range of the mold opening is 0.05-0.50mm. According to the distance between the main HUD and ADAS areas, the relative positions of the mold bolt control and the temperature control are calculated, and the temperature of the mold and the angle of the mold opening are adjusted. The mold is kept warm for 240s, cooled and formed to obtain the PVB intermediate film.

[0089] Comparative Example 1

[0090] The difference between this comparative example and Example 6 is that step S1 in Example 3 is eliminated, and the modified PVB in step S4 is replaced by an equal amount of polyvinyl butyral in step S1.

[0091] Comparative Example 2

[0092] The difference between this comparative example and Example 6 is that the method steps for preparing the auxiliary additive in step S2 of Example 3 are: adding 20 g of zinc acetate, 40 mL of methanol, and 32 mL of purified water into a three-necked flask and stirring until the system is dissolved, adding 4 g of an active agent into the three-necked flask, stirring for 15 min, dropping a 20 wt % potassium hydroxide aqueous solution into the three-necked flask, adjusting the system pH to 10, stirring the reaction at room temperature for 30 min, raising the temperature of the three-necked flask to 65° C. at a rate of 5° C. / min, keeping warm and stirring for 3 h, lowering the temperature of the three-necked flask to room temperature, centrifuging and washing to obtain a solid, transferring the solid to a drying oven at a temperature of 70° C., and drying with air for 48 h to obtain an auxiliary additive, wherein the active agent is composed of sodium dodecylbenzenesulfonate and isooctyl polyoxyethylene ether phosphate in a weight ratio of 2:1.

[0093] Comparative Example 3

[0094] The difference between this comparative example and Example 6 is that in step 2, each mold has 10 heating zones, the temperature setting of each zone is 180° C., the mold openings are all the same size, and the angle is 0.2 mrad.

[0095] Comparative Example 4

[0096] The difference between this comparative example and Example 6 is that the composite PVB in step 1 is replaced by an equal amount of polyvinyl butyral in Example 3.

[0097] Performance Testing:

[0098] The transmittance, tensile strength, radiation resistance, dimensional change rate, full-width wedge angle, main HUD angle, main ADAS angle, main HUD angle fluctuation value, main ADAS segment angle fluctuation value, and high and low body ghosting angle extreme difference of the PVB interlayer prepared in Examples 4-6 and Comparative Examples 1-4 were tested, wherein the full-width wedge angle, main HUD angle, main ADAS angle, main HUD angle fluctuation value, and main ADAS segment angle fluctuation value were measured using a fully automatic offline contact roller thickness gauge, model YAMABUN TOF-4R, and the results were calculated by the computer software of the instrument; the high and low body ghosting angle extreme difference was detected by a customized instrument for testing the HUD angle, which was developed by Shenzhen Aitexun Technology Co., Ltd., and the camera position was adjusted to simulate the high, medium and low body positions, and the angle difference was calculated by the software; the transmittance, tensile strength, radiation resistance, and dimensional change rate refer to the standard GB / T 32020-2015 "Polyvinyl butyral interlayer for laminated glass" was tested, and the specific test results are shown in the table below:

[0099]

[0100]

[0101] Data Analysis:

[0102] By comparing and analyzing the data in the above table, the full-width wedge angle of the PVB interlayer prepared by the present invention reaches 0.66°, the main HUD angle reaches 0.57°, the main ADAS angle reaches 0.57°, the main HUD angle fluctuation value reaches 0.0053°, the main ADAS segment angle fluctuation value reaches 0.006°, and the high and low body ghosting angle extreme difference reaches 0.02. All the test data are better than those of comparative examples 3-4, indicating that after the PVB is modified and compounded with polysiloxane to prepare the composite PVB material, the temperature and opening angle of the molding mold can be adjusted to accurately control the uniformity of the thickness of the PVB interlayer and the thickness gradient difference, so that two or more wedge angles can be effectively formed on the same gradient to expand the HUD The variable angle of the intermediate film can avoid seeing double images during driving, thereby improving driving safety. The light transmittance of the PVB intermediate film prepared by the present invention reaches 92.1%, the tensile strength reaches 28.4 MPa, the radiation resistance reaches 98.3%, and the dimensional change rate reaches 0.35%. All the test data are better than those of comparative examples 1-2, indicating that the present invention effectively improves the light transmittance, tensile strength, radiation resistance and high and low temperature resistance of the PVB intermediate film by compounding the modified PVB material with the prepared polysiloxane additive, and effectively improves the fluidity of the melt by compounding the modified PVB material with the prepared polysiloxane additive, so that the PVB intermediate film is easier to process and shape, and the molding accuracy of the PVB intermediate film is improved.

[0103] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field 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 structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

[0104] In the description of this 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.

[0105] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for manufacturing a variable-angle HUD visual enhancement PVB interlayer, characterized in that: The following steps are involved: S1, adding polyvinyl butyral, dihydrofurandione monopolybutenyl derivative, and N,N-dimethylformamide into a three-necked flask and stirring until the system is dissolved, adding a catalyst into the three-necked flask, raising the temperature of the three-necked flask to 60-70° C., keeping the temperature for reaction for 5-6 hours, and post-treating to obtain intermediate I; S2, adding intermediate I, modification aid, and N,N-dimethylformamide into a three-necked flask and stirring until the system is dissolved, adding a catalyst into the three-necked flask, raising the temperature of the three-necked flask to 80-90°C, and keeping the temperature for reaction for 6-8h, lowering the temperature of the three-necked flask to 40-50°C, slowly dropping isocyanatepropyltriethoxysilane into the three-necked flask, and after the dropping is complete, keeping the temperature for reaction for 60-90min, and post-treating to obtain modified PVB; S3, adding modified PVB and 92wt% methanol aqueous solution into a three-necked flask, heating and stirring until the system is dissolved, adding polysiloxane additive into the three-necked flask, raising the temperature of the three-necked flask to reflux the system, keeping the temperature for reaction for 6-8h, and post-treating to obtain composite PVB; S4. Add the composite PVB, plasticizer and antistatic agent into the extruder for plasticization and mixing, and melt extrude into the molding die. According to the distance between the main HUD and ADAS areas, calculate the relative position of the mold bolt control and the temperature control, adjust the temperature of the mold and the angle of the mold opening, keep the temperature for 180-240s, cool down and mold, and obtain the PVB intermediate film.

2. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 1, characterized in that: In step S1, the amount ratio of polyvinyl butyral, dihydrofurandione monopolybutenyl derivative, N,N-dimethylformamide and catalyst is 10g:1.5g:35mL:0.25g, and the catalyst is p-toluenesulfonic acid; in step S2, the amount ratio of intermediate I, modification aid, N,N-dimethylformamide, catalyst and isocyanatepropyltriethoxysilane is 10g:1g:30mL:0.1g:2g, and the catalyst is chloroplatinic acid.

3. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 1, characterized in that: The processing method of the polysiloxane additive is as follows: adding auxiliary additives, hydrogen-containing silicone oil and isopropanol into a three-necked flask and stirring, adding a catalyst into the three-necked flask, raising the temperature of the three-necked flask to 75-80° C., keeping the temperature for reaction for 6-8 hours, and post-treating to obtain the polysiloxane additive.

4. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 3, characterized in that: The weight ratio of the auxiliary additive, hydrogen-containing silicone oil, isopropanol and catalyst is 1:15:50: 0.1, the hydrogen content of the hydrogen-containing silicone oil is 1.5-1.6%.

5. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 1, characterized in that: The auxiliary additives are processed by the following steps: A1. Add vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane and methanol into a beaker and mix well to obtain a mixed solution for later use; A2. Add zinc acetate, methanol and purified water into a three-necked flask and stir until the system is dissolved. Add the activator into the three-necked flask and stir for 10-15 min. Add 20 wt % potassium hydroxide aqueous solution into the three-necked flask and adjust the pH of the system to 9-10. Stir the reaction at room temperature for 20-30 min. Heat the temperature of the three-necked flask to 55-65° C. at a rate of 3-5° C. / min, keep warm and stir for 2-3 h. Add the mixed solution into the three-necked flask and keep warm for 8-10 h after the addition is complete. Post-treat to obtain the auxiliary additive.

6. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 5, characterized in that: In step A1, the dosage ratio of vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane and methanol is 1 mol: 1 mol: 400 mL; in step A2, the weight ratio of zinc acetate, methanol, purified water, active agent and mixed solution is 5 g: 10 mL: 8 mL: 1 g: 6 g, and the active agent is composed of sodium dodecylbenzenesulfonate and isooctyl alcohol polyoxyethylene ether phosphate in a weight ratio of 2:

1.

7. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 5, characterized in that: The preparation method of the modified auxiliary agent is as follows: 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and toluene are added into a three-necked flask and stirred to dissolve, the temperature of the three-necked flask is increased to 55-65° C., 2-chloroethyl isocyanate is added dropwise into the three-necked flask, and after the addition is completed, the reaction is kept warm for 2-3 hours, and the modified auxiliary agent is obtained by post-treatment.

8. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 7, characterized in that: The usage ratio of the 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 2-chloroethyl isocyanate is 1 mol:1 mol, and the usage ratio of the 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and toluene is 1 g:3 mL.

9. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 1, characterized in that: In step S3, the usage ratio of modified PVB, 92 wt % methanol aqueous solution and polysiloxane additive is 10 g:50 mL:1 g. The post-treatment operation includes: after the reaction is completed, the solvent is evaporated under reduced pressure to obtain composite PVB.

10. The method for manufacturing a variable-angle HUD visual enhancement PVB interlayer according to claim 1, characterized in that: In step S5, the weight ratio of the composite PVB, the plasticizer, and the antistatic agent is 100:30:1, the plasticizer is dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di(2-ethyl)hexyl phthalate, and diisononyl phthalate, and one or more thereof, and the antistatic agent is dodecyl polyoxyethylene ether; the molding mold is a T-shaped mold, and the film-forming mold is composed of two-lobed molds. The total length of the mold is 2m, and each lobe mold has 10 heating zones, and the temperature settings are 180-230°C from low to high, and each zone rises in a step-by-step manner. The adjustment range of the mold opening is 0.05-0.50mm.

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