High-transparency PVB (Polyvinyl Butyral) intermediate film as well as production process and application thereof

Abstract

The invention discloses a high-transparency PVB intermediate film and a production process and application thereof, and relates to the technical field of PVB intermediate films, the high-transparency PVB intermediate film comprises the following raw materials by weight: 100 parts of PVB resin, 20-30 parts of a composite plasticizer, 0.5-0.9 part of an LDH-based composite antioxidant, 0.5-1 part of an ultraviolet light absorber, 0.1-1.5 parts of nano lanthanum hexaboride, 0.1-1.5 parts of porous hollow nano copper sulphide, and 0.1-2 parts of nano TiO2 / SiO2 core-shell particles. The PVB intermediate film provided by the invention is relatively high in light transmittance, low in haze value, and excellent in oxidation resistance, weather resistance and mechanical strength.

Description

Technical Field

[0001] This application relates to the field of PVB interlayer technology, and in particular to a high-transparency PVB interlayer, its manufacturing process and application. Background Technology

[0002] Polyvinyl butyral (PVB) is a product of the catalytic condensation of polyvinyl alcohol (PVA) and butyraldehyde under acidic conditions. Its main functional groups include hydroxyl and acetal groups, with a small amount of acetyl groups. The primary application of PVB resin is as an interlayer in laminated glass. This interlayer is made from high-molecular-weight PVB resin with the addition of a certain amount of plasticizer, and is produced through plasticizing and extrusion molding to form a translucent, impurity-free, smooth-surfaced polymer film with a certain degree of roughness and good flexibility. PVB interlayers exhibit excellent adhesion to inorganic glass and possess properties such as transparency, heat resistance, cold resistance, moisture resistance, and high mechanical strength.

[0003] With the continuous improvement of living standards, people are no longer satisfied with laminated glass being used merely as a single-function safety glass. Therefore, various functional laminated glass products have emerged. By modifying the interlayer, laminated glass is endowed with functions such as heat insulation, sound insulation, and explosion protection. However, the commonly used modifying materials are mainly inorganic nanofillers. But inorganic nanoparticles can cause high haze in the PVB interlayer, leading to a decrease in the light transmittance of the PVB interlayer and affecting the transparency and visual effect of the glass. Furthermore, the PVB interlayer still has problems such as insufficient weather resistance; under prolonged exposure to sunlight, it is prone to yellowing and aging, reducing the service life and visual effect of the laminated glass. Summary of the Invention

[0004] In order to improve the light transmittance of PVB interlayer, reduce haze value, and enhance oxidation resistance and weather resistance, this application provides a high-transparency PVB interlayer, its manufacturing process, and its application.

[0005] This application provides a high-transparency PVB interlayer film, which adopts the following technical solution:

[0006] A high-transparency PVB interlayer film, comprising, by weight, 100 parts PVB resin, 20-30 parts composite plasticizer, 0.5-0.9 parts LDH-based composite antioxidant, 0.5-1 part ultraviolet absorber, 0.1-1.5 parts nano-lanthanum hexaboride, 0.1-1.5 parts porous hollow nano-copper sulfide, and 0.1-2 parts nano-TiO2 / SiO2 core-shell particles.

[0007] Preferably, the raw materials include, by weight, 100 parts PVB resin, 25 parts composite plasticizer, 0.7 parts LDH-based composite antioxidant, 0.75 parts ultraviolet absorber, 1 part nano lanthanum hexaboride, 0.8 parts porous hollow nano copper sulfide, and 1.2 parts nano TiO2 / SiO2 core-shell particles.

[0008] Preferably, the LDH-based composite antioxidant is prepared from the following raw materials in parts by weight: 4-8 parts magnesium aluminum layered bimetallic hydroxide, 23-34 parts pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4.4-8.8 parts isophorone diisocyanate, 0.08-0.16 parts dibutyltin dilaurate, and 140-280 parts N,N-dimethylformamide;

[0009] Preferably, the magnesium-aluminum layered bimetallic hydroxide is prepared from the following raw materials in parts by weight: 5.13-7.7 parts magnesium nitrate hexahydrate, 3.75-5.63 parts aluminum nitrate nonahydrate, 2.4-3.6 parts sodium hydroxide, 2.12-4.24 parts sodium carbonate, and 200-400 parts water.

[0010] Preferably, the preparation method of the LDH-based composite antioxidant includes the following steps:

[0011] Under a nitrogen atmosphere, 4.4-8.8 parts of isophorone diisocyanate and 0.08-0.16 parts of dibutyltin dilaurate were added sequentially to 20-40 parts of N,N-dimethylformamide and stirred until homogeneous to obtain a mixed solution. Then, 23-34 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] were added to a solution dissolved in 80-160 parts of N,N-dimethylformamide and stirred until dissolved. This solution was then added dropwise to the mixed solution. In the liquid, the reaction is carried out at 25-35℃ for 6-8 hours; 4-8 parts of magnesium aluminum layered bimetallic hydroxide are dispersed in 40-80 parts of N,N-dimethylformamide, and after ultrasonic treatment to form a uniform suspension, they are added to the reaction system, heated to 65-75℃ and reacted for 8-10 hours. The solid product is collected by centrifugation, washed with ethanol several times, and then dried in a vacuum drying oven at 60-70℃ to constant weight to obtain the LDH-based composite antioxidant.

[0012] Preferably, the method for preparing the magnesium-aluminum layered bimetallic hydroxide includes the following steps:

[0013] Dissolve 5.13-7.7 parts of magnesium nitrate hexahydrate and 3.75-5.63 parts of aluminum nitrate nonahydrate in 100-200 parts of water to obtain mixed solution a; dissolve 2.4-3.6 parts of sodium hydroxide and 2.12-4.24 parts of sodium carbonate in 100-200 parts of water to obtain mixed solution b; mix mixed solution a and mixed solution b at room temperature, maintain the pH value at 9.0-10.0, and stir continuously for 1-2 hours. Then crystallize the mixture at 110-130℃ for 12-14 hours, cool, centrifuge, wash several times with water and ethanol, and vacuum dry at 60-70℃ for 12-16 hours to obtain magnesium-aluminum layered bimetallic hydroxide.

[0014] Preferably, the porous hollow nano-copper sulfide is prepared from the following raw materials in parts by weight: 3-5 parts copper nitrate trihydrate, 8.4-12.6 parts DL-tartaric acid, 10-15 parts polyvinylpyrrolidone, 5.5-11 parts sodium hydroxide, 2.4-3.6 parts anhydrous glucose, 4.4-6.6 parts ascorbic acid, 2-3 parts thiourea, and 500-800 parts water.

[0015] Preferably, the method for preparing the porous hollow copper sulfide nanoparticles includes the following steps:

[0016] 500-800 parts of water were heated to 60-70℃ in an oil bath. Then, 3-5 parts of copper nitrate trihydrate, 8.4-12.6 parts of DL-tartaric acid, and 10-15 parts of polyvinylpyrrolidone were added sequentially. The mixture was stirred at 1100-1300 rpm for 10-20 min. Then, 5.5-11 parts of sodium hydroxide were added, and the mixture was stirred for another 10-20 min. Then, 2.4-3.6 parts of anhydrous glucose and 4.4-6.6 parts of ascorbic acid were added, and the mixture was stirred for another 10-20 min. Then, 2-3 parts of thiourea were added, and the temperature was raised to 80-90℃. The mixture was stirred for 4-6 h. After stirring, the mixture was centrifuged. The precipitate was washed several times with water and ethanol, and then vacuum dried at 50-60℃ for 5-7 h. After drying, the precipitate was ground to obtain porous hollow nano-copper sulfide.

[0017] Preferably, the composite plasticizer is composed of triethylene glycol diisooctanoate, trimellitate, epoxidized soybean oil, and nano-montmorillonite; the mass ratio of triethylene glycol diisooctanoate, trimellitate, epoxidized soybean oil, and nano-montmorillonite is 5-7:2-4:1:0.05-0.1.

[0018] This application provides a manufacturing process for a high-transparency PVB interlayer film, which employs the following technical solution:

[0019] A manufacturing process for a high-transparency PVB interlayer film includes the following steps:

[0020] S1. Weigh out the following raw materials by weight: 100 parts PVB resin, 20-30 parts composite plasticizer, 0.5-0.9 parts LDH-based composite antioxidant, 0.5-1 part ultraviolet absorber, 0.1-1.5 parts nano lanthanum hexaboride, 0.1-1.5 parts porous hollow nano copper sulfide, and 0.1-2 parts nano TiO2 / SiO2 core-shell particles;

[0021] S2. Modified nanofillers are obtained by modifying nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 core-shell particles with silane coupling agents.

[0022] S3. Add PVB resin, LDH-based composite antioxidant, ultraviolet absorber, and modified nanofiller to a high-speed mixer and mix for 5-10 minutes. Then add composite plasticizer and continue mixing for 10-15 minutes to obtain a mixture. Extrude the mixture through an extruder, then form it through a mold. After cooling, a PVB intermediate film is obtained.

[0023] Preferably, the silane coupling agent modification treatment in S2 includes the following steps:

[0024] Dry lanthanum hexaboride nanoparticles, porous hollow copper sulfide nanoparticles, and TiO2 / SiO2 core-shell nanoparticles were dispersed in anhydrous ethanol and ultrasonically dispersed for 1-1.5 h to obtain a dispersion. Silane coupling agent KH-570 was added to an ethanol aqueous solution, and the pH was adjusted to 3-4. The mixture was stirred and hydrolyzed for 1-1.5 h to obtain a silane coupling agent ethanol aqueous solution. The silane coupling agent ethanol aqueous solution was added to the dispersion and stirred for 24-30 h. After stirring, the mixture was ultrasonically dispersed for 30-50 min and then refluxed at 70-80℃ for 3-5 h. After reflux, the mixture was centrifuged, and the precipitate was washed several times with anhydrous ethanol and water. It was then vacuum dried at 60-70℃ for 24-30 h. After drying, the precipitate was ground to obtain the modified nanofiller.

[0025] The mass of the silane coupling agent KH-570 is 2-3% of the total mass of nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 core-shell particles.

[0026] This application provides an application of a high-transparency PVB interlayer film, employing the following technical solution:

[0027] An application of a high-transparency PVB interlayer film, wherein the PVB interlayer film is used in laminated glass.

[0028] In summary, this application includes at least one of the following beneficial technical effects:

[0029] 1. The LDH-based composite antioxidant provided in this application covalently grafts the antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] onto the surface of a magnesium-aluminum layered bimetallic hydroxide through the bridging effect of isophorone diisocyanate. The resulting antioxidant can be uniformly dispersed in the PVB matrix, avoiding light scattering and increased haze caused by filler agglomeration, thereby maintaining the high transparency of the PVB interlayer. The synergistic effect of the antioxidant pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and LDH further improves the photoaging resistance of the PVB interlayer, enabling it to maintain good optical and mechanical properties even after long-term exposure to ultraviolet light.

[0030] 2. The porous hollow copper sulfide nanomaterial provided in this application was prepared by using copper nitrate trihydrate and thiourea as copper and sulfur sources, respectively, through a hydrothermal template method. Its porous hollow structure can be uniformly dispersed in the PVB matrix, forming an effective stress dispersion network, thereby enhancing the overall mechanical properties of the material, reducing haze, and improving transparency.

[0031] 3. The PVB interlayer provided in this application involves modifying inorganic fillers such as nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 core-shell particles with a silane coupling agent during the preparation process. This significantly improves the dispersion of the inorganic fillers in the PVB matrix, reduces light scattering and absorption, and significantly reduces the haze of the PVB interlayer, giving it higher transparency and visual effect. Detailed Implementation

[0032] The present application will be further described in detail below with reference to the embodiments.

[0033] The chemical reagents used in the preparation examples, embodiments, and comparative examples provided in this invention are all commercially available products.

[0034] Preparation Example 1: Preparation of LDH-based Composite Antioxidant

[0035] Preparation Example 1.1

[0036] S1. Dissolve 5.13g magnesium nitrate hexahydrate and 3.75g aluminum nitrate nonahydrate in 100g deionized water to obtain mixed solution a; dissolve 2.4g sodium hydroxide and 2.12g sodium carbonate in 100g deionized water to obtain mixed solution b; mix mixed solution a and mixed solution b at room temperature, maintain pH value at 9.0, stir continuously for 1h, crystallize the mixture in a high-pressure reactor at 110℃ for 12h, cool, centrifuge, wash three times with deionized water and ethanol, and vacuum dry at 60℃ for 16h to obtain magnesium-aluminum layered bimetallic hydroxide;

[0037] S2. Under a nitrogen atmosphere, 4.4 g of isophorone diisocyanate and 0.08 g of dibutyltin dilaurate were added sequentially to 20 g of N,N-dimethylformamide and stirred until homogeneous to obtain a mixed solution. 23 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] was added to 80 g of N,N-dimethylformamide and stirred until dissolved. The solution was then added dropwise to the mixed solution over 1 hour and reacted at 25 °C for 6 hours. 4 g of the magnesium-aluminum layered bimetallic hydroxide prepared in S1 was dispersed in 40 g of N,N-dimethylformamide, sonicated to form a uniform suspension, and then added to the reaction system. The temperature was raised to 65 °C and the reaction was continued for 8 hours. The solid product was collected by centrifugation, washed three times with ethanol, and then dried in a vacuum drying oven at 60 °C to constant weight to obtain the LDH-based composite antioxidant.

[0038] Preparation Example 1.2

[0039] S1. Dissolve 6.42g magnesium nitrate hexahydrate and 4.69g aluminum nitrate nonahydrate in 150g deionized water to obtain mixed solution a; dissolve 3g sodium hydroxide and 3.18g sodium carbonate in 150g deionized water to obtain mixed solution b; mix mixed solution a and mixed solution b at room temperature, maintain pH value at 9.5, stir continuously for 1.5h, crystallize the mixture in a high-pressure reactor at 120℃ for 13h, cool, centrifuge, wash 4 times with deionized water and ethanol, and vacuum dry at 65℃ for 14h to obtain magnesium-aluminum layered bimetallic hydroxide;

[0040] S2. Under a nitrogen atmosphere, 6.6 g of isophorone diisocyanate and 0.12 g of dibutyltin dilaurate were added sequentially to 30 g of N,N-dimethylformamide and stirred until homogeneous to obtain a mixed solution. 28.5 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] was added to 120 g of N,N-dimethylformamide and stirred until dissolved. The solution was then added dropwise to the mixed solution over 1.5 h and reacted at 30 °C for 7 h. 6 g of the magnesium-aluminum layered bimetallic hydroxide prepared in S1 was dispersed in 60 g of N,N-dimethylformamide, sonicated to form a uniform suspension, and then added to the reaction system. The temperature was raised to 70 °C and the reaction was continued for 9 h. The solid product was collected by centrifugation, washed 43 times with ethanol, and then dried in a vacuum drying oven at 65 °C to constant weight to obtain the LDH-based composite antioxidant.

[0041] Preparation Example 1.3

[0042] S1. Dissolve 7.7g magnesium nitrate hexahydrate and 5.63g aluminum nitrate nonahydrate in 200g deionized water to obtain mixed solution a; dissolve 3.6g sodium hydroxide and 4.24g sodium carbonate in 200g deionized water to obtain mixed solution b; mix mixed solution a and mixed solution b at room temperature, maintain pH at 10.0, and stir continuously for 2 hours. Then, crystallize the mixture in a high-pressure reactor at 130℃ for 14 hours, cool, centrifuge, wash 5 times with deionized water and ethanol, and vacuum dry at 70℃ for 12 hours to obtain magnesium-aluminum layered bimetallic hydroxide.

[0043] S2. Under a nitrogen atmosphere, 8.8 g of isophorone diisocyanate and 0.16 g of dibutyltin dilaurate were added sequentially to 40 g of N,N-dimethylformamide and stirred until homogeneous to obtain a mixed solution. 34 g of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] was added to 160 g of N,N-dimethylformamide and stirred until dissolved. The solution was then added dropwise to the mixed solution over 2 hours and reacted at 35 °C for 8 hours. 8 g of the magnesium-aluminum layered bimetallic hydroxide prepared in S1 was dispersed in 80 g of N,N-dimethylformamide, sonicated to form a uniform suspension, and then added to the reaction system. The temperature was raised to 75 °C and the reaction was continued for 10 hours. The solid product was collected by centrifugation, washed five times with ethanol, and then dried in a vacuum drying oven at 70 °C to constant weight to obtain the LDH-based composite antioxidant.

[0044] Preparation Example 2: Preparation of Porous Hollow Copper Sulfide Nanoparticles

[0045] Preparation Example 2.1

[0046] 500g of deionized water was heated to 60℃ in an oil bath. Then, 3g of copper nitrate trihydrate, 8.4g of DL-tartaric acid, and 10g of polyvinylpyrrolidone were added sequentially. The mixture was stirred at 1100rpm for 10min. 5.5g of sodium hydroxide was added, and stirring was continued for 10min. 2.4g of anhydrous glucose and 4.4g of ascorbic acid were added, and stirring was continued for 10min. 2g of thiourea was added, and the temperature was raised to 80℃. The mixture was stirred for 4h. After stirring, the mixture was centrifuged. The resulting precipitate was washed three times with deionized water and ethanol, and then vacuum dried at 50℃ for 5h. After drying, porous hollow nano-copper sulfide was obtained by grinding.

[0047] Preparation Example 2.2

[0048] 650g of deionized water was heated to 65℃ in an oil bath. Then, 4g of copper nitrate trihydrate, 10.5g of DL-tartaric acid, and 12.5g of polyvinylpyrrolidone were added sequentially and stirred at 1200rpm for 15min. 8.3g of sodium hydroxide was added and stirring was continued for 15min. 3g of anhydrous glucose and 5.5g of ascorbic acid were added and stirred for 150min. 2.5g of thiourea was added, and the temperature was raised to 85℃ and stirred for 5h. After stirring, the mixture was centrifuged, and the resulting precipitate was washed four times with deionized water and ethanol. It was then vacuum dried at 55℃ for 6h. After drying, porous hollow nano-copper sulfide was obtained by grinding.

[0049] Preparation Example 2.3

[0050] 800g of deionized water was heated to 70℃ in an oil bath. Then, 5g of copper nitrate trihydrate, 12.6g of DL-tartaric acid, and 15g of polyvinylpyrrolidone were added sequentially. The mixture was stirred at 1300rpm for 20min. 11g of sodium hydroxide was added, and stirring was continued for 20min. 3.6g of anhydrous glucose and 6.6g of ascorbic acid were added, and stirring was continued for 20min. 3g of thiourea was added, and the temperature was raised to 90℃. The mixture was stirred for 6h. After stirring, the mixture was centrifuged. The resulting precipitate was washed five times with deionized water and ethanol, and then vacuum dried at 60℃ for 7h. After drying, porous hollow nano-copper sulfide was obtained by grinding.

[0051] Example 1

[0052] S1. Weigh 100g of PVB resin, 20g of composite plasticizer, 0.5g of LDH-based composite antioxidant prepared in Preparation Example 1.1, 0.5g of ultraviolet absorber, 0.1g of nano-lanthanum hexaboride, 0.1g of porous hollow nano-copper sulfide prepared in Preparation Example 2.1, and 0.1g of nano-TiO2 / SiO2 core-shell particles; the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in this example is 5:2:1:0.05; the ultraviolet absorber used is Tinuvin P; the nano-TiO2 / SiO2 core-shell particles used are purchased from Zhongke Natong, model ZK-NT01, TiO2:SiO2=1:1.5, D50=35nm;

[0053] S2. Dry lanthanum hexaboride nanoparticles, porous hollow copper sulfide nanoparticles, and TiO2 / SiO2 core-shell nanoparticles were dispersed in anhydrous ethanol and ultrasonically dispersed for 1 h to obtain a dispersion. 0.006 g of silane coupling agent KH-570 was added to 0.594 g of an aqueous ethanol solution (ethanol to water mass ratio of 9:1), and the pH was adjusted to 4 with 1 mol / L dilute hydrochloric acid. The mixture was stirred and hydrolyzed for 1 h to obtain an aqueous ethanol solution of the silane coupling agent. The aqueous ethanol solution of the silane coupling agent was added to the dispersion and stirred for 24 h. After stirring, the mixture was ultrasonically dispersed for 30 min and then refluxed at 70 °C for 3 h. After reflux, the precipitate was centrifuged, washed three times with anhydrous ethanol and deionized water, and then vacuum dried at 60 °C for 24 h. After drying, the modified nanofiller was obtained by grinding.

[0054] S3. PVB resin, LDH-based composite antioxidant, UV absorber, and modified nanofiller are added to a high-speed mixer and mixed for 5 minutes. Then, composite plasticizer is added and the mixture is mixed for another 10 minutes to obtain a mixture. The mixture is extruded through an extruder at 165°C and then formed through a die. A high-precision wedge die is selected, and the inner surface of the die is polished to ensure its smoothness and dimensional accuracy. An efficient cooling device is used to combine air cooling and water cooling to quickly reduce the film temperature. After cooling, the PVB intermediate film is obtained.

[0055] Example 2

[0056] S1. Weigh 100g of PVB resin, 25g of composite plasticizer, 0.7g of LDH-based composite antioxidant prepared in Preparation Example 1.1, 0.75g of ultraviolet absorber, 1g of nano-lanthanum hexaboride, 0.8g of porous hollow nano-copper sulfide prepared in Preparation Example 2.1, and 1.2g of nano-TiO2 / SiO2 core-shell particles; the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in this example is 5:2:1:0.05; the ultraviolet absorber used is Tinuvin P; the nano-TiO2 / SiO2 core-shell particles used are purchased from Zhongke Natong, model ZK-NT01, TiO2:SiO2=1:1.5, D50=35nm;

[0057] S2. Dry lanthanum hexaboride nanoparticles, porous hollow copper sulfide nanoparticles, and TiO2 / SiO2 core-shell nanoparticles were dispersed in anhydrous ethanol and ultrasonically dispersed for 1.25 h to obtain a dispersion. 0.04 g of silane coupling agent KH-570 was added to 3.96 g of ethanol-water solution (ethanol to water mass ratio of 9:1), and the pH was adjusted to 3.5 with 1 mol / L dilute hydrochloric acid. The mixture was stirred and hydrolyzed for 1.25 h to obtain an ethanol-water solution of silane coupling agent. The ethanol-water solution of silane coupling agent was added to the dispersion and stirred for 27 h. After stirring, the mixture was ultrasonically dispersed for 40 min and then refluxed at 75 °C for 4 h. After reflux, the precipitate was centrifuged, washed four times with anhydrous ethanol and deionized water, and then vacuum dried at 65 °C for 27 h. After drying, the modified nanofiller was obtained by grinding.

[0058] S3. PVB resin, LDH-based composite antioxidant, UV absorber, and modified nanofiller are added to a high-speed mixer and mixed for 7 minutes. Then, composite plasticizer is added and the mixture is mixed for another 13 minutes to obtain a mixture. The mixture is extruded through an extruder at 170°C and then formed through a die. A high-precision wedge die is selected, and the inner surface of the die is polished to ensure its smoothness and dimensional accuracy. An efficient cooling device is used to combine air cooling and water cooling to quickly reduce the film temperature. After cooling, the PVB intermediate film is obtained.

[0059] Example 3

[0060] S1. Weigh 100g of PVB resin, 30g of composite plasticizer, 0.9g of LDH-based composite antioxidant prepared in Preparation Example 1.1, 1g of ultraviolet absorber, 1.5g of nano-lanthanum hexaboride, 1.5g of porous hollow nano-copper sulfide prepared in Preparation Example 2.1, and 2g of nano-TiO2 / SiO2 core-shell particles; the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in this example is 5:2:1:0.05; the ultraviolet absorber used is Tinuvin P; the nano-TiO2 / SiO2 core-shell particles used are purchased from Zhongke Natong, model ZK-NT01, TiO2:SiO2=1:1.5, D50=35nm;

[0061] S2. Dry nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 core-shell particles were dispersed in anhydrous ethanol and ultrasonically dispersed for 1 h to obtain a dispersion. 0.1 g of silane coupling agent KH-570 was added to 9.9 g of ethanol-water solution (ethanol to water mass ratio of 9:1), and the pH was adjusted to 3 with 1 mol / L dilute hydrochloric acid. The mixture was stirred and hydrolyzed for 1.5 h to obtain a silane coupling agent ethanol-water solution. The silane coupling agent ethanol-water solution was added to the dispersion and stirred for 30 h. After stirring, the mixture was ultrasonically dispersed for 50 min and then refluxed at 80 °C for 5 h. After reflux, the precipitate was centrifuged, washed 5 times with anhydrous ethanol and deionized water, and then vacuum dried at 70 °C for 30 h. After drying, the modified nanofiller was obtained by grinding.

[0062] S3. PVB resin, LDH-based composite antioxidant, UV absorber, and modified nanofiller are added to a high-speed mixer and mixed for 10 minutes. Then, composite plasticizer is added and the mixture is mixed for another 15 minutes to obtain a mixture. The mixture is extruded through an extruder at 175°C and then formed through a die. A high-precision wedge die is selected, and the inner surface of the die is polished to ensure its smoothness and dimensional accuracy. An efficient cooling device is used to combine air cooling and water cooling to quickly reduce the film temperature. After cooling, the PVB intermediate film is obtained.

[0063] Example 4

[0064] The difference between Example 4 and Example 1 is that the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in Example 4 is 6:3:1:0.075.

[0065] Example 5

[0066] The difference between Example 5 and Example 1 is that the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in Example 5 is 7:4:1:0.1.

[0067] Example 6

[0068] The difference between Example 6 and Example 1 is that the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in Example 6 is 4:1:1:0.025.

[0069] Example 7

[0070] The difference between Example 7 and Example 1 is that the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in Example 7 is 8:5:1:0.15.

[0071] Example 8

[0072] The difference between Example 8 and Example 1 is that the mass of silane coupling agent KH-570 used in Example 8 is 0.0075g, and the mass of ethanol aqueous solution (mass ratio of ethanol to water is 9:1) is 0.7425g.

[0073] Example 9

[0074] The difference between Example 9 and Example 1 is that the mass of silane coupling agent KH-570 used in Example 9 is 0.009 g, and the mass of ethanol aqueous solution (mass ratio of ethanol to water is 9:1) is 0.0891 g.

[0075] Example 10

[0076] The difference between Example 10 and Example 1 is that the mass of silane coupling agent KH-570 used in Example 10 is 0.003g, and the mass of ethanol aqueous solution (mass ratio of ethanol to water is 9:1) is 0.297g.

[0077] Example 11

[0078] The difference between Example 11 and Example 1 is that the mass of silane coupling agent KH-570 used in Example 11 is 0.012g, and the mass of ethanol aqueous solution (mass ratio of ethanol to water is 9:1) is 1.188g.

[0079] Example 12

[0080] The difference between Example 12 and Example 1 is that the LDH-based composite antioxidant used in Example 12 was prepared from Preparation Example 1.2.

[0081] Example 13

[0082] The difference between Example 13 and Example 1 is that the LDH-based composite antioxidant used in Example 13 was prepared from Preparation Example 1.3.

[0083] Example 14

[0084] The difference between Example 14 and Example 1 is that the porous hollow copper sulfide nanoparticles used in Example 14 were prepared by Preparation Example 2.2.

[0085] Example 15

[0086] The difference between Example 15 and Example 1 is that the porous hollow nano-copper sulfide used in Example 15 was prepared by Preparation Example 2.3.

[0087] Comparative Example 1

[0088] The difference between Comparative Example 1 and Example 1 is that in Comparative Example 1, an equal amount of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] was used instead of the LDH-based complex antioxidant.

[0089] Comparative Example 2

[0090] The difference between Comparative Example 2 and Example 1 is that, in Comparative Example 2, an equal amount of ordinary untreated nano-copper sulfide was used instead of porous hollow nano-copper sulfide.

[0091] Comparative Example 3

[0092] The difference between Comparative Example 3 and Example 1 is that in Comparative Example 3, an equal amount of triethylene glycol diisooctanoate was used instead of the composite plasticizer.

[0093] Comparative Example 4

[0094] The difference between Comparative Example 4 and Example 1 is that the nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 in Comparative Example 4 were not modified with silane coupling agents. The preparation method of the PVB interlayer is as follows:

[0095] S1. Weigh 100g of PVB resin, 20g of composite plasticizer, 0.5g of LDH-based composite antioxidant prepared in Preparation Example 1.1, 0.5g of ultraviolet absorber, 0.1g of nano-lanthanum hexaboride, 0.1g of porous hollow nano-copper sulfide prepared in Preparation Example 2.1, and 0.1g of nano-TiO2 / SiO2 core-shell particles; the mass ratio of the composite plasticizer triethylene glycol diisooctanoate, trimellitic acid ester, epoxidized soybean oil, and nano-montmorillonite used in this example is 5:2:1:0.05; the ultraviolet absorber used is Tinuvin P;

[0096] S2. PVB resin, LDH-based composite antioxidant, UV absorber, nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 are added to a high-speed mixer and mixed for 5 minutes. Then, a composite plasticizer is added, and the mixture is mixed for another 10 minutes to obtain a mixture. The mixture is extruded through an extruder at 165°C, and then formed through a die. A high-precision wedge die is selected, and the inner surface of the die is polished to ensure its smoothness and dimensional accuracy. An efficient cooling device is used, combining air cooling and water cooling to quickly reduce the film temperature. After cooling, the PVB interlayer film is obtained.

[0097] Performance testing

[0098] I. The transmittance and haze of the PVB interlayer films obtained in Examples 1-15 and Comparative Examples 1-4 were tested in accordance with GB / T 2410-2008 "Determination of transmittance and haze of transparent plastics". The results are shown in Table 1.

[0099] II. The tensile strength of the PVB interlayer films obtained in Examples 1-15 and Comparative Examples 1-4 were tested in accordance with GB / T 1040.1-2018 "Determination of tensile properties of plastics". The results are shown in Table 1.

[0100] III. Aging Resistance Test: The PVB interlayers obtained in Examples 1-15 and Comparative Examples 1-4 were subjected to UV 60 kWh / m 2 The PVB interlayer was aged at 60℃ for 90 days, and the transmittance and yellowing index of the aged PVB interlayer were tested. The results are shown in Table 1.

[0101] The specific test results are as follows:

[0102] Table 1 Performance Test Results

[0103]

[0104]

[0105] As can be seen from the test results in Table 1, the PVB interlayer provided in this application has high transmittance and low haze, with a UV transmittance of 60 kWh / m. 2 After aging at 60℃ for 90 days, the light transmittance only decreased slightly and the yellowing index was less than 1, indicating that the PVB interlayer provided in this application has high antioxidant properties and excellent stability; in addition, the PVB interlayer provided in this application also has high tensile strength.

[0106] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A high-transparency PVB interlayer, characterized in that: The raw materials, by weight, include 100 parts PVB resin, 20-30 parts composite plasticizer, 0.5-0.9 parts LDH-based composite antioxidant, 0.5-1 part ultraviolet absorber, 0.1-1.5 parts nano lanthanum hexaboride, 0.1-1.5 parts porous hollow nano copper sulfide, and 0.1-2 parts nano TiO2 / SiO2 core-shell particles.

2. The high-transparency PVB interlayer film according to claim 1, characterized in that: The raw materials, by weight, include 100 parts PVB resin, 25 parts composite plasticizer, 0.7 parts LDH-based composite antioxidant, 0.75 parts ultraviolet absorber, 1 part nano lanthanum hexaboride, 0.8 parts porous hollow nano copper sulfide, and 1.2 parts nano TiO2 / SiO2 core-shell particles.

3. The high-transparency PVB interlayer film according to claim 1, characterized in that: The LDH-based composite antioxidant is prepared from the following raw materials in parts by weight: 4-8 parts magnesium aluminum layered bimetallic hydroxide, 23-34 parts pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4.4-8.8 parts isophorone diisocyanate, 0.08-0.16 parts dibutyltin dilaurate, and 140-280 parts N,N-dimethylformamide; The magnesium-aluminum layered bimetallic hydroxide is prepared from the following raw materials in parts by weight: 5.13-7.7 parts magnesium nitrate hexahydrate, 3.75-5.63 parts aluminum nitrate nonahydrate, 2.4-3.6 parts sodium hydroxide, 2.12-4.24 parts sodium carbonate, and 200-400 parts water.

4. The high-transparency PVB interlayer film according to claim 3, characterized in that: The preparation method of the LDH-based composite antioxidant includes the following steps: Under a nitrogen atmosphere, 4.4-8.8 parts of isophorone diisocyanate and 0.08-0.16 parts of dibutyltin dilaurate were added sequentially to 20-40 parts of N,N-dimethylformamide and stirred until homogeneous to obtain a mixed solution. Then, 23-34 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] were added to a solution dissolved in 80-160 parts of N,N-dimethylformamide and stirred until dissolved. This solution was then added dropwise to the mixed solution. In the liquid, the reaction is carried out at 25-35℃ for 6-8 hours; 4-8 parts of magnesium aluminum layered bimetallic hydroxide are dispersed in 40-80 parts of N,N-dimethylformamide, and after ultrasonic treatment to form a uniform suspension, they are added to the reaction system, heated to 65-75℃ and reacted for 8-10 hours. The solid product is collected by centrifugation, washed with ethanol several times, and then dried in a vacuum drying oven at 60-70℃ to constant weight to obtain the LDH-based composite antioxidant. The method for preparing the magnesium-aluminum layered bimetallic hydroxide includes the following steps: Dissolve 5.13-7.7 parts of magnesium nitrate hexahydrate and 3.75-5.63 parts of aluminum nitrate nonahydrate in 100-200 parts of water to obtain mixed solution a; dissolve 2.4-3.6 parts of sodium hydroxide and 2.12-4.24 parts of sodium carbonate in 100-200 parts of water to obtain mixed solution b; mix mixed solution a and mixed solution b at room temperature, maintain the pH value at 9.0-10.0, and stir continuously for 1-2 hours. Then crystallize the mixture at 110-130℃ for 12-14 hours, cool, centrifuge, wash several times with water and ethanol, and vacuum dry at 60-70℃ for 12-16 hours to obtain magnesium-aluminum layered bimetallic hydroxide.

5. The high-transparency PVB interlayer film according to claim 1, characterized in that: The porous hollow nano-copper sulfide is prepared from the following raw materials in parts by weight: 3-5 parts copper nitrate trihydrate, 8.4-12.6 parts DL-tartaric acid, 10-15 parts polyvinylpyrrolidone, 5.5-11 parts sodium hydroxide, 2.4-3.6 parts anhydrous glucose, 4.4-6.6 parts ascorbic acid, 2-3 parts thiourea, and 500-800 parts water.

6. The high-transparency PVB interlayer film according to claim 5, characterized in that: The method for preparing the porous hollow nano-copper sulfide includes the following steps: 500-800 parts of water were heated to 60-70℃ in an oil bath. Then, 3-5 parts of copper nitrate trihydrate, 8.4-12.6 parts of DL-tartaric acid, and 10-15 parts of polyvinylpyrrolidone were added sequentially. The mixture was stirred at 1100-1300 rpm for 10-20 min. Then, 5.5-11 parts of sodium hydroxide were added, and the mixture was stirred for another 10-20 min. Then, 2.4-3.6 parts of anhydrous glucose and 4.4-6.6 parts of ascorbic acid were added, and the mixture was stirred for another 10-20 min. Then, 2-3 parts of thiourea were added, and the temperature was raised to 80-90℃. The mixture was stirred for 4-6 h. After stirring, the mixture was centrifuged. The precipitate was washed several times with water and ethanol, and then vacuum dried at 50-60℃ for 5-7 h. After drying, the precipitate was ground to obtain porous hollow nano-copper sulfide.

7. The high-transparency PVB interlayer film according to claim 1, characterized in that: The composite plasticizer is composed of triethylene glycol diisooctanoate, trimellitate, epoxidized soybean oil, and nano-montmorillonite; the mass ratio of triethylene glycol diisooctanoate, trimellitate, epoxidized soybean oil, and nano-montmorillonite is 5-7:2-4:1:0.05-0.

1.

8. The production process of a high-transparency PVB interlayer film according to any one of claims 1-7, characterized in that: Includes the following steps: S1. Weigh out the following raw materials by weight: 100 parts PVB resin, 20-30 parts composite plasticizer, 0.5-0.9 parts LDH-based composite antioxidant, 0.5-1 part ultraviolet absorber, 0.1-1.5 parts nano lanthanum hexaboride, 0.1-1.5 parts porous hollow nano copper sulfide, and 0.1-2 parts nano TiO2 / SiO2 core-shell particles; S2. Modified nanofillers are obtained by modifying nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 core-shell particles with silane coupling agents. S3. Add PVB resin, LDH-based composite antioxidant, ultraviolet absorber, and modified nanofiller to a high-speed mixer and mix for 5-10 minutes. Then add composite plasticizer and continue mixing for 10-15 minutes to obtain a mixture. Extrude the mixture through an extruder, then form it through a mold. After cooling, a PVB intermediate film is obtained.

9. The production process of a high-transparency PVB interlayer film according to claim 8, characterized in that: The silane coupling agent modification treatment described in S2 includes the following steps: Dry lanthanum hexaboride nanoparticles, porous hollow copper sulfide nanoparticles, and TiO2 / SiO2 core-shell nanoparticles were dispersed in anhydrous ethanol and ultrasonically dispersed for 1-1.5 h to obtain a dispersion. Silane coupling agent KH-570 was added to an ethanol aqueous solution, and the pH was adjusted to 3-4. The mixture was stirred and hydrolyzed for 1-1.5 h to obtain a silane coupling agent ethanol aqueous solution. The silane coupling agent ethanol aqueous solution was added to the dispersion and stirred for 24-30 h. After stirring, the mixture was ultrasonically dispersed for 30-50 min and then refluxed at 70-80℃ for 3-5 h. After reflux, the mixture was centrifuged, and the precipitate was washed several times with anhydrous ethanol and water. It was then vacuum dried at 60-70℃ for 24-30 h. After drying, the precipitate was ground to obtain the modified nanofiller. The mass of the silane coupling agent KH-570 is 2-3% of the total mass of nano-lanthanum hexaboride, porous hollow nano-copper sulfide, and nano-TiO2 / SiO2 core-shell particles.

10. The application of a high-transparency PVB interlayer film according to any one of claims 1-7, characterized in that: Application of the PVB interlayer in laminated glass.

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